Chemical Engineering Journal 452 (2023) 138980

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Chemical Engineering Journal

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Review

Photoreforming lignocellulosic biomass for hydrogen production:

Optimized design of photocatalyst and photocatalytic system
Cai Shi a, 1, Fuyan Kang a, 1, Yeling Zhu c, 1, Min Teng a, Junming Shi a, Houjuan Qi a,
Zhanhua Huang a, *, Chuanling Si b, *, Feng Jiang c, *, Jinguang Hu d, *
a
Key Laboratory of Bio-based Material Science and Technology, Ministry of Education, Material Science and Engineering College, Northeast Forestry University, Harbin
150040, China
b
Tianjin Key Laboratory of Pulp and Paper, College of Light Industry and Engineering, Tianjin University of Science and Technology, Tianjin 300457, China
c
Sustainable Functional Biomaterials Lab, Department of Wood Science, University of British Columbia, 2424 Main Mall, Vancouver V6T 1Z4, Canada
d
Department of Chemical and Petroleum Engineering, University of Calgary, 2500 University Drive, NW, Calgary, Alberta T2N 1N4, Canada

A R T I C L E I N F O A B S T R A C T

Keywords: Using renewable solar energy for clean hydrogen (H2) fuel production via photocatalysis is a promising low
Photocatalytic reforming carbon intensity strategy to address the energy crisis and environmental pollution issues. Biomass photorefinery
Biomass photorefinery is an emerging technology platform where biomass or its derivatives are employed as hole (h+) scavengers during
H2 evolution
photocatalysis, which not only reduces the thermodynamic barrier of the energy-demanding oxygen evolution
Solar energy
Biochemicals
reaction (OER, ΔE⁰ = − 1.23 V) in water splitting to favor H2 generation, but also endows the potential of biomass
valorization. This review provides an in-depth comprehensive overview of the co-production of H2 and value-
added biochemicals via lignocellulosic biomass photoreforming, with the special focuses on catalyst’s struc­
ture and photocatalytic system design. The photocatalyst structure is mainly elaborated from its band gap,
morphology and size, crystal phase, cocatalyst and surface group modification. Among them, the band gap
structure is crucial for the regulation of catalyst redox ability, which determines the high selectivity of photo­
catalyst to generate the desired biochemicals. As well as the catalytic system such as pH, solvent, the concen­
tration of catalyst and substrates, and the reaction temperature, matter much to enhance the solubility of
lignocellulose and the accessibility of catalysts to substrates. The performance of using raw and pretreated
biomass as h+ scavengers to boost H2 production as well as insights into their valorization pathways are deeply
discussed. Future perspectives and challenges for the further advancement of biomass photoreforming tech­
nologies are given at the end of this review.

1. Introduction effective technological alternative is to employ biomass or its derivatives

Energy crisis is as one of the world’s most pressing issues that urges
more efficient production of clean energy [1–3]. Sustainable H2, that can
be produced through redox splitting of water via solar driven photo­
catalysis, has been identified as a promising alternative to the dwindling
fossil fuels [4–7]. Nevertheless, the conventional photocatalytic H2
production technologies are still challenged by the low quantum yields
of water splitting, which is due to the large thermodynamic barrier of
oxygen evolution reaction (OER, ΔE⁰ =− 1.23 V), rapid recombination of
photogenerated charge carriers, and the existence of reverse-reactions
[8,9]. To promote photocatalytic water splitting for H2 production, an
as reductive substrate to substitute OER for holes (h+) consumption,
namely photocatalytic biomass reforming (or biomass photoreforming).
In this concept, upon photoexcitation, a photocatalyst generates h+ to
oxidize biomass and use the resultant electrons (e-) to reduce aqueous
proton (H+) to H2. In contrast to OER, the overall biomass photo­
reforming reaction is almost energy neutral, it can use highly abundant
low-energy photons (visible and IR light), it also has the potential to
generate value-added by-products from biomass [10–13]. Ever since the
first report of using biomass as photoreforming substrate in 1980 s [14],
lignocellulose, the most abundant biomass on earth, has demonstrated a
great potential biomass photoreforming. The reason for that is,

* Corresponding authors.
E-mail addresses: huangzh1975@163.com (Z. Huang), sichli@tust.edu.cn (C. Si), feng.jiang@ubc.ca (F. Jiang), jinguang.hu@ucalgary.ca (J. Hu).
1
These authors contributed equally.

https://doi.org/10.1016/j.cej.2022.138980
Received 20 June 2022; Received in revised form 23 August 2022; Accepted 30 August 2022
Available online 6 September 2022
1385-8947/© 2022 Elsevier B.V. All rights reserved.
C. Shi et al.
lignocellulose not only serves as an e- donor and/or h+ scavenger to
promote the separation and consumption of the photogenerated
charges, but also be simultaneously transformed into various value-
added biochemicals. Meanwhile, the photocatalytic H2 evolution effi­
ciency is enhanced as a result of being coupled with the photocatalytic
lignocellulose oxidation [15–17].
Despite these advantages, the incumbent lignocellulose photo­
reforming technology is still incapable of meeting the industrial expec­
tations. One bottleneck is the intractable deconstruction of common
lignocellulosic feedstocks, primarily due to the sophisticated structure of
lignocellulose that has evolved to protect against microbial and photo
degradation in nature [18,19]. Cellulose (a semi-crystalline poly­
saccharide, >40 % in dry weight), hemicelluloses (branched poly­
saccharides, 20–40 %), and lignin (crosslinked phenolic polymer, less
than35 %) represent the three largest fractions of lignocellulose. The
strong inter-chains hydrogen bonding within the cellulose microfibrils
and the encrusting recalcitrant lignin molecules make it resistant to
chemical transformation [20,21]. (Fig. 1) Other drawbacks encountered
in photoreforming lignocellulose include low selectivity toward
partially oxidized products (especially with water as the solvent), the
inhibitory effects of by-products in the liquid phase, and the demand of
high-energy UV light to activate certain photocatalysts [22–24].
To achieve high-efficiency photoreforming of lignocellulose and its
derivatives for H2 production and biomass valorization, considerable
progress have been witnessed in the past years in designing photo­
catalysts with optimized structure and/or developing novel photo­
catalytic system. Currently, there are several excellent reviews just focus
on the photocatalysts or systems designs for the photocatalytic H2 pro­
duction from H2O [25] or photoreforming of organics for oxidation re­
actions [26–28]. Afterwards, Qi et al. summarized the cooperative
coupling of oxidative organic synthesis (from alcohol, ether, hydrocar­
bon, and amine, etc. to value-added chemicals) and H2 production over
semiconductor-based photocatalysts [29]. In 2021, our group published
a mini-review on photoreforming biomass for the production of H2 and
chemicals. However, the effect of photocatalysts and systems optimi­
zation on the generation of H2 and chemicals in photoreforming are not
particularly clear and complete [30]. To further deepen the under­
standing of the effects of catalyst structure and catalytic system opti­
mization on lignocellulosic biomass photoreforming for H2 and
chemicals production, this review will provide a comprehensive over­
view on it. Furthermore, the performance of using lignocellulose and its
derivatives as h+ scavengers as well as insights into their valorization
pathways are deeply discussed. Specifically, the effects of the optimized
Fig. 1. Chemical structures of lignocellulosic components and photoreforming biomass to evolve H2 and oxidized organics on semiconductor.
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Chemical Engineering Journal 452 (2023) 138980
design of photocatalyst’s structure and catalytic system on photo­
reforming of different type of biomass are discussed in detail, starting
from the three major components of lignocellulose (cellulose, hemicel­
lulose, and lignin), followed by the raw biomass, wastes, and the small
molecules derived from biomass. Our opinions on the perspectives and
future challenges toward photocatalytic biomass reforming for H2 evo­
lution are given for the further advancement of novel photoreforming
technologies.
2. Fundamental principles of biomass photoreforming
As shown in Fig. 1, biomass photoreforming reaction is driven by the
excited state of semiconductor under solar irradiation, which consists of
two separate half-reactions, namely H2 evolution reaction (HER) and
biomass oxidation reaction (BOR). In general, photoreforming reaction
is mainly accomplished by three sub-processes: 1) activation of the
photocatalyst to generate photoexcited h+-e- pairs under the irradiation
of incident light with energy greater than the photocatalyst band gap
energy. The e- present in valence band (VB) can be excited and trans­
ferred to the conduction band (CB) of the semiconductor, while the same
number of h+ are simultaneously created and remain in the VB; 2)
migration of both types of the photogenerated carriers to the photo­
catalyst surface; 3) utilization of the photogenerated carriers by their
corresponding substrates to produce H2 and biochemicals, i.e., e- on the
photocatalyst surface reduces protons to H2, while the h+ oxidizes
biomass-derived reactants into corresponding chemicals.
HER is usually substrate independent, and is primarily a process in
which the protons from water are reduced by photogenerated e-.
Biomass photoreforming has a much smaller thermodynamic barrier
than that of photodecomposition of water, making the H2 evolution
reaction more likely to occur in theory. In addition, it facilitates more
sufficient use of solar energy with a wider range of wavelengths (e.g.
visible or even IR light), which is vital for practical application [11]. The
photoreforming HER reaction carried out in D2O clearly indicates that
the generated H2 is mainly derived from water rather than biomass [21].
For some specific reactions, like the photoreforming process of benzyl
alcohol, furfural alcohol, methanol, and ethanol, the protons could be
from alcohols substrates [31]. Yet biomass as proton sources for H2
evolution remains to be further explored.
BOR is a more complex process that involves a multi-step conversion
of biomass substrates. Different kinds of biomass and reaction systems
including catalysts and solvent types, pH and so on will affect the re­
action pathway and mechanism of biomass in photoreforming process.
C. Shi et al. Chemical Engineering Journal 452 (2023) 138980

Briefly, biomass consumes h+, ⋅OH, ⋅O–2 or 1O2 who can be transferred acid-base sites (Summarized in Table 1).
directly to the chemisorbed biomass substrates [32,33] to generate
corresponding chemicals in the process of photoreforming, in which
3.1. Photocatalyst band gap structure
active species were involved mainly depends on the oxidation capacity
determined by the band gap of the photocatalyst itself. In general, the
As described in Section 2, photoreforming reaction is mainly
consumption of oxidized active species would make more available e- for
accomplished by three sub-processes, and the band structure of photo­
HER, which is conducive to the improvement of HER efficiency.
catalyst mainly affects Steps 1 and 2. To ensure the forward reaction of
Nevertheless, the conversion pathway of biomass is up to the specific
photocatalytic HER during water splitting, the band gap of photocatalyst
reaction system. Taking the simple monosaccharide-glucose as an
needs to be greater than the potential barrier of HER (1.23 eV).
example, it could be photoreformed to generate small molecular acids
Considering the thermodynamic loss and overpotential in the reaction
such as lactic acid by isomerization, retro-aldol reaction, and dehydra­
process, the band gap energy in practical application typically needs to
tion [34]; also the C–C bond in glucose could be cleaved selectively,
be>1.8 eV [11]. However, photocatalyst with high band gap energy
and the glucose can be gradually converted into arabinose, erythrose,
suffers from insufficient utilization of solar energy. For instance, to make
and formic acid in photocatalytic glucose reforming [35]. This shows the
full use of the visible light that accounts for approximately 46 % of the
liquid products differ immensely with diverse photoreforming systems.
total solar energy [37], the band gap of the photocatalyst is preferably
It should be pointed out that the relationship between HER and BOR is
less than 3.2 eV. Therefore, the theoretical optimal band gap energy of
relatively complicated, which will be analyzed in detail in the following
the material used for photocatalytic HER should be between 1.8 and 3.2
sections combined with specific reaction systems.
eV [38–40].The absorption characteristics of a material depend on its
bandgap value. So, the selection of light source should be consistent with
3. Influences of photocatalyst structure on photoreforming H2
the absorption characteristics of the semiconductor in practical photo­
generation
reforming process. Other than the band gap energy, the band gap dis­
tribution is equally important for HER. The CB potential of photocatalyst
The structure of photocatalyst plays an important role in determining
needs to be more negative than the reduction potential of H2 (E0 = -0.41
the HER activity by affecting the physicochemical and optical proper­
V vs standard hydrogen electrode, at pH = 7), and the VB potential
ties, as well as the separation efficiency of the photogenerated charges
should be more positive than the oxidation potential of the sacrificial
[36]. In this part, the effects of catalyst structure on biomass photo­
agent (i.e., the biomass). It is worth mentioning that the light with less
reforming H2 production will be discussed from the following four as­
energy and longer wavelength (such as visible and IR light) in solar
pects: 1) band gap structure; 2) morphology and size; 3) crystal phase;
energy that used to be less useful in pure water splitting can be more
and 4) other factors such as cocatalyst loading, modification of transi­
sufficiently utilized to activate H2 production reaction during biomass
tion metals elements for selective adsorption of substrates and surface
phototreforming [11].

Table 1
Influence of photocatalyst structure on photoreforming H2 production performance.
Influence factor Entry Photocatalyst Substrate Light source, intensity (mW H2 evolution rate (mmol g- AQY/% (λex/ Reference
(Concentration, g L-1) cm− 2) 1 − 1
h ) nm)

Band gap structure 1 TiO2-NiO (0.50) Lignin UV–Vis 23.52 6.46 (3 6 5) [54]
TiO2 (0.50)NiO 6.60 2.54
(0.50) 2.11 (3 6 5)0.92
(3 6 5)
2 Sn0.24-Ru0.68/TiO2 (0.30) Glucose UV ~4.00 0.41 (3 6 5) [55]
Ru0.68/TiO2 (0.30) 0.33 0.30
Sn/TiO2 (0.30) 0.06 (3 6 5)0.06
TiO2 (0.30) 0.06 (3 6 5)0.01
(3 6 5)
3 ZnxCd1− xS-P (0.20)ZnS-P 5-HMF LED 0.79 – [63]
(0.20)CdS-P 0.006
(0.20) 0.06
4 Zn0.6Cd0.4S homojunction (2.00) Glucose Xe lamp 0.69 ~0.18 (4 2 0) [34]
ZnS
(2.00)CdS 0.02
(2.00) 0.11
5 ZnS-g-C3N4 (1.00) Glucose Xe lamp 0.21 – [70]
g-C3N4 (1.00) 0.08
6 UCN-NA0.5 (0.67)UCN Glucose LED ~1.91 – [71]
(0.67) 0.16
Morphology and 7 CdS/CdOx (0.50 μM) Lignocellulose Solar 2.57 – [21]
size light simulator
8 CdS nanosheets (0.50)CdS Lactic acid Xe lamp ~3.75 – [79]
nanospheres ~6.25
(0.50)CdS nanorods ~6.25
(0.50)CdS nanowires ~5.38
(0.50)Commercial CdS ~5.13
(0.50)
Plasma effect 9 3DOM TiO2-Au (0.20) Glucose Xe lamp ~10.90 [45]
TiO2 (0.20) ~0.67
Element 10 Ni-CdS (1.00) Furfural 8 W LED ~2.59 – [42]
modification alcohol
5-HMF ~0.47 –
Acid-base sites 11 SO2-
4 -P25-NixSy (0.20) Cellulose Xe lamp 3.02 – [94]
SO2-
4 -P25(0.20) (0.20) 0.19 –
Pt/P25 (0.20) 0.04 –

3
C. Shi et al.
Even though semiconductor with favored band gap energy and dis­
tribution was selected, its photocatalytic efficiency can still be low due
to the possible high recombination rate of the photogenerated carriers
and the limited reactive sites. To overcome such limitation, it is neces­
sary to regulate the structure of the band gap by conducting element
doping, heterojunction or homojunction construction, and surface
functional group modification. The effects of band gap structure of
commonly used photocatalysts on the biomass photoreforming will be
reviewed in the following section.
3.1.1. TiO2 based materials
Among various semiconductive materials, TiO2, CdS, CdS-based
bimetallic sulfides, and g-C3N4 have been widely studied in photo­
reforming biomass for H2 production due to their advantages of suitable
band gap structure and low cost [41–44]. Among them, TiO2 is the most
extensively and deeply studied owing to its non-toxicity, high chemical
stability, and low cost. However, pure TiO2 exhibits limited efficiency in
biomass photoreforming HER, due to its large band gap energy (around
3.20 eV) and the high recombination rate of photogenerated carriers
[45,46]. Both challenges can be overcome by modifying the band gap
structure of TiO2 for greater H2 production [47,48].
Constructing heterojunction is a common method to adjust the band
gap of TiO2 for the improved photoreforming performance [49]. The so-
called heterojunction is the interface region formed by the contact of
two different semiconductors [50–53]. For example, Zhao and his col­
leagues prepared TiO2-NiO core–shell heterojunction by one-step hy­
drothermal method, which was used for photocatalytic H2 production
with kraft lignin as substrate [54] (Entry 1 in Table 1). TiO2 and NiO
were closely combined to construct built-in electric field by forming type
II heterojunction, which significantly accelerated the separation rate of
e--h+ pairs and further improved the photocatalytic performance of TiO2
(Fig. 2a-d). The results showed that the H2 production rate of TiO2-NiO
core–shell catalyst reached 23.50 mmol g-1 h− 1, which was about 3.56
and 11.1 times higher than that of pristine TiO2 (6.60 mmol g-1 h− 1) and
NiO (2.11 mmol g-1 h− 1), respectively (Fig. 2a-b). Some fatty acids were
also obtained in the liquid phase as the lignin photoreforming products.
To further investigate the reason for improved photoreforming activity,
the structure of kraft lignin before and after the reaction was charac­
terized by Hetero Single Quantum Coherence-Nuclear Magnetic Reso­
nance (HSQC NMR) by using guaiacyl units (G2) as the internal standard
(Fig. 2c-d). The results showed that the content of β-O-4 in kraft lignin
decreased significantly after 12 h reaction catalyzed by TiO2-NiO,
Fig. 2. Photocatalytic H2 production using heterojunction TiO2-NiO core–shell catalyst: (a) Photocatalytic H2 evolution activities in water-methanol system; (b)
Corresponding rates of pure NiO, pure TiO2 and different nanocomposites; HSQC NMR spectrum of (c) lignin control and (d) depolymerized lignin. Reprinted with
permission from ref. [54]. Copyright 2021 Elsevier. Photoreforming H2 production over sn-Ru/TiO2: (e) Proposed reaction pathways for the photocatalytic reforming
of biomass-derived molecule. Reprinted with permission from ref. [55], Copyright 2013 Elsevier.
4
Chemical Engineering Journal 452 (2023) 138980
clearly indicating that lignin can be effectively depolymerized by the
accelerated separation of the photogenerated carriers in TiO2-NiO het­
erojunction photocatalyst. At the same time, though the mechanism was
not clear, the depolymerized lignin units can be partially converted into
fatty acids to consume more oxidative species, furthermore, promoting
the production of H2.
Gu and coworkers constructed two heterojunctions by grafting Ru/
TiO2 with Sn and tested them for H2 production by using different
biomass small molecules (glucose, methanol, ethanol, and glycerol) as
photoreforming reactants [55] (Entry 2 in Table 1). Two types of het­
erojunctions were formed within the photocatalyst by Ru and Sn
loading, as shown in Fig. 2e, which enabled the formation of a built-in
electric field within the photocatalyst. In the photoreforming process,
RuO2 functioned as h+-acceptor to facilitate the subsequent oxidation
reaction of biomass substrates, and the grafted atomic Sn species served
as e--acceptor to produce H2. As a result, the photogenerated charges can
be effectively separated, leading to improved photoreforming activity.
3.1.2. CdS and CdS-based bimetallic sulfides
For CdS photocatalyst, its narrow band gap (about 2.30 eV) enables a
wide photoresponse range and favors solar energy harvesting with wider
spectrum, yet simultaneously leading to serious photocorrosion issues
[56]. To restrain photocorrosion for the improved photocatalytic per­
formance (including organic pollutants degradation, H2 production
from water splitting and biomass photoreforming, etc.) [48,57,58], one
practical approach is to adjust the band gap structure of CdS. Early
research has demonstrated the effectiveness of conducting element
doping or heterojunction (or homojunction) construction in achieving
these targets [59–62]. Ye et al. prepared P-doped ZnxCd1-xS (ZnxCd1-xS-
P) by hydrothermal and high-temperature calcination [63] (Entry 3 in
Table 1). Firstly, the photocatalytic H2 evolution from pure water
without the assistance of h+ sacrificial agent was evaluated by ZnxCd1-xS
and ZnxCd1-xS-P (0 ≤ x ≤ 1) under visible light irradiation (Fig. 3a).
Regardless of the × value, no H2 was generated for all ZnxCd1-xS systems
in the absence of sacrificial reagents after 2 h irradiation, while all
systems carrying ZnxCd1-xS-P exhibited relatively high photocatalytic
activities under the same condition. Among all the tested, Zn0.5Cd0.5S-P
gave a maximum H2 production rate (0.42 mmol g-1 h− 1). This can be
attributed to the variation of the band gap of ZnxCd1-xS after P doping
(from 2.49 eV for ZnxCd1-xS to 2.43 eV for ZnxCd1-xS-P), and the
endowed visible light activity of ZnxCd1-xS. When using the same
optimal catalyst (Zn0.5Cd0.5S-P) for photoreforming
C. Shi et al. Chemical Engineering Journal 452 (2023) 138980

Fig. 3. Photoreforming H2 production performance of ZnxCd1-xS-P (0 ≤ x ≤ 1): (a) Comparison of photocatalytic hydrogen evolution rates of ZnxCd1-xS-P (0 ≤ x ≤ 1)
solid solutions from pure water without using of any electron sacrificial agents; (b) Comparison of photocatalytic H2 evolution rates of Zn0.5Cd0.5S-P from pure water
and 5-HMF solution at various times; (c and d) GC–MS traces of photocatalytic oxidation of 5-HMF by Zn0.5Cd0.5S-P. Reprinted with permission from ref. [63],
Copyright 2018 Elsevier. Photoreforming H2 evolution activity over Zn1-xCdxS homojunction: (e) Schematic atomic model of a Zinc blende-Wurtzite superlattice
structure, the twin boundaries in homojunction, and the migration of charge carriers; (f) Bandgap structure of various Zn1-xCdxS solid solutions; (g) Photocatalytic
hydrogen evolution rates of Zn1-xCdxS solid solutions in glucose solution. Reprinted with permission from ref. [34], Copyright 2021 Elsevier.

hydroxymethylfurfural (5-HMF), a H2 evolution rate of up to 0.79 mmol
g-1 h− 1 was obtained. More interestingly, Zn0.5Cd0.5S-P can maintain
good photocatalytic stability when coupled with 5-HMF photocatalytic
oxidation, as supported by a good retention of the H2 generation rate
(0.62 mmol g-1 h− 1) after 8 h light irradiation (Fig. 3b). In addition, the
liquid organic products from 5-HMF oxidization were further identified
by GC–MS (Fig. 3c and d). The peaks at around 19.50 and 14.80 min can
be ascribed to 5-HMF and 2, 5-diformylfuran (DFF), respectively,
showing clearly weakened 5-HMF peak and increased DFF peak over the
irradiation time. All these results suggested that P doping plays a
favorable role on narrowing the band gap and improving the photo­
reforming activity of CdS photocatalyst.
Beyond heterojunction, constructing homojunction is also a common
method to adjust the band gap of CdS materials [23,50–52,64–66]. Zhao
et al. introduced ZnS and prepared ZnxCd1-xS homojunction to produce
H2 and photoreform glucose into lactic acid [34] (Entry 4 in Table 1). As
these two crystal structures have almost the same lattice constants, a
homojunction structure by bridging cubic zinc blende and hexagonal
wurtzite segments can be constructed with long-range order, resulting in
a twinning superlattice. The formation of homojunction greatly pro­
moted the separation of photocharged carriers (Fig. 3e). A major
advantage of such design is that by controlling the molar ratio of Zn/Cd,
the band gap energy can be well regulated. As can be obviously seen
from Fig. 3f, the band gap gradually widens with the increase of Zn
content in the ZnxCd1-xS solid solution, from 2.25 eV (CdS) to 3.55 eV
(ZnS). When x = 0.6, a perfect homojunction is formed in Zn0.6Cd0.4S
(Fig. 3e), which exhibited the optimal H2 evolution rate of 0.69 mmol g-1
h− 1. Both the pristine CdS and ZnS exhibited a much lower H2 genera­
tion rate than that of Zn0.6Cd0.4S (Fig. 3g) [34], indicating that the as­
sembly of homojunction structure indeed affected the band gap of
photocatalysts and improved the separation efficiency of photo­
generated charge carriers.
3.1.3. g-C3N4 based materials
Carbon nitride is the most representative one among non-metallic
photocatalysts. It has received extensive attention in the field of
biomass photoreforming HER due to its environmentally friendly char­
acteristic, low cost, and unique two-dimensional structure [67].
However, the poor visible light response and high photogenerated
charges recombination rate limit the biomass photoreforming perfor­
mance of carbon nitride. Similar to the case of TiO2 and CdS, the biomass
photoreforming activity of carbon nitride can be tuned by adjusting the
band structure, following strategies such as heterojunction construction
and functional groups modification [53,68–71]. Xu et al. prepared ZnS-
modified g-C3N4 (MCN, DCN, and UCN derived from melamine,
dicyandiamide, and urea) composites by dipping and calcination, with
the formed heterojunctions denoted as ZMCN, ZDCN, and ZUCN,
respectively [70] (Entry 5 in Table 1). The photoreforming H2 produc­
tion activity of the three heterojunctions was evaluated using glucose as
model substrate. Compared with bare g-C3N4 samples (MCN and DCN),
the glucose photoreforming performances of the corresponding hetero­
junctions ZMCN and ZDCN were significantly improved. In contrast,
ZMCN achieved the highest H2 generation productivity (0.07 mmol g-1
h− 1), which was 2.51 times than that of MCN (0.03 mmol g-1 h− 1)
(Fig. 4a). The results showed the high-efficiency heterojunction was
formed between ZnS and g-C3N4, which broadened the catalyst’s pho­
toresponse range and enhanced the separation of photocarriers (Fig. 4b-
c). Surprisingly, the efficiency of ZUCN decreased by 36.6 % as
compared to the pure UCN (Fig. 4a). This might be ascribed to the wider
band gap of UCN (2.81 eV) and the associated CB position change, which
was closer to CB of ZnS than those of MCN and DCN (Fig. 4b-d). These
results clearly demonstrated the impact of band gap structure on pho­
toreforming H2 evolution.
Introducing functional groups can also affect the band gap of g-C3N4.
Liu et al. synthesized edge functionalized carbon nitride via an in-situ
C–N coupling method. The carbon nitride-N-acetylethanolamine
(UCN-NA) composites were synthesized by thermal pyrolysis of additive
NA and precursors urea, in which the hydroxyethyl groups were grafted
to the heptazine rings by substituting its terminal amino groups [71]
(Entry 6 in Table 1). The band gap structures, electronic distribution,
and energy-level structures were elucidated by density functional theory
(DFT) calculation and Gaussian 09 (Fig. 4e-h). The results showed that
the introduction of the hydroxyethyl created discrete energy levels in
the bandgap and enhanced the absorption of visible light (Fig. 4e-f);
Also, redistribution of e- clouds occur, and the spatial separation of
LUMO and HOMO in UCN-NA might also favor the separation of h+-e-

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C. Shi et al.
pairs compared to UCN (Fig. 4g-h). The UCN-NA0.5 (the volume of NA
solution added is 0.50 mL) displayed the detectable photoreforming
HER activity with various monosaccharides as substrates (Fig. 4i). In
detail, UCN-NA0.5 showed higher H2 production rates about 6 and 8.5
times than that of UCN for the photoreforming of glucose and xylose,
respectively. In conclusion, the significantly improved H2 evolution
activity further confirmed that the band gap structure of photocatalyst
truly plays a critical role in photoreforming reaction.
Different from traditional photocatalytic HER, little attention has
been paid to the development of the photocatalyst with suitable band
gap structure for biomass photoreforming process. In addition to satis­
fying the reduction potential of HER, controlling the oxidation ability of
the VB potential is also crucial to improve the selectivity of biomass
conversion. Otherwise, excessive oxidation products of the substrate or
other unexpected liquid products may accumulate on the surface of the
photocatalysts, resulting in its deactivation that is detrimental to its
long-term stability [72]. Meanwhile, more consideration should be
given to the effects of the pathway and degree of biomass oxidation on
H2 generation efficiency in photoreforming reaction. This is dramati­
cally vital to promote the development of the overall biomass photo­
reforming reaction.
3.2. Photocatalyst morphology and size
Morphology and size of photocatalysts are two important factors that
govern their photocatalytic performance. Firstly, morphology and size
of photocatalysts will affect its physicochemical properties, including
specific surface area (SSA) and surface active sites, which are directly
correlated with the effective contact between the catalysts and sub­
strates and subsequently impact the photoreforming reaction [73–76].
In general, the SSA and active sites of materials tend to increase as the
particle size decreases. In some cases, photocatalyst’s morphology also
affects the generation of reactive species, which plays a decisive role in
the biomass photoreforming reaction [77,78]. Here, the influence of
photocatalyst morphology and size on photoreforming HER activity is
reviewed.
Wakerley and his colleagues prepared CdS quantum dots by heat
reflow method for biomass photoreforming H2 evolution (Fig. 5a-c) [21]
(Entry 7 in Table 1). With cellulose as photoreforming substrates under
strong alkaline conditions, up to 5.57 mmol g-1 h-1 H2 production rate
was achieved. Such excellent photoreforming HER performance is not
only attributed to the improved catalyst stability and enhanced cellulose
6
Chemical Engineering Journal 452 (2023) 138980
Fig. 4. g-C3N4/ZnS composites pho­
toreforming H2 generation form
monosaccharide: (a) Photoreforming
H2 evolution on pure g-C3N4 (MCN,
DCN, and UCN) and g-C3N4/ZnS
(ZMCN, ZDCN, and ZUCN); Sche­
matic band structures for (b) ZMCN,
(c) ZDCN, and (d) ZUCN. Reprinted
with permission from ref. [70],
Copyright 2019 Elsevier. Edge func­
tionalization of terminal amino group
in carbon nitride by in-situ C–N
coupling: Calculated band structure of
(e) UCN and (f) UCN-NA by using DFT
calculation. Chemical structures of
the polymeric models of (g) UCN and
(h) UCNNA together with the calcu­
lated HOMO and LUMO energy levels;
(i) Photocatalytic H2 production using
UCN and UCN-NA0.5 with 100 mg
xylose, glucose, fructose and arabi­
nose under white LED irradiation for
4 h. Reprinted with permission from
ref. [71], Copyright 2020 Elsevier.
swelling under strong alkaline conditions, but also the favorable
morphology and size of the photocatalysts. Quantum dot-like CdS with
small size has a large SSA and abundant surface-active sites (Fig. 5a-b),
which can achieve effective contact between CdS photocatalyst and the
dissolved cellulose molecules, ultimately resulting in a significantly
enhanced H2 production rate in the system. Even for the less-processed
lignocellulosic substrates (wood from a tree branch, Fig. 5c), the pro­
posed quantum dot-like CdS catalyst still gave remarkable cellulose
photoreforming HER activity, i.e., H2 production rate of over 5 mmol g-1
h− 1. In another study, Song and his colleagues prepared CdS with
different morphologies (nanospheres, nanorods, nanowires, and nano­
sheets) by a simple hydrothermal method (Fig. 5d), and investigated
their photocatalytic performance for producing alanine (where glucose
and ammonia were used as biomass substrates and nitrogen source,
respectively) and H2 (where lactic acid was used as substrates) [79]
(Entry 8 in Table 1). The results indicated that the optimum photo­
forming H2 and alanine generation rates were achieved on catalysts with
different morphologies, respectively. CdS nanosheets exhibited the
worst H2 production ability but the optimal alanine generation, while
CdS nanorods showed the opposite (Fig. 5e-f). Free radicals capture
experiments showed that only nanosheets could generate oxygen-centric
free radicals (⋅OCR), which may be the primary reason for the highest
alanine generation rate. This work supported that the active species
produced in the reaction process could be controlled by photocatalyst
morphology. Meanwhile, it is also demonstrated that the production rate
of H2 and liquid product does not necessarily follow the same trend,
which requires case-by-case analysis in specific photoreforming
reaction.
3.3. Photocatalyst crystal phase
The crystal phase of catalyst is another key factor in biomass pho­
tocatalytic reforming process, which has an impact on HER by affecting
the selectivity to substrates or the acidity and alkalinity of catalyst
surface. It also affects the reaction pathway of biomass substrates and
products types in the photoreforming process, yielding different high
value-added chemicals [80].
3.3.1. The selectivity of photocatalyst crystal phase to lignocellulose
substances
In the traditional photocatalytic process, the difference in crystal
type has no obvious effect on the oxidation pathway of common
C. Shi et al.
sacrificial agents (triethanolamine, sodium sulfide, etc.). However, it
does play a decisive role in the transformation pathway of biomass and
products type in the photoreforming oxidation half-reaction, which af­
fects the corresponding HER rate as well [81]. Iervolino et al. prepared
TiO2 co-doped with fluorine and Pt (Pt-F-TiO2) for glucose photo­
reforming H2 evolution [81]. The results showed that the crystalline
phase of TiO2 in Pt-F-TiO2 catalyst was precisely in anatase form.
Despite a lower selectivity on arabinose and erythrose compared to
rutile, the anatase phase was more inclined to break the C–C bond in the
glucose molecules adsorbed on catalyst surface. This promoted the
generation of H2, CO2, and gluconic acid, whereas the production of
arabinose and erythrose on Pt-F-TiO2 was inhibited. Under the optimum
conditions, the H2 yield of Pt-F-TiO2 can reach 0.59 mmol g− 1 h− 1. In
addition to the effect of photocatalyst crystal on the oxidation products
selectivity, it is noteworthy that the BOR and HER are interrelated, but
neither in a simple synergistic nor in an antagonistic way. Of course, nor
can we primitively judge the oxidation pathway and the liquid product
types based on the performance of photoreforming H2 evolution only.
Therefore, it is significantly necessary to analyze the relationship be­
tween BOR and HER in combination with the specific reaction system in
the biomass photoreforming process.
7
Chemical Engineering Journal 452 (2023) 138980
Fig. 5. Photoreforming lignocellulose for H2 evolution
over CdS/CdOx: (a) TEM image of CdS/CdOx after
isolation from 10 M KOH; (b) Corresponding size dis­
tribution; (c) Photoreforming H2 generation from crude
lignocellulose when CdS/CdOx suspended in alkaline
solution and irradiated with sunlight. Reprinted with
permission from ref. [21], Copyright 2017 Nature.
Photoreforming biomass for synthesis alanine over
different morphology of CdS: (d) TEM image of a com­
mercial CdS, nanospheres, nanorods, and nanowires
(from left to right), scale bar = 200 nm; (e) In situ ESR
spectra for CdS nanosheets and nanorods in a mixture
solution of lactic acid and ammonia in the presence of
spin-trapping agent 5, 5-dimethyl-1-pyrroline N-oxide
(DMPO) with or without visible-light irradiation; (f) H2
production performance of CdS with different mor­
phologies. Reprinted with permission from ref. [79],
Copyright 2020 Nature.
3.3.2. Surface acidity/basicity property
For the general photoreforming reaction, the desired H2 is produced
by dehydrogenation of an oxygen-containing matrix, accompanied by
CO2 generation. Unfortunately, in certain systems the production of CO2
and H2 can be replaced by CO and H2O, making it less desirable for
direct application of H2 to fuel cells. Further investigation elaborated
that such selectivity in reaction pathway is closely associated with the
acidity/basicity of the photocatalyst used. For instance, formic acid-like
species are a common type of intermediate chemicals in the photo­
reforming biomass process. It has been identified that such formic acid-
like species tend to transform to CO and H2O when in contact with the
acid sites of photocatalysts, while the basic surfaces of catalysts are
favorable for their dehydrogenation to produce CO2 and H2 [47,82].
The surface acidity/basicity of catalysts, as well as the ⋅OH groups
present on their surface, are impacted by the ratio of different crystal
phases in photocatalyst and hence the hydroxylation degree of adsorbed
H2O molecules [82–85]. Xu et al. synthesized Pt/P25 photocatalysts
with different ratio of anatase and rutile phases, which were applied for
the photoreforming of methanol, glycerol, and glucose for H2 generation
[82]. The results showed that the ⋅OH group on the interface between
the anatase and rutile phases was removed after heat treatment, which
resulted in an increase of surface basicity, leading to a favored reduction
C. Shi et al.
in the CO/H2 ratio (the CO concentration in H2) of gas products. Under
the optimized condition, the CO/H2 ratio obtained by the optimal TiO2-
based photocatalyst was less than 5 ppm. In addition, the formic acid
photoreforming performance of P25-x%R (x%R means the ratio of rutile
in P25) were investigated to study the underlying reason of significantly
inhibited CO formation. The results suggested that the production
selectivity between CO and CO2, related to the dehydration or dehy­
drogenation of formic acid, is governed by the acidity/basicity of the
P25 surface; the acid sites are conducive to the dehydration reaction,
while the basic P25 surfaces are favorable for the dehydrogenation.
Thermal treatment of P25 is capable of increasing the photocatalyst’s
basicity by removing the ⋅OH at the anatase/rutile interface during the
amorphous to crystalline phase and/or from anatase to rutile trans­
formation. Therefore, thermal treatment seems to be a very promising
method to adjust the crystal phase of the photocatalyst by controlling its
preparation conditions and improve its selectivity of the products; yet
insights into the effect of crystal phases on the acidity/basicity of pho­
tocatalyst surface requires further study.
3.4. Other structural factors
In addition to the impact of band gap structure, morphology and size,
and crystal phase, other structural factors influencing the biomass
photoreforming efficiency and H2 production include: 1) Introducing
cocatalysts by depositing noble metals, metal phosphides and sulfides;
8
Chemical Engineering Journal 452 (2023) 138980
2) Enhanced selective adsorption of photocatalysts toward substrates by
introducing transition metals; and 3) Modification of surface acid/base
sites. These practices are capable of promoting the separation of pho­
tocarriers, leading to more active sites/species available for photo­
reforming reaction and therefore improved H2 evolution efficiency.
3.4.1. Cocatalysts
Cocatalysts, as an important component of photocatalysts, mainly
contribute to the efficient e- transportation and carriers’ separation.
Depositing noble metals, metal phosphides and sulfides is a promising
method, which can effectively promote the photoreforming efficiency.
The enhancement of the photocatalytic activity of loaded noble
metal particles is mainly derived from the plasma effect. Firstly, the
plasma effect enhances the photoresponse range and absorption capac­
ity and the utilization efficiency of catalysts towards light through local
plasma resonance effect (LSPR, a phenomenon in which the free e- of
metal particles resonance with the incident photoelectric magnetic
field). Secondly, the loaded metal particles, functioning as a proton
reduction site, could effectively reduce the overpotential of the photo­
catalysts. Because of the small Fermi level and large work function of
noble metals, e- can be effectively transferred from the semiconductor to
the surface of metal particles and participate in proton reduction, which
is conducive to hinder photogenerated carriers recombination rate and
improving the photocatalytic performance. Thirdly, plasma photo­
thermal effect can effectively increase the surface temperature of the
Fig. 6. Photoreforming glucose for H2 production over
3DOM TiO2-Au: (a) H2 production over different photo­
catalysts; (b) XPS Au 4f spectra of 3DOM TiO2-Au before and
after photocatalytic reaction; (c) H2 generation over 3DOM
TiO2-Au before and after treated by H2/Ar under 500 ◦ C. The
photocatalyst before treatment is labeled as 3DOM TiO2-
Au+/Au0 and the photocatalyst after treatment is labeled as
3DOM TiO2-Au0; (d) Glucose consumption, arabinose pro­
duction and arabinose selectivity over 3DOM TiO2-Au under
visible light (λ > 420 nm); (e) Schematic illustration for the
arabinose and gas co-production over 3DOM TiO2-Au.
Reprinted with permission from ref. [45], Copyright 2021
Elsevier.
C. Shi et al.
photocatalyst, thus increasing the specific reaction activity [86].
The use of plasma shows obvious effectiveness in improving the
biomass photoreforming efficiency, as it can facilitate depolymerization
of cellulose and lignin by cleaving the β-1, 4 glycosidic bond and β-O-4
bond, respectively. The produced small molecules can be further adop­
ted for photoreforming reaction [41]. Zhao et al prepared gold nano­
particles decorated three dimensional ordered macroporous TiO2-Au
(3DOM TiO2-Au) for glucose photoreforming for arabinose and gas fuel
(H2, CH4, and CO) co-production [45] (Entry 9 in Table 1). The catalyst
gave about 37 % glucose conversion and ended up with 0.2 g L-1 of
arabinose production after 8 h reaction, which were 2.8 and 10 times
higher than that of using conventional TiO2, respectively. For the gas
products, the H2 production of 3DOM TiO2-Au showed a linear increase
in the first 3 h at a rate of 10.90 mmol g− 1 h− 1, then gradually plateaued
after 7 h reaction (Fig. 6a). This may be due to the consumption of H2 by
the CO hydrogenation reaction to generate CH4. The XPS study of 3DOM
TiO2-Au before and after the reaction showed that a large amount of Au
(I) present before the reaction was reduced to Au(0) during the reaction
(Fig. 6b), which can be ascribed to the reducing effect of the H2 and CO
that were generated in situ. Meanwhile, the LSPR effect of Au NPs could
also promote the reduction of Au(I). As a result, the reduction of Au(I)
content may further decrease the arabinose selectivity and H2 produc­
tion, which was confirmed by a series of controlled experiments. Firstly,
the synthesized 3DOM TiO2-Au was pretreated with H2/Ar mixture at
500 ◦ C to reduce Au(I) to Au(0), to evaluate its performance discrepancy
in the production of arabinose and H2 during glucose photoreforming.
All the glucose conversion, arabinose, and H2 production (Fig. 6c) were
lower after H2/Ar treatment. In addition, results showed that the glucose
conversion under visible light was negligible, while the arabinose pro­
duction exhibited almost linear relationship with reaction time and the
selectivity was maintained as high as 80 % (Fig. 6d). This further sup­
ported that Au NPs were the key active sites for arabinose and gas
products production from glucose photoreforming (Fig. 6e). Similarly,
Hippargi et al. prepared Au-Pt/TiO2 for photoreforming acetic acid to
produce H2 and methane [87]. Under UV–Visible light (400 W) irradi­
ation, the newly prepared Au-Pt/TiO2 reported effective production of
H2 and methane at the rate of 9.39 and 2.21 mmol h− 1 (14.73 and 62.58
mmol g-1 h− 1), respectively, from acetic acid with apparent quantum
yield of 3.85 % at the bandgap of 3.2 eV. Overall, the plasma effect can
promote the reforming reaction of biomass effectively, but the rareness
of noble metals reduces their value in commercial applications.
Metal phosphides and sulfides (like Ni2P, CoP, and NixSy etc.) can
also work as an appropriate candidate for cocatalyst in photoreforming
[88–91]. Zhang et al. demonstrated an environmental-friendly CoP/
Zn2In2S5 catalyst for highly selective photoreforming methanol to
generate ethylene glycol (EG) and H2 under visible light and AM1.5
irradiation [88]. α–C–H in methanol was first activated to form
⋅CH2OH, then C–C coupling occurs and got EG. Furthermore, it was first
reported the activity of Zn2In2S5 system for photoreforming ethanol to
value-added 2, 3-butanediol and H2 under visible or solar light irradi­
ation (the oxidation pathway of ethanol: α–C–H activation to obtain
⋅CHCH3OH and C–C coupling). Tasleem et al. constructed a 2D Ti3AlC2
MAX dispersed TiO2 heterostructure with Ni2P as a cocatalyst for effi­
cient photoreforming H2 production in the presence of methanol–water
and glycerol-water mixture, accompanied by the production of CO2 with
a significant yield [90]. TiO2/Ni2P/Ti3AlC2 composites exhibited the
enhanced activity (1.29 times) than TiO2/Ti3AlC2, which could be
attributed to the significant increase in charge separation by Ni2P as
cocatalyst. In addition, glycerol-water mixture showed higher potential
for H2, CO2, and CH4 production due to the generation of more photon
and OH ions. Uekert and coworkers also confirmed the potential of Ni2P
as cocatalyst in photoreforming. They fabricated an inexpensive and
nontoxic carbon nitride/nickel phosphide (CNx/Ni2P) photocatalyst to
reform poly(ethylene terephthalate) (PET) and poly(lactic acid) (PLA) to
H2 and various organic chemicals under alkaline aqueous conditions
[89]. Loading NixSy cocatalyst on ZnS nanorods enabled the selective
9
Chemical Engineering Journal 452 (2023) 138980
oxidation of benzyl alcohols and H2 production in anaerobic water [91].
The NixSy nanoparticles showed the enhanced ternary effects in H2 yield,
alcohol conversion, and benzaldehyde selectivity, the H2 yield over ZnS-
NixSy (3.65 mmol g-1 h− 1) was 5 times than ZnS (0.73 mmol g-1 h− 1).
Considering the rareness of noble metals, environmental-friendly and
inexpensive transition metals phosphides and sulfides have great po­
tential in photoreforming field.
3.4.2. Enhanced selective adsorption of photocatalysts toward substrates by
introducing transition metals
Compared with the plasma effect of high cost and rare noble metals,
transition metals (such as Mn, Fe, Co, Ni, and Cu) play a more prominent
role by regulating their selectivity to biomass substrates for the
improved photoreforming efficiency. Ni is one of the most extensive
researched transitions metals in photoreforming. It has been identified
that metallic Ni is an excellent catalyst for H2 production while oxidized
Ni species can facilitate the oxidation reactions of organics [31,42,92].
Han et al. reported an ultrathin CdS nanosheets modified with co-
catalyst Ni (Ni/CdS) to upgrade furfural alcohol and 5-HMF to value-
added furfural and DFF with concomitant formation of H2 in neutral
water under visible light irradiation [42] (Entry 10 in Table 1). Aided by
theoretical computation, they found that the slightly stronger binding
affinity of the aldehyde group in 5-HMF with water/NiO (0 0 1) interface
in Ni/CdS resulted in the lower transformation of HMF to DFF compared
to that of furfural alcohol to furfural in neutral water. This also caused
the lower H2 production by photoreforming 5-HMF than furfural
alcohol. Furthermore, Han et al. prepared M/CdS (M = transition metals
in the first row of the periodic table, including Mn, Fe, Co, Ni, and Cu)
for photoreforming lignin model compounds to small aromatic products
and H2 [31]. Firstly, the photoreforming behaviors of the M/CdS sam­
ples were tested by benzylic alcohol oxidation. As given in Fig. 7a,
compared to pristine CdS nanosheets, the overall performance of M/CdS
samples were substantially improved, including benzylic alcohol con­
version, benzaldehyde yield, and H2 evolution. Among various types of
transition metal loaded catalysts, Ni/CdS achieved the most favored
performance, with a 93.4 % conversion of benzylic alcohol, nearly 100
% of benzaldehyde selectivity, 93.4 % of benzaldehyde and H2 yield.
Interestingly, unlike the traditional photoreforming reactions where H2
are sourced from water, in this system H2 was derived from benzyl
alcohol, which was evidenced by comparing the relationship between
benzyl alcohol consumption and H2 production with different solvents
(water and acetonitrile). It was found that the benzyl alcohol con­
sumption and H2 production were consistent, regardless of type of sol­
vent used. In addition, a control experiment was carried out by using
parent CdS without Ni to demonstrate the significant role of Ni species.
The corresponding 1H NMR spectra showed only a small amount of
hydrobenzoin was obtained while no benzaldehyde was detected, which
clearly proved the critical role of Ni species in the photocatalytic
oxidation of benzyl alcohol to benzaldehyde on Ni/CdS (Fig. 7b).
Considering the source of H, the efficiency of H2 production by photo­
reforming benzyl alcohol was correspondingly reduced.
3.4.3. Modification of acid-base sites
Apart from the impact of catalyst crystal phase on the acidity and
alkalinity of its surface, surface modification of acidic or basic functional
groups also has an effect on it. Surface acid-base sites of photocatalyst
play a crucial role in biomass photoreforming, since it likely affects the
depolymerization of the macromolecular biomass substrates and the
accessibility between the photocatalysts and the biomass [93,94]. Hao
et al. prepared chemisorbed SO2- 4 modified P25-NixSy composites for H2
evolution by photoreforming cellulose (Fig. 7c) [94] (Entry 11 in
Table 1). The H2 production rate was found to be 3.02 mmol g-1h− 1 at
80 ◦ C, which was 76 times higher than that of Pt/P25. This can be
attributed to the positive effect of the surface SO2-4 on the hydrolysis of
cellulose into small glucose molecules, which served as e- donor and
diproton donor in photoreforming reaction. Meanwhile, protons
C. Shi et al. Chemical Engineering Journal 452 (2023) 138980

Fig. 7. Photoreforming benzyl alcohol for H2 generation over M/CdS: (a) Activity comparison of M/CdS photocatalysts for the oxidation of benzyl alcohol; (b) 1H
NMR spectra of benzylic alcohol oxidation before and after photocatalysis using pure CdS as the photocatalyst. Reprinted with permission from ref. [31], Copyright
2019 American Chemical Society. SO2-4 modified P25-NixSy for photoreforming H2 evolution from cellulose: (c) Diagram H2 production by cellulose photoreforming
into over SO2-
4 modified P25-NixSy under solar irradiation. Reprinted with permission from ref. [94], Copyright 2018 Wiley.

reduction was accomplished on NixSy to generate H2. In terms of H2
production from biomass reforming, the acid-base sites modified on the
catalyst surface mainly trigger biomass hydrolysis, isomerization of
corresponding derivatives and dehydration. Recently, Wang et al.
showed that both proton and e- transfer can be enhanced by creating
SO2- 2-
4 on the surface of CdS. The bifunctional SO4 serves as proton
acceptor to promote proton transfer and can increase the oxidation
potential of the VB to enhance e- transfer. SO2-
4 /CdS can convert a variety
of saccharides (glucose, fructose, maltose, sucrose, xylose, lactose, in­
sulin, and starch) to syngas. For glycerol without CO2, the CO generation
rate (0.31 mmol g-1 h− 1) and the H2 generation (0.05 mmol g-1 h− 1) of
SO2-
4 /CdS were 9 and 4-fold higher than that of pristine CdS, respectively
[95]. However, the role of SO2- 4 in simultaneously promoting both pro­
ton and e- transfer during photocatalytic biomass reforming remains to
be further explored. Brønsted acid, commonly employed in biomass
photoreforming reactions, is generally used as a catalyst for acid depo­
lymerization of macromolecular biomass. However, more attempts are
needed to investigate the role of Brønsted acid in other photoreforming
reactions. Up to now, no substantive work has been reported on the
application of Lewis acid in biomass photoreforming. In addition, the
interaction between the Lewis acid/base and the Brønsted acid/base
sites also needs to be demonstrated by relevant work.
In conclusion, the photocatalyst structure (band gap, morphology,
size, and crystal phase) has a great impact on its photoreforming per­
formance. The band gap structure mainly affects the optical properties
and redox ability of the catalyst, which directly affect the light utiliza­
tion efficiency of the catalyst, the reaction pathway and degree of the
substrates. The morphology and size of photocatalyst may affect the
species of active free radicals and the accessibility between
photocatalyst and biomass substrates. The crystal phase of the photo­
catalyst mainly affects the photoreforming H2 production efficiency by
affecting its substrate selectivity and the acidity and alkalinity of the
catalyst surface. By adjusting the type and proportion of crystal phase of
photocatalyst, the composition of various liquid and gas phase products
can be effectively regulated, which is an important way to control the
selectivity and yield of biomass photoreforming reactions.
4. Influences of reaction conditions on photoreforming H2
generation efficiency
Apart from designing favored photocatalyst structure as discussed in
Section 3, properly adjusting photoreforming reaction conditions could
improve the performance of photocatalyst in photoreforming biomass
producing H2. In the following sub-sections, the effect of reaction pa­
rameters (light intensity, the concentration of photocatalyst and sub­
strate, temperature, pH, the involved metal salt solutions, reactor
configuration, and solvent type) will be elaborated with representative
examples on biomass photoreforming H2 production activity, which are
summarized in Table 2.
4.1. Effect of light
Light provides energy to move forward photochemical reactions.
Factors including the type of light source, spectral range (ultraviolet
(UV), visible, or near IR light) and irradiation intensity are all needed to
be considered. Generally, the selection of spectral range is based on the
light absorption characteristics of the photocatalyst, which is strongly
linked with the band gap of catalysts discussed in Section 3. As a type of

10
C. Shi et al. Chemical Engineering Journal 452 (2023) 138980

Table 2
Influences of reaction conditions on photoreforming H2 generation efficiency.
Influence factor Entry Photocatalyst Substrate Light source, range Temperature H2 evolution rate AQY/% Reference
(Concentration, g L-1) (Concentration, g L-1) (nm), and intensity (◦ C)/pH (mmol g-1h− 1) (λex/nm)
(mW cm− 2)

Effect of light 1 CdS/MoS2 (1.00) Glucose (18.02) Xe lamp, λ＞400, (300 55.00 – [101]
W)
NCN
2 CNx (0.17) 4-MBA (1.22) Xe lamp, AM1.5 (1 0 0) 34.48 – [103]
3 Pt/TiO2 (1.33) Methanol (3 mM) Near-UV, λmax = 365 – [107]
(0.50) ~5.63*10-5
(1.00) ~8.77*10-5
Methanol (1.90) ~0.00014
(100 mM) (3.00) ~0.00017
(0.50) ~0.00017
(1.90) ~0.00034
(2.30) ~0.00044
(3.00) ~0.00102
Photocatalyst 4 Pt/TiO2 (0.17) Methanol (3 mM) Near-UV, ~4.39*10-5 – [107]
concentration (0.33) λmax = 365 (3.00) ~7.94*10-5
(0.67) ~0.00013
(1.33) ~0.00016
(2.64) ~0.00019
(4.00) ~0.00019
(5.00) Methanol ~0.00021
(0.33) (100 mM) ~0.00026
(1.33) ~0.00050
(4.00) ~0.00054
5 Ru-doped LaFeO3 Glucose UV, 375＜λ＜380, (57) – [109]
(0.75) (1.00) ~0.49
(1.00) ~1.05
(1.50) ~1.30
(2.00) ~1.15
(3.00) ~0.55
Substrate 6 CdS/CdOx (3.00) α-cellulose (50.00) Xe lamp, AM1.5 (1 0 0) 2.57 – [21]
concentration Hemicellulose
(25.00)Lignin 2.32
(0.25)
0.53
7 Pt-TiO2 (1.33) Fructose Xe arc lamp (300 W) T: 40 0.00017 – [112]
(0.20 mM) T: 60 0.00023
8 TiO2/NiOx (0.20) Cellulose (20.00) Xe lamp T: 25 0.27 –
Reaction (300 W) T: 80 4.00
temperature 9 Pt/TiO2 (1.00) Corn stover (30.00) Xe lamp T: 30 ~0.15 – [117]
(300 W) T: 45 ~0.22
T: 60 ~0.27
10 Platinized TiO2 (0.20) Cellulose (0.05) UV–vis (250 W) T: 50 0.13 – [41]
T: 130 1.32
pH 11 Pt-F-TiO2 (1.50) Glucose (2.00) UV-LEDs strip (10 W) pH 2 0.59 – [81]
12 o-g-C3N4 (0.25) Glucose (0.1 M) Solar light (50) pH 11 1.37 – [69]

abundant and renewable energy, sunlight contains about 5 % UV light
(wavelength less than 400 nm), 40 % visible (400–800 nm), and 50 % IR
light (>800 nm). For semiconductors with broad band gap such as TiO2
(>3.2 eV), the photoreforming activity can only be triggered by high
energy photon illumination, such as UV light [24,41,81,94,96–100]. As
discussed above, more efficient use of sunlight can be realized by
designing materials that can initiate photocatalytic reforming activity
under low-energy photon radiation (visible light), like CdS and g-C3N4
based materials [17,21,36,42,69,101–104]. Li et al. synthesized a binary
heterostructure CdS/MoS2 flowerlike composite photocatalyst by a
simple one-pot hydrothermal method [101] (Entry 1 in Table 2). When
the mass ratio of CdS and MoS2 reached 40: 100, the photocatalyst
showed a superb H2 evolution rate of 55.00 mmol g-1 h− 1 with glucose as
the sacrificial agent under visible light irradiation. Kasap et al. reported
a cyanamide-functionalized carbon nitride, NCNCNx, which was used to
produce H2 via photoreforming under visible-light irradiation in the
presence of a molecular Ni bis (diphosphine) cocatalyst (NiP) in aqueous
media (Fig. 8a) [103] (Entry 2 in Table 2). The photoreforming H2
production rate can achieve 34.48 mmol g-1 h− 1 in potassium phosphate
solution (KPi, pH 4.5) at 25 ◦ C with 4-methyl benzylalcohol (4-MBA) as
easily oxidized model cellulose substrate, 1.12 mmol g-1 h− 1 with
glucose, and 0.20 mmol g-1 h− 1 even with sawdust, a raw and unpro­
cessed biomass samples, under the same conditions (Fig. 8b-c).
For evaluation of photocatalyst, solar simulator is often used as a
convenient and stable radiation source for photoreforming reactions.
Xenon lamp is a common type of solar simulators that can emit
continuous wavelengths, achieving the standard AM 1.5 average solar
radiation at ground level in temperate zones by adding filters (air mass
1.5 global filter). The light absorbed by the reaction system is signifi­
cantly critical for driving forward the photoreforming reaction, which is
correlated with the applied light intensity [10]. A lot of research has
been done on the influence of the applied light intensity on the photo­
catalytic reaction [105–108]. Nomikos et al. studied the kinetics and
mechanism of photoreforming methanol reaction over Pt/TiO2 irradi­
ated under near-UV light (λmax = 365 nm) [107] (Entry 3 in Table 2).
The influence of incident light intensity (I0) on the reaction rate was
investigated in the range of 0.5–3.0 mW cm− 2 with a constant Pt/TiO2
photocatalyst concentration (1.33 g L-1). It was observed that an in­
crease of I0 from 0.5 to 2.3 mW cm− 2 resulted in an increase of the
maximum H2 production rate (rmax) at lower initial methanol concen­
tration in solution (3 mM). With further increase of I0 to 3.0 mW cm− 2,
rmax did not improve significantly (Fig. 8d). For solution carrying higher
initial methanol concentration (100 mM), the rmax increases mono­
tonically with increase of I0 (Fig. 8e). Furthermore, they studied the
dependence of rmax on I0 for two different initial methanol concentra­
tions. The results showed that the rmax was proportional to I0 for 100 mM

11
C. Shi et al.
methanol concentration whereas the rmax follows a linear relationship
with the square-root of I0 for 3 mM methanol concentration, which
indicated that the dependence of the heterogeneous photocatalytic re­
actions rate on incident light intensity can be approximated by either
linear or square-root functions (Fig. 8f).
4.2. Photocatalyst concentration
With sufficient incident photons, the required concentration of the
photocatalyst mainly depends on the absorption capacity of photo­
catalyst to incident light, and the surface active sites present for biomass
photoreforming. At lower photocatalyst concentration, the biomass
photoreforming reaction is controlled by the amount of surface active
sites of photocatalyst. Therefore, the photoreforming rate increases with
increase of photocatalyst concentration. The maximum photoreforming
rate can be achieved when the photocatalyst concentration reaches the
saturation limit, at which point the photocatalysts can utilize the largest
proportion of photons irradiated into the catalytic system. Further
increasing the catalyst’s concentration beyond such saturation value
leads to reduced photoreforming rate. Decreased photoreforming rate is
generally observed at high photocatalyst concentrations, possibly due
to: 1) The reduced light absorption by light scattering and reflection of
photocatalyst particles as the opacity of reaction system increases; and
2) The decreased amount of active sites due to particles agglomeration
[41,97,99,103,107,109,110]. Nomikos et al. reported the relationships
12
Chemical Engineering Journal 452 (2023) 138980
Fig. 8. Photoreforming of lignocellulose into
H2 using nanoengineered carbon nitride under
benign conditions: (a) Schematic representation
of H2 generation through photoreforming of
lignocellulose with NCNCNx and H2 production
cocatalysts; Photocatalytic H2 formation using
activated and bulk NCNCNx (0.5 mg) with NiP
(300 nmol) in KPi (0.1 M, pH 4.5, 3 mL) with
(b) 4-MBA (30 μmol) and (c) purified lignocel­
lulose components (100 mg) under AM1.5G
irradiation at 25 ◦ C. Reprinted with permission
from ref. [103], Copyright 2018 American
Chemical Society. Photoreforming methanol
over Pt/TiO2: Effect of incident light intensity
[I0: a. 0.5, b. 1.0, c. 1.9, d. 2.3, and e. 3.0 mW
cm− 2] on the H2 evolution rate for Pt/TiO2
(Ccat. = 1.33 g/L) of initial methanol concen­
trations of (d) 3.0 mM and (e) 100 mM; (f) The
relationship between the rmax and I0 at different
initial methanol concentrations (a. 3.0, and b.
100 mM) obtained from (d) and (e). Reprinted
with permission from ref. [107], Copyright
2014 Elsevier.
between H2 generation rates and the amount of Pt/TiO2 photocatalyst in
photoreforming methanol tests, showing an optimal photocatalyst load
of 1.33 g L-1 [107], which supported the hypothesis (Entry 4 in Table 2).
In photoreforming glucose for H2 evolution using Ru-doped LaFeO3,
Iervolino and co-workers discovered the optimal photocatalyst loading
of 1.5 g L-1 [109] (Entry 5 in Table 2). In the photoreforming system
using C3N4 as photocatalyst, the optimal H2 evolution rate was obtained
at 0.16 g L-1 photocatalyst concentration with α-cellulose and purified
lignocellulose components as substrates [103]. In essence, the optimal
photocatalyst concentration, for which the whole photocatalyst surface
is effectively irradiated, should be analyzed in combination with the
reaction conditions and the geometrical characteristics of the light
source-photoreactor system [109,111].
4.3. Substrates concentration
Photocatalytic biomass or biomass-derivatives reforming for H2
production generally requires the participation of water, in which
biomass or biomass derivatives acting as h+ scavengers consume
oxidizing active species to obtain a series of liquid products, and where
e- reduces H+ to produce H2. It has been identified that properly tuning
the substrate concentration can achieve the maximum substrate acces­
sibility, which is conducive to achieve improved photoreforming activ­
ity and selectivity. Therefore, substrate concentration is a very
important factor in photocatalytic process. In the following sections, the
C. Shi et al.
effects of different substrates and different substrate concentrations on
the photoreforming H2 production rate and products selectivity are
summarized.
Many studies focused on the photoreforming glucose or other
monosaccharides [96,109,112], and it is worthwhile to note that an
increase of the H2 evolution was observed with up to 1000 mg L-1 of
initial glucose concentration [113]. The analysis of the liquid products
showed that gluconic acid was the only chemical in the liquid phase as
the glucose photoreforming product, and a small amount of CO2 was
further produced by the decarboxylation of gluconic acid. As glucose
concentration further increases, both the glucose degradation and
photoreforming H2 evolution rate decreased [109]. A similar trend has
been observed in photoreforming alcohols [107] and polysaccharides
[15,21,41,99,100,103] for H2 production.
Wakerley et al. used wood-derived highly crystalline α-cellulose to
test the photoreforming H2 production activity of CdS/CdOx in 10 M
KOH under simulated solar light (AM 1.5G, 100 mW cm− 2) [21] (Entry 6
in Table 2). Due to the low solubility of α-cellulose, optimization
experiment revealed that a photocatalyst dosage of 50 g L-1 led to the
highest photocatalytic activity (2.57 mmol g-1 h− 1). By examining the
13
C-labeled cellulose oxidation products using a 13C NMR spectroscopy,
the signals of polymeric cellulose resonances (δ = 55–110 ppm, i) were
found to show up under irradiation without photocatalyst, which
confirmed that α-cellulose can be partially dissolved under basic con­
dition, and the solvated cellulose acts as a substrate for photocatalysis.
13
Chemical Engineering Journal 452 (2023) 138980
In the presence of CdS/CdOx, in addition to signal i, a new signal of
polymeric carboxylic acid resonance (δ = 182 ppm, ii) appeared, which
corresponded to the oxidized polysaccharide end groups. However, the
sharp monosaccharide peaks introduced by cellulose decomposition did
not appear in the spectrum, which may have been oxidized rapidly and
completely into end products (Fig. 9a). It was confirmed that the pho­
tocatalyst exhibited better performance for the oxidation of mono­
saccharides by photoreforming 0.1 M glucose, and its H2 generation rate
was 130 % higher than that of α-cellulose.
Due to the different nature of substrate (structural complexity, light
absorption, and solubility), the same study has showed that the optimal
concentrations for hemicellulose and lignin are 25 and 0.25 g L-1,
showing H2 generation rates of 2.32 and 0.53 mmol g-1 h− 1, respectively
(Fig. 9b). As a control, CdS/CdOx without cellulose (Fig. 9c, black line)
present showed only 10 % of the H2 evolution activity for the first 24 h
and then ceased (4 % after six days), which originated from oxidation of
residual N, N-Dimethylformamide (DMF) from the CdS stock solution
[21]. The same conclusion can be drawn based on the study of homo­
geneous photoreforming system for H2 generation [15].
4.4. Reaction temperature
In terms of overcoming the activation energy to move forward
biomass photoreforming reactions, increasing temperature helps
improve biomass photoreforming efficiency. Many mechanisms have
Fig. 9. Solar-driven reforming of lignocellulose
to H2 with CdS/CdOx: (a) 13C NMR spectra of the
supernatant from a suspension of uniformly 13C-
labelled cellulose (10 mg) in 10 M NaOD in D2O
(1 mL) after three days of irradiation with and
without 1 nmol of CdS/CdOx QDs; (b) The rate of
H2 generation through photoreforming ligno­
cellulose (50 mg mL− 1 α-cellulose, 25 mg mL− 1
hemicellulose (xylan from beech wood), and
0.25 mg mL− 1 lignin over CdS/CdOx; (c) Long-
term photocatalytic cumulative production of
H2 by CdS/CdOx QDs (0.5 µM) with and without
50 mg mL− 1 α-cellulose in 2 mL KOH (10 M); (d)
The pH dependence of the photocatalytic H2
evolution from a 2 mL aqueous solution of
ligand-free CdS QDs (0.5 µM) with 50 mg mL− 1
α-cellulose after 18 h of irradiation. Reprinted
with permission from ref. [21]. Copyright 2017
Nature. Photocatalytic H2 generation on Ni-
decorated CdS nanorods: (e) Schematic of the
photocatalytic generation of H2 under the pro­
posed hole shuttle mechanism; (f) Energy dia­
gram for the two-step oxidation reaction
(https://doi.org/10.1038/NMAT4049). Reprin­
ted with permission from ref. [58]. Copyright
2014 Nature. Photoreforming of biomass in
metal salt hydrate solutions: (g) Photo-reforming
results after 24 h using different photocatalysts
and conditions using AM 1.5G, 100 mW cm− 2
irradiation at 25 ◦ C. Cellulose (50 mg) in 1 mL of
62.5 wt% LiBr in 0.1 M H2SO4 is added to 1.5 mL
aqueous solution containing 4 mg photocatalyst
to give 2.5 mL of 25 wt% LiBr. Reprinted with
permission from ref. [114]. Copyright 2020
Royal Society of Chemistry.
C. Shi et al.
been proposed to expound the effects of reaction temperature on pho­
toreforming H2 production: Firstly, in case that the irradiation flux is
intense enough to maintain a significant population of photogenerated
e--h+ in photocatalysts, the dependence of photoreforming H2 produc­
tion efficiency on temperature is affected by behaviors such as the
diffusion/adsorption of substrates and desorption of H2
[99,112,115,116]; Secondly, increasing temperature is conducive to
lignocellulose dissolution, which can provide sufficient e- donors for the
photocatalytic reaction and promote H2 generation
[41,94,103,111,117–119]. Therefore, it is strongly important to pay
attention to the specific reaction system when analyzing the effects of
reaction temperature on photoreforming H2 production.
By employing biomass-derived oxygenated substrates (glucose or
fructose) as e- donors, Kondarides et al. studied the photoreforming H2
production performance on Pt/TiO2 photocatalyst at different reaction
temperatures [112] (Entry 7 in Table 2). It was clearly demonstrated
that the beneficial influence of higher temperature on reaction rate,
which is likely due to the acceleration of “dark” catalytic reaction steps
(such as oxidation of oxygenated substrates by photogenerated O2)
occurring on the Pt surface, which was not directly associated with the
light-induced reaction steps. It is also possible that increasing temper­
ature also affected the mass transfer of fructose to the photocatalyst
surface and/or the desorption of H2, thereby enhancing the apparent H2
evolution rate in the gas-phase. It was observed that H2 production rates
could be enhanced by almost 50 % when increasing the reaction tem­
perature from 40 to 60 ◦ C (from 0.00017 to 0.00023 mmol g-1 h− 1),
while a less noticeable effect was observed at 80 ◦ C. It should be pointed
out that the temperature increase will affect the H2 production rate but
will not affect the overall H2 production of the system. The research of
Chiarello [115], Lan [99], and Kondarides [116] et al. also supported
that the light-driven reaction steps were not affected by a slight tem­
perature change. In contrast, photoreforming sub-processes that possess
small activation energy, such as adsorption/desorption dynamics, ma­
terials diffusion, dark oxidation steps involving photogenerated charges
or stabilization of transient intermediates, are more likely to be accel­
erated by mild heating.
As pointed out in Section 4.3, substrate accessibility is an important
prerequisite for photocatalytic biomass reforming for H2 production,
and increasing temperature is beneficial to not only improve material
diffusion but also promote lignocellulose dissolution into smaller, more
accessible fragments. This may account for the improved photo­
reforming H2 evolution of certain lignocellulose components with
complex structures (Fig. 1) when the temperature was elevated
[41,94,111,117,119]. Zhang et al. reported an enhanced H2 generation
by photoreforming cellulose catalyzed by a graphitic carbon layer
loaded TiO2/NiOx nanoparticles [119] (Entry 8 in Table 2). When the
temperature rose from room temperature to 80 ◦ C, the H2 production
rate increased from 0.27 to 4.00 mmol g-1 h− 1. Zhou et al. studied the
photocatalytic alkali pretreated corn stover photoreforming on Pt/TiO2,
showing enhanced H2 evolution when temperature was raised to 60 ◦ C
[117] (Entry 9 in Table 2). Furthermore, Zou and co-workers combined
photocatalysis and acid hydrolysis to simultaneously achieve biomass
conversion and H2 production [41] (Entry 10 in Table 2). Photo­
reforming H2 generation was accomplished by cellulose hydrolysis in
0.6 M sulfuric acid solution in the presence of a photocatalyst (such as
platinized TiO2) under UV-light irradiation. Results showed that H2
generation efficiency at 403 K was over 10-folds higher than that at 323
K, suggesting less sufficient acid hydrolysis of cellulosic feedstock at 323
K. In conclusion, temperature needs to be optimized individually for a
specific reaction.
4.5. Effect of initial pH
The medium pH has been identified to impact the following aspects
of the biomass photoreforming process: 1) Effects on the properties of
photocatalysts, including the surface charge and electrokinetic potential
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Chemical Engineering Journal 452 (2023) 138980
(which can be measured as zeta potential) of the photocatalyst surface,
chemical state of the substrate, adsorption or chemisorption processes
(interaction between substrates and photocatalyst), redox potentials of
both substrate molecules and protons, stabilization of either reaction
intermediates or products, or particle aggregation
[69,81,110,112–114,120]; 2) The influence on the semiconductor band
gap structure [58,72]; 3) The influence of pH on the solubility of
lignocellulose components with complex structure, as varying pH may
affect the substrate accessibility, and then affects the photoreforming H2
production efficiency [15,21,41,100,103,117,118]. Considering the
complex influence of pH on the photocatalytic system (the properties of
photocatalysts, substrates and products, proton redox potential and
different photocatalyst/substrate combinations), predicting the general
trends is a complicated task, thus we will describe the influence of re­
action pH on the photoreforming H2 generation rate.
4.5.1. Effects on photocatalyst’s surface properties
In Fu and co-workers’ work about photoreforming glucose using
powdered TiO2-based photocatalyst in water, they clearly demonstrated
that the correlation between acidity/basicity of the reaction medium
and the H2 production [81,110,112,113,120]. The effect of solution pH
on the H2 evolution is not straightforward, involving changes of the
catalyst surface charge, the chemical state of glucose (undissociated in
the pH range investigated (pKa ca. 12.3) and the oxidation reduction
potential of H+/H2. The different H2 yields obtained could be explained
by a combined impact of these different factors [10]. In one of the re­
ported works, they pointed out that a weak basic condition was more
favorable for photocatalytic H2 production, while acidic condition was
disadvantageous as shown by the low H2 generation efficiency in the pH
range (from 1 to 5) [113]. The glucose in the solution was mainly in
molecular form and would prefer to bond with undercoordinated surface
Ti atoms through its hydroxyl O when the pH < pKa (the pKa of glucose
is about 12.3). Increasing solution pH (in the range of pH < pKa) will
facilitate the adsorbed glucose to become deprotonated into RCH2–O-
that has been proven to capture h+ more efficiently than the neutral
molecule, thus, resulting in improved photoreforming performance.
When further increasing pH to exceed the glucose’s pKa, the TiO2 sur­
face was negatively charged because the pH value is higher than the
isoelectric point of TiO2 (pH = 6), and the glucose is also negatively
charged to introduce electrostatic repulsion that will hinder the contact
between glucose and TiO2, leading to decreased H2 production rate
[113].
Iervolino et al. reported the H2 evolution by photoreforming glucose
over Pt-F-TiO2. Different from the work by Fu et al., the H2 production
rate in Iervolino et al.’s study was found to increase with decreasing
initial solution pH, and can reach the maxima of about 0.59 mmol g-1
h− 1 at pH = 2 [81] (Entry 11 in Table 2). A different mechanism was
hypothesized to expound such discrepancy. In acidic condition, the
redox potential of H+/H2 would become more positive, and this condi­
tion was advantageous for efficient H2 generation. For different photo­
catalysts (such as g-C3N4 and CdS), the optimal pH of photoreforming H2
production is also different, suggesting that it is a case-specific param­
eter. For example, Speltini et al. reported an increased H2 production
was observed by either decreasing or increasing pH to more acidic or
more basic, and the highest and the lowest H2 evolution rates were
achieved at pH = 11 and 7, respectively [69] (Entry 12 in Table 2). This
is mainly due to the difference in surface charge of the photocatalyst and
the chemical state of glucose under different pH conditions.
4.5.2. Effects on photocatalyst’s band gap structure positions
The band gap positions of semiconductor may change with pH,
which will affect overall photoreforming efficiency. Simon’s work has
shown that increasing pH led to a cathodic shift in the CB and VB po­
tential of CdS. Since the VB potential of CdS is higher than that of
⋅OH/–OH, the –OH can be oxidized to ⋅OH with stronger oxidation
ability (when pKa = 11.9, ⋅OH is deprotonated), thus promoting the
C. Shi et al.
oxidation of the substrate. This was claimed to be the reason for the
higher ethanol photoreforming rate at high pH (the optimal H2 gener­
ation rate is 63.00 mmol g-1 h− 1 when pH = 14.7) (Fig. 9e-f) [58].
Meanwhile, the photocorrosion of CdS can be effectively suppressed
under strongly alkaline conditions. This result was different from the
previous Tsubomur’s report [121], which indicated that the flat band
potential of CdS is consistent at different pH conditions, but acidic
conditions is more conducive to H+ reduction as it gives stronger
negative polarity. For TiO2 materials [122,123], its VB position follows
the standard Nernstian behavior, which is parallel to the oxidation and
reduction potential of water.
It should be noted that the aforementioned behaviors must be also
taken into account the substrate nature, particularly for those with or
without acidic functional groups as the effect of pH could be dramati­
cally different on them. For acidic substrates, such as oxalic acid [124],
formic acid [125], lactic acid [126], etc., the photoreforming H2 pro­
duction rate decreases with increasing pH. This may be due to the in­
hibition of substrate adsorption on the negatively charged
semiconductor surface. Similarly, for substrates without acidic func­
tional groups, behaviors including that increased H2 production with
increasing alkalinity, as well as the widespread oxidation of –OH into
corresponding free radicals (⋅OH), have been recognized in many reports
[10]. Sanwald and co-workers indicated that changing pH could affect
the photoreforming rate by influencing the hydrolysis of the reaction
intermediate [72]. For example, formates can be converted into the
corresponding aldose intermediate through light-driven, redox-neutral
hydrolysis under pH-neutral and acidic conditions. The dynamics of this
reaction are slow, which requires the interaction of substrates with
negative and positive photogenerated charges, resulting in blockage at
the active sites of photoanode and severe e--h+ recombination. Under
alkaline conditions, stable H2 evolution and saccharides conversion
were achieved by rapid hydrolysis and cracking of formic acid in­
termediates induced by OH–.
4.5.3. Effect on the solubility of lignocellulose substrates
Improved substrates solubility and valorization rate can be achieved
by properly altering the system pH. Wakerley et al. proposed that the
photoreforming H2 evolution activities were improved with increasing
higher solubility of cellulose under alkaline conditions [21]. The
dependence of H2 evolution on pH (1.0, 2.5, 5.0, and 10.0 M KOH) was
studied in a 2 mL solution of ligand-free CdS QDs (0.5 µM) with 50 mg
mL− 1 α-cellulose substrate, demonstrating larger volumes of H2 were
produced at higher pH. Besides, they further coated the CdS surface with
CdOx monolayer or multilayer, which provided a thin surface-
passivating shell and improved the stability of CdS at high concentra­
tions of KOH (Fig. 9d). A similar result was also achieved by Kasap
[103], Achilleos [15], and Zhou et al. [117] In addition, there are also
some reports showing that acidic conditions are conducive to lignocel­
lulose hydrolysis [41,118], all aiming at improving the substrate
accessibility and promoting H2 production rate.
4.6. Other reaction conditions
Other reaction conditions, such as the use of metal salt hydrate so­
lutions (MSH), reactor configuration, and the type of solvent used in
photoreforming H2 production have also been investigated. Pichler et al.
demonstrated the use of MSH as a reaction medium for the photo­
catalytic lignocellulose reforming using different types of photocatalysts
such as TiO2 and cyanamide-functionalized carbon nitride (NCNCNx)
[114]. TiO2 photocatalysts showed a much higher H2 production rate in
LiBr MSH (62.5 wt% LiBr in 0.1 M H2SO4) in photoreforming cellulose
compared to that conducted in 2 M H2SO4. A possible reason, as claimed
by the researchers, was that LiBr MSH benefited the dissolution and
depolymerisation of cellulose and made them more readily to partici­
pate the photoreforming process. In particular, they explored basic
conditions for photoreforming and added 1 mL cellulose LiBr (62.5 wt%)
15
Chemical Engineering Journal 452 (2023) 138980
MSH containing 0.1 M H2SO4 into 1.5 mL of aqueous 0.1 M LiOH instead
of pure H2O, and the H2 production efficiency can reach 0.11 mmol g-1
h− 1 (Fig. 9g). All these studies demonstrated that MSH is a suitable
medium for lignocellulosic biomass photoreforming, as those lignocel­
lulosic biomasses can be depolymerized under relatively mild condi­
tions, converting them into arabinose, erythrose, and formic acid that
are easily accessible to colloidal photocatalysts in photoreforming
process.
The selectivity of substrate is influenced by the type of solvent used
in photoreforming reaction. In general, water is the preferred solvent for
photocatalytic oxidation because it offers many practical advantages,
such as the environmental friendliness and the availability of protons.
However, considering the improved selectivity and stability of liquid
products, the reduced ionization effects of the solvents on the photo­
catalyst surface, and the prolonged lifetime of radical specious (like
singlet oxygen) in solvent, organic solvents such as acetonitrile
[97,127], and tetrahydrofuran [128,129] etc., are also considered as
suitable medium for biomass photoreforming reaction. Reactor config­
uration is also a factor that affects the photocatalytic reforming activity.
Iervolino at al. investigated the effect of the reactor configuration with
the optimized photocatalyst [109]. It is observed that the percentage of
irradiated photocatalyst volume is the key factor, which is affected by
the inner diameter of the reactor. When the reactor volume is consistent,
the percentage of irradiated photocatalyst in reactor with smaller inner
diameter is higher than that of larger one. These results are in agreement
with a previous work [130].
In summary, photoreforming reaction conditions affect the proper­
ties of both photocatalyst and substrate, thus exerting more influence on
the H2 production efficiency. In the actual biomass photoreforming, it is
necessary to optimize these parameters collectively for maximum H2
evolution and biomass conversion.
5. Photoreforming lignocellulose and its derivatives
Lignocellulose is the most abundant biomass in nature. It has a
complex multi-component structure, which provides it strong mechan­
ical and chemical stability [131], as shown in Fig. 1. The main compo­
nent of lignocellulose is cellulose, which is composed of β-1, 4-glycosidic
bond linked anhydroglucose units and stabilized by intra- and inter-
molecular hydrogen bonds to form strong and insoluble elementary fi­
brils. Hemicellulose is a branched copolymer derived from different
types of pentoses and hexoses, which serves as a crosslinker to inter­
connect cellulose elementary fibrils and lignin. Lignin is an amorphous
polyether compound formed by connecting phenylpropane units
through C–C and ether bonds. It is derived from phenolic monomers (p-
coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol) of different
contents. Assembled by plant cells, cellulose, hemicellulose, and lignin
form recalcitrant lignocellulosic matrix that is resistant to external
physical and chemical treatment [81]. Direct photocatalytic lignocel­
lulose reforming under ambient conditions is challenging, and there is a
great incentive to optimize photocatalyst structure and photocatalytic
system for enhanced lignocellulose photoreforming performance. Here,
the recent progresses in photoreforming H2 generation using different
biomass-derived substrates, including cellulose, hemicellulose, lignin,
raw biomass, and small molecules derived from biomass (including
glucose, furfurals, and organic acid, alcohols, etc.), are critically
reviewed, which are shown in Table 3.
5.1. Cellulose and hemicellulose
Photoreforming of cellulose and hemicellulose into chemicals and
clean biofuels has attracted great interests due to the abundant feedstock
availability [132]. Compared to mono- or disaccharides, high efficiency
photoreforming of cellulose or hemicellulose requires sufficient acces­
sibility between the photocatalysts and substrates, which poses a chal­
lenge for the combination of insoluble polymer substrates with
C. Shi et al. Chemical Engineering Journal 452 (2023) 138980

Table 3
Photoreforming activity of different lignocellulose substrates.
Photocatalyst Entry Substrate Substrate pretreatment Light source, intensity (mW H2 evolution AQY/% (λex/ Reference
cm− 2) rate nm)
(mmol g-1h− 1)

CdS/CdOx QDs and Co 1 α-cellulose 10 M KOH Solar light simulator (1 0 0) 2.30 – [21]
(BF4)2 Xylan 25 ◦C 2.05
Lignin 0.26
Raw biomass 5.30
Rutile TiO2 2 Cellulose 62.5 wt% LiBr in 0.1 M Solar light simulator 0.18 – [114]
H2SO4) (1 0 0)
Pt/TiO2 3 Cellulose 0.6 M H2SO4 Iron doped halide lamp (250 1.32 – [41]
W)
Polymeric CN 4 Arabinose 5 M NaOH Xe lamp (300 W) 0.71 7.87 [135]
Xylan 1.17 (4 2 0)
Xylose 4.09
Galactose 5.21
NiP/NCNCNx 5 α-cellulose 0.1 M KPi (pH 4.5) 25 ◦C Solar light simulator (1 0 0) 0.25 – [103]
xylan 0.14
Cellobiose 0.51
Glucose 1.12
Xylose 0.55
Galactose 0.76
Sinapyl alcohol 0.04
Lingin 0.02
NiS/CdS 6 Lignin – Xe lamp 1.51 44.9 [17]
Eosin Y/Pt/TiO2 7 Olive mill wastewater pH = 3 Solar box (25) 0.18 – [138]
CoO/g-C3N4 8 Regenerated cellulose 1 M NaOH Xe lamp (300 W) 0.18 – [43]
II
Pt/TiO2 9 Glucose Hg lamp 0.21 [113]
Soluble starch Microwave (125 W) 0.19
Pt/(CNT-TiO2) 10 Arabinose – Heraeus TQ 150 medium 0.09 – [46]
Fructose pressure Hg lamp 0.05
Glucose 0.10
Cellobiose 0.08
SNGODs 11 Sucrose pH = 10 Xe lamp (300 W) 0.22 11.00 [142]
Glucose 0.16 (4 2 0)
Ni/CdS 12 5-HMF – Blue LED 0.03 – [42]
CdS/MoS2 13 5-HMF – Xe arc lamp (110.30) 27.16 – [153]
Zn0.5Cd0.5S/ 14 5-HMF – White LED bulbs (30 W) 0.06 24.5(4 5 0) [155]
MnO2
Ni-Cu-TiO2 15 Glycerol – Mediumpressure Hg lamp 1.62 – [157]
(450 W)

heterogeneous photocatalysts [133,134]. As described in Section 3 and 4,
for these types of substrates, the optimization of photocatalyst structure
and reaction system is particularly critical.
Many studies have been conducted to improve the accessibility of
cellulose and hemicellulose substrate. 1) Optimizing the solubility of
cellulose and hemicellulose helps enhance their accessibility to photo­
catalyst. To achieve so, it is usually necessary to tune the reaction
conditions such as the solvent system and pH (strong acid or base
environment) as mentioned in Section 4. 2). Hydrolysis of cellulose and
hemicellulose to produce biomass fragments with improved accessi­
bility, which can be facilitated by the introduction of solid acids into the
photocatalytic system [43].
cellulose photoreforming process (such as extreme alkaline or acidic
media for complete substrate dissolution) requires intensive energy
consumption and the use of chemical-resistant, anti-corrosive reactor, it
may not be suitable for large-scale production. To achieve a milder
photoreforming process, Reisner et al. incorporated MSH for biomass
photoreforming [114], as the lignocellulosic biomass can be dissolved in
MSH solution under relatively mild conditions (Entry 2 in Table 3). The
soluble polysaccharides can be easily exposed to colloidal photocatalysts
for H2 production during the photoreforming process. The cellulose
solution treated with MSH was used for photoreforming reaction over
TiO2 nanoparticles, reporting a maximum H2 evolution rate of over 0.18
mmol g-1 h− 1 (Fig. 9g).

5.1.1. Dissolved cellulose and hemicellulose
To improve the solubility of cellulose, it is usually required to
conduct the reaction under strong acid or alkali environment. As
described in Section 4.5.3, Wakerley et al. tested the catalytic efficiency
of CdS/CdOX quantum dots on photoreforming α-cellulose under high
concentration of KOH (10 M) solution [21] (Entry 1 in Table 3). The
yield of H2 evolution in such conditions was about 2.30 mmol g-1 h− 1.
Isotope labeling test proved that the H2 released by the photocatalyst
was mainly from the reduction of H2O, as the ratio of D2 to HD produced
by photocatalysis in D2O was 4:1, and the formation of HD was due to
the H/D exchange with the OH group of the cellulose. In the same
research, the reforming of hemicellulose (xylan from beech wood) was
also discussed in parallel, indicating xylan can be simultaneously pho­
toreformed to give a similar H2 production yield (over 2.00 mmol g-1
h− 1). Considering that the harsh reaction conditions of the most
5.1.2. Hydrolyzed cellulose and hemicellulose
Zou et al. employed acid hydrolysis to hydrolyze cellulose for
improved accessibility in biomass conversion and H2 production [41]
(Entry 3 in Table 3). The photoreforming process was carried out in 0.6
M sulfuric acid solution at 403 K under ultraviolet light irradiation, in
the presence of a platinized TiO2 (Pt/TiO2), achieving an efficient and
stable H2 production of 1.32 mmol g-1 h− 1. This also implied the stability
of photocatalyst in such strong acidic condition. Mono- or oligosaccha­
rides were produced in situ by acid hydrolysis of cellulose and then
served as substrate for photoreforming. In detail, glucose was produced
as the main hydrolysate, while other hydrolysates such as fructose
(isomer of glucose), 5-HMF (dehydration from fructose), and other
carbohydrates were also detected. According to HPLC analysis of the
liquid products, the cellulose transformation pathway during photo­
reforming was determined as shown in Fig. 10a. Liu et al. studied the H2

16
C. Shi et al.
generation by efficient photoreforming of different lignocellulose over
polymeric carbon nitride (PCN). As displayed in Fig. 10b, the photo­
reforming activity of cellulose hydrolysates, cellobiose and glucose, was
significantly higher than that of cellulose. Photoreforming of arabinose,
xylan, xylose, and galactose enable the HER of 0.71, 1.17, 4.09, and
5.21 mmol g-1 h− 1, respectively. The results demonstrated the difference
of H2 generation value in the presence of different lignocellulosic com­
ponents may be limited by the accessibility to trap the photoinduced h+
in PCN [135] (Entry 4 in Table 3).
Due to high degree of cellulose polymerization and the robust inter-
and intra-molecular hydrogen bonding, the application of photo­
catalytic degradation of cellulose and hemicellulose reforming for H2
production still needs more research. A simple, energy saving, and mild
reaction condition is necessary to depolymerize cellulose into smaller
saccharide molecules. It is also important to change the structure of
cellulose through certain physiochemical pretreatment to improve its
photoreforming efficiency.
5.2. Lignin
As another major component of lignocellulose, lignin has attracted a
great deal of attention due to its abundance and renewable properties.
Compared to cellulose and hemicellulose, the structure of lignin is more
complex, diverse, and stable. In addition, the brown color of lignin may
affect the absorption of light by photocatalyst. Therefore, photo­
reforming lignin to produce H2 is relatively more difficult. That being
said, some aromatic hydrocarbons can be generated in the lignin pho­
toreforming for H2 evolution process, which implies highly important
industrial value.
Considering the complexity of the lignin structure, researchers usu­
ally start with model lignin compound (sinapyl alcohol) to study its
photoreforming H2 production activity, though it is questionable
whether they perform alike. In a study focusing on activated NCNCNx and
NiP catalysts, photoreforming H2 production from sinapyl alcohol gave a
rate of 0.04 mmol g-1 h− 1, while the yield was only 0.002 mmol g-1 h− 1
from lignin under same condition [103] (Entry 5 in Table 3). In another
study, Li et al. synthesized a uniform one-dimensional NiS/CdS nano­
composite for H2 evolution [17] (Entry 6 in Table 3). A maximum H2
production yield of 1.51 mmol g-1 h− 1 was achieved when photo­
reforming both lactic acid and lignin as h+ scavengers, with apparent
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Chemical Engineering Journal 452 (2023) 138980
quantum efficiency (AQE) of H2 production being 44.9 %. When lignin
and lactic acid were simultaneously used as h+ scavenger, a variety of
liquid products including methanol, ethanol, formaldehyde, formic acid,
and oxalic acid can be generated. The h+ reaction, following the
pathway I and II in the Fig. 10c was the rate-limiting step in the whole
photocatalytic reaction. Alternatively, lignin can be photoreformed in
alkaline aqueous solution using CdS quantum dots [21]. The smaller
band gap of CdS/CdOX made it capable of absorbing visible light with
wavelengths above 420 nm. Since lignin showed a wide absorption peak
at 300 nm and a shoulder peak at 350 nm, there is no competition be­
tween the photocatalyst and the lignin in the utilization of light sources,
guaranteeing improved photoreforming efficiency. At lignin loadings of
0.25 mg mL− 1, CdS/CdOX catalyst was able to evolve H2 at a yield of
0.26 mmol g-1 h− 1. Nevertheless, most of the studies on photoreforming
lignin is in the preliminary stage (Entry 1 in Table 3). The complex and
diverse structural characteristics of lignin still make it difficult to un­
dergo photocatalytic reforming process.
5.3. Raw biomass and biomass wastes
H2 production from photoreforming raw biomass and biomass waste
can be considered more efficient biomass utilization than isolated and
purified components, as no separation and purification process is
required. This is a long-term and challenging goal for advancing biomass
conversion technology, with relatively few research at present.
It has been demonstrated that raw biomass, such as wood, grasses
stem (wheatgrass [136], straw, and fescue grass [137], etc.), and cotton
[21] can be used for H2 evolution by photoreforming. Reisner et al.
investigated the H2 generation activity by photoreforming raw biomass
with size less than 0.25 cm by coarse cutting using CdS/CdOX and CO
(BF4)2 co-catalysts in 2 mL KOH (10 M) (Fig. 5c) [21]. >5 mmol g-1 h− 1
of H2 production yield was observed using wood from branches, while
other raw biomass (sawdust and grass) showed lower activity (Fig. 11a).
In addition, some biomass waste, like bagasse, waste paper, cardboard,
newspaper, and olive mill wastewater (OMW) have also been used for
direct photoreforming H2 evolution [21,138]. Up to 0.18 mmol g-1 h− 1
of H2 productivity can be achieved from photoreforming OMW by Pt/
TiO2 (Entry 7 in Table 3). Therein, ⋅OH and h+ were considered as the
main oxidizing species to convert biomass. Meanwhile, the polyphenols
fraction in OMW, showing strong antioxidant properties, can act as the
Fig. 10. Photoreforming cellulosic
biomass waste to H2 by merging pho­
tocatalysis with acid hydrolysis: (a)
Proposed pathway of cellulose decom­
position in combined processes of hy­
drolysis and photocatalysis. Reprinted
with permission from ref. [41]. Copy­
right 2018 Elsevier. H2 generation by
efficient photoreforming of different
lignocellulose over polymeric carbon
nitride (PCN): (b) Photocatalytic H2
evolution rates using PCN as the pho­
tocatalyst with different purified
lignocellulose components (200 mg).
Reprinted with permission from ref.
[135]. Copyright 2020 Elsevier. H2
evolution by photoreforming of lignin
and lactic acid over NiS/CdS nano­
structures: (c) Scheme for the photo­
catalytic H2 production over NiS/CdS
nanocomposites under visible light.
Reprinted with permission from ref.
[17]. Copyright 2018 Elsevier.
C. Shi et al. Chemical Engineering Journal 452 (2023) 138980

Fig. 11. Photocatalytic H2 evolution from crude other biomass derivatives over CdS/CdOx: (a) Photoreforming 50 mg mL− 1 of raw and waste biomass substrates for
H2 generation on CdS/CdOx. Reprinted with permission from ref. [21]. Copyright 2017 Nature. Photoreforming of pinewood (Pinus ponderosa) acid hydrolysate for
H2 generation: (b) GCMS and HPLC identification of compounds in the hydrolysate and AC-treated hydrolysate. Reprinted with permission from ref. [118]. Copyright
2017 Elsevier.

sacrificial agents to promote H2 release from water [138].
As discussed earlier, photoreforming of raw biomass and biomass
waste is generally less active for H2 generation, pretreatment is also
essential to make better use of them. Reisner et al. employed high
alkaline conditions (10 M KOH) to provide an in-situ pretreatment of the
wood from branches for photoreforming H2 production [21]. Jaswal
et al. transformed ground pines into hydrolysate (containing sugars,
carboxylic acids, furfuryl acids, and phenols, Fig. 11b) using diluted acid
for photoreforming H2 generation [118]. The hydrolysate was treated
with activated carbon (AC), which removed phenols, followed by pho­
toreforming with 1 % Pt/TiO2. Under optimized reaction conditions, 8
consecutive photocatalytic cycles of the hydrolysates produced a cu­
mulative H2 yield of 19.9 mL g− 1 pinewood. In addition, Speltini et al.
used magnesium silicate (125 g L-1, 6 h exposure) to pretreat OMW. The
H2 production rate increased significantly by 81 % (i.e, 0.33 mmol g-1
h− 1 in H2 productivity) [138]. Wu et.al investigated the photoreforming
performance of raw lignocellulosic biomass wheat straw (WS), with/
without various biomass pretreatment strategies by using engineered
CoO/g-C3N4 [43] (Entry 8 in Table 3). It was found the pretreated
biomass had much higher H2 production and cellulose conversions as
compared with raw biomass, but the degree of improvement is highly
depended on pretreatment strategies.
Overall, high-value chemicals and clean fuels can be produced
through photoreforming of raw and biomass waste, which is in line with
the requirements of sustainable development. However, despite being a
promising substrate for H2 production by photoreforming, the poor
catalyst accessibility makes raw biomass a less efficient substrate for
photoreforming H2 production. More attention should be paid on it to

18
C. Shi et al.
realize carbon neutrality.
5.4. Small molecules derived from biomass
Compared with the complex structure of cellulose, hemicellulose,
lignin, and raw biomass, small molecules derived from biomass
(monosaccharide and disaccharides, furfurals, organic acid, and alco­
hols etc.) have less stringent requirements for photocatalysts and cata­
lytic systems, so they have also been studied more widely.
5.4.1. Monosaccharide and disaccharides
Monosaccharide and disaccharides are the most widely studied
model substrates for biomass photoreforming, due to their abundancy in
lignocellulose (i.e., cellulose and hemicellulose). They are ideal e- do­
nors for photocatalytic H2 production. Monosaccharides mainly include
five-carbon sugars (xylose [139,140] and arabinose [46]) and six-carbon
sugars (glucose [141,142], fructose [46,143,144], galactose, and
mannose [145]), as shown in Fig. 12a. Disaccharides that has been used
as biomass reforming substrates include cellobiose [46,146], sucrose
[38,113,147,148], maltose [116,149], lactose [112], etc. Glucose is the
most basic unit that constitutes cellulose and accounts for the most
significant part of the sugar monomers of lignocellulose, while the other
sugars are mainly from hemicellulose.
Glucose is widely studied for photocatalytic H2 production. Bellar­
dita et al. used Pt-loaded TiO2 as the photocatalyst and studied the
Fig. 12. (a) Structural formulae of several mono- and di-saccharides molecules. Reprinted with permission from ref. [11]. Copyright 2018 Wiley. (b) Schematic
model of the photoreforming of glucose on metal/TiO2 catalysts yielding H2 production with low CO selectivity. (c) Conceptual illustration of a graphene oxide dot
(GOD) for photocatalytic reforming of sugar and glucose into H2. Reprinted with permission from ref. [142]. Copyright 2019 Royal Society of Chemistry.
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Chemical Engineering Journal 452 (2023) 138980
photoconversion of glucose in aqueous solution under aerobic and
anaerobic conditions [96]. The Pt-brookite catalyst produced about
1.70 mmol of H2 after 7 h of radiation in anaerobic condition, and the
photoreaction resulted in isomerization of glucose into fructose, which
was further oxidized into high-value gluconic acid, arabinose, erythrose,
and formic acid. The loaded Pt was found to dominate the rate and
selectivity of brookite reforming glucose for H2 production. Wu et al.
carried out photoreforming glucose over M/TiO2 catalyst (M = Pt, Rh,
Ru, Ir, Au, Ni, and Cu) to improve the selectivity of gas products, i.e.,
producing H2 with low CO concentration (Fig. 12b) [150]. The selec­
tivity and the generation of H2 were largely dependent on the kinds of
metals deposited on TiO2. Among the tested, Rh/TiO2 catalyst gave a
high H2 production with the lowest CO concentration, with the product
selectivity increasing in the order of Ir < Ru < Au < Ni≈Cu≈Pt < Rh.
In addition to glucose, other monosaccharides (fructose and arabi­
nose, etc.) and some disaccharides, like cellobiose, have also been used
in photoreforming. Silva et al. prepared carbon nanotube-TiO2-T com­
posites ((CNTs-TiO2)-T, T annotating the temperature of calcination in
Kelvin) for H2 production from photoreforming of arabinose, glucose,
fructose, and cellobiose [46]. For the control photocatalyst (Pt/TiO2-
473), the H2 production efficiency increases following the order of
cellobiose, fructose, glucose, and arabinose, appearing to be related to
the complexity of the carbon skeleton [113,151] (Entry 9 in Table 3).
For biomass substrate with more complex carbon skeleton (glucose,
fructose, and cellobiose), the photoreforming efficiency of Pt/(CNT-
C. Shi et al.
TiO2)-473 was higher than that of Pt/TiO2-473. Especially for photo­
reforming cellobiose, the H2 generation rate of Pt/(CNT-TiO2)-473 was
2.8 folds of that for Pt/TiO2-473 after 2 h of light irradiation (Entry 10 in
Table 3). This may be related to the higher availability of e- at Pt par­
ticles and the higher surface area of the composite (61 m2 g− 1), which
resulted in the improved H+ reduction and reduced diffusion limit in the
case of larger molecules, respectively. Nguyen et al. reported an envi­
ronmentally friendly catalyst consisting of sulfur and nitrogen co-doped
GO dots (SNGODs) to effectively reform sugar (primarily sucrose) and
glucose (Fig. 12c) [142] (Entry 11 in Table 3). These functionalized
SNGODs expanded the e- resonance domain, narrowed the band gap,
and led to charge delocalization and separation. The SNGODs exhibited
higher photocatalytic activity of 0.22 and 0.16 mmol g− 1 h− 1 of H2
production from sucrose and glucose, respectively. The basal plane of
the SNGODs has a high concentration of quaternary N that repairs the
vacancy defects. The functional groups effectively adsorb deprotonated
glucose molecules through hydrogen-bonding in a basic environment. In
another study, Kasap investigated the photoreforming H2 evolution
using NCNCNx upon ultrasonication [103]. Within 24 h of irradiation, H2
were produced from glucose at 1.12 mmol g− 1 h− 1 with activated
NCN
CNx and NiP (Entry 5 in Table 3). When used to photoreform xylose,
galactose monosaccharides, and polymeric xylan, the H2 generation
rates were recorded as 0.17, 0.25, and 0.04 mmol g− 1 h− 1 within 24 h of
irradiation, respectively. Recently, Hu et al. group reported the cleavage
mechanism of cellobiose β-1, 4-glycosidic linkage [152]. They demon­
strated a all-solid-state 3DOM TiO2-Au-CdS Z-scheme heterojunction
materials for enhanced cellobiose photorefinery. The oxygen (from the
oxygen-containing free radicals produced during photocatalytic process
of 3DOM TiO2-Au-CdS) insertion at C1 position of cellobiose followed by
the elimination reaction, which oxidatively cleaves the β-1, 4-glycosidic
bond and results in gluconic acid and glucose generation. In presence of
oxygen, glucose is further oxidized into gluconic acid which is subse­
quently oxidized or decarboxylated into glucaric acid or arabinose. This
work may pave a novel way to rationally design photocatalyst to reveal
mechanistic understanding of biomass photoreforming towards high-
value fuels and chemical feedstocks. Photoreforming processes for H2
production with monosaccharides and disaccharides as substrates have
been extensively studied. However, the reaction mechanism and trans­
formation pathway of photocatalytic oxidation of saccharides to high
value-added small molecules are still not clear or not profound. There­
fore, more attention should be paid on the reaction mechanism of high
value-added products in liquid phase system while maximizing the yield
of photocatalytic H2 evolution.
5.4.2. Biomass-derived furfurals
In addition to mono-, di-, and polysaccharides, another important
biomass derivative used for photoreforming is furfurals. Furfurals can be
incorporated in photocatalytic H2 evolution system, by serving as re­
action substrate for effective H2 evolution. Among all types of biomass
derived furfurals, 5-HMF is considered to be the most important one due
to its environmentally friendly feature and the potential of producing
value-added biomass oxidation products. The pH of the system plays a
key role in the photoreforming reaction, and alkaline system is often
preferred for such catalytic reaction. Simultaneous H2 production can be
achieved upon visible light irradiation under ambient conditions using
the biomass intermediates as h+ scavengers, which demonstrated the
feasibility of producing H2 from photoreforming biomass-derived in­
termediates (5-HMF and furfural alcohol) in aqueous media [42] (Entry
12 in Table 3). The H2 evolution was found to increase during the first 8
h and reach a plateau of about 4.5 mL after 8 h. Under alkaline condi­
tions, both furfural alcohol and 5-HMF were quickly transformed to the
corresponding acids at nearly 100 % yield. In addition, Zhao proposed
CdS/MoS2 nano-octahedron heterostructures for reforming furfural
alcohol under alkaline conditions, which was claimed as a cheap and
effective way [153] (Entry 13 in Table 3). The significantly enhanced
photocatalytic H2 evolution rates of 5.29 mmol h− 1 g− 1 were recorded.
20
Chemical Engineering Journal 452 (2023) 138980
To photoreform 5-HMF under mild conditions, one promising way is
to design heterogeneous and the use of non-metallic photocatalysts.
Battula et al. synthesized a novel porous carbon nitride (SGCN) system,
which could accomplish the H2 evolution form H2O and the DFF pro­
duction from selective HMF oxidation [154]. 12 μmol h− 1 m− 2 of H2 was
achieved after 6 h visible light irradiation while the DFF yield of 13.8 %
with > 99 % selectivity. As runs longer (48 h), the selectivity of DFF was
maintained > 99 %, an improved DFF yield 38.4 %, and 36 μmol h− 1
m− 2 of H2 production rate. Moreover, 6.2 μmol h− 1 m− 2 of H2 with 7.2 %
DFF yield were produced under natural sunlight for 6 h. Dhingra et al.
synthesized Zn0.5Cd0.5S/xMnO2 (x represents the weight ratio of MnO2
loaded on Zn0.5Cd0.5S) heterojunction for photoreforming 5-HMF for
DEF and H2 production (Entry 14 in Table 3). Among all the formula­
tions analyzed, Zn0.5Cd0.5S/1%MnO2 showed the optimal H2 produc­
tivity of 0.06 mmol g-1 h− 1 [155]. DFF being the oxidation product of 5-
HMF was supported by GC–MS results, giving a yield of 46 % after 24 h.
The time-dependent 1H NMR and HPLC analysis further confirmed the
oxidation pathway from 5-HMF to DFF.
5.4.3. Other biomass derivatives
Other biomass derivatives that have been investigated for photo­
reforming H2 production mainly include organic acids (carboxylic acid
and lactic acid, etc.), alcohols (monoalcohols such as methanol and
ethanol; polyols such as glycerol, etc.), and aldehydes.
Organic acids are commonly used for photoreforming H2 evolution.
Cao et al used CdS nanorods (as a photosensitizer) modified Ni2P NPs for
photoreforming H2 generation with lactic acid as e- donor under visible
light irradiation [156]. A highest H2 evolution rate was achieved at pH
3.0, which can be attributed to greater affinity between organic acid and
catalyst due to restrained deprotonation of organic acid. The H2 evolu­
tion activity can sustain for>20 h and then slow down slightly. When
additional aliquots of CdS or a mixture of CdS and lactic acid was added
to the solution, the H2 production efficiency restored promptly to the
initial state. The reduced H2 evolution efficiency can be attributed to the
photocorrosion of CdS and the consumption of lactic acid.
Biomass derived alcohols and aldehydes are also competent sub­
strates for photoreforming H2 production. Taylor et al. firstly prepared a
novel Ni-Cu-TiO2 photocatalyst for photoreforming glycerol [157],
reporting a H2 productivity of 1.62 mmol g-1 h− 1, which was 44 times
than that of P25 (Entry 15 in Table 3). The Cu and Ni was found to
significantly enhance the H2 evolution performance upon photo­
reforming glycerol under near UV or visible light irradiation. Methanol
and ethanol can be photocatalyzed by TiO2 for H2 production [158,159].
The reaction mechanism suggests that the alcohols consume h+ and are
transformed to organic intermediates, and the H+ get reduced to pro­
duce H2. Interestingly, this also represents a useful approach to convert
aromatic alcohols into their corresponding aldehydes via photo­
reforming [160]. All these works provide a feasible process to utilize
biomass derivatives for H2 production and other value-added chemicals.
It is well known that the complex aldehydes are classified as sac­
charides, simple aldehydes are contained at significant levels in pyrol­
ysis bio-oils. Actually, they may make up 20-30 wt% of the total mass of
bio-oils [10]. Utilizing aldehydes for photoreforming H2 generation is
relatively less reported but worthy of study for the photocatalytic H2
production regarding a possible valorization approach of bio-oils. The
reduction of formaldehyde (HCHO) to H2 using H2O as one of the donors
can be considered as an efficient and promising H2 generation strategy
due to its high atomic economy and high gas purity (only H2 without CO
or CO2 production). Zhang et al. reported an amino functionalized
organosilica nanotubes internally modified with AuPd nanoclusters for
photoreforming H2 evolution from formaldehyde aqueous solution
[161]. Under visible light irradiation, aldehyde group was oxidized to
carboxyl group, and the H+ from H2O was reduced to H2. Photo­
reforming other aldehydes such as acetaldehyde, propyl aldehyde and
benzaldehyde was investigated for H2 production as well. Besides
formaldehyde, other aldehydes, including acetaldehyde, propanal, and
C. Shi et al.
benzaldehyde are also investigated to produce H2 [162].
6. Conclusion and outlook
In the face of environmental problems caused by global warming and
massive use of fossil fuels, photocatalytic reforming of biomass to pro­
duce high energy density H2 fuel has become one of the research hot­
spots in recent years because of the environmentally friendly nature.
Photoreforming biomass uses the renewable and low-cost biomass
sources from nature as substrate and solar light as energy source. It
provides a green and sustainable way to utilize solar energy, agricul­
tural, and forestry residues, suggesting its great potential in promoting
the resources circulation and mitigating environmental and energy
pressure [163,164]. In this review, the influence of photocatalyst
structures and photocatalytic system on H2 production from photo­
reforming biomass were discussed comprehensively with representative
examples.
To comprehend key structural and compositional parameters for
photocatalyst, Section 3 (photocatalyst structure) focuses on discussing
the effects of band gap structure, morphology and size, crystal phases
and other factors of photocatalyst on the generation of H2 by photo­
reforming. Our analysis shows that all these effects are interconnected to
some extent but can differ substantially from one system to another. In
addition, the interaction between H2 production and biomass oxidation
by photoreforming should be analyzed in a specific reaction system; in
other words, the one applied to one system may not be applicable to
another. At the same time, much attention should be paid to the impact
of the produced liquid products and by-products during the photo­
reforming process on the activity of photocatalyst. Particularly, for some
photocatalysts like CdS, though in many studies it gave satisfactory
photoreforming activity, its environmental toxicity remains to be
resolved. More attention should be paid to the development of catalysts
with not only high photocatalytic efficiency but also nontoxic and
environmentally compatible. For the part of photocatalytic system
(Section 4), the influence of the initial pH, reaction temperature, and
solvent medium on the H2 production by biomass photoreforming was
summarized. The influence of pH on photoreforming H2 evolution can
be mainly summarized as three aspects: firstly, the properties of pho­
tocatalysts, including the surface charge and electrokinetic potential
(which can be measured as zeta potential) of the photocatalyst surface,
chemical state of the substrate, adsorption or chemisorption processes
(interaction between substrates and photocatalyst), redox potentials of
both substrate molecules and protons, stabilization of either reaction
intermediates or products, or particle aggregation; Secondly, the influ­
ence on the semiconductor band gap structure positions; Thirdly, the
solubility of lignocellulose components with complex structure and the
substrate accessibility. Increasing temperature usually lowers the acti­
vation energy of the rate-limiting step of photoreforming, and may also
affect the type and yield of liquid products. Therefore, it is a key
parameter impacting the depolymerization of biomass macromolecules
into small molecules and hence directly influence the subsequent H2
production. Based on the current research on H2 generation form
biomass photoreforming, we put forward the following views and
opinions:
1) Developing an appropriate depolymerization method for raw
biomass or large biomass molecules is crucial for improved photo­
reforming H2 evolution. At present, most raw biomass undergoes a two-
step approach, i.e., depolymerization into smaller biomass derivatives,
photoreforming of the biomass derivatives. However, the low conver­
sion efficiency, high cost, and complicated processing procedure limit its
commercialization. For certain photoreforming systems, the production
of by-products and contaminants make such process even more unfa­
vorable. One potential approach to resolve these matters is properly
designing the catalyst structure and adjusting the photocatalytic system.
For photocatalyst, proper structural modification by solid acid and metal
with plasma effect may promote its performance in depolymerizing
21
Chemical Engineering Journal 452 (2023) 138980
biomass. The plasma effect of metal particles can promote biomass
depolymerization by increasing the catalyst’s surface temperature.
Screening the pH, temperature, and other variables of the reaction sys­
tem can also be employed to determine the optimal photoreforming
condition. An ideal photocatalyst should be able to sufficiently photo­
reform biomass in a high efficiency and mild way.
2) More efforts are required in understanding the relationship be­
tween HER and biomass oxidation. Generally, biomass participates in
the oxidation reaction as a sacrificial agent by consuming oxidizing
active species. Increasing biomass dosage may promote the availability
of active species with reductive properties, leading to improved pro­
duction of H2 and value-added platform compounds. The oxidation ca­
pacity of photocatalyst will affect the oxidation reaction pathway of
biomass, which in turn will influence the overall photoreforming H2
production efficiency. Therefore, the relationship between H2 genera­
tion and biomass oxidation should be analyzed with regard to relevant
characterization methods, reaction pathways, and mechanisms.
3) Developing photocatalyst specifically for H2 production. To date
there are few types of photocatalysts used for photoreforming H2 pro­
duction, and most of the studies only focus on TiO2, CdS, and bimetallic
sulfides (ZnxCd1-xS). Researchers should pay more attention to explore
more types of photocatalysts suitable for this field based on the reaction
pathways and reaction mechanisms, which will play a remarkable role
in promoting the performance of biomass photoreforming to produce
H2.
4) Optimization of photocatalyst structure and photoreforming sys­
tem. In photoreforming biomass for H2 generation reactions, it is more
necessary to design photocatalyst structure based on the reaction char­
acteristics in line with the reaction target. The modification of the ma­
terial’s band gap structure, crystal structure, and surface chemistry
should be conducted in consideration with its impact on the biomass
oxidation half reaction, with the target of maximizing the overall pho­
toreforming efficiency. Many previous reports focused merely on one
half reaction and may not fully reflect the whole results. Meanwhile, the
properties of the photocatalytic system also play an important but
underrated role, which could affect the reaction path and H2 production
rate as well.
At present, there is still great discrepancy between the current art
and industrial expectation in terms of H2 production, liquid product
selectivity and yield. In view of the above knowledge gaps in H2 gen­
eration by biomass photoreforming, technology transfer from different
research fields is highly recommended. Novel photocatalyst structure
designed for specific reactions and capable of photoreforming raw
biomass is of great interest to both academia and industry. Further at­
tempts are needed on investigate photocatalysts’ performance in pho­
toreforming biomass, as well as the reaction mechanism.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China (No. 32071713), the Fundamental Research Funds
for the Central Universities (No.2572020DX01), and the Natural Science
Funds for Distinguished Young Scholars of Heilongjiang Province (No.
JQ2019C001).
C. Shi et al. Chemical Engineering Journal 452 (2023) 138980

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