Adv Funct Materials - 2024 - Shelake - Emerging Photoreforming Process To Hydrogen Production A Future Energy - Shelake - 2024

REVIEW
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Emerging Photoreforming Process to Hydrogen Production:

A Future Energy
Sandip Prabhakar Shelake, Dattatray Namdev Sutar, B. Moses Abraham,
Tanmay Banerjee, Annadanam V. Sesha Sainath,* and Ujjwal Pal*
In the quest of renewable energy technologies, solar photoreforming emerges using renewable energy sources. Assum-
ing the rich chemistry produced in current
as one of the affordable yet challenging process for converting biomass into
years and the appropriateness of the result-
hydrogen, hydrocarbon fuels, and chemicals. This review highlights the ing biofuels to match present power and
state-of-the-art photoreforming, elucidating its underlying mechanisms for the transport infrastructures, the careful con-
conversion of dissipated polymers into H2 and valuable chemicals. Biomass version of biomass substrates into energy
feedstocks such as carbohydrates, agricultural residues, glycopolymers, food looks to be a practical approach in these
terms (Figure 1a).[1–8] In addition, it is be-
wastes, and waste plastics are evaluated based on their chemical composition,
lieved that the sun exists as the only long-
energy content, and sustainability aspects, exploring the selection of term, sustainable source of energy.[6,9] One
appropriate bio-renewable resources, considering their abundance, of the most interesting solutions is to store
availability, and potential for hydrogen production. The impact of diverse it using solar fuels.[10,11] Amongst such ap-
process parameters on photoreforming efficiency is explored, encompassing proaches, solar H2 generation as a clean en-
factors like reaction temperature, pH, catalyst loading, reactor design, solvent ergy source is among these particularly ap-
pealing approaches.[9,12–15] However, at low
effect, and light intensity across various sacrificial substrates. The discussion
efficiency in visible light-barely exceeding
also considers their correlation with hydrogen production rate, selectivity, and 5% for the best performers-photocatalytic
energy efficiency. This review buckles on the design and synthesis of or photo-electrocatalytic devices have been
functional photocatalysts for biomass-derived feedstock, highlighting their designed to permit the realization of total
photocatalytic (PC) properties in biomass reforming processes and related H2 O splitting in one process.[16–18] The en-
ergy requirements for the photo-assisted re-
feedstock into valuable chemicals and biofuel. The review also delves into
forming of biomass substrates are similar
potential pathways for future advancements including artificial intelligence to the total H2 O splitting process, with the
(AI) and machine learning (ML), alongside addressing the challenges and distinction that biomass substitutes H2 O
insightful perspectives within this evolving field of future green energy. as the source of electrons and protons.[19]
Despite how depressing they may seem;
these are great numbers because they open
1. Introduction the door to a straight solar-to-energy state
where solar light energy is stored as chemical energy. Approxi-
Future energy plans are predicted to be greatly influenced by mately 33.4 to 36.4 billion metric tons of CO2 were spread into
how rationally we switch from using fossil fuels to effectively the air from energy sources in this last decade.[20–22] This release
S. P. Shelake, D. N. Sutar, A. V. S. Sainath B. M. Abraham

Polymers and Functional Materials and Fluoro-Agrochemicals A.J. Drexel Nanomaterials Institute, and Department of Materials Science
Department and Engineering
CSIR-Indian Institute of Chemical Technology Drexel University
Uppal Road, Hyderabad 500007, India Philadelphia 19104, USA
E-mail: avss@iict.res.in T. Banerjee[+]
S. P. Shelake, D. N. Sutar, A. V. S. Sainath, U. Pal Department of Chemistry
Academy of Scientific and Innovative Research (AcSIR) BITS Pilani
Ghaziabad 201002, India Pilani, Rajasthan 333031, India
E-mail: ujjwalpal@iict.res.in U. Pal
The ORCID identification number(s) for the author(s) of this article Department of Energy and Environmental Engineering
can be found under https://doi.org/10.1002/adfm.202403795 CSIR-Indian Institute of Chemical Technology
Hyderabad 500007, India
[+] Present
address: Research & Development (Metals) Division, Quaker
Chemical India Pvt. Ltd. (A Quaker Houghton Company), Kolkata 700107,
India
DOI: 10.1002/adfm.202403795
Adv. Funct. Mater. 2024, 2403795 2403795 (1 of 46) © 2024 Wiley-VCH GmbH
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Figure 1. a) The literature trends in publications related to biomass research, and b) photocatalysis, illustrating the publication count derived from a
Google Scholar search conducted with the keyword “photoreforming” during the years 2010 to 2023.
enlarged the CO2 concentration to >400 ppm, which was not sions about the use of biomass substrates or sacrificial electron
noticed in the previous 4.5 × 105 to 6.0 × 105 years.[22] Despite donors (SEDs) for photoreforming to produce H2 and valuable
facing these difficulties, we presently do not have established feedstocks.
methods to consistently capture CO2 from the higher regions of Over the past 15 years, there has been a notable surge
the atmosphere, and its removal in the lower atmosphere (bio- in interest in the conversion of biomass to chemicals within
sphere) is a slow process. It may take too long until technologies both industrial companies and academia, supported by inter-
are available that aggressively consume the released CO2 .[23,24] national and national agencies. While the literature consis-
The rise in CO2 emissions has motivated researchers worldwide tently emphasizes the primary goal of photocatalysis as achiev-
to redirect their focus toward discovering economically viable, ing industrial-level operation and deployment, actual instances
carbon-neutral, and ecologically sustainable alternative energy of such accomplishments are rare. Global chemical manufac-
sources.[25–27] turers have increasingly explored renewable feedstocks for the
Moreover, addressing the escalating global energy demands production of both bulk and specialty chemicals. Simultane-
to sustain development is a crucial and urgent concern, ensur- ously, start-ups and small to medium-sized enterprises (SMEs)
ing the fulfillment of future energy requirements without com- have pioneered innovative processes to manufacture chemi-
promising environmental sustainability. Hydrogen fuel is recog- cals and materials in niche markets. The academic commu-
nized as a prominent avenue for clean energy sources because of nity, backed by national and multinational programs has closely
its abundant stored energy and minimal environmental impact, followed this momentum leading to a substantial spike in the
making it a fuel that produces no emissions.[28–32] At present, number of journal articles dedicated to biomass conversion
H2 serves as the main propellant in NASA’s space program, uti- to valuable chemicals over the past 7–8 years (source: Google
lized in space shuttles, satellites, and rockets for a range of space Scholar).[47] Despite the initial publication on this subject dat-
missions.[33] The potential uses of H2 fuel extend to numerous ing back to 1981, a significant uptick in publications did not
industries such as petrochemical manufacturing, refinery pro- occur until 2010. Subsequently, there was a remarkable surge
cesses including glass cleaning, gasoline desulfurization and re- from 2015 onward, culminating in 827 papers published in the
formulation, metallurgical applications, and steel processing for last year (2023) containing the keyword “photoreforming” high-
heat treatment where it can act as an O2 scavenger. Furthermore, lighting the speedy development of this area, as depicted in
there is an anticipation for the application of H2 as a fuel to be ex- Figure 1b, which illustrates emerging research trends in the
panded to include H2 -powered vehicles (zero-emission vehicles) literature.[48]
and household uses.[34,35] The extensive research on this subject After oil, natural gas, and coal, biomass is the 4th major en-
has significantly improved our understanding of photocatalysis ergy source in the world.[49–52] In nature, photosynthesis cap-
as an achievable method to produce hydrogen.[36–41] In addition tures carbon from atmospheric CO2 to produce 170 billion metric
to total photoreforming, H2 O splitting has appeared as an ex- tons of biomass each year.[53,54] Biomass resources are organic
tremely effective solar light that encouraged hydrogen genera- materials that are derived from living organisms, and they can
tion from water and oxygenated substrates.[42–46] In this review, be utilized as a source of solar energy and valuable chemicals.
we discussed practical and fundamental aspects of these conver- Biomass resources include a widespread choice of feedstocks
Figure 2. a) Representation of sources of biomass, b) graphic representation of the spatial and chemical structure of lignocellulose, c) data driven
approach, and d) roadmap to attain a benchmark product via photoreforming.
such as agricultural residues, forestry wastes, industrial residues, biomass resources requires careful consideration of environmen-
sewage, and municipal solid wastes (Figure 2a).[55–58] These feed- tal, social, and economic factors to ensure that their production
stocks can be converted into various forms of bioenergy such and conversion are socially just and environmentally sustainable.
as biogas, biofuels, and electricity through different conver- Plants containing generally carbohydrate polymers such as hemi-
sion technologies such as photoreforming,[59–65] pyrolysis,[66–71] cellulose and cellulose and an aromatic macromolecule (lignin)
gasification,[72–76] and fermentation (Figure 1a).[77–81] One sig- known as lignocellulose, which denotes over 90% of all plant
nificant advantage of organic reforming, which requires less biomass.[89–91]
energy, is its strong preference for the sluggish kinetics of The denoted structure of lignocellulose (biomass) is illustrated
O2 generation. This process eliminates the necessity for costly in Figure 2b. A lignin shelter encapsulated the cellulose and
or hazardous hole scavengers.[82] Biomass resources have the hemicellulose. Hydrogen bonding facilitates the binding of cel-
ability to give a sustainable energy future by providing a re- lulose fibres to hemicellulose and lignin, whereas hemicellu-
liable and secure source of energy,[83,84] reducing greenhouse lose forms covalent bonds with lignin. Depending on the type
gas emissions,[85–88] and creating new economic opportunities of plant, the proportion of each component varies, but typically,
for rural communities. However, the sustainable utilization of normal lignocellulose is made up of 30–50% cellulose, 25–30%
Table 1. Raw biomass and its chemical composition.[60,114] In a workflow related to PC H2 creation, it is crucial to un-
derstand the specific tasks or challenges that are addressed in
Biomass Lignin [%] Cellulose [%] Hemicellulose [%] the process. AIML is generally used for building conversational
Sugarcane straw 22–25 40–44 30–32 agents, and it might not be the primary tool for directly deal-
Sugarcane bagasse 23–32 32–48 19–24
ing with the scientific aspects of PC reactions. The schematic
representation demonstrates the ML workflow, starting with the
Hard wood 16–24 43–47 25–35
data processing derived from biomass information of both ex-
Soft wood 25–31 40–44 25–29
perimental and theoretical studies, followed by feature engi-
Corn stover 35 35 25
neering, model formulation, model validation, hyperparameter
Corncob 15 45 35 tuning, descriptor selection, and property prediction for mod-
Cotton 0.3 95 2 eling green hydrogen evolution and valuable feedstock genera-
Wheat straw 15 30 50 tion (Figure 2c).[105,106] Figure 2d represents a future objective, ex-
Sisal hemp 11 73.1 14.2 pected ≈in 2050, wherein the widespread adoption of renewable
Rice straw 16.3 43.3 26.4 energy is anticipated. This is attributed to governmental commit-
Coir 41–45 36–43 0.15–0.25 ments toward an energy transition by 2050, aimed at reducing
Banana fiber 5–10 60–65 6–8 emissions and minimizing the depletion of fossil fuels. The out-
Barley straw 14–19 31–45 27–38
lined plan aligns with multiple studies emphasizing the estab-
lishment of H2 source infrastructure by 2050.[60]
Switchgrass 5–20 30–50 10–40
The PC reforming process of biomass substrates has been
Rye straw 16–19 33–35 27–30
recently studied by top research groups (including Reisner,[107]
Oat straw 16–19 31–37 27–38
Wang,[103] Sun,[108] Soo,[109] and Stephenson[110] ) using several
Rice husk 26–31 25–35 18–21 catalytic systems. The current important research conducted by
Sweet sorghum 14–21 34–45 18–27 Reisner’s and colleagues indicates that photoreforming of waste
Corn leaves 15.18 26.93 13.27 materials has the potential to be highly effective in generating re-
Bamboo 20.81 39.80 19.49 newable and sustainable energy. This method not only produces
Hazelnut shell 42.1 25.2 28.2 ecologically H2 fuels, but also generates valuable chemicals.[107]
Miscanthus 24–25 38–40 18.24 The attractiveness of photoreforming degrades different kinds of
Cork 30 44 21 waste polymers (plastic and biomass) and is nonselective.[111,112]
Herb 22 38 24
Even food waste existing in the H2 O does not disturb the reaction
feedback but expands efficacy. This method has the capability to
convert large quantities of raw biomass into both H2 and valuable
chemicals using solar light, resulting in economic and environ-
hemicellulose, and 15–25% lignin.[92–94] Dissimilar to cellulose, mental benefits.[107,113] The initiation of this comprehensive re-
hemicellulose is a diverse polysaccharide consisting of randomly view entails a precise evaluation of photoreforming aimed at mit-
arranged and branched molecules. It is composed of various sug- igating biomass waste issues. In review, numerous green hydro-
ars such as mannose, arabinose, xylose, glucose, galactose, rham- gen methodologies have been devised to tackle these challenges,
nose, uranic acids, and fucose including methyl glucuronic acid, although encountering significant economic and technological
galacturonic acid, and glucuronic acid.[95,96] The process of pho- barriers in real-world implementation. In tandem with advance-
toreforming has been effectively employed to break down saccha- ments in recycling technologies, our focus gravitates toward se-
rides (such as monosaccharides, disaccharides, and polysaccha- lection and design of materials and catalysts for efficient pho-
rides), which serve as the fundamental units or building blocks tocatalytic (PC) transformations of wide range of biomass, plas-
of structural biomacromolecules, resulting in the production of tics, solid waste, and glycopolymers into hydrogen, biofuel, and
environmentally-friendly hydrogen.[97] Lignin is a widely avail- valuable chemicals. Furthermore, we undertake a thorough re-
able organic polymer found in nature that is resistant to chem- view of various process parameters and relevant aspects, includ-
ical reactions and is not soluble in water. It is composed of hy- ing the influential factors in photoreforming processes, physico-
drophobic and non-crystalline propyl-phenolic (aromatic) units chemical characteristics, mechanistic elucidations, future oppor-
of biopolymers.[98] Usually, hardwood and agricultural waste tunities, and the integration of artificial intelligence (AI), and ma-
have a lesser lignin portion than softwood.[99,100] The Table 1 illus- chine learning (ML) methodologies that help to design PC system
trates the chemical alignment of lignocellulosic biomass derived for large scale and improved performance of hydrogen genera-
from various sources. Lignocellulose, the abundant biomass on tion (Scheme 1).
earth, has shown a tremendous ability for biomass PC reform-
ing ever since the primary report of employing biomass as PC
reforming substrate in the 1980s.[101] This is attributed to lig- 2. Moving toward Photocatalysts Boosted by
nocellulose serving not only as an e− donor and/or h+ scav- Sunlight for Energy Production
enger to encourage the departure and feasting of the photo-
generated charges, but also be concurrently altered into sev- Sun-driven hydrogen evolution methods harness solar energy
eral valuable feedstocks. Additionally, the PC hydrogen produc- to produce hydrogen through various processes. Two common
tion efficacy is boosted through coupling with PC lignocellulose approaches for solar-driven hydrogen evolution are photoelec-
oxidation.[102–104] trochemical (PEC) and PC water splitting. Each method has its
Scheme 1. General classes of photoreforming substrates discussed in this review.
rewards and limitations, and the choice between them depends to be improved due to the irregular nature of sunlight and the spa-
on the specific application and requirements. tial and temporal difference between supply and demand. PEC
H2 O splitting using earth-abundant semiconductor electrodes of
2.1. PEC Water Splitting the solar energy translation and storage revolt, has received much
attention.[115] If the quest for the successful development and im-
Sustainable energy sources are required because of the imbal- plementation of hydrogen-based fuel systems is accomplished, it
ance between the world’s population growth, rising energy con- could create opportunities for hydrogen to be used widely as an
sumption, and reducing fossil fuel supplies. The hunt for renew- environmentally friendly fuel. For a semiconductor electrode to
able and ecologically acceptable energy sources has received a lot be used as a device for PEC H2 O splitting, it needs to fulfil sev-
of attention to this point. Solar energy harvesting and storage are eral essential criteria such as appropriate band gap, possessing
Figure 3. a) Band gap position of some common photocatalysts used for photoreforming, and the pathways of b) photoreforming, c) photocatalytic
water splitting in anaerobic conditions, and d) organic photo-oxidation in the presence of oxygen.
valence and conduction band places that are suitable concerning choice of catalysts, stability, and upscaling capability. To attain a
the potentials for water oxidation and reduction, being able to supreme semiconductor for H2 O splitting, its VB and CB edge
absorb visible light effectively, demonstrating chemical stability positions should be positioned in a way that they sandwich the
both in the absence and presence of light, and being commer- potentials for H2 O oxidation and reduction (i.e., Ev < Eox,water and
cially viable, etc.[116–118] In the 1970s, researchers became inter- Ec > Ered,water ), the band edge places of some semiconductors
ested in PEC water splitting after Fujishima and Honda’s catalyst relative to H2 O redox potentials was shown in Figure 3a. Various
research. They were able to split water via a PEC cell that had a MOFs, ZIFs, metal oxides and sulphides photoelectrode materi-
single crystalline TiO2 (rutile) anode and a Pt cathode, with the als have since been developed, including TiO2 , CdS, MoS2 , GaP,
help of UV radiation and an external bias. Although PEC water ZnO, g-C3 N4 , SiC, UiO-66, ZIF-8, graphene oxide dots (GOD’s),
splitting systems have demonstrated potential in several appli- Carbon dots (CD’s) and PANI have been widely utilized for PEC
cations and achieved numerous notable accomplishments, they H2 O splitting.[119–128] The process of oxidizing H2 O to obtain
still face several challenges/limitations such as complex setups, electrons in a photocatalytic system requires a considerable
choice of electrodes, stability across larger surface areas, and cor- amount of energy. Therefore, in most artificial photocatalytic
rosion of electrodes. This shows that the search for H2 O splitting systems used for producing hydrogen, sacrificial agents are
photoelectrode materials is still in development. To overcome frequently utilized. To help in the reduction of protons, these
some limitations of PEC water splitting, researchers are moving substances function as donor of electrons, and they also work as
toward photocatalytic water splitting. scavengers or hole carriers, which prevents the recombination
of e− and h+ and enhances the efficacy of the process.[129–133] The
H2 O splitting reaction is a huge uphill reaction with a Gibbs free
2.2. Photocatalytic Water Splitting energy change of ΔG = +237.1 kJ mol−1 . The photocatalysis with
a sacrificial donor remains challenging, although it is relatively
Following the groundbreaking research conducted by Honda less difficult compared to the process of water splitting.[134,135]
and Fujishima in the 1970s, showcasing the PEC H2 O splitting Currently, the main portion of the H2 is generated from fossil-
into hydrogen and oxygen, numerous strategies and photocat- derived coal, oil, and natural gas while a slight fraction is from
alysts have been employed for catalytic H2 production driven biomass.[136,137] Producing hydrogen from renewable sources
by solar light. Among these methodologies, the most fasci- like biomass, water, and solar energy is achievable but presents
nating and challenging is the photocatalytic H2 production significant challenges.[138] To improve H2 evolution, commonly
from water, conducted under ambient conditions (pressure and employed sacrificial agents like triethanolamine (TEOA), sul-
temperature) with SEDs (Figure 3c). This approach represents fides, and methanol are both costly and non-renewable, posing a
a self-contained process capable of capturing and converting drawback.[139,140] Photoreforming of biomass delivers an auspi-
solar energy into chemical energy. Photocatalytic hydrogen evo- cious way for sustainable and scalable H2 generation compared
lution is a promising method for its simplicity, flexibility in the to conventional photocatalytic method.[107,141]
2.3. Organic Photo-Oxidation 2.4.2. Mechanistic Insights of Photo-Assisted Biomass Reforming
Extensive research has been conducted on the photo-oxidation of Photoreforming can be viewed as a transition phase between
organic molecules with oxygen, to effectively decompose environ- photo-oxidation and photocatalytic water splitting, as shown in
mentally harmful organic compounds. In this context, it is note- the next example. If one employs a quintessential photocatalyst
worthy that, in contrast to the photocatalytic reforming process, such as Pt-TiO2 for total H2 O splitting, generation of O2 and H2
the organic photocatalytic oxidation method involves molecular may be detected under appropriate conditions, although at lower
O2 serving as an e− trap instead of H2 O or H+ , as illustrated in quantum yields due to sluggish rates, deactivation events, and
Figure 3d. Therefore, the formation of H2 does not occur in this back reactions.[18,46]
process.[142] Hydrogen Evolution Reaction (HER): When the photocatalyst
absorbs light of energies larger than its band gap, an e− is excited
from the VB to the CB. The CB e− possesses strong reducing
properties, facilitating the HER responsible for energy formation
2.4. Photoreforming General Overview
[(HER, Equation (1)].
Biomass Oxidation Reaction (BOR): Simultaneously, the va-
Photoreforming of biomass is a process that involves using light-
lence band (VB) generates oxidizing holes that drive the BOR
driven reactions to convert biomass feedstocks into valuable
[(BOR, Equation (2)].
products, typically focusing on producing H2 as a clean energy
Isotopic Study: The utilization of D2 O instead of regular H2 O
with liquid hydrogen carriers such as formate and formaldehyde
in photoreforming was explored as a means to validate that the
(Figure 3b). As an alternative to conventional water splitting, pho-
initiation of hydrogen generation primarily initiates from the
toreforming utilizes oxygenated organic substrates and solar en-
H2 O rather than the biomass feedstock.[165]
ergy. When bio-available oxygenates serve as sacrificial agents in
Photoreforming Comprises Two Distinct Half-Reactions:
this process, it is considered nearly carbon-neutral because the re-
sulting CO2 can be reconverted into biomass through plant pho- i) The first half-reaction is the HER facilitated by semiconduc-
tosynthesis. The overall sustainability of the method is closely tors alongside metal cocatalysts like Pt. In this process, the
tied to the source of the organic substrate, i.e., non-sustainable metal cocatalysts serve as catalysts for HER while simultane-
first-generation biomasses, and or attractive second/next gener- ously acting as Schottky barriers to accelerate efficient charge
ation biomasses. separation.[166,167]
ii) The second half-reaction is the biomass substrates as a reduc-
tive moiety to replace OER (oxygen evolution reaction) for the
2.4.1. Sacrificial Agents/Substrates for Photoreforming consumption of h+ is an efficient technical alternative to en-
hance photocatalytic H2 O splitting for the creation of H2 , this
Sacrificial e− donors used in photocatalytic hydrogen evo- process is known as biomass photoreforming [(OER, Equa-
lution can be of an inorganic or organic nature. A com- tion (3)]. In this idea, a semiconductor produces h+ upon pho-
monly utilized inorganic sacrificial agent is a mixture of toexcitation to oxidise biomass and then uses the resultant
Na2 S and Na2 SO3 , this mixture is primarily employed in the e− to convert aqueous proton to H2 gas. Contrary to OER,
presence of metal sulfide photocatalysts like CdS, CuInS2 - the total biomass photocatalytic reforming reaction may ex-
AgInS2 , and CdSe.[143,144] A extensive diversity of organic sac- ploit plentiful low-energy photons (IR and visible light), is
rificial agents has been used in literature such as acids (e.g., nearly energy neutral, and has the potential to produce valu-
formic acid, acetic acid, and dichloroacetic acid),[145] alcohols able chemicals from biomass (Figure 2c).[97,168–171]
(methanol and ethanol),[146–149] biomass derivatives,[107,150,151]
plastic waste,[152–154] glycopolymer,[155] and other organic com- 2H+ + 2e− ⇌ H2 E0 = 0 V vs. RHE (1)
pounds as azo dyes, TEOA, and EDTA.[156,157] Between organic
compounds, alcohols are extensively employed as sacrificial C6 H12 O6 + 6H2 O ⇌ 6CO2 + 24H+ + 24e− E0 = −0.001 V vs.RHE (2)
agents in photocatalytic processes for hydrogen production, es-
1
pecially when using photocatalysts based on TiO2 .[158,159] Specifi- H2 O ⇌ O + 2H+ + 2e− E0 = +1.23 V vs.RHE (3)
cally, compounds featuring a higher number of -OH groups and 2 2
increased 𝛼-H content exhibit superior rates of H2 production. 1
Glycerol has garnered considerable attention as a sacrificial agent H2 O ⇌ H2 + O2 E0 = −1.23 V (4)
2
due to its exceptional hydrogen production rate.[134,160,161] In or-
der to boost the efficacy of H2 evolution from pure water, vari- C6 H12 O6 + 6H2 O ⇌ 12H2 + 6CO2 E0 = +0.001 V (5)
ous hole scavengers are required as SEDs (organic and inorganic)
to avoid electron-hole recombination rate. This strategy leads to Thermodynamic Aspects: The thermodynamic aspects of pho-
certain adverse consequences, including environmental and eco- toreforming in the context of biomass involve the study of energy
nomic drawbacks. Hence, it is crucial from a technological per- changes and transformations during the process. The H2 O split-
spective to utilize readily abundant resources like biomass and ting is a huge uphill reaction with a Gibbs free energy change of
its derived compounds, plastic waste, and food waste as a scav- ΔG = +237.1 kJ mol−1 . Hydrogen production through H2 O split-
enger to enhance the generation of hydrogen and the concurrent ting [Equations (3) and (4)] has a huge thermodynamic barrier
synthesis of valuable chemicals.[162–164] (ΔE0 = −1.23 V) because of the energy-demanding OER [OER,
Equation (3)]. It also produces explosive combinations of H2 and Nonetheless, the true process is likely more intricate, which
O2 . In contrast, the total biomass photoreforming [Equation (5)] trusts on monitoring reactants, intermediates, products, and
is nearly energy neutral (ΔE0 = +0.001 V).[168] The photo-assisted even radicals. Additional research with the support of progres-
reforming reaction is less endergonic and overcomes limits re- sive instruments and in situ methods is imperative for further
lated to the evolution of H2 by H2 O dissociation and is thus exploration.
more cautious. By accepting such techniques, it can be recycled
into valuable feedstocks and hydrogen fuel.[172,173] The thermo- 3. Factors Affecting Photoreforming to H2
dynamics of photoreforming in biomass involves assessing the
Gibbs free energy change, entropy, enthalpy, temperature depen-
Evolution Efficiency
dence, equilibrium constants, redox potentials, and activation en- 3.1. Photocatalyst Structure
ergy. These considerations contribute to a complete understand-
ing of the energetics and efficiency of biomass photoreforming The efficiency of biomass photoreforming and the production of
processes. H2 are influenced by various structural factors. These include
the band gap, morphology, size, and crystal phase of the pho-
tocatalyst. Additionally, the introduction of cocatalysts such as
2.4.3. Mechanistic Insights and Various Intermediates for Liquid metal phosphides, noble metals, and sulfides plays a role. Fur-
Hydrogen Carriers ther enhancements involve the discerning adsorption of semi-
conductors toward sacrificial substrates through the introduc-
A possible mechanism of photocatalytic reforming of saccharides tion of transition metals and the alteration of surface acid or
to H2 is proposed.[134,174] First, a saccharide (shown as RCH2 OH) base sites. These performances facilitate the separation of pho-
molecule favors to bond with under coordinated surface Ti atoms tocarriers, increasing the availability of active places/species for
over its -OH oxygen. Then, the -OH group dissociates to proton the photoreforming and thereby enhancing the efficiency of H2
and RCH2 -O− , followed by RCH2 -O− deceiving a h+ and itself evolution.[175]
oxidization to RCH2 -O• radical.
3.2. Reaction Conditions
Photocatalyst + h𝜐 → Photocatalyst∗ + e− + h+ (6)
In addition to designing a preferred photocatalyst structure as
h+ + H2O → · OH + H+ (7)
outlined in Section 3.1, optimizing the conditions of the pho-
toreforming reaction can enhance the activity of the semiconduc-
RCH2 OH → H+ + RCH2 − O− (8)
tor in generating H2 from biomass substrates. In the subsequent
RCH2 − O− + h+ → RCH2 − O∙ (9) subsections, we delve into the impact of various reaction param-
eters including light intensity, semiconductor and substrate con-
This RCH2 -O• radical will attack the alternative saccharide centrations, pH, temperature, metal salt solutions used, solvent
(shown as R′CH2 OH) molecule and the radical e− transferences type, and reactor configuration.
to the carbon atom of the latter, and then produce a R′CH2 OH
radical. R′CH2 OH continues deprotonating later to form R′CHO 3.2.1. Light Intensity
by repetition of the process. The R′CHO was additionally ox-
idized by the surface-coordinated -OH radical, transporting to Light serves as the energy source for advancing photochemical
[R′COOH]− . reactions. Considerations such as the light source type, spec-
tral array (UV, visible, or near-IR light), and irradiation power
RCH2 − O∙ + R′ CH2 OH → ∙ CH (R) OH + RCH2 OH (10) are crucial. Typically, the choice of the spectral array depends
on the light absorption features of the semiconductor, which
∙
CH (R) OH + h+ → H+ + ∙ CH (R) O∙ (11) is closely associated with the catalysts’ band gap. Sunlight, be-
ing an abundant solar energy source, comprises ≈5% UV light
∙
CH (R) O∙ → R′ CHO (12) (wavelength < 400 nm), 40% visible light (400–800 nm), and
[ ]− 50% IR light (wavelength>800 nm). For photocatalysts with wide
R′ CHO + ∙ OH → R′ COOH + H+ (13) band gaps such as TiO2 (>3.2 eV), the initiation of photocat-
alytic reforming performance requires high-energy photon expo-
Finally, [R′COOH] eliminated CO2 via a photo-Kolbe reaction.
sure, like UV light.[176] As previously discussed, the more effec-
tive utilization of solar light can be achieved by developing ma-
[ ′ ]− terials capable of initiating photoreforming performance under
R COOH + h+ → R′ H + CO2 (14)
low-energy photon irradiation (visible light), as seen in materials
In the course of the reaction, the H+ ions deprotonated from like CdS and g-C3 N4 .[104,177]
glucose throughout the entire process will migrate to the loaded
Pt particles (Pt cathode), where they undergo reduction to form 3.2.2. Reaction Temperature
H2 through the action of photogenerated electrons.
To overcome the activation energy barrier in biomass pho-
2H+ + e− → H2 (15) toreforming reactions and enhance efficiency, increasing the
temperature proves beneficial. Several mechanisms elucidate ture of the substrate, adsorption/chemisorption processes (in
the impact of reaction temperature on hydrogen evolution in photocatalyst and substrates), redox properties of the sub-
photoreforming: First, under conditions where the irradiation strate and H+ , steadiness of reaction intermediates or prod-
flux is intense sufficient to preserve substantial photogenerated ucts, and atom accretion.[177]
electron-hole pairs in semiconductors, the efficiency of photocat- ii) Effect on the photocatalyst band gap.[182]
alytic reforming H2 creation is influenced by factors like the ad- ii) Impact of pH with complex structure substrates solubility.
sorption and diffusion of substrates and the desorption of hydro- Variable pH might affect substrate accessibility, thereby in-
gen. Second, an increase in temperature facilitates the solubility fluencing the efficiency of photocatalytic reforming hydro-
of substrate, providing a sufficient supply of electron donors for gen creation. Researchers investigated photoreforming under
the photoreforming reaction and promoting hydrogen creation. acidic, basic, and neutral pH conditions. Given the complex
Hence, careful consideration of the exact reaction scheme is cru- impact of pH on the photoreforming system, predicting gen-
cial when analyzing the effects of reaction temperature on pho- eral trends becomes a challenging task.[183]
tocatalytic reforming hydrogen creation.[178]
3.2.5. Additional Reaction Parameters

3.2.3. Photocatalyst and Substrate Concentration
Various reaction parameters, including the utilization of metal
With sufficient number of incident photons, the necessary con-
salt hydrate solutions (MSH), reactor setup, and the selectivity
centration of the semiconductor primarily relies on its absorp-
of solvent in photocatalytic reforming hydrogen creation have
tion ability for incident light and the presence of surface-active
been explored. The presence of MSH proved advantageous in
places for biomass photocatalytic reforming. At minor concentra-
the solubility and depolymerization of the substrate, rendering
tions of the semiconductor, the biomass photocatalytic reforming
it more amenable to participate in the photoreforming process.
reaction is governed by the number of surface-active places on
Across multiple studies, it was consistently established that MSH
the semiconductor. Consequently, the photocatalytic reforming
serves as an appropriate path for biomass photocatalytic reform-
rate increases with the increase in the semiconductor concentra-
ing. This is attributed to its ability to facilitate the depolymeriza-
tion. The extreme photocatalytic reforming rate is attained when
tion of biomasses under comparatively mild parameters, trans-
the semiconductor concentration spreads its overload limit, al-
forming them into valuable feedstocks that are simply available
lowing the photocatalysts to use the major number of irradiated
to colloidal semiconductors during the photocatalytic reforming
photons within the reaction system. However, further elevating
method.[184]
the catalyst’s concentration beyond this overload point leads to
The substrate selectivity in photoreforming reactions is af-
a compact photocatalytic reforming rate. A decrease in photocat-
fected by the choice of solvent. Generally, H2 O is the ideal sol-
alytic reforming rate is commonly observed at high semiconduc-
vent for photooxidation due to its practical advantages, includ-
tor concentrations, potentially attributed to: i) the less light ab-
ing eco-friendliness and the accessibility of H+ . However, to
sorption because of light scattering and reflection by semicon-
improve the choosiness and stability of liquid compounds, re-
ductor particles as the opacity of the reaction system increases,
duce ionization effects on the semiconductor surface, and pro-
and ii) the reduced number of active places resulting from parti-
long the lifetime of singlet oxygen, organic solvents like CH3 CN
cle agglomeration.[179,180]
and THF are also suitable for biomass photocatalytic reform-
The photocatalytic reforming of biomass substrates for hydro-
ing reactions.[180,185] The configuration of the reactor is another
gen creation typically involves the presence of H2 O. In this pro-
factor influencing photocatalytic reforming activity. It has been
cess, biomass substrates act as hole scavengers, consuming ox-
noted that the crucial factor is the percentage of the irradiated
idizing active class to generate a range of liquid compounds,
photocatalyst volume, and which is influence by the reactor in-
while e− reduce proton to generate hydrogen. It has been de-
side diameter. In cases where the reactor capacity remains con-
termined that fine-tuning the biomass substance concentration
stant, the % of irradiated semiconductors in a reactor with a
is crucial for achieving maximum substrate accessibility, leading
lesser inside diameter is higher compared to that in a bigger
to enhanced photocatalytic reforming performance and selectiv-
one.[181]
ity. Consequently, material concentration emerges as a vital factor
In summary, the conditions of the photoreforming reaction
in the photocatalytic process. As the substrate concentration in-
impact both the features of the semiconductor and the biomass,
creases, both substrate degradation and the rate of photoreform-
playing a significant role in determining hydrogen creation effi-
ing H2 evolution decrease. It has been established that the semi-
cacy. In the practical photoreforming of biomass, it is essential
conductor exhibits optimal activity for the oxidation of biomass
to collectively optimize these conditions to achieve supreme H2
through photocatalytic reforming in the concentration range of
creation and biomass conversion.
0.1–2.4 M.[107,181]
3.2.4. Effect of pH 4. Photoreforming of Biomass

The pH of the medium has been found to influence various fea- Biomass is a highly important and renewable resource found
tures of the photoreforming method, including: in nature that has the potential to substitute fossil resources
due to its renewable nature and environmental benefits. The
i) Effects on photocatalyst features such as surface charge, elec- generation of bioenergy and valuable chemicals using feed-
trokinetic potential (measured as zeta potential), chemical na- stocks produced from biomass substrates would be significantly
harmless, less expensive, and more ecofriendly than using fossil such, this technology holds promise for an extremely sustain-
resources. Hence, the transformation of biomass resultant feed- able and eco-friendly future with decreased dependence on fossil
stocks has attracted more attention. The conventional approach fuels.
to convert biomass primarily involves thermal catalysis, which
requires a significant amount of energy.[186–189] In recent times, 4.1.1. Glucose Photoreforming
there has been an increasing focus on photocatalysis owing to
its numerous benefits, including reduced energy requirements, TiO2 ‑Based Photocatalysts and Cocatalyst Loading: The most
gentle reaction conditions, user-friendly operation, and minimal potent photoreforming building block is glucose and is widely
secondary contamination. The specific biomass sources that are studied using Pt/TiO2 . The recent discovery demonstrates the
being focused on and not yet utilized, like untreated lignocel- successful transformation of glucose and fructose into their
lulosic biomass, do pose challenges due to their low solubility entirety through photoreforming, accomplished by employing
and lack of reactivity with chemicals. These challenges can be ad- Pt/TiO2 catalysts and simulated solar light, while maintaining a
dressed through pre-processing techniques like acid hydrolysis constant flow of inert gas.[195,196] For the first time, researchers
or ball-milling, although this would result in increased energy re- have reported the selective photocatalytic oxidation of glucose
quirements for the entire reaction, thereby incurring additional with unmodified TiO2 as a photocatalyst, with the process driven
costs. This section will examine the variety of natural and syn- by visible light.[180] The surprising photocatalytic behaviour of
thetic substrates that can be used as suitable sources for gener- TiO2 under visible light exposure, as well as the observed pattern
ating hydrogen gas through photocatalytic reforming processes. in the impact of substrate concentration, can be understood by
The attention will go first to monomeric carbohydrates such as considering the formation of the TiO2 -glucose LMCT (ligand-to-
glucose, galactose, mannose, ribose, xylose, fructose, other hex- metal charge transfer) complex, which was first identified by Kim
oses and pentoses. Then, it moves to disaccharides such as sugar, et al. in 2015.[197] The utilization of photocatalysis for enhancing
lactose, cellobiose and maltose, afterward polysaccharides, plastic biomass, specifically glucose, is gaining significant interest. Nu-
waste, food waste and ending with glycopolymers. Reported effi- merous researches have attention on the photoreforming of glu-
ciencies for photoreforming and H2 yields are considered with cose to produce hydrogen, where glucose serves as a sacrificial
the problems, benefits, and value-added chemicals of given sub- substrate and undergoes degradation during the reaction. Ramis
strates. and coworkers have investigated the photoreforming of glucose
using a TiO2 photocatalyst in various photoreactors. They specif-
ically examined the impact of reaction conditions, such as pres-
4.1. Monomeric Substrates sure, temperature, photocatalyst, and substrate concentration.
Notably, pressure had a substantial effect, leading to a decrease in
In practical terms, free monomeric sugars serve as valuable sub- the rate of H2 evolution but an enhancement in substrate conver-
strate models for investigating photoreforming. The presence of sion. Moreover, operating at a moderately higher pressure than
numerous -OH units in their structures ensures the potential for ambient enabled the system to operate at a high temperature
hydrogen creation through dehydrogenation. In 1972, the pho- of 80 °C, resulting in increased hydrogen productivity.[198] St.
tocatalytic division of water using TiO2 was initially discovered John and colleagues had foreseen this occurrence in a ground-
and reported by Fujishima and Honda.[190] Another method of us- breaking research concerning glucose.[167] Bellardita et al. used
ing TiO2 to produce photocatalysis from organic substances like Pt-TiO2 as the semiconductor and studied the photocatalytic con-
methanol, glucose, starch, and even cellulose was documented version of glucose in aq. solution under anaerobic and aerobic
in the research conducted by Kawai and Sakata in 1980.[101] conditions.[199] After subjecting the Pt-brookite photocatalyst to
Monosaccharides have been extensively investigated as a model anaerobic conditions for 7 h, almost 1700.0 micromole of H2
substrate for photocatalytic reforming due to their more occur- was generated under solar radiation. The photoreaction led to the
rence in lignocellulose (i.e., hemicellulose and cellulose). They conversion of fructose from glucose, which was subsequently ox-
are supreme electron donor for photocatalysis. Monosaccharides idized to produce valuable arabinose, erythrose, formic acid, and
primarily contain pentoses (ribose, xylose, and arabinose) and gluconic acid. The presence of Pt was observed to have a substan-
hexoses (galactose, glucose, mannose, sorbose, and fructose) tial influence on both the selectivity and rate of glucose reforming
as shown in Figure 4a.[191,192] These systems demonstrated re- into hydrogen. Wu and colleagues conducted a study in which
markable photocatalytic redox activity, resulting in the produc- they utilized an M/TiO2 photocatalyst (M = Ru, Ir, Pt, Rh, Au,
tion of lactic acid and hydrogen through sugar oxidation and Cu, and Ni) to enhance the choosiness of gaseous products dur-
hydrogen release.[193] Glucose is a widely available bioresource ing the photoreforming of glucose. Their goal was to achieve the
and a product of photosynthesis, possessing characteristics such production of hydrogen while minimizing the presence of car-
as renewability, non-toxicity, affordability, and carbon-neutrality bon monoxide.[200] Amid studied, Rh/TiO2 photocatalyst demon-
throughout its entire life cycle.[194] Cellulose is primarily com- strated the highest hydrogen production which was ≈3000.0 mi-
posed of glucose, serving as its fundamental building block, cromole of H2 /g.h (Table 2 and Entry no. 15) and the lowest
and making up the majority of the sugar monomers in ligno- concentration of carbon monoxide, with the product choosiness
cellulose. On the other hand, hemicellulose predominantly con- growing in the sequence of Ir < Ru < Au < Ni≈Cu≈Pt < Rh.
tributes other sugars in this context. In conclusion, the photore- Other cocatalysts (Pd and Au).[201,202] showed improved results,
forming of carbohydrates is an area of active research and de- with AuPd/TiO2 reaching 8800.0 micromole of H2 /g.h.[203]
velopment, with significant potential for producing renewable The loading of Cu to TiO2 catalysts, with a CuO incorporation
energy from abundant and sustainable biomass resources. As of 1 wt.% using the precipitation with organic molecules method,
Figure 4. a) Structures of monosaccharides, b) photoreforming of glucose for H2 creation with ZMCN, c) glucose photoreforming and mechanistic
insights with various intermediates, d) photoreforming of glucose to hydrogen production with various photocatalysts, and e) photoreforming of various
pentoses and hexoses to hydrogen production with Ptx -C3 N4 photocatalyst.
has shown a rise in hydrogen creation up to 9.7 molh−1 kg−1 . TiO2 -based photocatalysts, specifically incorporated with CuO or
This increase can be accredited to the improved dispersion of NiO.[204] Conte et al reported the catalysts based on TiO2 , loaded
the Cu metal on the photocatalyst surface, leading to a more ef- with noble metals (0.36 wt.% Pt/TiO2 and 1.0 wt.% Aux Pty /TiO2 ),
ficient sequestration of electrons. The research presented in this demonstrated the maximum results among all tested catalysts.
study focuses on generating H2 from biomass substrates through They exhibited glucose conversion rates exceeding 15.2% after
the photocatalytic reforming of an aq. glucose solution using 5 h of irradiation and H2 productivity exceeding 4.1 molh−1 kg−1
Table 2. Photocatalytic reforming data for glucose with various photocatalysts.
Sr. No. Photocatalyst Reaction condition Energy source Substrate (SED) H2 activity Remarks Ref.
1) C3 N4 based catalyst 20 mg photocatalyst, 5 W white Xylose 136.9 The fabrication of an [210]

30 mL 5 M NaOH, LED light Fructose ≈20.0 edge functionalized
100 mg saccharide, Arabinose ≈20.0 C3 N4 for
0.8 wt.% Pt as the Glucose ≈156.0 photoreforming of
co-catalyst micromole of H2 several
monosaccharides
into H2 .
2) ZnS modified g- C3 N4 50 mL glucose Xe lamp Glucose 209.4 ZnS and hybridized [208]
(50 ppm) 300 W micromole of ZnS/g- C3 N4
H2 /g.h nanosheets for
photoreforming of
glucose into H2
3) TiO2 decorated with photocatalyst 75 mg, Xe lamp Glucose 140.0 Photoreforming of [151]
Rh, Pd, or Pt. 100 mL-20 mM aq. 300 W micromole of carbohydrate
reactant solution H2 /h aldoses on M-TiO2
Under neutral and
acidic pH
4) Graphene oxide dot Carbohydrate 35 mW cm−2 Glucose 164.0 Pt/SNGODs efficiently [211]
(GOD). (0.35 mol L−1 ), pH micromole of catalyzed H2
10-aqueous H2 /g.h creation from aq.
solutions, 5 wt.% Pt solutions of glucose
doped SNGODs (AQY-7.4%) under
and NGODs (0.4 g) visible light
irradiation for above
80 h
5) Nobel metal loaded 50 mg photocatalyst, 125 W Glucose 285.0 Anaerobic [227]
TiO2 50 mg glucose, high-pressure micromole of photoreforming of
200 mL DI water mercury H2 /g.h glucose over
lamp M-TiO2 with rates
H2 creation are
reduced in the order
Pd > Pt > Au
≈Rh > Ag ≈Ru.
6) Pt/TiO2 80 mg photocatalyst, Xe lamp Glucose 2400.0 micromole Pt/TiO2 efficiently [196]
60 mL DI water, 300 W of H2 /g.h catalyzed H2
carbohydrate, creation from aq.
NaOH or HNO3 solutions of mono-,
di-, and
polysaccharides
(conc. 0–0.5 M)
under unaerated
conditions with
solar lights
7) Pt/Holey CN-N-acetyl 30 mg photocatalyst, Xe lamp Glucose 5580.8 Polymeric carbon [209]
ethanolamine 0.8 wt.% Pt, 80 mL 300 W micromole of nitride (PCN) with
(HCN-NEA) 5 M NaOH H2 /g.h Pt cocatalyst for
solution, photoreforming of
different
carbohydrate
substrates in
alkaline condition
with AQY-7.87%
8) Au/CdS-nanorods 100 mg photocatalyst, Xe lamp Glucose 90.0 micromole of H2 production from [228]
100 mL water 300 W H2 /g.h glucose over
Au/CdS-nanorods
(solvothermal
method)
(Continued)
Table 2. (Continued)
9) Pt/TiO2 80 mg photocatalyst, Xe lamp Galactose 5.5 micromole of – [196]

60 mL DI water, 450 W H2 /min
NaOH or HNO3
10) HCN-NEA 30 mg photocatalyst, Xe lamp Galactose 156.3 micromole – [209]
0.8 wt.% Pt, 80 mL 300 W of H2 /h
5 M NaOH solution
11) Pt/TiO2 80 mg photocatalyst, Xe lamp Mannose 1725.0 micromole – [196]
60 mL DI water, 300 W of H2 /g.h
NaOH or HNO3
12) Pt/TiO2 80 mg photocatalyst, Xe lamp Ribose 2175.0 micromole – [196]
60 mL DI water, 300 W of H2 /g.h
NaOH or HNO3
13) Rh/TiO2 0.1 g photocatalyst, Xe lamp Glucose 846.0 micromole Photoreforming for [229]
100 mg glucose 300 W of H2 oxidation of glucose
into valuable
feedstocks
(erythrose and
arabinose) and H2
over noble metal
loaded TiO2
(without additional
acid or base)
14) DMASnBr3 /g-C3 N4 500 mg photocatalyst, Simulated Glucose 925.0 micromole DMASnBr3 /g-C3 N4 [230]
Pt as co-catalyst solar light of H2 /g.h /Pt for the hydrogen
500 Wm−2 evolution from
saccharides
aqueous solution,
i.e.,15- times
improved in aq.
glucose than in
pure water
15) Rh/TiO2 500 mg photocatalyst, 300 W Hg Glucose ≈3000.0 Hydrogen with small [200]
800 mL glucose aq. lamp micromole of CO concentration is
solution H2 /g.h generated via
photoreforming of
glucose on M/TiO2
photocatalyst
(metals: Ru, Ir, Pt,
Rh, Au, Ni, Cu)
16) Sn/TiO2 50 mg photocatalyst, 125 W high- Glucose 334.2 The collaborative [231]
165 mL water, pressure micromole of improvement of
100 mg glucose Hg lamp H2 /g.h photocatalytic H2
creation from a
biomass-H2 O is
accomplished by
using anatase TiO2
with single-site
Sn-oxo species and
RuO2
17) Au/TiO2 Photocatalyst-20 mg, LED 365 nm Glucose 5000.0 The photocatalytic H2 [202]
aqueous solution of lamp micromole of creation
glucose-40 ml H2 /g.h performance over
TiO2 was improved
by simultaneous
metal deposition for
Au
(Continued)
18) Pd/TiO2 Photocatalyst-20 mg, LED 365 nm Glucose 8900.0 – [202]

aqueous solution of lamp micromole of
glucose-40 ml H2 /g.h
19) Au/TiO2 25 mg TiO2 Xe lamp Glucose 1.6 Au/TiO2 for [201]
photocatalyst, 300 W micromole of photoreforming of
1.26 µmol H2 /mg.h different alcohols
NaAuCl4 ·2H2 O, and glucose
4.0 g glucose in
10 mL water
20) Ni/TiO2 -SiO2 500 mg photocatalyst, 300 W Hg Glucose ≈4000.0 Nano-sized Ni [232]
300 mL glucose lamp micromole of particles on
aqueous solution H2 /g.h TiO2 -SiO2 for
photoreforming of
glucose with
production of low
CO concentration
21) Polymeric carbon Photocatalyst 10 mg, 40 W blue Glucose 3390.0 Ptx -C3 N4 for [141]
nitride (Ptx -C3 N4 ) glucose 100 mg, LED light micromole of photoreforming of
NaOH 10 M H2 /g.h glucose solution at
aqueous solution pH range 1–15
22) Polymeric carbon Photocatalyst 10 mg, 40 W blue Fructose 3100.0 Ptx -C3 N4 for [141]
nitride (Ptx -C3 N4 ) fructose 100 mg, LED light micromole of photoreforming of
NaOH 10 M H2 /g.h fructose solution
aqueous solution
23) Polymeric carbon Photocatalyst 10 mg, 40 W blue Furfural 760.0 Ptx -C3 N4 for [141]
nitride (Ptx -C3 N4 ) furfural 100 mg, LED light micromole of photoreforming of
NaOH 10 M H2 /g.h furfural solution
aqueous solution
24) Polymeric carbon Photocatalyst 10 mg, 40 W blue Xylose 2540.0 Ptx -C3 N4 for [141]
nitride (Ptx -C3 N4 ) xylose 100 mg, LED light micromole of photoreforming of
NaOH 10 M H2 /g.h xylose solution
aqueous solution
25) Polymeric carbon Photocatalyst 10 mg, 40 W blue Guaiacol 400.0 Ptx -C3 N4 for [141]
nitride (Ptx -C3 N4 ) guaiacol 100 mg, LED light micromole of photoreforming of
NaOH 10 M H2 /g.h guaiacol solution
aqueous solution
26) Fe/TiO2 1.0 g photocatalyst, 150 W Glucose 48.0 micromole of Fe-TiO2 for [233]
350 mL water medium- H2 /g.h photocatalytic
pressure hydrogen (CO2 ,
Hg lamp CH4 ) production
with glucose
27) Pt/CdZnS 100 mg photocatalyst, 400 W high- Glucose 485.0 Utilizing glucose as a [212]
0.10 mol L−1 pressure micromole of sacrificial substrate
NaOH, 100 mL of mercury H2 /g.h for photocatalytic
aq. solution lamp H2 creation over
containing Pt/CdZnS in
0.05 mol L−1 alkaline solution
glucose
28) ZnS/ZnIn2 S4 100 mg photocatalyst, 400 W metal Glucose 174.0 ZnS coated ZnIn2 S4 [213]
100 mL halide lamp micromole of with Pt cocatalyst
0.10 mol L−1 glucose, H2 /g.h for
0.10 mol L−1 NaOH photoreformation of
and glucose to
2.6 × 10−5 mol L−1 hydrogen. Influence
H2 PtCl6 of glucose
concentration on
the H2 creation rate
is consistent with a
Langmuir model
(Continued)
29) CdS/MoS2 100 mg photocatalyst, Xe lamp Glucose 55000.0 A binary [214]

100 mL glucose 300 W micromole of heterostructured
solution H2 /g.h CdS/MoS2
flowerlike
composite with
glucose solution for
photocatalytic H2
creation
30) Co/CdS/CdOx QDs (0.5 M) with 100 mWcm−2 Glucose 81000.0 Light-driven [107]
50 mg micromole of photoreforming of
mL−1 cellulose in H2 /g.h glucose to hydrogen
2 mL KOH (10 M) using
semiconducting
CdS quantum dots
with Co cocatalyst in
alkaline aq. solution
31) Zn-Doped Cu2 O 10 mg photocatalyst, Xe lamp Glucose 3820.0 Under the light and [234]
aq. solution of 300 W micromole of presence of glucose
NaOH H2 /g.h CuWO4 was
(0.1 mol L−1 ), and reduced in situ into
glucose Cu2 O with hollow
(0.05 mol L−1 ) microcube
morphology and
hydrogen
production
32) 𝛽-Fe2 O3 /Si – 150 W Glucose 225.0 Photoreforming of [235]
Xe-lamp micromole of glucose to hydrogen
H2 /g.h with 𝛼- Fe2 O3 ,
𝛽-Fe2 O3 , 𝛾- Fe2 O3
33) Pt/(CNT-TiO2 ) 170 mg photocatalyst, 150 W Arabinose 35.7 Hydrogen creation [222]
170 mL solution of medium- Fructose 11.9 from
saccharide pressure Glucose 24.4 photoreforming of
Hg lamp micromole of saccharides was
H2 /g.h performed over
TiO2 and CNT-TiO2
with Pt cocatalyst
34) Carbon nitride/Ni2 P Photocatalyst 1.5 mg 100 mW cm−2 Food waste 1330.0 Photoreforming of [236]
mL−1 , substrate (glutamic acid) micromole of food waste into
25 mg mL−1 , 10 M H2 /g hydrogen over
KOH visible-light carbon
nitride/Ni2 P
35) Ru-doped LaFeO3 Photocatalyst UV-LEDs Glucose 2128.0 micromole 0.47% Ru has revealed [181]
1.5 g L−1 , of H2 /g high efficacy under
substrate 1 g L−1 , visible light obtaining
≈40% of glucose
decomposition
36) 1%Pt/CdZnS Photocatalyst 50 mg, 450-nm LED Glucose 3400.0 micromole Examine the kinetic [226]
100 mL glucose of H2 /g.h modeling of
solution photocatalytic H2
generation from
solutions of xylose
and glucose
saccharide with
sulfide-based
photocatalysts
under visible light.
(Continued)
37) o-g-C3 N4 Photocatalyst Solar Box Glucose 1370.0 micromole For the photocatalytic [177]
0.25 g L−1 , 1500e of H2 /g.h hydrogen creation
3 wt% Pt, from H2 O,
Glucose 0.1 M chemically modified
g-C3 N4 was
investigated.
38) Zn0.6 Cd0.4 S Photocatalyst 10 mg, 300 W Xe Glucose 690 ± 27.6 The Zn0.6 Cd0.4 S for [215]
glucose100 mg, lamp micromole of the photoreforming
5 mL NaOH (1 M) H2 /g.h of glucose into
formation H2 and
lactic acid
39) 3D ordered Photocatalyst 10 mg, 300 W Xe Glucose 645.1 micromole Photocatalytic activity [206]
macroporous 15 mL glucose lamp of H2 /g.h was reduced when
TiO2 -Au-CdS solution (2 g L− 1 ) the substance was
changed from
glucose to
cellobiose
over the 1.0 wt.% Aux Pty /TiO2 photocatalyst. The utilization of pressively encouraged due to the band structure and microstruc-
photoreforming has been investigated as a method to gener- ture of the modified materials.[208] Yet, the study only examined
ate hydrogen and other gaseous fuels by converting waste in- the reduction reaction of glucose and the generation of hydrogen
dustrial solutions such as tartaric acid, glucose, and simulated and carbon dioxide. Liu et al. enhanced the photocatalytic activ-
pulp processing waste liquors. This approach aims to valorize ity of thin porous polymeric g-C3 N4 (PCN) by introducing organic
and make productive use of these waste solutions.[205] Zhong amine during the nucleation process, resulting in a revised mate-
et. al. used glucose, as an e- donor for photocatalytic H2 cre- rial called HCN-NEA.[209] In this process, the addition of glucose
ation with a hierarchical three-dimensional (3D) ordered macro- to 5 M KOH was utilized as a sacrificial substrate and produced
porous (3DOM) TiO2 -Au-CdS catalyst. According to expectations, 5500.0 micromole of H2 /g.h (Table 2 and Entry no.7). The HCN-
the made-up photocatalyst produces a considerable amount of hy- NEA material exhibited improved separation of photo-generated
drogen from glucose (645.1 micromole of H2 /g.h) (Table 2 and charges and a prolonged lifespan of e-h pairs. Liu et al. inves-
Entry no. 39).[206] Substantial generation was also seen in the tigated the impact of functional group defects in carbon nitride
ocean and river, with outcomes significantly superior (≈2500.0 (CN), focusing on the substitution of terminal amino groups with
micromole of H2 /g.h) to cTiO2 when illuminated by sunlight.[177] ethanol groups. This substitution resulted in enhanced adsorp-
Lan and coworker reported mechanistic insights of glucose pho- tion of organic compounds and facilitated the solar-light driven
tocatalytic reforming with TiO2 and Pt/m-TiO2 photocatalysts photocatalytic reforming of various monomeric substrates into
and they found Pt loading on m-TiO2 (39.8 micromole) greatly H2 and their equivalent oxidized organics.[210] A. Speltini’s arti-
increased H2 generation in the glucose photoreforming process, cle describes a unique use of chemically altered g-C3 N4 for the
increasing it by 13.4 times over the pure m-TiO2 (3.0 micro- photocatalytic creation of H2 from H2 O in the attendance of glu-
mole). The examination of the substances produced during the cose as a sacrificial donor. Before and after the one-pot oxidation
procedure confirmed that glucose oxidation follows an 𝛼-scission in HNO3 , the bulk material was characterized. It was simply syn-
mechanism, resulting in the formation of arabinose (a sugar with thesised by thermal condensation of dicyandiamide. Under vir-
one less carbon) and formic acid during the initial oxidation stage tual sunlight, the changed material (o-g-C3 N4 ) had much more
(Figure 4c). Remarkably, investigations into the isotopic aspects H2 evolution activity than the unmodified material. Sonication
of formic acid photoreforming in deuterated water, varying in before irradiation further increased this activity. The results show
concentrations, revealed that the origin of H+ (resulting in H2 that growing glucose concentration up to 0.1 M and Pt incorpo-
evolution at Pt places) depended on the proportionate surface ration up to 3 wt.% favour H2 generation, and that it is greatly
coverage of adsorbed formic acid and water.[207] The incorpora- boosted using a small quantity of o-g-C3 N4 (0.25 g L−1 ). o-g-C3 N4
tion of noble metals and metal oxide co-catalysts into TiO2 is cru- has better photocatalytic performance (≈26 times more than pris-
cial for augmenting the H+ reduction during the photoreforming tine g-C3 N4 ), with hydrogen evolution rates up to ≈1370.0 micro-
of biomass substrates. mole of H2 /g.h which is further enhanced by ultrasound-assisted
g-C3 N4 ‑Based Photocatalysts and Cocatalyst Loading: Lately, exfoliation (Table 2 and Entry no. 37).
Xu et al. studied ZnS modified g-C3 N4 nanosheets (mentioned Graphene Oxide‑Based Photocatalysts: The utilization of semi-
as ZMCN) exhibited outstanding performance for photoreform- conductors that absorb light in the visible region of the solar
ing of glucose to 209.4 micromole of H2 /g.h (Figure 4b, Table 2, spectrum (which accounts for ≈50% of the sunlight at 800 nm)
and Entry no. 2). The introduction of ZnS in the study led to a presents an opportunity to enhance spectral absorption. Nguyen
significant enhancement in charge separation. Moreover, the ef- and colleagues studied an eco-friendly photocatalyst containing
ficacy of the photoreforming of glucose to H2 with ZMCN was ex- S and N co-doped graphene oxide dots (SNGODs) to efficiently
Figure 5. a) Structures of disaccharides, and b) photoreforming of glucose and sugar with SNGOD.
reform glucose to hydrogen evolution (Figure 5b).[211] The elec- hydrogen production efficiency of the optimised Zn0.6 Cd0.4 S cat-
tron resonance domain was expanded, the band gap was nar- alyst (690 ± 27.6 micromole of H2 /g.h) are all features of this cat-
rowed, and charge separation and delocalization were achieved alyst (Table 2 and Entry no. 38).[215] Other suitable materials also
using these functionalized SNGODs. These graphene oxide dots used for the photoreforming of glucose consist of LaFeO3 ,[216]
exhibited moderate photocatalytic activity of 160.0 micromole of Bix Y1-x VO4 ,[217] CaTa2 O6 ,[218] La:NaTaO3 ,[219] and SrTiO3 ,[220] to
H2 /g.h creation from glucose (Table 2 and Entry no. 4). hydrogen production. Correspondingly, the photoreforming of
CdS, CdO, and ZnS‑Based Photocatalysts: Peng et al. reported glucose to hydrogen production with various photocatalysts is
the quantum dots with Pt as a cocatalyst (e.g., Cd/ZnS with Pt) shown in Figure 4d.
displayed photoreforming of glucose under visible light with H2
creation rate up to 485.0 micromole of H2 /g.h (Table 2 and Entry
no. 27),[212] whereas a solid solution of ZnS and ZnIn2 S4 (with a 4.1.2. Other Monomeric Substrates
larger band gap) had a lesser activity (174.0 micromole of H2 /g.h)
(Table 2 and Entry no. 28).[213] Li et al. reported CdS/MoS2 hetero- Apart from glucose, additional hexoses and pentoses like
junction repressed the recombination of photogenerated h+ -e− fructose,[203,221,222] galactose,[195] sorbose,[223] xylose,[224,225]
pairs, resulting in a quicker interfacial charge transmission and arabinose,[222] ribose, and mannose[223] have been utilized as
an enhanced total photocatalytic H2 creation with glucose sub- sacrificial donors in the photocatalytic creation of hydrogen
strate up to 55000.0 micromole of H2 /g.h (Table 2 and Entry no. using Pt/TiO2 in aqueous environments. These all substrates
29).[214] Wakerley et al. studied Co/CdS/CdOx quantum dots, tran- show similar hydrogen production capabilities but have not been
sition metal Co as cocatalyst with 10 M KOH and they observed studied extensively as glucose. Wang et al. reported the poly-
enhanced activity for H2 creation from glucose photoreforming meric CN with Pt cocatalyst (Ptx -C3 N4 ) for the photoreforming of
up to 81000.0 micromole of H2 /g.h (Table 2 and Entry no. 30).[107] various substrate to hydrogen evolution such as glucose (3390.0
Other Photocatalysts: For the first time, the generation of re- micromole of H2 /g.h), fructose (3100.0 micromole of H2 /g.h),
newable hydrogen from the photocatalytic conversion of glucose furfural (1110.0 micromole of H2 /g.h), xylose (760.0 micromole
with Ru-LaFeO3 semiconductors under solar light has been as- of H2 /g.h), and guaicoal (400.0 micromole of H2 /g.h) (Figure 4e)
sessed, the outcomes show that the photocatalytic H2 generation (Table 2 and Entry no. 21–25).[141] Kurenkova et al concluded
from the glucose solution may be greatly increased (0.47 mol% of a novel multiphase photocatalyst with a high performance for
Ru) in LaFeO3 utilising a particular quantity (2179.0 micromole producing H2 from xylose and glucose aq. solutions with visible
of H2 /g after 4 h of UV irradiation) (Table 2 and Entry no. 35).[181] light were made using a straightforward two-stage process. For
Zhao et al reported an intelligent design for a Zn0.6 Cd0.4 S solid so- xylose and glucose, a highly alkaline medium yielded the maxi-
lution homojunction semiconductor over a pseudo-periodic cu- mum hydrogen evolution rate above the suggested photocatalyst.
bic zinc blende (ZB) and hexagonal wurtzite (WZ) shape for ef- The photocatalyst composed of 1%Pt/Cd0.6 Zn0.4 S/Cd0.1 Zn0.9 S
fective glucose transformation to concurrently create H2 and lac- displayed good stability in alkaline environments, mostly as a
tic acid. The tunable bandgap, twinning superlattice, and high result of the incorporation of Pt nanoparticles. In the case of the
glucose aq. solution with a sodium hydroxide content of 5 M, the absorption range. These led to a very high visible-light H2 cre-
maximum activity was more than 3400.0 micromole of H2 /g.h ation performance of 5500.0 micromole of H2 /g.h (with 1 wt.%
(Table 2 and Entry no. 36).[226] Pt), which is ≈17 times greater than bulk PCN (Table 3 and Entry
no. 8).[240]
Considerable research has been conducted on photoreforming
4.2. Dimeric Substrates methods for generating hydrogen using both monosaccharides
and disaccharides as substrates. Still, the precise reaction mech-
Disaccharides play a crucial role as beneficial components in anistic insights for the photo-oxidation of saccharides into valu-
the medicinal and food areas. Certain disaccharides, such as lac- able small molecules remain unclear and not well-understood.
tose or sucrose, can be derived from plant crops, whereas mal- Hence, it is crucial to focus on comprehending the mechanis-
tose and cellobiose are acquired by breaking down polysaccha- tic insights of valuable products in liquid-phase systems, while
rides through hydrolysis.[97] The hydrogen yields obtained from simultaneously improving the yield of photocatalytic hydrogen
the photoreforming of disaccharides (Figure 5a) were lower com- creation.
pared to monosaccharides due to the disaccharides having more
structural complexity, stable hydrogen bonding, higher molecu-
4.3. Polymeric Substrates
lar weight, and larger molecular size.
Lactose (a glucose and galactose dimer) can be totally con-
Polysaccharides are complex carbohydrates composed of multi-
verted by photocatalytic reforming on Pt/TiO2 yielding supreme
ple sugar molecules linked together. Examples include starch,
quantities of H2 .[195,196] The fact that hydrogen and carbon diox-
cellulose, and glycogen, which play essential roles in energy stor-
ide are the sole products observed when utilizing sucrose (a
age. The photoreforming of polysaccharides refers to the process
dimer composed of glucose and fructose) as the feedstock un-
of using light-induced reactions to transform complex carbohy-
der comparable conditions indicated that complete mineraliza-
drates into energy and valuable feedstocks. This method often
tion was occurring.[101,211,223,227,237] Significant rates of H2 cre-
involves the utilization of photocatalysts to drive the conversion
ation, reaching up to 3100.0 micromole of H2 /g.h, have been
of polysaccharides through photochemical reactions.
documented when aqueous sucrose is subjected to Xe lamp light
in the occurrence of nitrogen and boron-doped titania materials
with platinum deposition.[238] Yasuda et al. reported that Pt/TiO2 4.3.1. Photoreforming of Cellulose
photocatalyst for the sacrificial hydrogen generation from dis-
accharides like cellobiose and sucrose.[223] CdS-based photocat- Cellulose signifies the primary constituent of the indigestible
alysts also demonstrated considerable effectiveness in facilitat- lignocellulosic biomass on earth, along with lignin and hemi-
ing the photoreforming of sucrose. Nguyen et al. reported that cellulose. Moreover, cellulose plays a vigorous role in plants
Pt/SNGODs effectively catalyzed H2 creation from aq. solutions as it serves as the primary structural element, imparting sta-
of sugar (AQY-11%) under visible light for above 80 h (Figure 5b, bility and strength to cell walls and fibres. Cellulose, which
Table 3, and Entry no. 1).[211] Silva et al. reported that H2 creation has the general molecular formula (C6 H12 O5 )n , has the most
from the photoreforming of fructose, arabinose, glucose, and cel- basic structure compared to further polysaccharides. It is a
lobiose was performed using a comparative study of Pt/TiO2 and glucose unit consisting of homopolymer chains known as 𝛽-
Pt/CNT-TiO2 based photocatalysts.[222] Saiki et al presented the D-anhydroglucopyranose (AGPs) that are connected through
biohydrogen production system that combines the degradation 𝛽−1,4-glycosidic linkage amid the equatorial hydroxyl units of
of polysaccharides like maltose and sucrose with invertase and C1 and the C4 carbon atoms (Figure 6a).[241] The degree of poly-
glucose dehydrogenase (GDH) and H2 evolution with colloidal merization (DP) of cellulose refers to the number of repeating
Pt as a photocatalyst has been investigated. This scheme uses vis- AGPs that make up the polymer chain. Wood pulp-derived cellu-
ible light to induce photosensitive reactions in the water-soluble lose typically has a DP value of ≈300–1700, while cotton and other
zinc porphyrin. The system utilizing maltose and sucrose was plant fibres have a DP value of ≈800–10000.[242] The presence of
estimated to produce 3.1 and 0.35 micromole of H2 , respectively numerous -OH units along the cellulose structure enables the
(Table 3 and Entry no. 6).[239] formation of hydrogen bonds, both within the same chain (intra-
Zhong et. al. reported the glucose as well as cellobiose (a molecular) and between different chains (inter-molecular). These
cellulose unit), and dissolving pulp (pre-treated cellulose) as a bonds play a crucial role in creating strong connections that re-
sacrificial substrate for photocatalytic H2 creation with a TiO2 - sult in the formation of microfibrils, which possess high tensile
Au-CdS photocatalyst because cellulose, the main component of strength. Therefore, it is challenging to dissolve cellulose in typ-
biomass, contains an abundance of hydroxyl groups. According ical solvents without undergoing chemical modifications.[243,244]
to expectations, the made-up photocatalyst produces a consider- Owing to its inherent stability, cellulose can only be broken down
able amount of hydrogen with cellobiose (273.9 micromole of into glucose through the action of powerful acids in the occur-
H2 /g.h) to dissolving pulp (79.7 micromole of H2 /g.h) (Table 3 rence of H2 O, which results in the cleavage of the glycosidic
and Entry no. 7).[206] Li et. al. studied an ultrathin porous N- linkage.[245,246] The selective conversion of cellulose into valuable
vacancy PCN semiconductor employing carbohydrates (mono-, chemicals and fuels has garnered significant interest in the field
di-, and polysaccharides) for visible-light photocatalytic hydrogen of photoreforming. The initial step for various catalytic reactions
creation using a template-free technique with calcination. The involves the breaking of 𝛽−1,4-glycosidic linkage in two anhydro-
modified PCN photocatalyst showed improvements in the carrier glucose units through hydrolytic cleavage, resulting in the forma-
migration rate, the amount of exposed active places, and the light tion of glucose.[247,248]
Table 3. Comparative table of disaccharides.
1) Graphene oxide Carbohydrate (0.35 mol L−1 ) 35 mW cm−2 Sugar 221.0 Pt/SNGODs efficiently catalyzed [211]
dot (GOD). aq. solutions (at a pH of 10) micromole of H2 creation from aq.
5 wt.% Pt doped SNGODs H2 /g.h solutions of glucose
and NGODs (0.4 g) (AQY-11%) under visible light
irradiation for above 80 h
2) Pt/TiO2 80 mg photocatalyst, 60 mL DI 300 W Xe lamp Lactose 4.0 micromole of – [196]
water, NaOH or HNO3 H2 /min
3) HCN-NEA 30 mg photocatalyst, 0.8 wt.% 300 W Xe lamp Cellobiose 75.6 micromole – [209]
Pt, 80 mL 5 M NaOH of H2 /h
solution
4) Pt/(CNT-TiO2 ) 170 mg photocatalyst, 170 mL 150 W Hg lamp Cellobiose 9.59 micromole Hydrogen generation from [222]
solution of saccharide of H2 /g.h photocatalytic reforming of
cellobiose was performed with
TiO2 and CNT-TiO2 with Pt
cocatalyst
5) Pt/TiO2 80 mg photocatalyst, 60 mL 300 or 450 W Lactose ≈4.0 H2 is produced at ambient [195]
triply distilled water Xe-lamp Cellobiose ≈3.9 conditions via an effective,
Maltose ≈3.5 simple, eco-friendly, and
micromole of possibly very low-cost process
H2 /min over Pt/TiO2 with abundant
and renewable sources: solar
light, water, and biomass
6) Zinc porphyrin invertase (4.0 units) 200 W tungsten lamp Sucrose Maltose ≈3.10 The visible light-illuminated H2 [239]
based GDH (5.0 units) ≈0.35 creation system that couples
photocatalyst NAD+ (11 µmol) micromole of H2 the polysaccharide (sucrose
(ZnTPPS) Polysaccharide (0.30 mmol) and maltose) degradation
ZnTPPS (3.0 nmol) with invertase and GDH
methyl viologen (1.2 µmol)
colloidal platinum (0.12 µmol)
3.0 mL of 10 mmol/dm3
phosphate buffer (pH = 7)
7) 3D ordered Photocatalyst 10 mg, 15 mL of 300 W Xe lamp Cellobiose 273.9 micromole Photocatalytic performance [206]
macroporous a 2 g L−1 solution with of H2 /g.h decreased when the
TiO2 -Au-CdS glucose substrates were changed from
glucose to cellobiose
8) Polymeric carbon photocatalyst 20 mg, 300 W Xe lamp TEOA 5500.0 Photocatalyst derived from [240]
nitride (PCN) 1 wt.% of Pt cocatalyst micromole of mono-, di-, and
H2 /g.h polysaccharides for
visible-light photocatalytic
hydrogen creation
TiO2 ‑Based Photocatalysts and Cocatalyst Loading: Kawai et al. ployed). Importantly, this process does not impact the stability
reported for the first time the cellulose suspensions with Pt/TiO2 of the photocatalyst.[179]
semiconductors irradiated with UV–vis light under the same con- By immobilizing cellulose onto a TiO2 photocatalyst, Zhang
ditions and generated 13.0 micromole of H2 /g.h hydrogen.[166] et al. accomplished the photocatalytic oxidation of cellulose into
Kawai and Sakata proved in their ground-breaking studies un- sugars and CO2 , accompanied by hydrogen creation (up to 195.2
der extended irradiation periods, that RuO2 /Pt/TiO2 in aqueous micromole of H2 /g.h) through cellulose decomposition under so-
suspensions can enable near-stoichiometric and complete pho- lar light illumination (Table 4 and Entry no. 21). This method al-
toreforming of cellulose, albeit at low quantum efficiencies.[101] lows for hydrogen generation from water without the need for
Also revealed that adding NaOH enhanced the H2 evolution. costly sacrificial agents and opens up the potential for the re-
Zou et al. showed that a combination of acid hydrolysis and trieval of sugars as liquid fuels (Figure 6b).[176] Lam et al reported
photocatalytic H2 O dissociation can overcome the insolubility of the phosphonate cobalt bis(terpyridine) catalyst is immobilized
cellulose. Through hydrolysing cellulose into glucose, its solu- on TiO2 [TiO2 -Co(terpyridine)2 ], it produces a photocatalyst ca-
bility increases, leading to a fivefold improvement in the pho- pable of coupling the aqueous CO2 to CO and H2 with the se-
tocatalytic H2 creation over Pt/TiO2 (activity increased from lective conversion of cellulose to formate.[249] Speltini et al. re-
≈33.0 micromole of H2 in the absence of cellulose hydrolysis ported the photoreforming of cellulose on Pt/TiO2 under UV
to 170.0 micromole of H2 when cellulose hydrolysis was em- light. Based on studies of the liquid phases, they recognized
Figure 6. a) Chemical structures of natural polysaccharides, b) photoreforming of cellulose to hydrogen evolution with TiO2 , c) proposed mechanistic
pathway of photoreforming of cellulose into H2 using TiO2 -SO4 2− -Nix Sy photocatalyst, d) conceptual illustration of sulphur and nitrogen-doped GOD
for photoreforming of cellulose into hydrogen under alkaline conditions, and e) photocatalytic H2 creation rates with cellulose as the sacrificial substrate
over different photocatalysts.
minor amounts of 5-(hydroxymethylfurfural) and glucose; they holes generated by light absorption oxidize water, resulting in
rationalized their creation and succeeding dehydration by hydrol- the production of OH radicals. These radicals then react with
ysis on surface acidic places on TiO2 , respectively.[250] Also, el- glucose, leading to the generation of protons and the formation
evation in H2 yield was achieved (up to 33.0 micromole of H2 of a formic intermediate. Meanwhile, Nix Sy cocatalysts enhance
over 4 h) (Table 4 and Entry no. 9). Despite significant advance- the separation of charges and function as places for generating
ments in the photo-enhanced hydrolysis of cellulose using solid H2 . Still, the excessive accumulation of formate on the surface
acid-catalysts, the effective transformation of cellulose is still hin- of the catalyst can adsorb and occupy the active places respon-
dered by the limited mass dispersion between the catalyst and sible for reducing the rates of H2 creation. A substantial ad-
crystalline cellulose. However, by simultaneously modifying the vancement in hydrogen activity was attained using TiO2 -SO4 2− -
TiO2 catalyst with chemisorbed SO4 2− and Nix Sy , TiO2 gains an Nix Sy , reaching 3020.0 micromole of H2 /g.h average through-
additional characteristic as a solid acid catalyst.[251] The presence out the first 3 h, which was ≈76 times more than that of pris-
of coordinated SO4 2− species on the TiO2 surface aids in the hy- tine TiO2 (Table 4 and Entry no. 15). In order to gain insights
drolysis of cellulose into glucose, making it more achievable for into the photocatalytic nature of the system, a comprehensive in-
catalysts (Figure 6c). Under the influence of photocatalysis, the vestigation was conducted on the hydrogen production through
Table 4. Comparative table of polysaccharides.
1) CoO/g-C3 N4 5.0 mg cellulose, 10 mg 300 W Xe lamp Cellulose 178.0 Biomass photoreforming utilizing [253]
photocatalyst, 10 mL of micromole of low-cost CoO/g-C3 N4
1 M NaOH solution, H2 /g.h photocatalysts to generate H2
50 mL DI H2 O and lactic acid under visible
light illumination
2) CdS/regenerated Pt-loaded nanocomposite 250 W Xe lamp Na2 S (0.25 M)- 1344.2 CdS/RC/Pt porous films with [254]
cellulose films (0.050 g) Pt Na2 SO3 micromole of Na2 S & Na2 SO3 for the H2
(CdS/RC) co-catalyst (0.35 M) H2 /g.h production via green process
nanocomposite mixed
films solution −100
mL
3) CdOx/CdS/SiC photocatalyst (50 mg),10 M 300 W Xe lamp Albumin 654.2 CdOx/CdS/SiC for [255]
NaOH solution (5 mL), micromole of photoreforming of organic
Organic waste (100 mg) H2 /g.h waste (cellulosic and animal
biomass, plastic) to hydrogen
with almost 20% quantum
yield in the ultra violet region
(380 nm)
4) Graphite carbon 50 mL of g-C3 N4 300 W Xe-lamp Lignocellulose 72.66 Monolayer g-C3 N4 prepared by [256]
nitride (g-C3 N4 ) dispersions micromole of nitrogen-protected balls for
(1.0 mg mL−1 ), 0.50 g of H2 /g.h photoreforming of
lignocellulose dispersed lignocellulose to hydrogen
into 100 mL aq. Sol.
(pH = 10), Pt, 1.0% wt)
co-catalyst
5) SNGOD 𝛼-cellulose-1.0 g, 20 mL of 100 mW cm−2 Cellulose 100.0 Functionalized GO dots with [165]
Photocatalyst 10 M NaOH diluting the micromole of Pt-cocatalyst to photoreform
solution to 250 mL with H2 /h cellulose in an alkaline solution
deionized water under solar light illumination
with complete mechanism
6) CdS/CdOx QDs (0.5 M) with 50 mg 100 mWcm−2 Cellulose 2300.0 Light-driven photocatalytic [107]
quantum dots mL−1 cellulose in 2 mL micromole of reforming of lignocellulose to
KOH (10 M) H2 /g.h hydrogen using CdS quantum
dots in alkaline solution.
7) Metal salt hydrate 4 mg photocatalyst, 1 mL 100 mWcm−2 Cellulose 180.0 Photocatalyst such as CN and [184]
(MSH) cellulose lysate in LiBr micromole of TiO2 can be employed in MSH
solution/TiO2 MSH solution H2 /g.h to evolve hydrogen and
valuable products under more
benign conditions
8) Pt/TiO2 Cellulose 0.5-4.0 LED Light Cellulose 104.0 Hydrogen production from [257]
gL−1 , 0.5 wt.% Pt/TiO2 micromole of Pt/TiO2 and cellulose, attained
H2 /g.h through the photoconversion
of cellulose I to II via a simple
pretreatment step with
efficiency 9.4%
9) Pt/TiO2 2 gL−1 photocatalyst, Natural Cellulose 33.0 micromole Aqueous cellulose suspension [250]
200 mg Cellulose, 60 mL Sunlight of H2 over 4 h irradiated under solar light with
DI water, NaOH or Pt/TiO2 behaves as a hydrogen
H2 SO4 evolving system and
5-hydroxy-methylfurfural
(HMF) intermediate is
identified.
10) CNx /Ni2 P Photocatalyst, 0.5 M KOH, Simulated Cellulose 38.0 micromole The inexpensive CNx /Ni2 P panels [111]
50 mg cellulose sunlight (100 of H2 /g.h reform mixed waste into H2
mWcm−2 ) and organic feedstocks
(Continued)
11) NCN CN -NiP Photocatalyst 0.5 mg, Simulated Cellulose 1690.0 Activated NCN CN -NiP agrees for [258]
x x
co-catalyst 300 nmol, sunlight (100 micromole of the photoconversion of
phosphate solution mWcm−2 ) H2 /g.h purified and raw lignocellulose
samples into hydrogen with
numerous proton reduction
cocatalysts (pH ≈2–15)
12) Ni/TiO2 150 mg photocatalyst, 150 W Xe-lamp Cellulose 40.0 ml/min H2 creation by the [259]
200 mL DI water photoreforming of cellulose
and raw biomass using Pd, Pt,
Au, and Ni (economic and
eco-friendlier) on TiO2
13) Cu-Ni or – Solar Box 1500e Starch 593.0 (o-g-C3 N4 )- an economical, [260]
Pt/o-g-C3 N4 micromole of eco-friendly, and
H2 /g.h non-nanometric catalyst] over
Cu-Ni or Pt cocatalysts for
photocatalytic reforming of
biomass and sugar rich waste
water
14) Cd0.7 Zn0.3 S – 14 mW cm−2 Starch 730.0 Green H2 creation from starch [226]
LED micromole of over a CdZnS based
H2 /g.h semiconductors in the
presence of 5 M NaOH with
AQE = 1.8%
15) TiO2 /Nix Sy 20 mg photocatalyst, 1 g 500 W Xe-lamp Cellulose 3020.0 Photocatalytic reforming of [251]
cellulose, 100 DI water micromole of cellulose into hydrogen over
H2 /g.h TiO2, i.e., altered with nickel
sulfide and chemisorbed
sulfate species, 76-fold higher
than that of TiO2
16) TiO2 /NiOx @Cg 20 mg photocatalyst, 2.0 g 500 W Xe-lamp Cellulose 4000.0 Photo-assisted reforming of [64]
cellulose, 100 mL water, micromole of cellulose attained by
temperature 80 °C H2 /g.h incorporation a graphitic
carbon layer on TiO2 /NiOx to
hydrogen and valuable
byproducts such as CO2 , CO,
CH4
17) Polymeric carbon Photocatalyst 10 mg, 40 W blue 𝛼-Cellulose 1110.0 Ptx -C3 N4 (synthesized by [141]
nitride 𝛼-cellulose 100 mg, LED light micromole of supramolecular self-assembly)
(Ptx -C3 N4 ) NaOH 10 M aqueous H2 /g.h for photoreforming of
solution 𝛼-Cellulose solution
18) Polymeric carbon Photocatalyst 10 mg, xylose 40 W blue Xylan 570.0 Ptx -C3 N4 for photoreforming of [141]
nitride 100 mg, NaOH 10 M LED light micromole of xylose solution
(Ptx -C3 N4 ) aqueous solution H2 /g.h
19) Polymeric carbon Photocatalyst 10 mg, alkali 40 W blue Alkali lignin 310.0 Ptx -C3 N4 for photoreforming of [141]
nitride lignin 100 mg, NaOH LED light micromole of alkali lignin solution
(Ptx -C3 N4 ) 10 M aqueous solution H2 /g.h
20) Pt/TiO2 80 mg photocatalyst, 60 mL 300 or 450 W Starch ≈1.2 Hydrogen created at mild [195]
triply distilled water Xe-lamp Cellulose ≈0.8 conditions via an efficient,
micromole of technically simple, eco-friendly,
H2 /min and potentially cost effective,
with the use of a Pt/TiO2 with
abundant and renewable
sources
21) Pt/TiO2 15 mg photocatalyst, 50 mL 250 W metal Cellulose 195.2 – [176]
DI water, halide lamp micromole of
H2 /g.h
(Continued)
22) C, N, S-doped 100 mg photocatalyst, 300 W Lignin 643.0 The simultaneous water splitting [261]
ZnO/ZnS 200 mL DI water, 20 mg Xe-lamp micromole of and lignin (biomass)
lignin H2 /g.h degradation using C, N and
S-doped ZnO/ZnS into
hydrogen with good stability
23) Pt/CdS/SiC 50 mg photocatalyst, 10 M 300 W Cellulose 321.7 Highly efficient hydrogen [262]
NaOH solution, 100 mg Xe-lamp micromole of production from lignocellulosic
cellulose H2 /g.h biomass at higher
temperatures in an alkaline
solution utilizing a stable
CdS/SiC composite with good
quantum yield
24) Pt/CdS/SiC 50 mg photocatalyst, 10 M 300 W Lignin 11.0 – [262]
NaOH solution, 100 mg Xe-lamp micromole of
lignin H2 /g.h
25) Al-doped 150 mg photocatalyst, 300 W Cellulose Methyl orange Methyl orange degradation by [263]
ZnO/cellulose methyl orange 50 mL Xe-lamp degradation using Al-doped ZnO/cellulose
(10 mg L−1 ), 1 g cellulose
for synthesis of
photocatalyst
26) Pt/PC500 20 mg photocatalyst, 20 µL sunlight Cellulose 4400.0 The TiO2 photocatalyst [264]
TiO2 photocatalyst EtOH, 180 µL nafion simulator micromole of modification PC500 for
modification H2 /g.h photoreforming of cellulose
under sunlight simulator
the photoreforming of cellulose in aqueous environments. Lan Other Photocatalysts: Nguyen et al. reported the utilization of
et al specifically focused on the utilization of Pt catalysts sup- S- and N-doped GO dots with a Pt cocatalyst in alkaline envi-
ported on m-TiO2 (Pt/m-TiO2, i.e., mixed TiO2 , 80% of anatase ronments for the solar driven reforming of cellulose. The pro-
and 20% of rutile) for the photoreforming of cellulose into H2 cess of reforming cellulose was initiated by the detachment of
(132.6 micromole of H2 /g.h).[178] Belda-Marco et al reported the D-glucose units, which were subsequently transformed into de-
various preparation methods for TiO2 -Cu photocatalysts have re- protonated isosaccharinic acid (C6 ). Later, the C6 molecule is sub-
sulted in distinct copper species being supported. TiO2 -Cu cat- sequently broken down into C5 -C1 compounds through a series
alysts exhibit considerably higher H2 production activity (731.0 of successive hydrolysis of the C-eliminating moiety and oxida-
micromole of H2 /g.h) compared to TiO2 (297.0 micromole of tion of C6 and its derivatives. According to the authors’ claim,
H2 /g.h) through cellulose photoreforming. This enhanced ac- the resulting carbon-containing molecules are likely to be for-
tivity can be accredited to factors such as the preservation of mate, contrary to the previously held notion of HCO3 − or CO2
the surface structure of TiO2 or the presence of copper species (Figure 6d).[165] Additionally, it was suggested that the reform-
that are more active or capable of being activated during their ing of cellulose generated a continuous production of H2 up to
utilization.[252] 100.0 micromole of H2 /g.h for a duration of six days, with min-
CdS and CdO Based Photocatalysts: To improve cellulose sol- imal rate decay (Table 4 and Entry no. 5). This achievement cor-
ubility, it is typically essential to carry out the reaction in a highly responds to ≈35% of the final theoretical value used in cellulose
acidic or alkaline environment. Wakerley et al. studied the cat- photocatalytic reforming. Zhang et al. introduced a photocatalytic
alytic efficacy of CdS/CdOx quantum dots under high concentra- system, denoted as TiO2 /NiOx @Cg , which involved the deposi-
tion of KOH (10 M) on the photoreforming of cellulose to H2 tion of a graphitic carbon layer onto TiO2 /NiOx .[64] This system
and they achieved a significant elevation in hydrogen yield up to facilitated the photoreforming of cellulose into H2 within a neu-
2300.0 micromole of H2 /g.h (Table 4 and Entry no. 6). The iso- tral aqueous solution. Improved hydrogen production yields of
tope labeling test provided evidence that the photocatalyst primar- ≈270.0 micromole of H2 /g.h and ≈4000.0 micromole of H2 /g.h
ily released H2 through the reduction of H2 O. This was indicated were found at room temperature and 80 °C, respectively (Table 4
by the ratio of D2 to HD generated throughout photoreforming and Entry no. 16). Temporarily, alkoxide anion left behind is
in D2 O, which was 4:1. The creation of HD occurred as a result oxidized to CO, CO2 , and CH4 by holes. Wang et al. studied
of the H/D altered with the hydroxyl units of the cellulose.[107] the polymeric CN with Pt cocatalyst (Ptx -C3 N4 ) for the photore-
Reisner et al. reported the cellulose solution treated with metal forming of cellulose to H2 creation up to 1110.0 micromole of
salt hydrate solutions under mild conditions and it was used for H2 /g.h under the LED light (Table 4 and Entry no. 17).[141] Over-
photocatalytic reforming with TiO2 and achieved supreme hydro- all, photocatalytic H2 creation rates consuming cellulose as the
gen production rate over 180.0 micromole of H2 /g.h (Table 4 and sacrificial substrate with different photocatalysts are shown in
Entry no. 7).[184] Figure 6e.
Further research is required to apply photocatalytic conver- promising renewable feedstock, lignin shows potential for var-
sion of cellulose for H2 creation, mainly due to the high de- ious applications.[272] Cellulose, hemicellulose, and lignin, the
gree of polymerization and strong hydrogen bonding in cellulose three primary constituents of biomass, constitute more than 90%
such as inter- and intra-molecular hydrogen bonding. Achieving of lignocellulosic or raw biomass. Accordingly, the study of pho-
easy, energy-efficient, and mild reaction parameters is crucial for tocatalytic reforming of lignin and hemicellulose is discussed in
breaking down cellulose into smaller saccharide molecules. In the photoreforming of raw biomass section.
addition, the photoreforming efficiency of cellulose can be im-
proved by modifying its structure using various physiochemical
pre-treatments. 4.4. Photoreforming of Raw Biomass
Raw biomass composition can vary depending on the specific

4.3.2. Photoreforming of Starch source. However, in general, raw biomass is primarily composed
of various constituents such as cellulose, hemicellulose, lignin,
The rate of H2 creation decreased with growing molecular proteins, and lipids.[273] The utilization of raw biomass as pro-
complexity, but microwave pre-treatment of soluble starch dis- ton and electron sources in the photocatalytic creation of H2
played significantly enhanced H2 evolution. Kurenkova et al. represents the ultimate application. Employing raw biomass or
reported the photocatalytic reforming of corn starch and rice waste materials directly as substrate has emerged as an auspi-
over a Cd0.7 Zn0.3 S-based photocatalyst and 5 M NaOH at 70 °C cious approach, considering both economic and environmental
with simultaneous hydrogen production.[226] The supreme rate considerations.[19] The complicated structural and chemical com-
of hydrogen evolution was 730.0 micromole of H2 /g.h with position of raw biomass presents challenges in its application for
AQE = 1.8% at 450 nm (Table 4 and Entry no. 14). Kondarides photocatalytic processes, necessitating pretreatment methods to
et al. studied the H2 creation by photo-induced reforming of facilitate the valorization of lignocellulosic materials. This area
starch (raw biomass) over Pt/TiO2 and the rate of H2 creation was of research is currently active and evolving.[274] Additionally, the
up to 1.2 micromole of H2 /min (Table 4 and Entry no. 20). Hydro- limited solubility of biomass prevents the photocatalytic process
gen generated at mild conditions via an efficient, technically sim- for hydrogen production,[168] The solubility of biomass plays a
ple, economically benign, and cost effective process, with the use critical role in achieving high photoreforming performance. It
of a Pt/TiO2 with abundant and renewable sources such as starch has been demonstrated that the addition of detergents can en-
(raw biomass), sunlight, and H2 O.[195] Speltini et al. reported o-g- hance the photoreforming rate of castor oil when using aque-
C3 N4 and cTiO2 with Pt, Cu-Ni cocatalysts for photocatalytic H2 ous Pt/TiO2 as the catalyst.[275] Although pretreatment methods
creation from aqueous starch under simulated sunlight.[260] The contribute to the overall process cost, they are currently essential
hydrogen evolution rate is affected by cocatalyst type and incor- for achieving high yields of hydrogen.[276] Despite these limita-
poration, with the maximum H2 production rate up to 168.0 and tions, wide research has been conducted on diverse types of raw
593.0 micromole of H2 /g.h using TiO2 loaded with 3 wt.% Cu- biomass products,[107,277] ranging from farming waste to dead
Ni or 3 wt.% Pt respectively (Table 4 and Entry no. 13). Although insects,[166] with Pt/TiO2 being the effective and most widespread
H2 creation reactions were lower compared to Pt/TiO2 , a cheap, choice of semiconductor. The process of biomass photoreform-
ecological, and non-nanometric catalyst like o-g-C3 N4 , attached to ing resembles the photooxidation of several organic substances.
non-noble metals, providing a more efficient H2 generation. In this process, both UV and visible light trigger the generation of
e-h pairs within photocatalysts, which are then utilized to oxidize
biomass. Also, the ongoing availability of electrons necessary for
4.3.3. Photoreforming of Hemicellulose and Lignin proton reduction and the release of H2 are sustained through
biomass oxidation. This is supported by relevant experimental
Hemicellulose is a complex carbohydrate that plays a criti- observations (Table 5).[47,278]
cal part in the structure of plant cell walls. It is one of the
core components of the cell wall matrix, along with lignin and
cellulose.[265] Hemicellulose, a significant constituent of ligno- 4.4.1. TiO2 -Based Photocatalysts with Cocatalysts
cellulosic biomass, contains ester-containing structures consist-
ing of monomeric carboxylic acid compounds. In the process of Speltini et al. effectively studied photocatalytic hydrogen creation
photoreformation, these carboxylic acid substrates have the abil- over Pt/TiO2 using raw biomass such as rice husk and alfalfa
ity to strongly bind to metal-oxide catalysts like TiO2 through stems and maximum hydrogen yield was observed up to 24.0
their hydroxyl and carbonyl functional groups. However, this micromole of H2 /g (Table 5 and Entry no. 2).[250] Jaswal et al
interaction can yield varied outcomes in terms of hydrogen reported the pinewood was subjected to dilute acid hydrolysis
production.[266,267] Hemicellulose is a diverse group of polysac- at 160 °C and 10 bar pressure, resulting in a hydrolysate that
charides that show a wide range of structures and properties, proved suitable for high-yield photoreforming over Pt/TiO2 with
making it a fascinating and important area of study in the field an output of 19.9 mL H2 /g pinewood.[183] Yasuda et al studied
of photoreforming to hydrogen and valuable products.[107] Lignin sacrificial H2 creation from enzymatically hydrolyzed chlorella
constitutes a substantial portion of lignocellulosic biomass and with Pt/TiO2 semiconductor. H2 (57.9 mg) was attained from
serves as a main reservoir of aromatic polymers or carbon com- 1.0 g of dried chlorella over protease-hydrolysis and photocat-
pounds with immense potential for conversion into high-value alytic H2 creation Pt/TiO2 .[279] Zhao et al studied the fabricated
products and hydrogen fuel.[268–271] Despite being viewed as a TiO2 -NiO core-shell heterojunction synthesized by the single step
Table 5. Comparative table photoreforming of raw biomass.
Sr. No. Photocatalyst Reaction condition Energy source Substrate H2 activity Remarks Ref.
(SED)
1) Pt/TiO2 Photocatalyst 150 mg, 150 W Xe Fescue grass 61.0 H2 creation by the [259]
200 mL DI water lamp micromole of photo-assisted reforming
H2 /g.h of raw biomass such as
fescue grass using Pt
(economical and
eco-friendly) on TiO2
2) Pt/TiO2 2 gL−1 photocatalyst, Natural Rice husk 24.0 Aqueous cellulose [250]
200 mg substrate, Sunlight micromole of suspension irradiated
60 mL DI water, NaOH H2 /g under solar light in the
or H2 SO4 presence of Pt/TiO2
performs as a hydrogen
evolving system and
5-hydroxy-methylfurfural
(HMF) intermediate is
identified.
3) Co/CdS/CdOx QDs (0.5 M) with 100mWcm−2 Wooden 5310.0 Light-driven photo-assisted [107]
quantum 50 mg mL−1 substrate branch micromole of reforming of raw biomass
dots (QDs) in 2 mL 10 M KOH H2 /g.h to H2 using CdS quantum
dots in alkaline aqueous
solution with Co
cocatalyst.
4) Co/CdS/CdOx QDs (0.5 M) with 100mWcm−2 Sawdust 750.0 micromole – [107]
quantum dots 50 mg mL−1 substrate of H2 /g.h
(QDs) in 2 mL 10 M KOH
5) Co/CdS/CdOx QDs (0.5 M) with 100mWcm−2 Grass 1000.0 – [107]
quantum dots 50 mg mL−1 substrate micromole of
(QDs) in 2 mL 10 M KOH H2 /g.h
6) Co/CdS/CdOx QDs (0.5 M) with 100mWcm−2 Bagasse 370.0 micromole – [107]
quantum dots 50 mg mL substrate in of H2 /g.h
(QDs) 2 mL 10 M KOH
7) Cyanamide- Photocatalyst 0.5 mg, 100mWcm−2 Sawdust 202.0 micromole Activated NCN CNx -NiP [258]
functionalized co-catalyst 300 nmol, of H2 /g.h agrees for the light driven
carbon nitride phosphate solution photoconversion of
(NCN CNx /NiP) purified and raw
lignocellulose into
hydrogen in the presence
of numerous proton
reduction cocatalysts (pH
≈2–15)
8) CoO/g-C3 N4 5.0 mg cellulose, 10 mg Xe lamp Wheat straw 129.0 micromole Biomass photo-assisted [253]
photocatalyst, 10 mL of 300 W of H2 /g reforming using cost
1 M NaOH solution, effective CoO/g-C3 N4
50 mL DI H2 O catalysts to produce H2
and lactic acid under
visible light illumination
9) Au/CdS Photocatalyst-100 mg Xe lamp Waste paper 27.0 micromole H2 production from waste [228]
and 100 mL H2 O 300 W scraps of H2 /g.h paper scraps over
Au/CdS-nanorods
(solvothermal metho
10) Pt/TiO2 2 gL−1 photocatalyst, UV Alfalfa stems 24.0 micromole – [250]
200 mg Cellulose, of H2 /g
60 mL DI water, 5 M
NaOH
11) Pt/TiO2 Photocatalyst 300 mg, Pt Xe lamp Rice plant 175.0 micromole – [166]
5 wt.%, 5N NaOH, 500 W of H2
30 mL water, 100 mg
substrate
(Continued)
Sr. No. Photocatalyst Reaction condition Energy source Substrate H2 activity Remarks Ref.
(SED)
12) Pt/TiO2 Photocatalyst 300 mg, Pt Xe lamp 500 Turf 98.0 micromole – [166]
5 wt.%, 5N NaOH, W of H2
30 mL water, 100 mg
substrate
13) Pt/TiO2 Photocatalyst 300 mg, Pt Xe lamp 500 Chlorella algae 270.0 micromole – [166]
30 mL water, 100 mg
substrate
14) Pt/TiO2 Photocatalyst 300 mg, Pt Xe lamp 500 laver 332.0 micromole – [166]
30 mL water, 100 mg
substrate
hydrothermal method, which was employed as a catalyst for the (virgin lignocellulose). After 12 h of irradiation, up to 1000.0
photocatalytic creation of H2 (450.0 micromole of H2 /g.h) and micromole of H2 /g were produced from poplar and toilet pa-
valuable coproducts such as CH4 and fatty acids using kraft lignin per (waste lignocellulose) produced 2167.0 micromole of H2 /g.h
as the sacrificial substrate.[280] of H2 over monolayer g-C3 N4 . Wu et al. solar-driven biomass
photoreforming for creation of H2 fuel and valuable chemicals
over CoO/g-C3 N4 photocatalyst.[253] The pretreated wheat straw
4.4.2. g-C3 N4 and CdS Based Photocatalysts with Cocatalysts showed higher H2 production than raw wheat straw, wherein
the greatest activity with 129.0 micromole of H2 /g after 12 h of
Visible light-responsive photocatalysts such as carbon nanoma- reaction and formed lactic acid as a valuable product (Table 5
terials (g-C3 N4 )[256,258] and sulfides (CdS)[104,107,281] have been es- and Entry no. 8).
tablished for hydrogen creation from photoreforming of lignocel- Wang et al. studied the photocatalytic H2 creation from
lulosic substrates. Kasap et al. introduced a cyanamide-modified biomass on Au/CdS nanorods with Au3+ self-reduction.[228] The
CN, denoted as NCN CNx , which was utilized for the creation of H2 creation rate was 27.6 micromole of H2 /g.h for the paper
H2 through visible-light-induced photoreforming. This process scraps and the total H2 creation yield was 138.0 micromole of
took place in the occurrence of a molecular cocatalyst called H2 /g (Table 5 and Entry no. 9). Hydrogen can also be gener-
Ni bis(diphosphine) (NiP) and was carried out in an aqueous ated through photocatalysis using waste paper scraps, showcas-
medium (Figure 7a).[258] The photo-assisted reforming H2 cre- ing not only the efficient utilization of waste, but also the maxi-
ation rate can attain 200.0 micromole of H2 /g.h in K3 PO4 solu- mization of global resource utilization. Wakerley et al. reported
tion (KPi, pH = 4.5) at 25 °C with sawdust, (Table 5 and Entry no. the CdS quantum dots to achieve high rates of hydrogen genera-
6) (Figure 7d). Furthermore, the raw and unprocessed biomass tion from the photoreforming of hemicellulose and lignin up to
samples such as bagasse, wooden branches, paper, and cardboard 2000.0 and 260.0 micromole of H2 /g.h respectively, under highly
showed hydrogen production rate up to 34.8, 35.7, 42.7, and 46.9 basic conditions.[107] Furthermore, raw biomass such as news-
micromole of H2 /g.h respectively, under the similar parameters paper, bagasse, cardboard, sawdust, grass, paper, and wooden
(Figure 7d). branches are also employed for photocatalytic reforming to hy-
Rao et al. reported the photo-assisted reforming of lignocel- drogen evolution under similar conditions (Table 5 and Entry no.
lulose and raw biomass into hydrogen and by intrinsic mono- 3–6) (Figure 7d). The catalyst’s enhanced rates of H2 production
layer CN with 1 wt.% Pt cocatalyst.[256] Presently, catalytic sys- might be accredited to the occurrence of CdOx , which covers the
tems typically exhibit limited efficiency when exposed to ultra- CdS surface and facilitates stronger interactions between the sub-
violet light, thereby restricting the improvement of this reac- strates and photocatalysts. Consequently, the efficient transfer of
tion. However, a promising solution lies in utilizing metal-free H+ and the subsequent weakening of C-C bonds occurred, re-
2D graphite-phased carbon nitride (g-C3 N4 ), which responds to sulting in the oxidation of substrates and the evolution of H2 .
visible light and serves as a strong contender for photocatalytic However, a comprehensive evaluation of the sustainability and
H2 generation (Figure 7b). The activity of photo-assisted reform- environmental implications of photocatalytic H2 production ne-
ing of lignocellulose over the bulk g-C3 N4 into hydrogen was cessitates the inclusion of precursor materials utilized in catalyst
very low (hemicellulose-54 micromole of H2 /g and lignin-trace). synthesis.
However, the monolayer g-C3 N4 showed an improvement in hy-
drogen evolution reaction (HER) and the maximum yield was
719.0 and 249.0 micromole of H2 /g over 12 h for hemicellulose 4.4.3. Other Photocatalysts
and lignin respectively. The substrates for the photo-assisted re-
forming of biomass into hydrogen are further extended into raw Cellulose calcination has been employed to synthesize carbon
biomass such as toilet paper (waste lignocellulose) and poplar dots, which are now being utilized as light absorbers for the
Figure 7. a) Graphic representation for photocatalytic reforming of raw biomass (lignocellulose) over H2N CNx to H2 creation, b) schematic represen-
tation for photo-assisted reforming of raw biomass over g-C3 N4 to H2 creation, c) schematic representation for photoreforming of raw biomass over
carbon dot to H2 production, and d) photoreforming of raw biomass over NCN CNx with NiP cocatalyst and CdS/CdOx with CoBF4 cocatalyst.
photoconversion of biomass-derived substrates into hydrogen mogeneous carbon dots and a notable quantity of hydrogen was
and a range of organic products (Figure 7c).[102,282] Achilleos generated. Additionally, the co-catalyst facilitated the oxidation of
et al. studied photocatalytic H2 creation coupled to pollute uti- 𝛼-cellulose, resulting in the predominant formation of C6 H12 O6
lization using biomass produced ultra-scalable and low-cost car- and C6 H10 O5 liquid organic compounds. The NiP-loaded carbon
bon nanodots which when joined with a non-precious Ni-based dot semiconductor has demonstrated effectiveness in reforming
co-catalyst. They studied the polluted sea and river water into various intricate biomass-derived products, including lignin and
energy carriers in most inhabited locations worldwide.[282] Fur- xylan.[102] Kadam et al. reported the sustainable technique utiliz-
ther, Achilleos et al. reported the incorporation of a nickel ing nanostructured C, N, S-incorporated ZnO under solar light
bis(diphosphine) (NiP) co-catalyst onto the cellulose-derived ho- has been established for effective degradation of lignin (biomass)
and simultaneous H2 production through H2 O splitting.[261] type of linkage in their core chain, these plastics can be cate-
Preparation of C, N and S-incorporated ZnO was accomplished gorized into two primary groups. At first, plastics were synthe-
via calcination of bis-thiourea zinc acetate complex. Excellent hy- sized through addition polymerization, consists of C-C backbone.
drogen production, i.e., 6430.0 micromole of H2 /g.h was attained The second group includes plastics produced through conden-
for the sample calcined at 600 °C (Table 4 and Entry no. 22). sation polymerization with heteroatoms in the core backbone
Ren et al conducted research highlighting the significance of pri- chains (C-O or C-N). PUR, PLA, and PET have C-O or C-N
oritizing the cleavage of C-C bonds in carbohydrates to enable bonds in their macromolecular chain and are prepared by con-
efficient photocatalytic H2 production over Ta-CeO2 photocata- densation polymerization whereas, PE, PS, PP, and PVC have
lyst. This strategy focuses on fully breaking the C-C bonds in C-C linkages in their backbone and are prepared by addition
biomass, resulting in the generation of liquid LHCs (Low Hy- polymerization.[299] The stability of heteroatom contained plas-
drogen Content) as the primary products. By utilizing a syner- tics (such as PET, PUR, and PLA) makes it interesting to achieve
gistic Ta-CeO2 catalyst that harnesses both solar and thermal photocatalytic degradation, especially when compared to plastic
energy, the C-C bonds in carbohydrates are effectively broken, polymers with purely carbon-based backbones. They are theoret-
yielding LHCs such as HCOOH and HCHO with yields rang- ically prone to hydrolytic breaking of the amide and ester bonds
ing from 62% to 86%. The resulting LHCs capable of trans- in the core chain.[302–304]
portation, solely release H2 and CO2 irrespective of solar light Plastic photoreforming presents an optimistic strategy for pro-
irradiation.[283] ducing ecological fuels like H2 and CO.[111] One notable benefit
In summary, while numerous studies have focused on is the use of plastic wastes as sacrificial substrates for hole scav-
raw biomass substrates, their photocatalytic activities cur- enging, efficiently reducing the recombination of photogener-
rently remain inferior to those achieved with pure sub- ated charges and improving total photocatalytic efficiency.[305] Ad-
strates. However, the photoreforming of renewable biomass ditionally, from a thermodynamic perspective, generating green
substrates holds significant appeal for sustainable economic fuels through plastic photoreforming demands less energy com-
purposes, and further investigations require a multifaceted pared to water oxidation.[306] This substantial thermodynamic
approach. benefit arises from the lesser energy needed for the waste plas-
tic oxidation. As a result, the process of fuel production through
plastic photocatalytic reforming has attracted significant interest.
4.5. Recent Advances in the Photoreforming of Plastic Waste
The complex structure of synthetic plastic waste makes them 4.5.1. Photocatalyst Optimization Strategies for Highly Selective
highly unaffected by degradation in the atmosphere. Owing to Photoreforming
this issue, environmental agencies and municipalities face a sig-
nificant obstacle.[284] Even with extensive media coverage and ef- To accomplish the exceptionally selective photoreforming of plas-
forts by lawmakers to address the issue, achieving a world with- tics, it is crucial to investigate catalyst optimization approaches
out plastic will be a challenging task. Plastics possess beneficial that possess broader pertinence. Recently, Yue et al. described
characteristics but also hurt our atmosphere.[285] Real reprocess- some photocatalyst optimization strategies in detail.[307] These
ing procedures for plastic wastes are the present bottlenecks. A strategies primarily encompass the following:
probable outcome is to use plastic waste as a substrate for H2
creation (Figure 8a).[152] Every year, over 50 million tons of H2 i) Synthesis methods
are manufactured globally to serve the chemical, pharmaceuti-
cal, and agricultural sectors.[286–291] Approximately 300 M tons The performance of photocatalysts is significantly influenced
of waste plastic is generated globally yearly, with ≈90% of it by the synthesis methods employed, as these methods and condi-
classified as waste.[292] Given the lengthy lifespan of plastics, a tions determine the crystallinity and particle size of the resulting
mere 10% recycling rate falls short, necessitating the exploration photocatalytic materials.[308] A recent study by Nguyen et al. de-
of innovative strategies to minimize plastic consumption.[293,294] tailed the synthesis of g-C3 N4 by controlling its fabrication us-
Consequently, there is ongoing research into energy-efficient, ing a range of earth-abundant precursors, including dicyandi-
low-temperature, and low-pressure processes rooted in pyroly- amide, melamine, urea, and thiourea. Notably, g-C3 N4 derived
sis to harness unused energy and transform plastic waste into from melamine exhibited superior performance compared to al-
hydrogen fuel, which could potentially benefit the automotive ternative precursors. It achieved the highest rates of hydrogen
industry.[111,152,295] evolution while concurrently effectively converting plastic into
Plastics are extensively utilized on an industrial scale due valuable organic products with exceptional photocatalytic stabil-
to their lightweight, toughness, flexibility, water-resistant, cost ity. The enhanced performance of melamine-derived g-C3 N4 can
effectiveness, and versatility.[296,297] The extensive utilization of be attributed to its higher crystallinity and enhanced chemical
plastics in our everyday lives presents difficulties in terms of in- resistance, which play crucial roles in stabilizing its morphology
creasing their recycling, removal, and degradation.[298] PET, PE, and surface properties. These findings shed light on the crucial
PP, PVC, PS, PLA, and PUR (Figure 8b) are the most commonly impact of precursor selection, synthesis methodology, and struc-
used plastics, comprising ≈80% of the total plastic demand.[299] tural properties on the photocatalytic activity of g-C3 N4 . Such in-
Owing to high durability and stability, these plastics have lengthy sights lay the groundwork for advancing photocatalytic processes
decomposition times and thus remain as waste materials for the aimed at simultaneously producing green hydrogen and reform-
atmosphere.[300,301] Based on their degradation pathways and the ing plastic waste.[309]
Figure 8. a) The procedure of utilizing plastic waste as an energy source to facilitate the production of sustainable fuels, b) structures of synthetic
polymer wastes or plastics, c) graphic representation for photo-assisted reforming of pretreated waste plastics with CdS/MoS2 , d) schematic design
of the photoreforming of organic waste into H2 using Pt-deposited CdOx /CdS/SiC composite photocatalyst, e) hydrogen evolution rates from the
photoreforming of plastic wastes with various photocatalysts, and f) the oxidative way of PLA through the photoreforming process.
ii) Morphology engineering Once the positions of CB and VB align to facilitate the redox
ability for hydrogen generation and plastic degradation, the
Nanomaterials have emerged as crucial elements in effectively band gap can be further adjusted to enhance light absorption.
mitigating charge recombination and enhancing photocatalytic In the realm of photocatalysts, creating junctions between
efficiency with reliability. This is attributed to the substantial semiconductors with varying band gaps can enhance light
enlargement of the surface area in nanostructured photocata- absorption properties. This can be achieved through meth-
lysts, coupled with the reduced travel distance of photogenerated ods such as element doping, heterojunction formation, and
charges. These factors collectively increase the probability of de- other techniques.
sired reactions occurring without encountering charge recom- vi) Surface defect engineering: This method centers on present-
bination. Over time, numerous nanomaterials have been devel- ing defects or heteroatoms to enhance photocatalyst activ-
oped for employment in photocatalytic reactions, encompassing ity. Through the creation of active places on the photocata-
nanostructured photocatalysts such as nanospheres, nanodots, lyst surface and the optimization of its energy band struc-
and nanorods, as well as carbon-based materials like graphene ture, the energy barrier can be markedly reduced, thereby
and CN. Notably, quantum dots composed of CdS/CdOx and improving the photocatalytic performance at the reaction
nanosheets of d-NiPS3 /CdS have exhibited remarkable hydrogen centre through the adsorption method.[315] Qiao et al. in-
evolution activity (discussed in detail in subsection 4.5.2).[112,152] troduced a defect-rich chalcogenide-coupled photocatalyst
This underscores the significance of photocatalyst morphology for solar-driven plastic photoreforming, aimed at producing
as a critical determinant in the photoreforming of plastics. hydrogen and high-value chemicals. They had successfully
constructed a defect-rich nickel-based chalcogenphosphate-
iii) Material hybrid approaches: Hybridizing semiconductors coupled cadmium sulfide photocatalyst (d-NiPS3 /CdS) capa-
with non-metallic elements, such as carbon-based materi- ble of concurrently converting plastic wastes under ambi-
als or metal oxides, allows for the utilization of distinct ent conditions. The efficiency of the plastic photoreforming
properties from various materials. This grants researchers process was attributed to the rapid separation of photogen-
a potent means to control strategies related to light harvest- erated electron-hole pairs facilitated by d-NiPS3 nanosheets,
ing, adsorption capacity, catalytic activity, and selectivity.[310] along with efficient redox reactions occurring at the defect-
Gong et al. reported that coupling CN with carbon nanotubes activated P and S sites on the photocatalyst surface. This
(CNTs) provided an ideal scenario for enhancing the activity study provided new insights for designing efficient photocat-
of photoreforming of plastics. This was because CNTs acted alysts and achieving sustainable conversion of plastics into
as an excellent charge transport layer, facilitating an effective high-value chemicals and green fuels.[112]
electron transfer network through the 𝜋-conjugative struc-
ture. Although functionalized CNTs had been combined with
CN via electrostatic interactions, they were unable to estab- 4.5.2. Photoreforming of Nonrecyclable PET, PLA, and PUR
lish a strong connection with CN and exhibited poor effi-
ciency in photo-generated charge separation. Therefore, they The three examples analyzed for photoreforming were PET, PLA,
developed a straightforward approach to enhance the close and PUR. These plastic wastes have C-N or C-O linkages in their
interaction between CN and CNTs in the photoreforming of backbone. Uekert et al. reported the use of plastic waste as a
plastic systems. To promote the transfer of electrons from feedstock for solar-driven H2 generation, employing inexpensive
CN to NiMo, it was an effective strategy to integrate NiMo CdS/CdOx quantum dots in an alkaline aqueous solution via pho-
nanoparticles and CNTs into a heterogeneous structure, with toreforming. Photoreforming decomposition resulted in the pro-
CNTs serving as an intermediate electron transport layer.[311] duction of valuable byproducts such as formate, acetate, pyru-
iv) Incorporation of cocatalysts: Incorporating metals as cocat- vate, and hydrogen.[152] They achieved maximum hydrogen pro-
alysts has the potential to augment charge transference at duction rate for PET, PLA, and PUR up to 3420.0, 64000.0, and
the interface. Furthermore, the surface plasmon resonance 850.0 micromole of H2 /g.h, respectively (Table 6 and Entry no.
effect can be utilized to modulate the redox potential of the 2) (Figure 8e). The feasibility of this process was tested by photo-
photo-generated transporters.[312] In a recent study by Han assisted reforming PET bottles to generate H2 and other valu-
et al., they investigated the efficiency of single atom Pt1 /TiO2 able organic feedstocks. Du et al. reported the photocatalytic re-
and Pt nanoparticles supported on TiO2 photocatalysts for forming of waste plastic into hydrogen and valuable chemicals
photoreforming of plastic waste, specifically PET, into hydro- over MoS2 -tipped CdS nanorods.[316] The design of the MoS2 /CdS
gen fuel. Their research delved into the role of Pt cocatalysts structure capitalizes on the unique shape and efficient charge
in this photoreforming process, revealing their bifunctional- transfer characteristics of nanorods. It effectively gathers e− at
ity. The Pt cocatalysts were found to serve as electron transfer the tip of MoS2 for H2 creation, while simultaneously employ-
mediators facilitating hydrogen evolution, while also acting ing the whole sidewall of CdS nanorods with abundant holes for
as reactive sites for the adsorption of molecules involved in plastic degradation (Figure 8c). It is revealed that continual hy-
the reaction.[313] drogen can be produced from photocatalytic reforming of PLA
v) Band engineering regulation: Through the establishment of and PET up to 6680.0 and 3900.0 micromole of H2 /g.h, respec-
a well-matched energy band structure, it becomes possible tively (Figure 8e) (Table 6 and Entry no. 3). Alternatively, the
to generate an electric field at the surface. This facilitates plastic photooxidation half-reaction is initiated via the direct hole
the transference of photogenerated transporters, leading to a transference from CdS to plastic sacrificial agents and results in
substantial improvement in photocatalytic performance.[314] an excess of valuable chemicals (such as formate, glycolate, and
Table 6. Comparative table of plastic waste.
1) Carbon nitride/nickel Photocatalyst Simulated Plastic waste 141.0 & 427.0 Photoreforming of plastic [317]
phosphide 1.6 mg mL−1 , solar light, (PET & PLA) micromole of waste, i.e., PET & PLA
(NH2 CNx |Ni2 P) substrate 100 mW H2 /g by using NH2 CNx |Ni2 P
25 mg mL−1 , 1 M cm−2 in alkaline solution to
KOH hydrogen
2) CdS/CdOx quantum Photocatalyst Simulated Plastic waste 3420.0, 64000.0 CdS/CdOx quantum dots [152]
dots 1 nmol, (50 mg solar light, [PET, PLA & PUR & 850.0 for photoreforming of
mL−1 PLA, 25 mg 100 mW (polyurethane)] micromole of waste plastic to
mL−1 PET, PET cm−2 H2 /g.h hydrogen in alkaline
bottle or PUR, solution
10 M NaOH
3) MoS2 -tipped CdS Photocatalyst 300 W Xe lamp Plastic waste (PET 3900.0 & 6680.0 Photo-assisted reforming [316]
nanorod 100 mg, 60 mL & PLA) micromole of of plastic into valuable
pretreated plastic H2 /g.h products and H2 with
waste, MoS2 /CdS with alkaline
pretreatment
4) Ni0·1 Co0·9 P/rGO/CN Photocatalyst 300 W Xe lamp PLA 576.7 Ternary Nix Co1-x P/reduced [318]
10 mg, 1 g PLA, micromole of GO/g-C3 N4
100 mL KOH H2 /g.h photocatalyst for
synergetic PLA
photo-assisted
reforming and H2
creation in alkaline
aqueous solution.
5) 0.2 M PET, 1 M 100 mW cm−2 PET 174.0 Reforming of plastic using [319]
Cu30 Pd70 /perovskite/Pt KOH micromole of a bias-free
H2 /g.h Cu30 Pd70 |Perovskite|Pt
PEC Device
6) Pt/TiO2 Photocatalyst Xe lamp PVC 45.0 Photoreforming of PVC [166]
300 mg, 150 mg PTFE 3.5 and PTFE to hydrogen
substrate, 5N micromole of by using Pt/TiO2 with
NaOH H2 /g.h alkaline solution
7) CdOx /CdS/SiC Photocatalyst Xe lamp 300 W PE 25.0 The photoreforming of PE [255]
50 mg, PS 19.4 and PS into hydrogen
Substrate 100 mg, micromole of using a CdOx /CdS/SiC
10 M NaOH H2 /g.h photocatalyst
5 mL,
0.5 wt.%
8) MXene/Znx Cd1-x S Photocatalyst Xe lamp 300 W PET 14170.0 MXene/Znx Cd1-x S has [320]
0.10 mg, 50 mL micromole of been effectively
PET alkaline H2 /g.h fabricated to
solution accomplish
highly-efficient H2
production integrated
with the degradation of
microplastic
9) Pt/Benzenesulfonyl Photocatalyst Xe lamp 300 W PLA 1890.0 Benzenesulfonyl [321]
chloride 10 mg, alkaline micromole of chloride-incorporated
incorporated g-C3 N4 solution of PLA H2 /g.h g-C3 N4 for
100 mL photocatalytic H2
creation by using PLA
with alkaline solution
and Pt cocatalyst
10) Ag2 O/Fe-MOF Photocatalyst Xe lamp 300 W PEG 3600.0 In-situ formation of [322]
100 mg, 500 mg PET 1900.0 Ag2 O/Fe-MOF for
substrate, PE 1700.0 light-driven upcycling of
100 mL DI water, micromole of microplastics with H2
1 M NaOH H2 /g.h creation
(Continued)
11) CN-CNTs-NiMo Photocatalyst Xe lamp 500 W PET 90.0 Photo-assisted reforming [323]
10 mg, KOH micromole of of plastic waste PET via
10 mL (5 M), H2 /g.h in-situ derived
PET 10 mg mL−1 CN-CNTs-NiMo hybrids
to H2 production with
alkaline condition
12) d-NiPS3 /CdS Photocatalyst 1 mg, Xe lamp 300 W PET 3138.0 Boosted photocatalytic [112]
500 mg PET or PLA 3976.0 reforming of plastic
100 mg PLA, micromole of waste via d-NiPS3 /CdS
10 mL KOH H2 /g.h nanosheets into H2 and
solution (2 M), valuable organic acid
13) Co-Ga2 O3 – Simulated PE 647.8 Utilize solar light to [324]
sunlight PP 600.0 realize the sustainable
PET 385.0 and effective
micromole of plastic-to-syngas (H2
H2 /g.h and CO) conversion
with the aid of H2 O at
ambient conditions
acetate) and gaseous alkanes (such as methane, propane, ethane, glycolate) yield up to 78.0 micromole within 9 h, together with
and n-pentane) are formed. outstanding stability beyond 100 h in photo-assisted reforming
The poisonous Cd metal was substituted by harmless, cheap, of viable waste plastic PLA and PET.[112]
and eco-friendly materials. Therefore, Uekert et al. reported the
Ni2 P /CNx semiconductor for photo-assisted reforming of PLA
and PET to H2 fuel and valuable chemicals under alkaline aque- 4.5.3. Photoreforming of Nonrecyclable PE, PS, and PVC
ous conditions.[317] The Ni2 P/CN photocatalyst exhibited effec-
tive charge separation and maintained catalytic stability for a Plastics such as PVC, PS, and PE have carbon-carbon linkage in
period of five days. Hydrogen can be generated from photo- their core. These materials have been utilized for an extended pe-
assisted reforming of PLA and PET up to 427.0 and 141.0 mi- riod as packing materials, which are rejected in the atmosphere
cromole of H2 /g.h, respectively (Figure 8e) (Table 6 and Entry in huge amounts after usage. Kawai et al. degraded plastics pre-
no. 1). By utilizing the CNx /Ni2 P combination, polymer photore- pared by addition polymerization into fine substances with the
forming harnesses an overlooked resource to effectively tackle generation of hydrogen fuel at room temperature using Pt/TiO2
plastic pollution, while also generating hydrogen and organic photocatalyst.[166] The side chains of hetero atoms such as chlo-
compounds through an affordable, sustainable, and sunlight- rine, exist as soluble substances (HCl) in the aq. phase. PVC has
powered approach. For the degradation or hydrolysis of plastics, served as a representative polymer for synthetic polymers con-
the CdS/CdOx and CNx /Ni2 P photocatalytic systems necessitate taining chlorine and having carbon-carbon bonds in their core
an initial high pH or alkaline pretreatment. Initially, the trans- structure. At room temperature, a PVC powder and Pt/TiO2 in
lation efficacy of waste polymers is reasonable, resulting in the water with a 1:2 ratio were exposed to a 300 W Xe lamp. A spec-
transformation of the carbon content in the plastics into carbon- troscopic analysis suggested that pure H2 up to 45.0 micromole
ates. of H2 /g.h were produced in an aqueous solution (Table 6 and En-
Yan et al. studied the ternary composite (Ni0.1 Co0.9 P/rGO/g- try no. 6). Nagakawa et al. studied the photocatalytic reforming of
C3 N4 ) of photocatalyst for photocatalytic reforming of polylac- PE and PS into H2 using a CdOx /CdS/SiC photocatalyst.[255] The
tic acid (PLA) into acetate and formate with simultaneous gen- CdS/SiC composite photocatalyst was prepared by subjecting the
eration of hydrogen 576.0 micromole of H2 /g.h in the aqueous SiC oxide film to etching and the CdS surface to oxidation in an
condition (Table 6 and Entry no. 4).[318] To examine the valuable alkaline solution, resulting in the formation of a CdOx /CdS/SiC
products, the accurate structure of both the reactant and isolated composite (Figure 8d). This composite is employed for the pho-
product was determined using 13 C- and 1 H-NMR spectra before toreforming of organic wastes such as PE and PS to H2 genera-
and after the photoreforming. Figure 8f illustrates the photoox- tion. The maximum hydrogen rate was achieved for PE and PS
idative pathways of PLA as it undergoes the photoreforming pro- up to 25.0 and 19.4 micromole of H2 /g.h, respectively (Table 6
cess to yield valuable products. Recently, Zhang et al reported and Entry no. 7).
the photo-assisted reforming of plastic waste over the defect-rich Photoreforming of plastic waste is an auspicious approach to
NiPS3 (d-NiPS3 /CdS) nanosheets with 2 M KOH solution for tackle the growing problem of plastic pollution in society. Pho-
H2 evolution. The supportive photoredox via defect-rich chalco- toreforming of plastics involves using photocatalytic processes
genide nanosheet-coupled semiconductors, e.g., d-NiPS3 /CdS to degrade plastic waste and generate valuable products such
give a high H2 creation of 40000.0 micromole of H2 /g.h (Table 6 as H2 and commodity chemicals. It offers several advantages
and Entry no. 12) and organic acid (pyruvate, acetate, formate and such as environmental sustainability, valuable products, selective
Table 7. Comparative table of glycopolymer.
1) Hierarchical 15 mg HPT, 50 mg Xe lamp 420 W, PNVK-b-PMDG 881.0 First time carbazole based [155]
porous TiO2 glycopolymer, 30 mL DI 𝜆 ≥ 380 nm micromole of glycopolymers used with
(HPT) water, 3 wt.% Pt as a H2 /g.h Pt/HPT for photocatalytic
co-catalyst, 1 mL NaOH hydrogen production with
(10 M) alkaline solution.
2) HPT – Xe lamp 420 W, PNVK-b-PMDM 730.0 – [155]
𝜆 ≥ 380 nm micromole of
H2 /g.h
3) HPT – Xe lamp 420 W, PMDG 312.0 – [155]
H2 /g.h
4) HPT – Xe lamp 420 W, PMDM 258.0 – [155]
H2 /g.h
5) HPT – Xe lamp 420 W, Glucose 156.0 – [155]
H2 /g.h
6) HPT – Xe lamp 420 W, Maltose 128.0 – [155]
H2 /g.h
degradation, renewable hydrogen generation, and versatility. H2 /g.h (Table 7 and Entry no. 2). The probable mechanism for the
Overall, the photoreforming of plastics presents a promising photocatalytic reforming reaction of glycopolymer over Pt/HPT
avenue for transforming plastic waste into valuable feedstocks is as shown in Figure 9b. The hydrogen production rate of various
while dropping ecological impacts and encouraging a more sus- glycopolymers over Pt/HPT is shown in Figure 9c.
tainable circular economy. Glycopolymer materials have not been extensively studied for
photocatalytic hydrogen production, but they offer unique prop-
erties that could be explored in this context. Glycopolymers are
4.6. Photoreforming of Glycopolymers known for their free -OH groups and these can provide electrons
to the semiconductor to fill the holes generated at the time of
Glycopolymers refer to synthetic polymer structures that incor- photoreforming. This exclusiveness could lead to a more effec-
porate attached carbohydrate groups.[325] Glycopolymer materi- tive photo-assisted reforming path of work-of-fiction glycopoly-
als have gained considerable attention in the scientific commu- mers to harvest renewable H2 energy.
nity as a notable class of biopolymers with promising appli-
cations. They have recently been recognized as a distinct syn-
thetic biomaterial and have been utilized in a range of fields 4.7. Photoreforming of Food Waste into Valuable Products
such as therapeutic approaches, medical adhesives, drug/gene
delivery systems, biosensors, membranes, and photocatalytic Around the world, the production of ≈1.3 billion tons of food
H2 evolution.[155,326–331] Recently Shelake et al. (our group) first waste yearly leads to significant consequences for society, the
time reported the photocatalytic hydrogen generation over hier- economy, and the environment. The components of food waste
archical porous TiO2 (HPT), sacrificial glycopolymer substrate primarily include carbohydrates, proteins, lipids, and small
with alkaline medium and the structures of polymers shown amounts of inorganic compounds. The specific composition
in Figure 9a.[155] The photocatalytic hydrogen generation from of food waste varies depending on the type of food and its
HPT without glycopolymer substrate was too low up to 78.0 constituents.[332] For instance, food waste that predominantly
micromole of H2 /g.h, but enhanced after the addition of gly- consists of rice and vegetables is rich in carbohydrates such as
copolymer substrate with aq. NaOH solution. Nevertheless, the sugars, starch, lignin, hemicellulose, and cellulose.[333] Most of
production of photocatalytic hydrogen was less effective when the food waste is presently disposed of in landfills or incinerated,
using deacetylated homopolymers, specifically PMDM (maltose leading to the release of greenhouse gases and the squandering of
based homopolymer) and PMDG (glucose based homopoly- energy and nutrients.[334] There is a scarcity of research reports
mer), in comparison to the results achieved by incorporating that focus on waste solutions as substrates, which would allow
a 9-vinylcarbazole macromolecular segment into the individual for addressing both the pressing issue of waste disposal and the
PMDM and PMDG blocks. The maximum hydrogen generation production of clean fuels.[335] The primary components of house-
was observed for the eblock of glucose (PNVK-b-PMDG) up to hold solid waste, constituting ≈75% of it, consist of food waste,
881.0 micromole of H2 /g.h (Table 7 and Entry no. 1) compared paper and cardboard, and plastic waste. These materials can be
to eblock of maltose (PNVK-b-PMDM) up to 730.0 micromole of utilized in biomass photoreforming reactions. An encouraging
Figure 9. a) Chemical structures of deacetylated homopolymers and diblock copolymers, b) mechanistic pathway for photocatalytic H2 generation, c)
graphical representation of hydrogen production over HPT with various saccharides and glycopolymers, d) photoreforming schematic representation
of food waste over CdS/CdOx quantum dots or H2N CNx |Ni2 P to hydrogen, and e) photo-assisted reforming of real-life waste, including apple, cheese,
and bread over CdS and H2N CNx .
alternative is anaerobic digestion, a process in which microor- biogas.[336] Innovative technologies are therefore required to re-
ganisms generate biogas (consisting of methane, CO2 , and hy- trieve the economic and material cost of food waste. Conse-
drogen) from food waste. While this method enables energy quently, photocatalytic reforming presents a straightforward ap-
retrieval, it incurs significant primary capital expenses, can- proach that utilizes sunlight to convert food waste into value-
not accommodate mixed waste, and frequently yields impure added chemicals and clean hydrogen.[236]
There has been imperfect research on mixed waste or food Table 8. Summary of popular ML algorithms for materials research.
waste. The limited publications on photocatalytic reforming of
food waste all exploited a TiO2 semiconductor attached to Pt ML algorithm Application
cocatalyst.[166] The effectiveness and practical use of these sys- RF regression Catalytic activity prediction[ 342]
tems were constrained due to their ability to absorb only ultravi- Kernel ridge regression Determining molecular orbital
olet light and their high cost. Uekert et al. present a method for energy[ 343]
efficiently converting food and mixed wastes using visible light, Gradient boosting algorithm Identifying key features[ 344]
without noble metals (cocatalyst). They utilize two distinct cata-
Support vector machines Property prediction through materials
lysts, namely homogeneous CdS/CdOx quantum dots and hetero- screening[ 345]
geneous H2N CNx |Ni2 P cocatalyst (Figure 9d).[236] These catalysts
Gaussian process regression Adsorption energy prediction[ 346]
enable the transformation of various substances such as proteins,
Convolutional neural network Prediction of binding energies[ 347 ]
carbohydrates, and fats into hydrogen and organic valuable prod-
Artificial neural network Design and discovery of materials[ 348]
ucts in both neutral and alkaline aqueous environments. Pre-
treated bread, apples, and cheese three of the most normally dis- Generative models New materials innovation[ 349]
carded food items were tested. As anticipated, in alkaline condi-

tions, CdS/CdOx exhibits ≈8 to 15 times greater activity compared
to H2N CNx |Ni2 P (Figure 9e) However, H2N CNx |Ni2 P also demon- factors that are commonly derived from the materials’ composi-
strates the ability to efficiently reform waste in water, yielding tion and structure.
moderate amounts of desired products. ML techniques have recently been utilized in photocatalysis
The photoreforming process extends beyond food waste and to enhance the H2 creation process. It highlights the limitations
encompasses mixed and municipal wastes, which encompass of traditional experimental approaches, which are often labori-
various materials such as food, biomass, and plastics. This em- ous and time-consuming in analyzing the relationship between
phasizes a significant advantage of photoreforming over alterna- input parameters and H2 yield. By incorporating computational
tive technologies for managing food waste. Given the significant techniques and ML models, one can efficiently analyze exten-
amount of food waste generated annually, photo-assisted reform- sive datasets from experimental and theoretical studies, leading
ing presents a distinctive and sunlight-driven approach to convert to the development of predictive models for biomass conversion
this resource, even in conjunction with other waste types, into processes. The quoted examples illustrate the efficacy of ML al-
valuable hydrogen and organic chemicals. gorithms like multilayer perceptron neural networks (MLPNN),
RF, and artificial neural networks (ANN) in accurately predict-
ing H2 creation across different systems, from catalytic steam
4.8. AI/ML-Based High Throughput Screening methane reforming to supercritical water gasification of biomass
waste. These methods not only enhance accuracy and efficiency,
In the vast domain of artificial intelligence (AI), machine learn- but also offer valuable insights into the mechanisms governing
ing (ML) has emerged as a powerful tool for addressing mul- photocatalyst activity, paving the way for the design of highly ef-
tidimensional datasets, utilizing a range of algorithms to con- ficient photocatalytic materials. However, challenges persist in
struct predictive models by identifying patterns within the fully integrating material insights with ML-driven predictions,
data.[337] In particular, ML algorithms has accelerated the op- highlighting the need for further research to maximize the po-
timization and discovery of materials for practical applications tential of data-driven approaches in photocatalysis.
such as photovoltaics, catalysts, thermoelectric, and optoelec- Employing traditional methodologies for assessing H2 pro-
tronic materials.[338–341] The learning and prediction process of duction and its connection to input parameters, such as gasi-
ML is influenced by three main factors: algorithms, data or fication conditions, proximate, and ultimate compositions in-
databases, and descriptors, wherein algorithms are responsible volve extensive experimentation labor-intensive, and consumes
for tasks such as data extraction, filing, and mathematical deriva- a significant amount of time and resources. Amidst the indus-
tion propagation. Various frequently employed ML algorithms trial revolution, manufacturing sectors are experiencing remark-
are detailed in Table 8, along with examples demonstrating their able growth, with computational techniques emerging as a sig-
application in materials research. Although comprehensive ex- nificant technological frontier especially in the field of cataly-
planations of these algorithms are readily accessible, the chal- sis research.[350,351] Integrating these methods with experimen-
lenge lies in selecting the most suitable algorithm for a given tal analysis is essential to develop photoactive and highly effi-
objective. There are specific guidelines that are outlined in pre- cient devices.[352–354] Through quantum mechanical and molec-
vious references, yet these rules are established upon simplified ular mechanical explorations of electronic structures, computa-
assumptions. However, the accuracy of predictions is highly de- tional studies provide detailed material reactivities and proper-
pendent on descriptors that possess a unique quality across dif- ties, offering insights into essential indicators that govern photo-
ferent materials and properties, provided the algorithm selection catalyst activity, including adsorption mechanisms on active sur-
is appropriate and the dataset is comprehensive. In the field of faces, band structure, and photogenerated charge recombination
catalysis, descriptors capture essential physicochemical charac- behavior.[355,356] Beyond conventional approaches, the future of
teristics that reveal the relationship between structure and its ac- photocatalysis is anticipated to be influenced by ML, a branch
tivity, selectivity, and stability. Therefore, identifying potential fea- of (AI) dedicated to constructing models that can learn from
tures is pivotal for predicting target properties, which can range data to make insightful predictions and decisions.[344,345,357] This
from physical properties to synthesis methods or other relevant technology is extensively utilized across various industrial
sectors, including pharmaceuticals, process industries, manufac- the dependent variable.[160] Their results highlighted the supe-
turing, and the petroleum industry,[358,359] where it plays a crucial rior accuracy and reliability of the artificial NN model, prompt-
role in tasks such as fault diagnosis, optimization, and process ing its application in optimizing H2 production. Sheng et al. es-
controls. In contrast to experimental and thermodynamic inves- tablished four distinct ML models through SCWG of biomass
tigations, ML models employ the specific operational conditions to predict the H2 creation (Figure 10e).[366] The outcomes re-
and input parameters of biomass to develop prediction models. vealed the RF model’s superior capability in predicting H2 yield
Applying these models allows for a comprehensive understand- (R2 = 0.9782) compared to SVM, NN, and GPR models. Using
ing of how input parameters impact supercritical water gasifi- partial dependence and feature importance analysis, they pre-
cation, facilitating accurate predictions of H2 production with- dicted the significance and average partial relationship of par-
out the need for prolonged time consumption.[360] Figure 10a il- ticular process parametric and biomass properties that impact
lustrates the comprehensive process of employing the ML tech- H2 yield. The application of ML algorithms expands the scope
nique to model green hydrogen evolution and valuable feedstock of modeling of H2 creation from various wastewater sources.
generation. The initial phase in ML workflow involves data pre- Ghasemian et al. utilized ANN for the predictive modeling of
processing, where a dataset is generated from both experimen- biohydrogen production from synthetic wastewater.[367] Sridevi
tal and theoretical studies on the photocatalytic conversion of et al. implemented a backpropagation ANN to characterize biohy-
biomass resources, serving as training data for the ML model. drogen creation using distillery wastewater, achieving a substan-
Subsequently, parametric engineering is applied to create a dis- tial R2 of 0.97 through the Levenberg-Marquardt (LM) algorithm,
tinctive set of ML descriptors covering the entire materials design highlighting the model’s reliability in predicting biohydrogen
space. Choosing the right ML algorithm is essential for accurate yield from distillery wastewater.[368] Ramesh et al. demonstrated
and interpretable models, given the array of options like Bayesian the significant influence of the MLPNN-BR model (R2 = 0.999,
optimization (BO), decision trees (DT), gradient boosting regres- RMSE = 0.138) in predicting biohydrogen creation from pho-
sion (GBR), partial least squares regression (PLS), RF, neural net- tocatalytic wastewater conversion, highlighting radiation inten-
works (NN), Gaussian process regression (GPR), support vector sity, irradiation time, catalyst size, reaction temperature, and cata-
machines (SVM), K-Nearest Neighbours (KNN), among others, lyst amount, as key parametric through independent variable im-
each with specific strengths and weaknesses, and no one algo- portance analysis.[369] These findings emphasize the importance
rithm excels universally in all applications. Finally, the stability of ML in the efficient screening of photocatalysis, yet the criti-
and accuracy of all models are assessed through metrics such cal challenge remains in elucidating the connection among the
as the coefficient of determination (R2 ) and mean absolute error property-selectivity criteria guided by material insights and iden-
(MAE). tifying areas where ML tools can contribute to the development
Employing MLPNN,[361–363] researchers modeled catalytic of highly selective photocatalytic materials.
steam methane reforming to produce simulated biohydrogen
production from sugarcane molasses, and predicted microbial
kinetics in the dark fermentation process. These investigations
5. Future Challenges
demonstrated that MLPNN models exhibit enhanced accuracy, Comparable to photocatalytic reforming, biomass electro-
rapid convergence, facilitating direct statistical analysis with clear reforming offers significant benefits in terms of H2 creation
visualization, providing an effective means to accurately model and the manufacturing of chemicals, thereby enhancing its
biohydrogen production. Jie et al. developed an ML framework value. There are notable similarities between the challenges
specifically tailored for predicting the composition of H2 -rich faced and their corresponding solutions. One of the primary
syngas produced through the supercritical water gasification challenges, akin to photoreforming, is the use of electrocatalysts
(SCWG) process (Figure 10b), covering both catalytic and non- that can endure the demands of the feedstock while exhibiting
catalytic systems.[364] The NN model, at the core of this frame- favorable selectivity to produce valuable products. Renewable
work consistently achieved a commendable level of accuracy electricity and solar energy can both be utilized, but it is critical
(R2 > 0.85) across all evaluated systems, playing a pivotal role in to minimize the ecological consequences related to the reactants
systematically screening catalysts and determining optimal con- to improve the appeal of deploying this technology based on
ditions to expedite experiments with the primary aim of maxi- its global potential and cost-benefit ratio.[370–372] In addition to
mizing H2 yield while minimizing CO2 yield. Subsequently, they the common drawbacks shared with H2 O electrolysis, such as
introduced four data-driven ML approaches to effectively model reliance on noble metals or platinum moiety metals and slow
the gasification process of biomass waste,[365] aiming for process anode kinetics, there exist specific challenges associated with
optimization and product prediction (Figure 10c,d). Notably, the biomass electrolysis.
GBR model demonstrated robust predictive performance, yield- Biomass photocatalytic reforming is an auspicious technology
ing test R2 values between 0.82 and 0.96, and its interpretation that uses solar energy and catalysts to convert biomass feedstocks
highlights the substantial impact of various parametrics such into valuable fuels and chemicals. While it holds great potential,
as gasification temperature, oxygen, nitrogen, carbon content, numerous challenges want to be addressed for its extensive adop-
and feedstock ash on the distribution of char, tar, and syngas tion and commercialization in the future. Some of these chal-
in the gasification process of biomass waste. Estahbanati et al. lenges include:
utilized ML to expect H2 creation rates in the photo-assisted re-
forming of glycerol, utilizing four pivotal operating parameters, • Efficiency: One of the key challenges is enhancing the ef-
namely pH, Pt%, catalyst incorporation and glycerol%, were cho- ficacy of biomass photoreforming processes. Increasing the
sen as independent variables with the created H2 amount as conversion efficiency and overall energy efficacy is crucial for
Figure 10. a) Schematic representation of a typical ML workflow, and b) the associated catalyst screening for H2 -rich syngas production. Reprinted with
permission from ref. [364]. Copyright 2021 Elsevier, c,d) graphical illustration of ML methodology for enhancing the gasification of biomass waste, with
the objective of optimizing the production of H2 -rich syngas. Reprinted with permission from ref. [365]. Copyright 2023 Elsevier, e) ML guided hydrogen
production through the supercritical water gasification of biomass. Reprinted with permission from ref. [366]. Copyright 2019 Elsevier.
manufacturing the technology economically viable and inex- in hydrogen production, it may not outweigh the costs and en-
pensive with other renewable energy sources. vironmental impact associated with sourcing the feedstock, es-
• AI/ML High throughput screening: The application of ML to pecially when considering the cost-effectiveness of electricity
predict structural information holds promise for understand- from renewable sources.
ing reaction mechanisms; however, its implementation in pho-
tocatalysis for intricate organic substrates, like polymers or Addressing these challenges will require interdisciplinary re-
biomass, poses challenges, including calculating DFT-based search efforts, including materials science, catalysis, process en-
adsorption energies or determining active sites over diverse gineering, and system integration. Continued innovation and
surfaces. collaboration between industry and academia will be crucial for
• Photocatalyst optimization: Developing efficient and stable the upcoming development and positioning of biomass photore-
catalysts for biomass photoreforming is another challenge. forming technologies.
Catalysts play a crucial role in facilitating the conversion of
biomass into valuable fuels and chemicals. Researchers need
to discover and optimize catalyst materials and compositions 6. Conclusions and Outlook
to enhance their performance, stability, and selectivity.
• Photoreactor design: The aim is to develop innovative pho- In conclusion, the most feasible and straightforward strate-
toreactors capable of optimizing mass transference, photon gies for H2 production are photocatalytic H2 O splitting and
transference, light distribution, and utilization, while also be- the photoreforming of oxygenated substrates or renewable
ing readily scalable and adaptable for integration into existing biomass derivatives. Utilizing biomass photoreforming holds
systems. great promise as a sustainable method for producing energy
• Reaction condition: To optimize the operational reaction con- and valuable feedstocks. The straightforwardness of this room-
ditions in biomass photoreforming, which include factors temperature process in generating H2 fuel provides a significant
such as photocatalyst loading, light intensity, early pressure, benefit over thermochemical methods. However, its competen-
pH, and reactant feed ratio, among others. It is critical to cies have not yet reached the levels of conventional processes.
widely assess the effects and interactions between these pa- Historically, the emphasis in this field has been on developing
rameters for improved understanding and performance eval- materials and catalysts specifically tailored for solar H2 O split-
uation. ting, which has restricted the photocatalytic activity to UV light.
• Photoredox properties: Selecting the optimal sacrificial sub- Several studies have focused on enhancing photocatalysts to ef-
strates and their concentration in a photocatalytic H2 creation fectively utilize visible photons from solar light and optimizing
system is primarily based on empirical methods, considering reaction parameters, such as light irradiation and choice of sac-
the system components and the reaction medium. Neverthe- rificial reagents, for efficient H2 generation. It is difficult to envi-
less, it is crucial to consider the relative redox potentials of the sion a sustainable society that effectively reduces our carbon foot-
materials within the system and the pH of the reaction system print without utilizing biomass to produce essential compounds
to ensure effective performance in the photocatalytic creation like fuel and fine chemicals that are crucial for our daily lives.
of H2 . We provided an outline of the photo-assisted reforming of carbo-
• Product recovery: In the context of biomass photoreforming, hydrate derivatives, waste polymers, food wastes, and glycopoly-
achieving energy recovery requires minimizing conversion mers by unraveling the fundamental reaction mechanisms, and
steps and reducing process times. Efficient product recovery is pathways. To attain practical photocatalytic hydrogen generation
a critical aspect of the photoreforming process. After the pho- using renewable biomass, it is necessary to enhance the selec-
tochemical reactions have taken place, it is essential to recover tivity of the organic oxidation half-reaction. This improvement
and isolate the desired end-products from the reaction mix- is crucial to reduce the generation of detrimental organic waste
ture. products and to encourage the creation of valuable chemicals. We
• Availability and reproducibility of feedstock: Biomass with car- summarize the selectivity enhancement in organic photoreform-
bon capture and storage plays a crucial role in established cli- ing reactions, emphasizing the significance of various factors
mate change mitigation strategies outlined by numerous in- such as reaction conditions, pH, substrate type, and the meth-
tergovernmental panels. Its upscale arrangement could affect ods employed for preparing substrates. Simultaneous H2 cre-
the accessibility of biomass for photocatalysis. ation and selective oxidation reactions are the focus. To enhance
• Product value chain: The selection between biomass partial selectivity in organic photoreforming systems and attain better
oxidation processes can influence the overall product value control, it is crucial to prioritize the advancement of photocata-
chain, contingent on the type and yield of the final products. lysts. In the future, research efforts should concentrate on creat-
Partial oxidation may lead to the retrieval of valuable feed- ing narrow band-gap materials specifically optimized for biomass
stocks, albeit with potential drawbacks such as lower activity, photoreforming to improve performance under natural sunlight
reduced hydrogen recovery rates, and the necessity for prod- conditions.
uct recovery facilities, thereby escalating investment costs. Full Overall, photocatalytic processes are highly appealing and
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Sandip Prabhakar Shelake obtained his M. Sc in 2018 from Shivaji University-Kolhapur, India. Sub-
sequently, he joined as a junior research fellow and a Ph.D. student in Dr. A. V. Sesha Sainath’s group
at the Polymers and Functional Materials and Fluoro-Agrochemicals Department, CSIR-Indian In-
stitute of Chemical Technology, Hyderabad, India. His research interest is focused on the design and
synthesis of glycopolymers and the engineering of semiconductor materials for hydrogen generation
applications from water, which includes energy conversion, storage, and utilization.
Dattatray Namdev Sutar obtained his M. Sc in 2018 from Savitribai Phule Pune University, India.
Then, he joined as a junior research fellow and a Ph.D. student in Dr. A. V. Sesha Sainath’s group at
the Polymers and Functional Materials and Fluoro-Agrochemicals Department, CSIR-Indian Institute
of Chemical Technology, Hyderabad, India. His research interest is focused on the design and syn-
thesis of glycopolymer architectures and the engineering of semiconductor materials for hydrogen
generation applications from water, which includes energy conversion, storage, and utilization.
B. Moses Abraham is a Fulbright-Kalam Climate Post-doctoral Fellow at the A.J. Drexel Nanomate-
rials Institute, Drexel University, Philadelphia, USA. He received his PhD in 2020 from the School of
Physics, University of Hyderabad, India. Thereafter, he moved to IIT Kanpur, India and worked as a
National Postdoctoral Fellow. Later he was awarded Juan de la Cierva-Formación Fellowship funded
by Government of Spain and joined University of Barcelona. His research expertise is centered on em-
ploying advanced computational techniques and data-driven approaches to conduct high throughput
screening of materials for sustainable energy and environmental applications.
Tanmay Banerjee received his Ph.D. from CSIR – National Chemical Laboratory, Pune, India in 2014.
Between 2014 and 2022, he had been working on various aspects of electron- and energy-transfer
processes pertinent to heterogenous photocatalysis and DSSC applications at Florida State Univer-
sity, USA, MPI for Solid State Research, Germany, and in his independent career at BITS Pilani, India,
as a Ramanujan Fellow. From 2023 onward, he has been working as a formulation and product de-
velopment scientist for Quaker Houghton in India exploring aspects of surface chemistry, tribology,
molecular synthesis, and oleochemistry for various industrial process fluid applications.
Annadanam V. Sesha Sainath is a polymer scientist, currently serving as a Senior Principal Scientist
and Professor at CSIR-IICT, India. Dr. Sainath has over thirty years of experience in polymer basic re-
search and product R&D, both, in industry and academia. He earned his Ph.D. in 1998 from SKU, AP,
India, in collaboration with CSIR-CSMCRI, Gujarat. He worked as a research associate at CSIR-NCL,
Maharashtra, YUVBL, Japan and as a JST-CREST fellow at Tokyo Institute of Technology, Japan. Sub-
sequently, he moved to MCI, Japan, and from there, he moved to CSIR-IICT, in 2009. His expertise
includes polymer architecture syntheses, and hydrogen generation.
Ujjwal Pal is a Senior Principal Scientist and Professor of Chemical Sciences (AcSIR) at CSIR-Indian
Institute of Chemical Technology (CSIR-IICT), India and is affiliated with the Department of Energy
and Environmental Engineering. He received his M. Sc. (2000) from Jadavpur University, Kolkata, and
Ph.D. from CSIR-IICT (2008). Then, he worked as a Postdoctoral Fellow at Mexico State University,
USA, and later at Moffitt Cancer Centre Research Institute, USA. He commenced his independent
research career in Renewable Energy Research at CSIR-CMERI, India, in 2010 and later he moved to
CSIR-IICT. His research interest is focused on semiconductor photocatalysis for hydrogen generation
and CO2 reduction applications.

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REVIEW

Emerging Photoreforming Process to Hydrogen Production:

S. P. Shelake, D. N. Sutar, A. V. S. Sainath B. M. Abraham

Scheme 1. General classes of photoreforming substrates discussed in this review.

2.3. Organic Photo-Oxidation 2.4.2. Mechanistic Insights of Photo-Assisted Biomass Reforming

3.2.5. Additional Reaction Parameters

3.2.4. Eﬀect of pH 4. Photoreforming of Biomass

Table 2. Photocatalytic reforming data for glucose with various photocatalysts.

1) C3 N4 based catalyst 20 mg photocatalyst, 5 W white Xylose 136.9 The fabrication of an [210]

9) Pt/TiO2 80 mg photocatalyst, Xe lamp Galactose 5.5 micromole of – [196]

18) Pd/TiO2 Photocatalyst-20 mg, LED 365 nm Glucose 8900.0 – [202]

29) CdS/MoS2 100 mg photocatalyst, Xe lamp Glucose 55000.0 A binary [214]

Table 3. Comparative table of disaccharides.

Table 4. Comparative table of polysaccharides.

Raw biomass composition can vary depending on the speciﬁc

Table 5. Comparative table photoreforming of raw biomass.

Table 6. Comparative table of plastic waste.

Table 7. Comparative table of glycopolymer.

carded food items were tested. As anticipated, in alkaline condi-

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