Journal of Cleaner Production 286 (2021) 124970

Contents lists available at ScienceDirect

Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Review

Hydrogen: Current advances and patented technologies of its

renewable production

Martinez-Burgos a, Esteffany de Souza Candeo b,
Walter Jose
Adriane Bianchi Pedroni Medeiros a, Julio Cesar de Carvalho a,
Valcineide Oliveira de Andrade Tanobe a, Carlos Ricardo Soccol a,
Eduardo Bittencourt Sydney b, *
a
, Department of Bioprocess Engineering and Biotechnology, Centro Polit

Federal University of Parana
, Brazil
ecnico, 81531-990, Curitiba, Parana
b
Universidade Tecnolo
gica Federal Do Parana
(UTFPR), Department of Bioprocess Engineering and Biotechnology, Rua Doutor Washington Subtil Chueire,
330, 84017-220, Ponta Grossa, Parana
, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Hydrogen is considered the energy of the future. In order to meet the requirements of a green pro-
Received 17 June 2020 duction, many technological advances were achieved in the last 20 years. Reviewing these advances
Received in revised form allows the understanding the constraints of the sector and the identification of the paths for future
29 September 2020
research. In this work three routes for renewable hydrogen production from renewable sources were
Accepted 3 November 2020
reviewed with focus on patented technologies: dissociation of the H2O molecule, microbial production
Available online 6 November 2020
and thermochemical processes. Three patent databases were accessed, covering documents written in
Handling editor: M.T. Moreira English, Spanish and Portuguese. Water dissociation is the only commercial technology and most efforts
were identified in new materials for electrodes, new catalysts and reagent recycling. Microbial pro-
Keywords: duction is thermodynamic limited but strategies to maximize the production and overcome economic
Bioenergy barriers are mostly related to the use of wastewaters, improving microbial communities’ composition
Sustainable production and genetic manipulation. Most patents of thermochemical production patents brought contributions to
Biohydrogen the efficient use of energy especially by the combination with other energy producing technologies. The
Water dissociation
establishment of a green hydrogen society is strongly dependent of future developments on new ma-
Gasification
terials, recycle of chemical catalysts and efficient use of energy in the short-term.
© 2020 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3.1. Hydrogen production by water dissociation: current strategies and advances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3.1.1. Thermolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3.1.2. Electrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.1.3. Photolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2. Bio-based hydrogen production processes: strategies and patented advances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2.1. Dark fermentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2.2. Photosynthetic processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2.3. Microbial hydrogen production patents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2.4. Strategies to maximize bioH2 production and overcome economic barriers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.3. Hydrogen production by thermochemical processes: technological advances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.4. Nanotechnologies applied to hydrogen production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

* Corresponding author.
E-mail address: eduardosydney@utfpr.edu.br (E.B. Sydney).

https://doi.org/10.1016/j.jclepro.2020.124970
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
W.J. Martinez-Burgos, E. de Souza Candeo, A.B. Pedroni Medeiros et al. Journal of Cleaner Production 286 (2021) 124970

4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

1. Introduction 2. Methodology

Hydrogen gas (H2) is a raw material widely used in different The research was made using the Science Direct and Google
industrial sectors, such as chemical, petrochemical, metallurgy, Scholar article databases and the following patent databases: Der-
food, electronic and energy. Hydrogen can be produced from went Innovation Index, National Institute of Industrial Property of
renewable sources and sometimes using industrial wastes Brazil (INPI) and Latipat-Espacenet. The patent search period
(Martinez-Burgos et al., 2019); (Rafa et al., 2018). It has the highest ranged from 2000 to 2019 and the keywords used are presented in
energy per mass of any fuel (Rafa et al., 2018; Wang and Yin, 2018), Table 1.
its combustion is clean (Claassen et al., 1999; Han and Shin, 2004)
and can be safely stored and transported. Moreover, it can be used 3. Results and discussion
for the production of electrical, thermal and chemical energy.
Renewable hydrogen can be obtained using water as a raw 3.1. Hydrogen production by water dissociation: current strategies
material through processes such as electrolysis, thermolysis, and and advances
photolysis; employing different types of waste as substrates for bio-
photolysis, dark fermentation and photo-fermentation; through A renewable way to obtain hydrogen is the dissociation of water
the reformulation of bio-methane; or by thermochemical pro- (H2O), which is a low cost and abundant raw material on Earth
cessing (Pyrolysis, Gasification, Combustion, Liquefaction) using (Nikolaidis and Poullikkas, 2017; Sattler et al., 2017). Despite the
different types of biomass (Fig. 1). However, approx. 95% of the H2 is environmental advantages of using a renewable raw material and
currently produced from petroleum-derived hydrocarbons (coal, not generating CO2 (Sattler et al., 2017), the process always de-
petroleum, among others) (Jun and Yu, 2018), which is incompat- mands huge energy input (Du and Eisenberg, 2012; Liu et al., 2012).
ible with global sustainability concerns. Among the renewable The source of this energy is highly determinant of the process
technologies, electrolysis is the only used at commercial scale. The sustainability. Three water dissociation routes are currently known:
production of biohydrogen from biomethane reforming is also thermolysis, electrolysis and photo-electrolysis (Table 2).
gaining importance because it uses the same well-stablished Hydrogen production by water dissociation (Thermolysis, Elec-
technology for natural gas reforming (Badoga and Dalai, 2017). trolysis, Photolysis) is one of the most evolved technologies in
In this context and considering the global energy and clime recent years. Between 2000 and 2019, 199 patents in the theme
crisis, the depletion of fossil fuels, the increasing demand and were filed, among which 70% describe electrolysis processes, 27%
men’s dependence on energy, the production of hydrogen from photolysis and 3% thermolysis. Currently, hydrogen production via
agricultural, industrial and agroindustrial biomasses are gaining electrolysis is the only large-scale renewable process.
importance in the last decades (Nikolaidis and Poullikkas, 2017). The countries that filed most patents are China (CN), Japan (JP)
The biological route is considered more environmentally friendly and the United States of America (USA) (Fig. 2). China, for example,
when compared to thermochemical and electrochemical processes filed 78 patents on electrolysis and 34 on photolysis on the last 2
because they require smaller amounts of energy (Lamaison, 2009). decades. In this country, the main companies involved are HEMPEL
Despite renewable hydrogen production has presented enor- HEATING POWER DEV CO LTD®, which works in the area of
mous scientific progress in recent years, the information is diffuse corrosion coating of metals, and WANG S. NANTONG ANSIZHUO
in many research articles and patented technologies. The present NEW ENERGY CO LTD®, a manufacturer of solar panels, photovol-
work aimed to determine the prevailing technical knowledge in taic inverters and electronic equipment. In Japan, the companies
renewable hydrogen of the last 19 years and identify the challenges that most filed patents on water dissociation were TOSHIBA®,
and opportunities for future research. which uses hydrogen in semiconductor manufacturing, HONDA
MOTOR CO LTD®, SUZUKI® and MITSUBISHI CORP®, all focusing on
the use of hydrogen-based fuel cell in the transportation sector.
Other companies focused on gas technology, such as TOKYO GAS CO
LTD®, must also be mentioned. In the United States, PHILIPS® filed
the most patents.

3.1.1. Thermolysis
Direct thermolysis of H2O molecule has an entropy (DS) of 40
units and requires high temperatures and pressures, which are the
main bottlenecks of this technology. Moreover, high costs of
equipment are entangled due to the requirement to withstand with
such process characteristics. Different technologies are thus being
developed so that thermolysis can be carried at lower tempera-
tures. One strategy is to carry the reaction in several steps using
catalysts, but the need of highly corrosive reagents also poses
Fig. 1. Classification of hydrogen production routes from renewable sources. Adapted equipment challenges and possible environmental impacts.
(Nikolaidis and Poullikkas, 2017). (Kasai and Bishop, 1976), have presented a single reaction
2
W.J. Martinez-Burgos, E. de Souza Candeo, A.B. Pedroni Medeiros et al. Journal of Cleaner Production 286 (2021) 124970

Table 1
Keywords used to search the patent database for the period 2000e2019.

Categories Patent Databases

INPI Latipat-Espacenet Derwent Innovation

Thermolysis Termolise e agua Termo
lisis y agua Hydrogen production or thermolysisa and water
Electrolysis Eletrolise e agua
lisis y agua
Electro Electrolysisa and water
Photolysis
lise e agua
Foto
lisis y agua
Foto Photolysisa and water
Dark Fermentation Bio-hidroge ^nio, Bio-hidroge ^nio e bacte

ria Biohidrogeno e bacteria Biohydrogen or bio-hydrogen and bacteria
Photo Fermentation Fotofermentaç~ ao, Fotofermentaç~ ao e bacteria Fotofermentacion y bacteria Photo-fermentationa and biohydrogen or Bio-hydrogen
Bio-photolysis Bio-hidroge ^nio e microalgas Bio-hidro
geno y microalga Biohydrogen or bio-hydrogen and microalgae
Pyrolysis Bio-hidroge ^nio e Piro

lise Bio-hidrogeno e piro
lisis Biohydrogen and Pyrolysisa
Gasification Bio-hidroge ^nio e gaseificaça ~o Bio-hidrogeno y gasificacio
n Biohydrogen and Gasificationa
Combustion Bio-hidroge ^nio e Combust~ ao Bio-hidrogeno y combustio
n Biohydrogen and Combustiona
Liquefaction Bio-hidroge ^nio e liquefaça ~o Bio-hidrogeno y licuefaccio
n Biohydrogen and Liquefactiona
Nanotecnologia Nanotecnologia e produç~ ^nio
ao de hidroge Nanotecnología y produccio
n de hidro

geno Nanoa and hydrogen production
a
Term of truncation.

Table 2
Water dissociation methods for the production of hydrogen.

Thermolysis Electrolysis Photolysis

Theoretical The H2O molecule is dissociated at temperatures ofIt is an electrochemical process that basically It uses photoelectrochemical photon collection
basis approx. 1800
C (Sattler et al., 2017). The yieldconsists of passing continuous electric current systems. The photoelectrodes once exposed and
increases proportionally with the temperature, through two electrodes (Jun and Yu, 2018), where submerged in the aqueous electrolyte generate the
achieving a maximum of 50% at approximately the following reactions occurs: electric energy required for the reaction (1.23 V).
5000
C (Acar and Dincer, 2018). Cathode: 2H2 O /H2 þ 2OH  2e The most common electrodes in the process are
1 made of TiO2, IrO2, RuO2.
Anode: 2OH / O2 þ H2 O þ 2e
2
Advantages Solar energy and different types of biomass can be It is the most effective technique to date, reaching Uses solar (renewable) energy.
used as source of heat to drive the reaction 60% efficiency. Produces O2 as the only reaction
(Bhaskar et al., 2013); (Orfila et al., 2016; Sattler byproduct. Solar energy can be used to boost
et al., 2017). reaction. (Orfila et al., 2016; Sattler et al., 2017).
The effectiveness of the reaction may be increased
by the addition of electrolytes such as salts, alkalis
or acids.
Disadvantages Extremely high-energy demand. It is a reversible Requires high power (Harrison and Levene, 2008). Energy conversion efficiencies between 0.1 and
reaction at low temperature so an effective 1.0% (Juodkazis et al., 2010).
technique to H2 from O2 at high temperature is
crucial. The maximum described efficiency is 40%.
Technological Growing Mature Emerging
maturity

Fig. 2. Major patent filing countries in the field of electrolysis (A). Major patent filing countries in the field of photolysis (B).

system that can achieve entropic exchange for hydrogen produc- added to the medium, resulting in a decrease in the reaction tem-
tion via thermolysis using zeolites. Rehydration of zeolites pro- perature (Equations (1) and (2)).
duces free hydrogen and oxidizes bivalent cations, occurring at
temperatures around 400
C (U.S. Patent No. 3963830). (Kuai-Teng I2 þ SO2 þ 2H2 O/2HIðlÞ þ H2 SO4ðlÞ (1)
and Clarksville, 2007), developed a Raney Nickel Plate Reactor (90%
Nickel and 10% Aluminum) that acted as a catalytic surface to alter 2HIðlÞ / H2ðgÞ þ I2ðlÞ ð200 z 400
CÞ (2)
the energy activation of the reaction. In addition, I2 and SO2 were
3
W.J. Martinez-Burgos, E. de Souza Candeo, A.B. Pedroni Medeiros et al. Journal of Cleaner Production 286 (2021) 124970

Other compounds, such as SO2 and NH3, have also been tested as
catalysts for the dissociation of water. According to (Taylor et al.,
2014) significant amounts of hydrogen via thermolysis can be
produced at low temperatures (Equations (3) and (4)).
SO2 þ 2NH3 þ H2 O/ðNH4 Þ2 SO3 ð25 z 50
CÞ
membranes. The use of hollow fibers has the advantages of
increasing the surface area of the membrane, minimizing the vol-
ume required. The utility model depicted at DE102014012436-B3
focused on the thermal production of hydrogen in several stages
and using self-propagating syntheses of titanium and urotropin at
(3) high temperature (Gleich, 2015).

ðNH4 Þ2 SO3 þ H2 O/ðNH4 Þ2 SO4 þ H2 ð80 z 150
CÞ (4) 3.1.2. Electrolysis

The main advantage of these methods is the significative
reduction of energy demand. On the other hand, dependence of
chemical reagents comes as a disadvantage and their recycling
should be considering to gather sustainability. Table 3 presents the
reactions described in some patents of hydrogen production with
the regeneration and recycling of reagents. Some technologies are
accompanied by the use of solar energy as input energy for
reactions.
Magnesium (Mg) -based compounds, such as the ternary Nd-Ni-
Mg compound (Alasmar et al., 2018), are also being studied as
catalysts for water dissociation, however the yield achieved is as
lower as 8% (Tan et al., 2019). The main advantage of these methods
is the significative reduction of energy demand. On the other hand,
dependence of chemical reagents One of the alternatives to a more
sustainable process is the use of reagent-recycling strategies, such
as those presented in Table 3. Some technologies are accompanied
by the use of solar energy as input energy for reactions.
Other patents focused on the design of reactors. The utility
model US 6521205B1, for example, describes a tubular reactor with
a vortex in which the solar energy is concentrated and the water
molecule dissociated with the help of metallic catalysts (Pt) at
1400
C (Beck, 2003). (Rohrich et al., 2011) presented a reactor with
a thermal gradient controlled for the production of pure hydrogen.
The heating system consists of several concentrators of sunlight.
This utility model, unlike other patents, separates oxygen and
hydrogen in the hot zone using thermal selective membranes,
because isolating the gases in other areas of the bioreactor makes
the process counterproductive as part of the energy is lost (Elkind,
2014). designed a thermal reactor to dissociate the water molecule
and produce hydrogen via thermolysis. The system consisted
mainly of a decomposition camera, a solar energy absorption
mechanism, a concentration element and a set of hollow fiber
Water electrolysis is an oxide reduction reaction that mostly
depends on electric energy (Basile and Iulianelli, 2014) (Equation
(6)) and is currently an industrial-scale method for obtaining
hydrogen.


2H2 O / 2H2ðgÞ þ O2ðgÞ E ¼ 1:23 V (6)
Among the main drawbacks of electrolysis, the use of highly
expensive electro-catalytic metals such as platinum (Yang et al.,
2018), process efficiency (despite it is the highest among ther-
molysis methods), the high demand of energy (Lu et al., 2020) and
the observed corrosion at the cathode (Suguru et al., 2018) must be
highlighted and shows up as opportunities for technology
development.
It was observed that some patented technologies were mainly
focused on the search for materials for the construction of elec-
trodes, conductive materials, etc., because cathodes and anodes
undergo poisoning processes in the reaction (Grigoriev et al., 2020).
Patent WO2008061975A3, for example, describes the preparation
of electrodes, which contain metallic catalysts of cobalt, nickel,
iridium, ruthenium, rhodium, platinum, and their combinations, it
is highlighted that the electrode bases are always cobalt and nickel,
the which are always in a proportion of around 0.7 and 0.92%,
respectively (Bert et al., 2008). (Reece et al., 2011) established that
the electrodes for the production of hydrogen should be composed
of three elements: Molybdenum, Zinc and Nickel with a proportion
that can be in the range between 0.1% and 90% (Bulovic et al., 2012).
Presented an electrode made with Cobalt or Nickel which is resis-
tant to corrosion or poisoning explained by the fact that the metal
species can change to an oxidation state greater than zero at volt-
ages from 0.1 to 10V (Takahashi et al., 2014). Presented a high
durability electrolytic cell working with reverse current due to the
inclusion of a current collector in the cathode chamber, which is

Table 3
Hydrogen production by thermolysis with regenerated and recycled reagents.

Synopsis Pantent number References

Photoreactor using solar energy and metal oxides to dissociate H2O. US2006/0188433 A1 Weimer et al. (2006)
Reactions of ZnO-based process:
1
1. ZnO /Zn þ O2 (Metal oxide decomposition)
2
2. Zn þ H2 O/ZnO þ H2 (H2 liberation)
Process temperature: 1600K
Reactions of Mn2O3/MnO-based process:
1
3. Mn2 O3 /2MnO þ O2 (Metal oxide decomposition)
2
1 1 1
4 MnO þ NaOH /NaMnO2 þ H2 NaMnO2 þ H2 O / Mn2 O3 þ NaOH(Water dissociation)
2 2 2
Process temperature: 1800K
Use of solar energy for H2O decoupling. US8691068 B1 Wood and Offices (2014)
SO2 þ 2NH3 þ H2 O/ðNH4 Þ2 SO3 (Chemical absorption)
ðNH4 Þ2 SO3 þ H2 O/ðNH4 Þ2 SO4 þ H2 (30e80
C) (Solar photocatalytic)
ðNH4 Þ2 SO4 þ MO/2NH3 þ MSO4 þ H2 O (thermocatalysis 400
C)
1
MSO4 /SO2 þ MO þ O2 (thermocatalysis 850e1100
C)
2
Cu-Cl Cycle US2017/0015552 A1 Abdulrahman (2016)
2CuCl þ 2HCl/2CuCl2 þ H2 (100
C)
2CuCl2 þ H2 O /CuOCl2 þ 2HCl(375
C)
1
CuOCl2 /2CuCl þ O2 (530
C)
2

4
W.J. Martinez-Burgos, E. de Souza Candeo, A.B. Pedroni Medeiros et al.
composed of nickel (45e90% w/w) (Yang et al., 2018). Presented a
“cobalt phosphide/nitrogen-doped porous carbon composite cata-
lytic” which guarantees excellent yield and stability at different pHs
(Weizhi et al., 2018). Manufactured CoSe2 nanomaterials with high
catalytic efficiency in the electrolysis reaction. However, despite
advances in different materials for electrocatalysts, they are still
highly costly (Lu et al., 2020). According to (Grigoriev et al., 2020),
the main difference among the different industrial scale technolo-
gies for the production of hydrogen is in the type of electrolyte used
in the cells.
Other inventions are focused on the design of reactors mainly
electrolytic cells for the transportation sector. Patent
US2007138006-A1, one of the most cited patents (65 times) among
the cited in this study, describes a hydrogen generation system for
mobile vehicles composed of a hydrogen generator, high pressure
storage tank (5000 and 10,000 psi) and a vehicle propulsion sys-
tem. The gas is generated via electrolysis and stored, then the
hydrogen flows to the propulsion system (fuel cell) where energy is
generated to propel the vehicle. Utility model EP2221204A1 also
features a vehicle propulsion system which operates on oxyhy-
drogen and an auxiliary electricity generation unit (Jenkins et al.,
2009). (Wold, 2014) showed a “Power Generation System” which
consists mainly of an internal combustion engine, that works with
liquid fuels and hydrogen, where the energy produced is converted
into electricity which is used to dissociate the water molecule
producing hydrogen. According (Sako and Ken, 2019), one of the
main problems of fuel cells was the size and practicality, especially
for small artifacts; in the patent US10364009B2 they presented a
"fuel cell watercraft" designed so that its components fulfill
different functions as the possible solution. In the case, the electric
motor serves as a source of energy and propulsion system, the
electrolytic cell adapted to supply the electrical energy required by
the fuel system propulsion and the dissociation system of the water
molecule, a secondary battery serving as an auxiliary power source
for the fuel cell unit and energy regulation means.
3.1.3. Photolysis
Photolysis consists of the dissociation of the H e O bonds by
photons, which occurs at approx. 190 nm (Furatian and Mohseni,
2018). The photolysis process, as well as thermolysis, requires
chemical catalysts such as zinc oxide (ZnO), tin oxide (SnO), zir-
conium dioxide (ZrO2) and other semiconductor sulfur oxides
(Zhang, 2010) (Equations (7) and (8)). Water photolysis technology
development started in the 1970’s and emerged as a possible so-
lution to mitigate the global and environmental energy crisis.
Nowadays, it presents the major challenges for commercial use
among the water dissociation technologies. Generally, patented
technologies in this area use transparent materials for harnessing
sunlight. However, some types of catalysts such as the europium
and platinum salts used in photo-oxidation and recombination are
also required (Fletche and Ryason, 1977), which are expensive.
MoxZþ þ H2 O /MoxðZþ1Þ þ H þ OH
2H /H2
(Nocera et al., 2010) presented a photoanode (photoactive
electrode, ionic metal species, and a catalytic material) that when
exposed to the sun transports excited electrons to the semi-
conductor, where they react with water and generates H2 and O2.
The major advantage is the independence of transparent reactors.
Other invention presents catalysts composed of TiO2 (75e98%;) C
(1.0e20%) and C (0e10%) that have showed high activity in the
visible range (400e620 nm) reaching production efficiency of
100 mmol g1 h1 (Zhang, 2010). Another hot topic is the
Journal of Cleaner Production 286 (2021) 124970
development of different photo-catalyst polymers, such as
graphitic carbon nitride (g-C3N4) (Yaping et al., 2020), carbon
nitrate-based compound similar to graphite (g-C) (Chengqun et al.,
2020), Cu-TiO2 B12 (Wei et al., 2020), perovskite (LaNiO3) (Zhaoyu
et al., 2020).
3.2. Bio-based hydrogen production processes: strategies and
patented advances
Reduce pollution, encourage material reuse, harness waste and
effluents, foster circular savings, usage of environmentally friendly
processes and systems are some of the motivations behind the
production of hydrogen through biological processes. Despite the
current limitations for commercial production, the biological
pathway is considered one of the most promising alternatives to
meet future energy vector demands (Guo et al., 2010) especially
due to the diversity of raw materials that could be processed and
microorganisms that can be used as bioH2 biofactories (Adenike,
2018). Organisms such as microalgae, cyanobacteria, fermentative
bacteria, and photosynthetic bacteria can produce bioH2 through
different metabolic pathways (Cai and Wang, 2016), presenting
different yields and productivities. Unlike the water dissociation
processes, bioH2 production does not require high amounts of en-
ergy because occurs at ambient temperature and pressure (Afzal
et al., 2017).
3.2.1. Dark fermentation
The dark fermentation has been considered one of the best al-
ternatives among the biological routes (Wong et al., 2014) because
it utilizes simple process configuration, traditional fermentation
equipment, lowest energy demand in comparison to other biolog-
ical, chemical and conventional processes (Jarunglumlert et al.,
2018) and can be carried using a wide variability of renewable
substrates (Table 4) including domestic and industrial agro-
industrial effluents (Chairattanamanokorn et al., 2009; Wong
et al., 2014). When effluents are used as a substrate, bioH2 pro-
duction results in a decrease in the effluent Chemical Demand of
Oxygen (COD) (Prazeres et al., 2012; Wong et al., 2014) associated
with CO2 evolution and the production of short chain organic acids
(C1-C7).
Despite at commercial scale it is preferred that bioH2 production
via dark fermentation occurs continuously, the batch process is the
most described in the scientific literature. It occurs in several steps:
(i) substrate suitability, which involves the removal of larger par-
ticles, particle size reduction and/or hydrolysis (chemical, physical
or enzymatic); (ii) supplementation with micro and macronutri-
ents, followed by pH adjustment, oxygen purge using inert gases
(N2, Ar or CO2) and sterilization; (iii) inoculation (5e20% v/v) and
control of culture conditions (pH, temperature, agitation). The
development of stable and reproductible batch process using
wastes is an important step towards the great challenge of the
continuous process: achieving long-period stable H2 production
(7) using non-sterilized substrates and stable microbial consortia.
3.2.2. Photosynthetic processes
(8)
BioH2 can also be produced by photosynthetic processes using
organisms such as photosynthetic bacteria, macro and microalgae,
and cyanobacteria. Biophotolysis occurs in the presence of inor-
ganic CO2 and photons (Dolly et al., 2015), resulting in the con-
version of protons (Hþ) to H2 by the action of enzymatic complexes
(hydrogenases and nitrogenases). Light intensity directly influences
biophotolysis and should be properly balanced (Rashid et al., 2013),
which is not an easy task when considering the use of natural light;
while using artificial light results in great economic impacts. It is
noteworthy that microalgae and cyanobacteria have high efficiency
5
W.J. Martinez-Burgos, E. de Souza Candeo, A.B. Pedroni Medeiros et al.
Table 4
Substrates for bioH2 production via dark fermentation.
Substrate Yield
Cassava processing 4.12mol H2 molmaltose
wastewater
Vinasse wastewater 13.5 molH2 m3day1 with H2 content of Albanez et al. (2016)
39%
Slaughterhouse effluent 149 mLH2 g1SSV
Palm oil mill effluent 5980 mLH2 L1
Dairy wastewater 0.113 molH2 g1
COD
Molasses 26.13 molH2 kg1
COD
in solar energy conversion (Sengmee et al., 2017), which is bio-
transformed into biomass and hydrogen (Mun ~ oz and Gonzalez-
Fernandez, 2017; Skjånes et al., 2013).
Hydrogenases are metalloenzymes, enzymes whose active sites
contains metal (Meyer, 2007). Three groups of hydrogenasses are
known: [Fe-Fe]- hydrogenases, [Ni-Fe]- hydrogenases and [Fe]-
hydrogenases (Khetkorn W, Rastogi R, Incharoensakdi A, Lindblad
P, Madamwar D, Pandey A, 2017; Kim and Kim, 2011; Meyer, 2007).
Ni-Fe-hydrogenases function bidirectionally (Equation (9)) and is
usually present in cyanobacteria (Tamagnini et al., 2007). In the
particular case of cyanobacteria, bioH2 can also be produced using
other enzymatic consortia called nitrogenase (Carrieri et al., 2011),
that convert N2 to ammonia and hydrogen, however, this reaction is
energetically inefficient (Rashid et al., 2013). Fe-hydrogenases
cannot catalyze the reversible reaction and therefore generally
have greater efficiency (Kim and Kim, 2011; Sundararajan and
Hilllier, 2013; Yang and Hall, 2008).
hidrogenase
2Hþ þ 2e 4 H2
Microalgae represent one of the most promising microbial
classes in bioH2 generation. Different species have been studied,
especially Chlorella vulgaris, Chlorella protothecoides (Sengmee
et al., 2017), Chlamydomonas reinhardtii (Kosourov et al., 2002;
Markov et al., 2006), Dunaliella tertiolecta (Lakaniemi et al., 2011),
Nannochloropsis ocea ^nica (Xia et al., 2013). Among these Chlamy-
domonas reinhardtii, is widely recognized as a potential strain
whose ability to produce H2 is derived from a enzymatic activity
that is generally 10e100 higher than other species (Amaro et al.,
2013).
Microalgae-based bioH2 production requires anaerobic condi-
tions and sulfur limitation (Sengmee et al., 2017). Anaerobic con-
ditions are necessary due to the high sensitivity of enzymes to
oxygen, while sulfur generates reversible respiration inhibition due
to the impedance of protein biosynthesis and is considered one of
the variables that most affect bioH2 production (Rashid et al., 2011).
The production of bioH2 by microalgae is usually carried out in
two steps (Fig. 3). The first aims cells multiplication and the accu-
mulation of organic compounds by culturing the microalga in a
nutrient-rich medium for 8e72 h (Rashid et al., 2013). In the second
step the microalgae biomass is then recovered, washed to remove
adhered nutrients and inoculated in a sulfur-free medium usually
supplemented with an organic carbon source under anaerobic
conditions. At this condition the stored compounds are degraded,
hydrogenases are induced and the BioH2 production occurs.
The scientific literature is vast on bioH2 production from
microalgae. Studies differ on the species of microalga used,
nutrient-rich medium composition, process parameters (mainly
Journal of Cleaner Production 286 (2021) 124970
Reference Substrate Yield Reference
Martinez-Burgos et al. Galactose 2.23 molH2 Xia et al. (2016)
(2020) mol1
galactose
Potatoes wastes, 126.4e252.7 mLH2 Salem et al. (2018)
g
1
TVS
Boni et al. (2013) Bean wastes 93.0e152.1 mLH2
g1
TVS
Norfadilah et al. (2016) Corncob 102.62 mLH2 g1
ST Tandon et al.
(2018a)
Wong et al. (2018) Rice bran and de-oiled rice 545 ± 5 ml H2 L1 Tandon et al., 2018
bran
Bundhoo (2017a) Sweet potato starch 3501 mLH2 L1 Vi et al. (2017)
(26.73 g L1)
temperature and pH) and the external carbon source added (type,
source and quantity). Productivities vary significantly, from
24 ml L1 h1 (Rashid et al., 2013) to 238 ml L1 h1 (Song et al.,
2011).
Considering that even the best productivities are significantly
low, metabolic and genetic engineering have emerged as alterna-
tives to improve bioH2 production using microalgae. Different
strategies are being evaluated (Lindberg et al., 2002). inactivated
the hupL gene encoding a large subunit of the hydrogenase enzyme
in the Nostoc punctiform strain ATCC 29133 and obtained a bioH2
production rate of 14 ± 3.5 nmol H2 (mgChla)1 h1. Other emerging
strategy is to modify the nitrate assimilation pathway, which is a
competitive pathway that can limit the flow of electrons to the
hydrogenase enzyme and thereby decrease hydrogen production
(Baebprasert et al., 2011). increased bioH2 production by redirect-
ing electron supply via the nitrate assimilation pathway using ge-
netic engineering techniques, reaching maximum bioH2 rates of
0.143 nmol H2 (mgChla)1 h1 and 0.186 nmol H2 (mgChla)1 h1 for
nitrate and nitrite reductase modified strains, respectively
(9) (Baebprasert et al., 2011). used the same strategy in Synechocystis
sp. PCC 6803 and achieved >15x higher H2 production (200 versus
13 nmol H2 (mgChla) 1 h 1).
3.2.3. Microbial hydrogen production patents
Different technologies have been patented for bioH2 production
using bacteria and microalgae. Between 2000 and 2010, 115 patents
were filed (Olivo et al., 2011), especially by China, Japan, the Re-
public of Korea, United State and EU. Approx. 80% were filed be-
tween 2005 and 2009, what can be attributed to the 2003e2008
energy crisis.
Between 2011 and 2019, another 86 patents related to bioH2
production were filed. These can be grouped into two large groups
according to the World Intellectual Property Organization (WIPO)
classification: approx. 72% belong to “Fermentation processes or
processes that use enzymes to synthesize a desired chemical
composition or compound or to separate optical isomers from a
racemic mixture” (C12P) and 13% to “Enzyme or microbiology
apparatus” (C12M). The remaining 15% included “Water, sewage,
sewage or sludge treatment” (C02F), “Solid Waste Disposal” (B09B),
and other classifications. Approximately 60% of the deposits were
made by universities or research institutes.
The most representative countries were China, the US and
Moldova (Fig. 4). It is noteworthy that China and the US are also
among those that have filed most patents for electrolysis and
photolysis (Fig. 2), thus standing out as world leaders in the
development of new hydrogen production technologies.
The production of biohydrogen (bacteria and microalgae) is a
technology under development. The increasing number of patents
6
W.J. Martinez-Burgos, E. de Souza Candeo, A.B. Pedroni Medeiros et al.
Fig. 3. Representative scheme of bioH2 production from microalgae.
Fig. 4. Major patent-filing countries related to bioH2 production biologically (using
bacteria and microalgae).
reflects the significant environmental advantages when compared
to the production from fossil sources, mainly due to the use of
renewable sources such as industrial, agro-industrial and agrofor-
estry wastes. However, reaching commercial scale depends on
overcoming economic aspects. However, no clear route of devel-
opment in the last 19 years could be identified.
(Guangyu et al., 2004) presented a continuous process using
agro-industrial effluents under anaerobic conditions and using
bacteria as an inoculum. The focus of the invention is the treatment
of wastewater. The process conditions must be maintained in the
following ranges: temperature (25e35
C), COD (1000 and 150,000
mgO2/L), and the retention time (2 and 4 months). According to the
inventors, a flow of 1680 L/day of brewery effluent (COD:
12500 mg/L) could produce 4.0 m3/day of biohydrogen at 34
C.
Some patents describes heat-treatment to enrich the natural
hydrogen-producing bacteria (HPB) in wastewaters. (Lin et al.,
2006), for example, achieved stable H2 production by heat-
treating sewage and food factories wastewaters at 80e120
C for
7
Journal of Cleaner Production 286 (2021) 124970
20e60 min, while pharmaceutical industries’ wastewaters were
treated at 40e70
C for 10e20 min.
Despite wastewaters are mostly studied, solid organic wastes
can also be converted into biohydrogen. Patent US7083956B2
presents a two-step process carried out in two bioreactors; the first
was a acidogenic reactor fed with liquid effluents and at least one
solid biodegradable residue, and the second contained semi-
permeable microfibers where bioH2 producing bacteria producing
forms a biofilm (Lin et al., 2006). The growth of methanogenic
bacteria was inhibited initially by the addition of bromoethane
sulfonic acid (BSC) and then by using retention time of the second
bioreactor between 1 and 2 days.
Microalgae processes have also been patented (Wei et al., 2009).
used the microalgae Platymonas subcordiformis cultured in a pho-
tobioreactor on Kangweifang Medium supplemented with CO2
(0.03e30%), under anaerobic condition. After inoculation
(1106 cell/ml), the bioreactor was kept in the dark for 4e24 h fol-
lowed by the addition of carbonyl cyanide m-chlorophenylhy-
drazone 5e25 mM. Subsequently, it was subjected to a luminous
intensity of 4000e6000 Lux, resulting in continuous bioH2
production.
Utility models for biohydrogen production are not common. In
patent WO2009034439A2 a fluid bed bioreactor for the production
of hydrogen that could be operated in mesophilic and thermophilic
conditions is described. The bioreactor consisted of two coupled
reactors, the primary being inside the secondary and at the base of
the primary, there was a fixed bed of bacteria producing bio-
hydrogen (Gray, 2009).
Potentially hydrogen-producing strains such as Halanaerobium
sapolanicus (US20110136196A1) have also been patented. This
strain can ferment cellulosic biomass to produce hydrogen at
alkaline conditions (pH ¼ 10) (Elias et al., 2011). (Mingjun and
Binbin, 2016) patented a strain of Thermoanaerobacterium thermo-
saccharolyticum (CN106635887A), which can easily ferment pen-
toses and hexoses in acidic media, which is advantageous when
lignocellulosic materials are pre-treated by acid hydrolysis.
3.2.4. Strategies to maximize bioH2 production and overcome
economic barriers
BioH2 yields described in the scientific literature are up to 90% of
the theoretical maximum (Sydney et al., 2014). However, frequently
wastewater containing media are supplemented with pure
W.J. Martinez-Burgos, E. de Souza Candeo, A.B. Pedroni Medeiros et al.
reagents (salts, carbon sources, nitrogen sources), which makes
industrial scale production unfeasible (Yokoi et al., 2002). Different
pretreatment strategies have been developed to improve yields,
involving actions at the level of microorganisms or substrates. Ac-
cording to (Chang et al., 2011), the enrichment of HPB, is one of the
variables that most affect bioH2 production. Therefore, when
working with microbial consortia, the identification of the micro-
bial community is a variable that must be fully known and adjusted
to improve the desired product yield (Liu et al., 2009).
The bioH2 producing microorganisms are the most varied and
the main ones usually grow in pH in the range between 4.0 and 7.0.
Regarding temperature, dark fermentation can be developed by
psychophilic (20e30
C), mesophilic (30e40
C) thermophilic
(45e65
C) and hyperthermophiles and extreme thermophiles
>65
C. Thus (Guzma
n et al., 2016), achieved a maximum yield of
1.7 mol H2 mol1glucose using a Polaromonas rhizosphaerae, psy-
chrophilic strain (Baghchehsaraee et al., 2010). achieved yields of
2.18 and 1.25 mol H2 mol1glucose using sludge as inoculum under
mesophilic (37
C) and thermophilic (5
C) conditions, respectively.
Finally (Eriksen et al., 2009), achieved a yield of 2.4 ± 0.3 mol H2
mol1glucose using an extreme thermophile (Thermotoga neapoli-
tana DSM 4359) strain at 80
C. Some bioH2-producing bacteria
such as Halanaerobium sapolanicus, Thermoanaerobacterium ther-
mosaccharolyticum MJ1 form part of patent applications. From an
industrial point of view, it is more interesting to work with meso-
philic microorganisms in the production of bioH2, because working
at high temperatures leads to excessive energy costs, as well as
more sophisticated equipment made from more resistant materials.
In addition, the best yields have been obtained in this temperature
condition. Examples of some hydrogen-producing bacteria are
presented in Fig. 5.
The main drawback in the use of microbial consortia is the
Fig. 5. Examples of psychophilic, mesophilic and thermophilic bacteria associated to
hydrogen production. Adapted from: (Cheng and Zhu, 2013); (Nguyen et al., 2010)
(Ivanova et al., 2009) (Talluri et al., 2013) (Keskin et al., 2018) (Baghchehsaraee et al.,
2010) (O-Thong et al., 2011) (Ferraz Júnior et al., 2015) (Ferraz Júnior et al., 2015);
(Junior et al., 2014); (Thungklin et al., 2011) (Azman et al., 2016) (Garcıa-Depraect et al.,
2016) (Seifert et al., 2010); (Tosuner et al., 2018) (Patel et al., 2016) (Estevam et al.,
2018) (Xiao et al., 2013) (Alvarado-Cuevas et al., 2015) (Cisneros de la Cueva et al.,
2018) (Guzm
an et al., 2016); (Chou et al., 2007) (Eriksen et al., 2009) (Eriksen et al.,
2009) (Soboh et al., 2004); (Kanai et al., 2005).
8
Journal of Cleaner Production 286 (2021) 124970
presence of methanogens, homoacetogens, and sulfate-reducing
bacteria, which use the hydrogen present in the medium to
obtain their energy, thus affecting the final hydrogen yield in the
process (Cai et al., 2004; Chang et al., 2011; Chenlin and Herbert,
2007). Physicochemical pretreatments in the inoculum have been
evaluated to improve bioH2 yield. The main feature explored in
these processes is the ability of many hydrogen-producing bacteria
(HPB) to sporulate under adverse conditions, while hydrogen-
consuming bacteria (HCB) are unable to produce spores.
Heat treatment of sludge and other inoculum sources for bioH2
production processes is the most common strategy, especially for
simplicity of operation and avoidance of the use of toxic chemicals.
The most effective heat treatments uses high temperatures
(approximately 100
C) combined with short exposure times
(approximately 10 and 25 min) or low temperatures (approxi-
mately 60
C) and long times (approximately 30 and 45 min) (Wong
et al., 2014). Increased production of bioH2 up to 2e5 times relative
to the control are described (Baghchehsaraee et al., 2008); (Chang
et al., 2011) (Fig. 6). At commercial continuous biohydrogen pro-
duction the heat-treatment of the substrate is an important pre-
treatment to guarantee the absence of methanogens and sulfate-
reducing bacteria.
Other physical pretreatments have been also studied, such as
ultrasonication, ultraviolet radiation, and aeration (Fig. 6), however
they are less effective and non-selective. Ultrasound frequencies
above 20,000 Hz results in the destruction of HCB and HPB.
Nonetheless, it is necessary to control the intensity and time (be-
tween 20 and 30 min) to keep HPB alive (Elbeshbishy et al., 2010;
Wang et al., 2010). It was found that this treatment could improve
hydrogen production on average 2.2 times. Nevertheless, according
to (Xiao and Liu, 2009) ultrasonic treatment might not even inhibit
methanogenic bacteria.
Ultraviolet (UV) irradiation is another physical method for the
enrichment of HPB. UV also affect BPH, thus controlling exposure
time is important and should not exceed 15 min (Wang et al., 2010).
improved hydrogen production by 39% using as a inoculum sludge
irradiated for 15 min with UV light (25W). Another physical method
evaluated for the enrichment of HPB is aeration for 12e24 h (Ren
et al., 2008; Wang et al., 2010). This generates oxidative stress on
microorganisms causing the destruction of non-sporulating
anaerobic strict microorganisms (such as methanogens). This
strategy could improve bioH2 production up to two times with
respect to the untreated inoculum (Fig. 6). However, some authors
have not observed an improvement of bioH2 productivity using this
method (Zhu and Be
land, 2006).
Chemical methods are also used for HPB enrichment. Among
these, pH shocks and the use of toxic chemicals such as
Fig. 6. Effect of different inoculum treatments (thermal, sonification, aeration, acid or
alkaline) in biohydrogen productivity. Adapted from: (Elbeshbishy et al., 2010); (Wang
et al., 2010); (Xiao and Liu, 2009); (Chang et al., 2011) (Wan et al., 2013); (Rafieenia
et al., 2018) (Wang and Wan, 2008) (Chang et al., 2011) (Elbeshbishy et al., 2010)
(Liu et al., 2009); (O-Thong et al., 2009); (Chang et al., 2011); (Wang et al., 2012)
(Chenlin and Herbert, 2007) (Baghchehsaraee et al., 2008).
W.J. Martinez-Burgos, E. de Souza Candeo, A.B. Pedroni Medeiros et al.
iodopropane (Zhu and Be
land, 2006), chloroform (Mohammadi
et al., 2011) and 2-bromoethanesulfonate (Zhu and Be
land, 2006)
are most commonly used. Comparing the physical and chemical
methods, the latter use longer times. Acid treatments, for example,
should be performed for 24 h at a pH range of 3.0e4.0. In general,
the choice of a treatment for the enrichment of HPB depends
directly on the physiology of microorganisms to promote the
necessary selectivity. Inducing HPB sporulation by heat and pH
shocks are the most efficient treatments described in the literature.
Effective biological conversion of effluents, waste or biomass to
bioH2 largely depends on the availability of nutrients. Generally, the
substrates need to be enriched with micro or macronutrients or be
previously treated for their transformation by different microor-
ganisms (Sun and Cheng, 2002; Teli et al., 2014). Trace metal ions
(Iron, Nickel, Zinc, Cobalt, Copper, Manganese, among others) affect
metabolic pathways (Lee et al., 2009) and are important for mi-
crobial growth, improving enzymatic and co-enzymatic activity
(Khan et al., 2018), especially the activity of hydrogenases (Wang
and Wan, 2008; Yang and Shen, 2006). (Lee et al., 2009) showed
that FeSO4 supplementation (6.6e21 mg/L) improved bioH2 pro-
ductivity between 2.2 and 2.7 times compared to control, similar to
(Yang and Shen, 2006) which achieved an yield increase of 2.6
times using 200 mgFeSO4 L1. Nevertheless, high concentrations of
these metal ions may also inhibit biogas production. According (Bao
et al., 2013), Mg is an enzyme activator and cofactor of the enzymes
involved in bioH2 production which when used at concentrations
above 20 ppm (Mg þ2) suppresses bioH2 production. A similar effect
was observed with Naþ and Caþ2 ions, which with concentrations
above 2000 and 100 ppm respectively, cease bioH2 production
(Bundhoo and Mohee, 2016). (Gou et al., 2015) observed an increase
in bioH2 production using 0.6 ppm Niþ2, but the opposite effect
when the concentration was increased to 1.8 and 9.0 ppm. The
addition of these compounds re undoubtedly efficient, but should
be analyzed case by case.
Substrate mechanical (grinding, screening), chemicals (acids
and alkalis etc.), physical (microwave, ultrasound irradiations),
biological and enzymatic pre-treatment, or their combination, can
also be used to improve the yield of bioH2 (Nasirian et al., 2011).
Mechanical pretreatments do not chemically alter the nature of the
sample, only reduce the size of the substrate, increase the surface
area, the porosity of the bed, thus providing greater reactivity (De
Vrije et al., 2002). The substrates that require the most pre-
treatments are those of lignocellulosic origin (Fan et al., 2006).
These materials are attractive residues for bioH2 production due to
their low cost, high availability (220 million tons year1) (Kumar
et al., 2015), renewable origin and currently underused (Łukajtis
et al., 2018), besides having great energy content. In this case,
bioH2 is mainly generated from cellulose and hemicellulose that
need to be hydrolyzed to fermentable sugars (Wu et al., 2013a). The
different pretreatments aim to decompose the structure of lignin,
increasing the access to cellulose and decreasing the crystallinity of
the structure (Alvira et al., 2010), thereby optimizing the accessi-
bility of microbial enzymes (Alvira et al., 2010). Microwave (MW)
and ultrasound irradiations (UI) have also been used for the treat-
ment of lignocellulosic substrates, resulting in the decomposition
of cellulose chains, making them more biodegradable. Some au-
thors indicate that the physical treatments should be employed in
combination with chemical or enzymatic (Fan et al., 2006).
(Bundhoo, 2017b), for example, used MW and UI as sole pre-
treatments (0e6946 kJ kg1 solids) and did not observed an in-
crease in bioH2 production.
Chemical treatments include acid (sulfuric, hydrochloric, acetic,
phosphoric and nitric) (Monlau et al., 2013), alkaline (sodium,
calcium, potassium and ammonium hydroxides (Panagiotopoulos
et al., 2010)) and highly oxidizing agents (ozone, hydrogen
9
Journal of Cleaner Production 286 (2021) 124970
peroxide) (Wu et al., 2013a). Generally, these pretreatments of
lignocellulosic materials are made at high temperatures
(120e180
C) between 30 and 90 min (Alvira et al., 2010). As a
consequence, undesirable fermentation inhibiting compounds such
as furfural and 5-hydroxymethylfurfural can be generated (Saha
et al., 2005).
Ozone pretreatment comes as an alternative, with encouraging
results. The main advantage of using ozone is that it does not
generate toxic waste, as with acid and alkaline treatments. Also,
ozone treatments are conducted at ambient pressure and temper-
ature and do not generate inhibitory compounds that affect mi-
croorganisms (Wu et al., 2013b). increased hydrogen production by
0.99, 1.33, 1.66 and 0.94 times by treating ozone barley straw for 15,
30, 45 and 90 min, respectively (Tanikkul et al., 2018). Performed
the Palm oil mill effluent treatment and also observed improve-
ment in yields and production rates of bioH2.
3.3. Hydrogen production by thermochemical processes:
technological advances
Hydrogen can also be produced from thermochemical processes
employing different types of biomass. Thermochemical technology
mainly involves the following processes: pyrolysis, gasification,
combustion, and liquefaction (Nikolaidis and Poullikkas, 2017)
(Table 5). The first two mainly produce CO2, carbon monoxide (CO)
and CH4, the latter, as above, is later converted to hydrogen by
processes such as steam reforming, partial oxidation, autothermal
reforming, etc.
Between 2000 and 2019, 209 patents were filed in the area of
hydrogen production by thermochemical processes. The main
holders of these technologies are China, Japan, and the United
States with 65%, 12% and 9% respectively (Fig. 7A). On the other
hand, according to WIPO patents are grouped into three large
groups (Fig. 7B): “Production of carbon monoxide and hydrogen
containing gases” (C10J3), “Hydrogen; Gaseous mixtures contain-
ing hydrogen; Separation of hydrogen from gas mixtures contain-
ing it” (C01B3) and “Destructive distillation, specially adapted for
certain solid or special solid raw materials” (C10B53).
Among the main patents’ depositor companies are MITSUBISHI,
CHEVRON®, PHILLIPS Company®, NIPPON STEEL CORP®.
Notwithstanding, the largest number of patents of thermochemical
processes was carried out by universities and research institutes.
Different from the other technologies discussed in this work,
patents in the area of thermochemical processes are generally
mixed processes that involves more than one thermochemical
process. Pyrolysis and gasification are commonly used together and
associated with combustion. (Lightner, 2002), for example, pre-
sented a hydrogen production method using a gasification process
combined with a combustion process using biomass. After com-
plete combustion, the gas mixture was reformed to H2 and CO using
catalysts. Among the main novelties of the method is the fact that
the combustion heat was used in the process of reforming the gases
stands out (Rongfeng et al., 2007). have developed a method and a
device for the production of hydrogen-rich biogas from biomass.
Initially, the biomass is processed in pyrogenic decomposition
(350e650
C) in a drum-type reactor and then gasified, achieving a
gasification efficiency of more than 80%.
(Xueli et al., 2007) patented the production of a hydrogen-rich
gas (12e50%) using pyrolysis (300e500
C) at low pressures
(0.3e3.5 MPa) and gasification. The device of this invention com-
prises a sprayer, a moisture eliminator, low-temperature pyroge-
nation stove, ball mill, airflow bed gasification oven, and oil-gas
separator (Min et al., 2014). Presented a high efficiency combined
cycle device for the production of energy from biomass and CO2
separation that can also be operated at low pressures and can
W.J. Martinez-Burgos, E. de Souza Candeo, A.B. Pedroni Medeiros et al. Journal of Cleaner Production 286 (2021) 124970

Table 5
Thermochemical technologies to produce hydrogen from biomass.

Pyrolysis Gasification Combustion Liquefaction

Theoretical The organic matter is
basis decomposed at high
temperatures (500e1400
C) in
oxygen-free environments
(Zhiznin et al., 2019)
Advantages Economically competitive with
a valued by-product that can be
easily transported.
Disadvantages Greenhouse gas production
Technological Mature
maturity
Biomass is converted into a
gaseous fuel at temperatures
between 500 and 1400
C and
pressure up to 33 bars (Iribarren
et al., 2014)
Yield better than pyrolysis.
Sensitive to variations in
production parameters
(temperature, pressure, particle
size)
Mature
The chemical reaction that occurs It is the conversion of a substance in the
between oxygen and an oxidizable gaseous state to the liquid state. Usually
material, which is accompanied by the using alkaline, salt or Ni catalysts (Maldas
release of energy (Meier and Faix, and Shiraishi, 1997; Minowa et al., 1998)
1999).
Releases a lot of thermal energy Very efficient for transportation
Low performance, emit environmentally polluting by-products and pressure
regulation in the operating system is difficult
Decline

Fig. 7. Distribution of countries participation in patents filed in the area of hydrogen production by thermochemical processes (A). WIPO classification of the referred patents (B).

effectively reducing the discharge of greenhouse gas. The biomass
is fed to a pyrolysis system that produces bio-oil and biogas, a
chemical chain manufacturing system is then used for the separa-
tion of the CO2 from H2, which is in turn directed to a solid oxide
fuel battery. The gas that does not react with the battery system is
burned in a burning chamber, generating electricity.
Because energy demand in thermolysis is very high, different
strategies to save and recycle energy where patented in the last
years. (Rolf, 2011) presented a utility model composed of pyrolysis
chamber and a recombination chamber where heat exchangers
allow energy recycling. Another novelty was presented by
(Stolyarevsky, 2015) and consisted of a fluidized bed pyrolytic
equipment where the heat is produced by a flow of overheated
steam that used the energy of the gases which reduces the energy
consumption in the process. (Yimeng, 2018) patented a device that
has a solar energy unit that produces electricity and a thermal
chemistry unit for the production of hydrogen from biomass via
pyrolysis and gasification. Also, the system contains a hydrogen
storage unit and an electrolytic cell that guarantees the temporary
production of energy also in the absence of sunlight.
Today, traditional hydrogen production methods from natural
gas reforming, such as steam reforming, partial oxidation, auto-
thermal reforming, and hydrocarbon pyrolysis, have gained
particular attention as they are well-known techniques that can
also be used for hydrogen production using biomethane (bio-CH4).
Bio-CH4 is obtained by anaerobic digestion of several types of
substrates (Martins and Vessoni, 2009; Rick et al., 2013) and is an
established commercial technology (Patterson et al., 2013). It is
expected that biomethane reforming to be a dominant bio-
10
hydrogen production technology in the medium-term.
3.4. Nanotechnologies applied to hydrogen production
In order to optimize some aspects related to hydrogen produc-
tion and thereby obtain higher gas concentrations, nanotechnology
has been introduced in several bioH2 production routes. In dark
fermentation, for example, there is the application of organic and
inorganic nanoparticles (such as metals and oxides) to the biore-
actor material. The addition of nanoparticles to biomaterials have
presented positive effects on hydrogen production rate and yield,
investment capital and other essential parameters (Kumar et al.,
2019; Pugazhendhi et al., 2019).
Within the scope of nanomaterials, there is the development of
materials with nanostructures based on magnesium or carbon.
These materials can be applied to the development of structures
capable of efficiently storing hydrogen by sorption processes to
develop low-cost storage forms and thus consolidate the technol-
ogy and use of hydrogen as fuel (Shao et al., 2012). An example of
such a feat is patent RU2296046-C1 which deals with the manu-
facture of carbon nanotubes for hydrogen storage and transport.
Metallic nanoparticles also serve as enzymatic cofactors,
increasing the metabolic activity of the microorganisms that make
up the bioH2-producing microbiota and, besides, they optimize the
transfer of electrons in the microorganisms, providing protons that
then arrange themselves in bioH2. In hydrogen production by
photofermentation, nanotechnology is employed to minimize
photocorrosion occurring in semiconductor materials, especially in
anodizing processes with inert metal nanodevices and using UV
W.J. Martinez-Burgos, E. de Souza Candeo, A.B. Pedroni Medeiros et al.
irradiation adsorbent metal oxides (Taylor et al., 2019). Another
strategy is to optimize the visible light absorption capacity by the
addition of photocatalysts nanoparticles such as zinc (ZnS) and
graphitic carbon nitride. The nanoparticles in this system promote
a localized surface plasmon resonance effect (LSPR) that favors free
electron oscillation by the formation of various induced dipoles and
thus allows the system to increase the light absorbance capacity of
the system (Reddy et al., 2019; Xu et al., 2019).
A total of 224 patents related to the application of nanotech-
nology to hydrogen production were filed between 2000 and 2019.
Approx. 81% were filed by China, 4% by the United States and 3% by
Russia, the other 12% were filed mainly by Germany, Japan, Brazil,
Mexico and others. The patents deal mainly with the development
of electrodes, anodes and other nanostructured materials for
hydrogen production by dissociation of the water molecule or
photovoltaic processes, but aa considerable number of patents
describing the development of photocatalysts were also found. The
development of nanotechnologies in the production of hydrogen is
recent, and the real impact of nanotechnologies in the production
of hydrogen is probably one of the greatest expectations of the
coming years.
4. Conclusions
The compatibility of current modes with the need to preserve
the environment will certainly involve the widespread use of
hydrogen and the technological advances in this regard have been
significant over the past 20 years. Waster dissociation is the main
commercial technology for hydrogen production nowadays. Major
advances in the field were directed towards new resistant and less
expensive materials for electrodes (electrolysis) and the search for
new catalysts to operate at low temperatures and pressures
(photolysis and thermolysis). In the case of microbial hydrogen
production technologies, which is considered the most environ-
mentally friendly technology, no trend was identified. Patents de-
posits in this field is still dominated by universities and research
institutes, which indicates that there is a long way down its
commercialization. Finally, patents of thermochemical processes
focused mainly on efficient use of the spent energy by the combi-
nation of energy producing technologies, especially pyrolysis. In
relation to greener hydrogen production, the use of more efficient
materials and the efficient use of renewable energy is believed to
deserve efforts in the short-term.
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.
Acknowledgement
This work was supported by CNPq (Brazilian National Council
for Scientific and Technological Development) and CAPES (Coor-
dination for Improvement of Higher Education Personnel in Brazil).
References
Abdulrahman, M.W., 2016. Direct Contact Heat Transfer in the Thermolysis Reactor
of Hydrogen Production Cu-Cl Cycle. US patent 2017/0015552 A1 1..
Acar, C., Dincer, I., 2018. 3.1 Hydrogen Production. https://doi.org/10.1016/B978-0-
12-809597-3.00304-7.
Adenike, A., 2018. Role of microorganisms in achieving the sustainable develop-
ment goals. J. Clean. Prod. 182.
Afzal, I., Shahid, A., Ibrahim, M., Liu, T., Nawaz, M., Mehmood, M.A., 2017. Micro-
algae: A Promising Feedstock for Energy and High-Value Products, Algae Based
Polymers, Blends, and Composites: Chemistry, Biotechnology and Materials
11
Journal of Cleaner Production 286 (2021) 124970
Science. Elsevier. https://doi.org/10.1016/B978-0-12-812360-7.00003-3.
Alasmar, E., Awad, A.S., Hachem, D., Tayeh, T., Nakhl, M., Zakhour, M., Gaudin, E.,
Bobet, J.L., 2018. Hydrogen generation from Nd-Ni-Mg system by hydrolysis
reaction. J. Alloys Compd. 740, 52e60. https://doi.org/10.1016/
j.jallcom.2017.12.305.
Albanez, R., Lovato, G., Zaiat, M., Ratusznei, S.M., Rodrigues, J.A.D., 2016. Optimi-
zation, metabolic pathways modeling and scale-up estimative of an AnSBBR
applied to biohydrogen production by co-digestion of vinasse and molasses. Int.
J. Hydrogen Energy 41, 20473e20484. https://doi.org/10.1016/
j.ijhydene.2016.08.145.
Alvarado-Cuevas, Z.D., Lo
pez-Hidalgo, A.M., Ordon ~ ez, L.G., Oceguera-Contreras, E.,
Ornelas-Salas, J.T., De Leo
n-Rodríguez, A., 2015. Biohydrogen production using
psychrophilic bacteria isolated from Antarctica. Int. J. Hydrogen Energy 40,
7586e7592. https://doi.org/10.1016/j.ijhydene.2014.10.063.
Alvira, P., Toma
s-Pejo

, E., Ballesteros, M., Negro, M.J., 2010. Pretreatment technol-
ogies for an efficient bioethanol production process based on enzymatic hy-
drolysis: a review. Bioresour. Technol. 101, 4851e4861. https://doi.org/10.1016/
j.biortech.2009.11.093.
Amaro, H., Esquivel, G., Pinto, T., Malcata, X., 2013. Hydrogen production by
microalgae. J. Appl. Phycol. https://doi.org/10.1023/a:1008175112704, 231e214.
Azman, N.F., Abdeshahian, P., Al-Shorgani, N.K.N., Hamid, A.A., Kalil, M.S., 2016.
Production of hydrogen energy from dilute acid-hydrolyzed palm oil mill
effluent in dark fermentation using an empirical model. Int. J. Hydrogen Energy
41, 16373e16384. https://doi.org/10.1016/j.ijhydene.2016.05.085.
Badoga, S., Dalai, A.K., 2017. Liquid fuels from oil sands. In: Sustainable Utilization of
Natural Resources. CRC Press, Boca Raton, pp. 121e143. https://doi.org/10.1201/
9781315153292-5. Taylor & Francis, a CRC title, part of the Taylor & Francis
imprint, a member of the Taylor & Francis Group, the academic division of T&F
Informa, plc, [2017].
Baebprasert, W., Jantaro, S., Khetkorn, W., Lindblad, P., Incharoensakdi, A., 2011.
Increased H2 production in the cyanobacterium Synechocystis sp. strain PCC
6803 by redirecting the electron supply via genetic engineering of the nitrate
assimilation pathway. Metab. Eng. 13, 610e616. https://doi.org/10.1016/
j.ymben.2011.07.004.
Baghchehsaraee, B., Nakhla, G., Karamanev, D., Margaritis, A., Reid, G., 2008. The
effect of heat pretreatment temperature on fermentative hydrogen production
using mixed cultures. Int. J. Hydrogen Energy 33, 4064e4073. https://doi.org/
10.1016/j.ijhydene.2008.05.069.
Baghchehsaraee, B., Nakhla, G., Karamanev, D., Margaritis, A., 2010. Fermentative
hydrogen production by diverse microflora. Int. J. Hydrogen Energy 35,
5021e5027. https://doi.org/10.1016/j.ijhydene.2009.08.072.
Bao, M.D., Su, H.J., Tan, T.W., 2013. Dark fermentative bio-hydrogen production :
effects of substrate pre-treatment and addition of metal ions or L -cysteine. Fuel
112, 38e44. https://doi.org/10.1016/j.fuel.2013.04.063.
Basile, A., Iulianelli, A., 2014. Advances in Hydrogen Production, Storage and Dis-
tribution, Animal Genetics.
Beck, T., 2003. Process for the Production of Hydrogen by Thermal Decomposition
of Water, and Apparatus Therefor. US patent US 6521205 B1..
Bert, P., Bianchini, C., Catanorchi, S., Filpi, A., Nugent, D., Ragnoli, M., Tampucci, A.,
Vizza, F., Ren, X., 2008. Electrodes for the Production of Hydrogen by the
Electrolysis of Aqueous Solutions of Ammonia, Electrolyser Containing Them
and Their Use. International application published under the patent coopera-
tion treaty (PCT) WO2008061975A3.
Bhaskar, T., Balagurumurthy, B., Singh, R., Poddar, M.K., 2013. Thermochemical route
for biohydrogen production. Biohydrogen 285e316. https://doi.org/10.1016/
B978-0-444-59555-3.00012-X.
Boni, M.R., Sbaffoni, S., Tuccinardi, L., 2013. The influence of slaughterhouse waste
on fermentative H2 production from food waste: preliminary results. Waste
Manag. 33, 1362e1371. https://doi.org/10.1016/j.wasman.2013.02.024.
Bulovic, V., Nocera, D., Young, E., Costi, R., Paydavosi, S., 2012. Methods for Forming
Electrodes for Water Electrolysis and Other Electrochemical Techniques, p. 354.
https://doi.org/10.1037/t24245-000. US patent 2012/0156577 A1. 002.
Bundhoo, Z.M.A., 2017a. Effects of microwave and ultrasound irradiations on dark
fermentative bio-hydrogen production from food and yard wastes. Int. J.
Hydrogen Energy 42, 4040e4050. https://doi.org/10.1016/
j.ijhydene.2016.10.149.
Bundhoo, Z.M.A., 2017b. Effects of microwave and ultrasound irradiations on dark
fermentative bio-hydrogen production from food and yard wastes. Int. J.
Hydrogen Energy 42, 4040e4050. https://doi.org/10.1016/
j.ijhydene.2016.10.149.
Bundhoo, M.A.Z., Mohee, R., 2016. Inhibition of dark fermentative bio-hydrogen
production: a review. Int. J. Hydrogen Energy 41, 6713e6733. https://doi.org/
10.1016/j.ijhydene.2016.03.057.
Cai, J., Wang, G., 2016. Comparison of different pre-treatment methods for enriching
hydrogen-producing bacteria from intertidal sludge. Int. J. Green Energy 13,
292e297. https://doi.org/10.1080/15435075.2014.893436.
Cai, M., Liu, J., Wei, Y., 2004. Enhanced biohydrogen production from sewage sludge
with alkaline pretreatment. Environ. Sci. Technol. 38, 3195e3202. https://
doi.org/10.1021/es0349204.
Carrieri, D., Wawrousek, K., Eckert, C., Yu, J., Maness, P.C., 2011. The role of the
bidirectional hydrogenase in cyanobacteria. Bioresour. Technol. 102,
8368e8377. https://doi.org/10.1016/j.biortech.2011.03.103.
Chairattanamanokorn, P., Penthamkeerati, P., Reungsang, A., Lo, Y.C., Lu, W. Bin,
Chang, J.S., 2009. Production of biohydrogen from hydrolyzed bagasse with
thermally preheated sludge. Int. J. Hydrogen Energy 34, 7612e7617. https://
W.J. Martinez-Burgos, E. de Souza Candeo, A.B. Pedroni Medeiros et al.
doi.org/10.1016/j.ijhydene.2009.07.034.
Chang, S., Li, J.Z., Liu, F., 2011. Evaluation of different pretreatment methods for
preparing hydrogen-producing seed inocula from waste activated sludge.
Renew. Energy 36, 1517e1522. https://doi.org/10.1016/j.renene.2010.11.023.
Cheng, J., Zhu, M., 2013. A novel anaerobic co-culture system for bio-hydrogen
production from sugarcane bagasse. Bioresour. Technol. 144, 623e631.
https://doi.org/10.1016/j.biortech.2013.07.018.
Chengqun, X., Jiale, Y., Xiaolu, L., Zeyuan, C., 2020. Graphite-like Carbon Nitride-
Based Photocatalytic Composite Material and Preparation Method and Appli-
cation Thereof. CN patent 111298824A.
Chenlin, L., Herbert, F., 2007. Fermentative hydrogen production from wastewater
and solid wastes by mixed cultures. Crit. Rev. Environ. Sci. Technol. 37, 1e39.
https://doi.org/10.1080/10643380600729071.
Chou, C., Shockley, K.R., Conners, S.B., Lewis, D.L., Comfort, D.A., Adams, M.W.W.,
Kelly, R.M., 2007. Impact of substrate glycoside linkage and elemental sulfur on
bioenergetics of and hydrogen production by the hyperthermophilic archaeon
pyrococcus furiosus y. Appl. Environ. Microbiol. 73, 6842e6853. https://doi.org/
10.1128/AEM.00597-07.
Cisneros de la Cueva, S., Alvarez Guzma
n, C.L., Balderas Hern
andez, V.E., De Leo
n
Rodríguez, A., 2018. Optimization of biohydrogen production by the novel
psychrophilic strain N92 collected from the Antarctica. Int. J. Hydrogen Energy
43, 13798e13809. https://doi.org/10.1016/j.ijhydene.2017.11.164.
Claassen, M., Lier, J.B. van, Contreras, A.M., van Niel, E., Sijtsma, L., Stams, M., Vries, S.
de, Weusthuis, A., 1999. Wind farm modelling. Appl. Microbiol. Biotechnol. 52,
741e755. https://doi.org/10.1007/s002530051586, 1999.
De Vrije, T., De Haas, G.G., Tan, G.B., Keijsers, E.R.P., Claassen, P.A.M., 2002. Pre-
treatment of Miscanthus for hydrogen production by Thermotoga elÿi. Int. J.
Hydrogen Energy 27, 1381e1390.
Dolly, S., Pandey, A., Pandey, B.K., Gopal, R., 2015. Process parameter optimization
and enhancement of photo-biohydrogen production by mixed culture of Rho-
dobacter sphaeroides NMBL-02 and Escherichia coli NMBL-04 using Fe-nano-
particle. Int. J. Hydrogen Energy 40, 16010e16020. https://doi.org/10.1016/
j.ijhydene.2015.09.089.
Du, P., Eisenberg, R., 2012. Catalysts made of earth-abundant elements (Co, Ni, Fe)
for water splitting: recent progress and future challenges. Energy Environ. Sci.
5, 6012e6021. https://doi.org/10.1039/c2ee03250c.
Elbeshbishy, E., Hafez, H., Nakhla, G., 2010. Enhancement of biohydrogen producing
using ultrasonication. Renew. Energy 35, 6184e6193. https://doi.org/10.1016/
j.ijhydene.2010.03.119.
Elias, D.A., Mormile, M.R., Begemann, M.B., Wall, J.D., 2011. New Haloalkaliphilic
Strain Sapolanicus of Halanaerobium, Useful for Producing Hydrogen. https://
doi.org/10.1037/t24245-000. US patent 2011136196A1.
Elkind, J.L., 2014. Separating hydrogen from disassociated water. US patent
8709132B1 1.
Eriksen, N., Nielsen, T., Iversen, N., 2009. Hydrogen production in anaerobic and
microaerobic Thermotoga neapolitana. Biotechnol. Lett. 30, 103e109. https://
doi.org/10.1007/s10529-007-9520-5.
Estevam, A., Arantes, M.K., Andrigheto, C., Fiorini, A., da Silva, E.A., Alves, H.J., 2018.
Production of biohydrogen from brewery wastewater using Klebsiella pneu-
moniae isolated from the environment. Int. J. Hydrogen Energy 43, 4276e4283.
https://doi.org/10.1016/j.ijhydene.2018.01.052.
Fan, Y.T., Zhang, Y.H., Zhang, S.F., Hou, H.W., Ren, B.Z., 2006. Efficient conversion of
wheat straw wastes into biohydrogen gas by cow dung compost. Bioresour.
Technol. 97, 500e505. https://doi.org/10.1016/j.biortech.2005.02.049.
Ferraz Júnior, A.D.N., Etchebehere, C., Zaiat, M., 2015. High organic loading rate on
thermophilic hydrogen production and metagenomic study at an anaerobic
packed-bed reactor treating a residual liquid stream of a Brazilian biorefinery.
Bioresour. Technol. 186, 81e88. https://doi.org/10.1016/j.biortech.2015.03.035.
Fletche, J.C., Ryason, P.R., 1977. Solar photolysis of water. US. 4045315, 1-6 2e7..
Furatian, L., Mohseni, M., 2018. Temperature dependence of 185 nm photochemical
water treatment e the photolysis of water. J. Photochem. Photobiol. Chem. 356,
364e369. https://doi.org/10.1016/j.jphotochem.2017.12.030.
Garcıa-Depraect, O., Gomez-Romero, J., Leon-Becerril, E., Lopez-Lopez, A., 2016.
A novel biohydrogen production process: Co-digestion of vinasse and Nejayote
as complex raw substrates using a robust inoculum. Int. J. Hydrogen Energy
1e12. https://doi.org/10.1016/j.ijhydene.2016.11.204.
Gleich, P., 2015. Two-stage Thermochemical Process for the Production of Hydrogen
and a Reactor for Carrying Out the Production Process. DE patent
102014012436B3.
Gou, C., Guo, J., Lian, J., Guo, Y., Jiang, Z., Yue, L., Yang, J., 2015. Characteristics and
kinetics of biohydrogen production with Ni2þusing hydrogen-producing bac-
teria. Int. J. Hydrogen Energy 40, 161e167. https://doi.org/10.1016/
j.ijhydene.2014.10.100.
Gray, V.M., 2009. Bioreactor for Mesophilic And/or Thermophilic Fermentation.
International Application Published under the Patent Cooperation Treaty (PCT)
WO2009034439A2 2009.
Grigoriev, S.A., Fateev, V.N., Bessarabov, D.G., Millet, P., 2020. Current status ,
research trends , and challenges in water electrolysis science and technology.
Int. J. Hydrogen Energy. https://doi.org/10.1016/j.ijhydene.2020.03.109.
Guangyu, L., Yongfang, Z., Jianquan, S., Shen, C., 2004. Biological Hydrogen Gener-
ating Method Utilizing Industrial Organic Effluent. CN patent 1506465A.
Guo, X.M., Trably, E., Latrille, E., Carrre, H., Steyer, J.P., 2010. Hydrogen production
from agricultural waste by dark fermentation: a review. Int. J. Hydrogen Energy
35, 10660e10673. https://doi.org/10.1016/j.ijhydene.2010.03.008.
Guzm
an, C.L., Contreras, E., Salas, J.T., Hern
andez, V.E., Rodríguez, A., 2016.
12
Journal of Cleaner Production 286 (2021) 124970
Biohydrogen production by the psychrophilic G088 strain using single carbo-
hydrates as substrate. Int. J. Hydrogen Energy 41, 8092e8100. https://doi.org/
10.1016/j.ijhydene.2015.11.189.
Han, S.-K., Shin, H.-S., 2004. Biohydrogen production by anaerobic fermentation of
food waste. Int. J. Hydrogen Energy 29, 569e577. https://doi.org/10.1016/
j.ijhydene.2003.09.001.
Harrison, K., Levene, J., 2008. Electrolysis of water. J. Phys. Chem. 7, 190e193.
https://doi.org/10.1021/j150048a002.
Iribarren, D., Susmozas, A., Petrakopoulou, F., Dufour, J., 2014. Environmental and
exergetic evaluation of hydrogen production via lignocellulosic biomass gasi fi
cation. J. Clean. Prod. 69, 165e175. https://doi.org/10.1016/j.jclepro.2014.01.068.
Ivanova, G., Ra
khely, G., Kova
cs, K.L., 2009. Thermophilic biohydrogen production
from energy plants by Caldicellulosiruptor saccharolyticus and comparison
with related studies. Int. J. Hydrogen Energy 34, 3659e3670. https://doi.org/
10.1016/j.ijhydene.2009.02.082.
Jarunglumlert, T., Prommuak, C., Putmai, N., Pavasant, P., 2018. Scaling-up bio-
hydrogen production from food waste: feasibilities and challenges. Int. J.
Hydrogen Energy 43, 634e648. https://doi.org/10.1016/j.ijhydene.2017.10.013.
Jenkins, R., David, P., Street, J., 2009. Oxyhydrogen vehicle, 1, 1e12. European patent
application EP2221204A1.
Jun, C., Yu, H., 2018. Water electrolysis based on renewable energy for hydrogen
production. Chin. J. Catal. 39, 390e394. https://doi.org/10.1016/S1872.
Junior, A., Wenzel, J., Etchebehere, C., Zaiat, M., 2014. Effect of organic loading rate
on hydrogen production from sugarcane vinasse in thermophilic acidogenic
packed bed reactors b. Int. J. Hydrogen Energy 1e11. https://doi.org/10.1016/
j.ijhydene.2014.08.017.
Juodkazis, K., Juodkazyte, J., Kalinauskas, P., Jelmakas, E., Juodkazis, S., 2010. Pho-
toelectrolysis of water: solar hydrogen - achievements and perspectives. Optic
Express: Energy Exp. 18, A147eA160. https://doi.org/10.1364/OE.18.00A147.
Kanai, T., Imanaka, H., Nakajima, A., Uwamori, K., 2005. Continuous hydrogen
production by the hyperthermophilic archaeon , Thermococcus kodakaraensis
KOD1. J. Biotechnol. 116, 271e282. https://doi.org/10.1016/j.jbiotec.2004.11.002.
Kasai, P., Bishop, R., 1976. Thermolysis of water in contact with zeolite masses. US
3963830, 1-6..
Keskin, T., Arslan, K., Nalakth Abubackar, H., Vural, C., Eroglu, D., Karaalp, D.,
Yanik, J., Ozdemir, G., Azbar, N., 2018. Determining the effect of trace elements
on biohydrogen production from fruit and vegetable wastes. Int. J. Hydrogen
Energy 1e12. https://doi.org/10.1016/j.ijhydene.2018.01.028.
Khan, M.A., Ngo, H.H., Guo, W., Liu, Y., Zhang, X., Guo, J., Chang, S.W., Nguyen, D.D.,
Wang, J., 2018. Biohydrogen production from anaerobic digestion and its po-
tential as renewable energy. Renew. Energy 129, 754e768. https://doi.org/
10.1016/j.renene.2017.04.029.
Kim, D., Kim, M., 2011. Bioresource Technology Hydrogenases for biological
hydrogen production. Bioresour. Technol. 102, 8423e8431. https://doi.org/
10.1016/j.biortech.2011.02.113.
Kosourov, S., Tsygankov, A., Seibert, M., Ghirardi, M.L., 2002. Sustained hydrogen
photoproduction by Chlamydomonas reinhardtii: effects of culture parameters.
Biotechnol. Bioeng. 78, 731e740. https://doi.org/10.1002/bit.10254.
Kuai-Teng, H., Clarksville, R., 2007. COLD CHEMICAL WATER-SPLITTING HYDROGEN
GENERATION SYSTEM. https://doi.org/10.1093/iwc/iwv022. US 20070017154
A1.
Kumar, G., Bakonyi, P., Periyasamy, S., Kim, S.H., Nemesto
thy, N., Be

lafi-Bako
, K.,
2015. Lignocellulose biohydrogen: practical challenges and recent progress.
Renew. Sustain. Energy Rev. 44, 728e737. https://doi.org/10.1016/
j.rser.2015.01.042.
Kumar, G., Mathimani, T., Rene, E.R., Pugazhendhi, A., 2019. ScienceDirect Appli-
cation of nanotechnology in dark fermentation for enhanced biohydrogen
production using inorganic nanoparticles. Int. J. Hydrogen Energy 44,
13106e13113. https://doi.org/10.1016/j.ijhydene.2019.03.131.
Lakaniemi, A.-M., Hulatt, C.J., Thomas, D.N., Tuovinen, O.H., Puhakka, J.A., 2011.
Biogenic hydrogen and methane production from Chlorella vulgaris and Duna-
liella tertiolecta biomass. Biotechnol. Biofuels 4, 34. https://doi.org/10.1186/
1754-6834-4-34.
Lamaison, F., 2009. Aplicaça ~o da
agua residua
ria do processamento da mandioca
como substrato para a produça ~o de hidroge ^nio por processo fermentativo.
Federal University of Santa Catarina.
Lee, D.Y., Li, Y.Y., Oh, Y.K., Kim, M.S., Noike, T., 2009. Effect of iron concentration on
continuous H2production using membrane bioreactor. Int. J. Hydrogen Energy
34, 1244e1252. https://doi.org/10.1016/j.ijhydene.2008.11.093.
Lightner, G., 2002. Production of hydrogren from biomass. US patent 0155062, A1.
Lin, Q., Wu, R., Lin, C., Chen, J., 2006. Method for Fast Algae Proliferation Directly
Used for Bio-Hydrogen Production by Using CO2. https://doi.org/10.1111/
jocn.12647. CN patent 101033473A.
Lindberg, P., Schütz, K., Happe, T., Lindblad, P., 2002. A hydrogen-producing,
hydrogenase-free mutant strain of Nostoc punctiforme ATCC 29133. Int. J.
Hydrogen Energy 27, 1291e1296. https://doi.org/10.1016/S0360-3199(02)
00121-0.
Liu, H., Wang, G., Zhu, D., Pan, G., 2009. Enrichment of the hydrogen-producing
microbial community from marine intertidal sludge by different pretreatment
methods. Int. J. Hydrogen Energy 34, 9696e9701. https://doi.org/10.1016/
j.ijhydene.2009.10.025.
Liu, S., Fan, M.Q., Wang, C., Huang, Y.X., Chen, D., Bai, L.Q., Shu, K.Y., 2012. Hydrogen
generation by hydrolysis of Al-Li-Bi-NaCl mixture with pure water. Int. J.
Hydrogen Energy 37, 1014e1020. https://doi.org/10.1016/j.ijhydene.2011.03.029.
Lu, S., Zhao, B., Chen, M., Wang, L., Fu, X., 2020. Electrolysis of waste water
W.J. Martinez-Burgos, E. de Souza Candeo, A.B. Pedroni Medeiros et al.
containing aniline to produce polyaniline and hydrogen with low energy con-
sumption. Int. J. Hydrogen Energy 45, 22419e22426. https://doi.org/10.1016/
j.ijhydene.2020.06.116.
Łukajtis, R., Hołowacz, I., Kucharska, K., Glinka, M., Rybarczyk, P., Przyjazny, A.,
Kamin
ski, M., 2018. Hydrogen production from biomass using dark fermenta-
tion. Renew. Sustain. Energy Rev. 91, 665e694. https://doi.org/10.1016/
j.rser.2018.04.043.
Maldas, D., Shiraishi, N., 1997. Liquefaction of biomass in the presence of phenol and
H2O using alkalies and salts as the catalyst. Biomass Bioenergy 12, 273e279.
Markov, S.A., Eivazova, E.R., Greenwood, J., 2006. Photostimulation of H2 production
in the green alga Chlamydomonas reinhardtii upon photoinhibition of its O2-
evolving system. Int. J. Hydrogen Energy 31, 1314e1317. https://doi.org/
10.1016/j.ijhydene.2005.11.017.
Martinez-Burgos, W.J., Sydney, E.B., Brar, S.K., Tanobe, V.O. de A., Medeiros, A.B.P.,
De-Carvalho, J.C., Soccol, C.R., 2019. The effect of hydrolysis and sterilization in
biohydrogen production from cassava processing wastewater medium using
anaerobic bacterial consortia. Int. J. Hydrogen Energy 4, 25551e25564. https://
doi.org/10.1016/j.ijhydene.2019.08.085.
Martinez-Burgos, W.J., Sydney, E.B., Paula, D.R., Medeiros, A.B., Carvalho, J.C.,
Soccol, V.T., Vandenberghe, L.P. de S., Woiciechowski, A.L., Soccol, C.R., 2020.
Biohydrogen production in cassava processing wastewater using microbial
consortia : process optimization and kinetic analysis of the microbial com-
munity. Bioresour. Technol. 309, 1e11. https://doi.org/10.1016/
j.biortech.2020.123331.
Martins, L.C., Vessoni, T.C., 2009. Biogas Production : New Trends for Alternative
Energy Sources in Rural and Urban Zones 1147e1153. https://doi.org/10.1002/
ceat.200900051.
Meier, D., Faix, O., 1999. State of the art of applied fast pyrolysis of lignocellulosic
materials - a review. Bioresour. Technol. 68, 71e77. https://doi.org/10.1016/
S0960-8524(98)00086-8.
Meyer, J., 2007. [FeFe] hydrogenases and their evolution: a genomic perspective.
Cell. Mol. Life Sci. 64, 1063e1084. https://doi.org/10.1007/s00018-007-6477-4.
Min, Z., Wei, C., Min, Z., 2014. Method and Device for Biomass Combined Cycle
Power Generation and Carbon Dioxide Separation. CN patent 103972559A.
Mingjun, Z., Binbin, H., 2016. Thermoanaerobacterium Thermosaccharolyticum and
Application Thereof to Biological Hydrogen Production. CN patent 106635887A.
Minowa, T., Zhen, F., Ogi, T., 1998. Cellulose decomposition in hot-compressed water
with alkali or nickel catalyst. J. Supercrit. Fluids 13, 253e259. https://doi.org/
10.1016/S0896-8446(98)00059-X.
Mohammadi, P., Ibrahim, S., Mohamad Annuar, M.S., Law, S., 2011. Effects of
different pretreatment methods on anaerobic mixed microflora for hydrogen
production and COD reduction from palm oil mill effluent. J. Clean. Prod. 19,
1654e1658. https://doi.org/10.1016/j.jclepro.2011.05.009.
Monlau, F., Aemig, Q., Trably, E., 2013. Specific Inhibition of Biohydrogen-Producing
Clostridium Sp . After Dilute-Acid Pretreatment of Sunflower Stalks, vol. 8.
https://doi.org/10.1016/j.ijhydene.2013.07.018.
Mun ~ oz, R., Gonzalez-Fernandez, C., 2017. Microalgae-based Biofuels and
Bioproducts.
Nasirian, N., Almassi, M., Minaei, S., Widmann, R., 2011. Development of a method
for biohydrogen production from wheat straw by dark fermentation. Int. J.
Hydrogen Energy 36, 411e420. https://doi.org/10.1016/j.ijhydene.2010.09.073.
Nguyen, T.A.D., Kim, K.R., Kim, M.S., Sim, S.J., 2010. Thermophilic hydrogen
fermentation from Korean rice straw by Thermotoga neapolitana. Int. J.
Hydrogen Energy 35, 13392e13398. https://doi.org/10.1016/
j.ijhydene.2009.11.112.
Nikolaidis, P., Poullikkas, A., 2017. A comparative overview of hydrogen production
processes. Renew. Sustain. Energy Rev. 67, 597e611. https://doi.org/10.1016/
j.rser.2016.09.044.
Nocera, D., Kanan, M., Moore, T., Surendranath, Y., Reece, S., Esswein, A., 2010.
Catalytic Materials, Photoanodes, and Photoelectrochemical Cells for Water
Electrolysis and Other, Electrochemical Techniques. https://doi.org/10.1037/
t24245-000. US patent 20100133110A1.
Norfadilah, N., Raheem, A., Harun, R., Ahmadun, F., 2016. Bio-hydrogen production
from palm oil mill effluent (POME): a preliminary study. Int. J. Hydrogen Energy
41, 11960e11964. https://doi.org/10.1016/j.ijhydene.2016.04.096.
O-Thong, S., Prasertsan, P., Birkeland, N.-K., 2009. Evaluation of methods for pre-
paring hydrogen-producing seed inocula under thermophilic condition by
process performance and microbial community analysis. Recht. Psychiatr. 100,
909e918. https://doi.org/10.1016/j.biortech.2008.07.036.
O-Thong, S., Hniman, A., Prasertsan, P., Imai, T., 2011. Biohydrogen production from
cassava starch processing wastewater by thermophilic mixed cultures. Int. J.
Hydrogen Energy 36, 3409e3416. https://doi.org/10.1016/
j.ijhydene.2010.12.053.
Olivo, C., Lebedeva, I., Chu, C., Lin, C., Wu, S., 2011. A patent analysis on advanced
biohydrogen technology development and commercialisation : scope and
competitiveness. Int. J. Hydrogen Energy 6. https://doi.org/10.1016/j.ijhy-
dene.2011.04.100, 0e7.

Sanz, R., Maruga
Orfila, M., Linares, M., Molina, R., Botas, J.A.,
n, J., 2016. Perovskite
materials for hydrogen production by thermochemical water splitting. Int. J.
Hydrogen Energy 41, 19329e19338. https://doi.org/10.1016/
j.ijhydene.2016.07.041.
Panagiotopoulos, I.A., Bakker, R.R., Vrije, T. De, Koukios, E.G., Claassen, P.A.M., 2010.
Pretreatment of sweet sorghum bagasse for hydrogen production by Caldi-
cellulosiruptor saccharolyticus. Int. J. Hydrogen Energy 35, 7738e7747. https://
doi.org/10.1016/j.ijhydene.2010.05.075.
13
Journal of Cleaner Production 286 (2021) 124970
Patel, A.K., Vaisnav, N., Mathur, A., Gupta, R., Tuli, D.K., 2016. Whey waste as po-
tential feedstock for biohydrogen production. Renew. Energy 98, 221e225.
https://doi.org/10.1016/j.renene.2016.02.039.
Patterson, T., Esteves, S., Dinsdale, R., Guwy, A., Maddy, J., 2013. Bioresource Tech-
nology Life cycle assessment of biohydrogen and biomethane production and
utilisation as a vehicle fuel. Bioresour. Technol. 131, 235e245. https://doi.org/
10.1016/j.biortech.2012.12.109.
Prazeres, A.R., Carvalho, F., Rivas, J., 2012. Cheese whey management: a review.
J. Environ. Manag. 110, 48e68. https://doi.org/10.1016/j.jenvman.2012.05.018.
Pugazhendhi, A., Shobana, S., Duc, D., Banu, R., Sivagurunathan, P., Chang, S.W.,
Ponnusamy, V.K., Kumar, G., 2019. Application of nanotechnology (nano-
particles) in dark fermentative hydrogen production. Int. J. Hydrogen Energy 44,
1431e1440. https://doi.org/10.1016/j.ijhydene.2018.11.114.
Rafa, Ł., Ho, I., Kucharska, K., Glinka, M., Rybarczyk, P., 2018. Hydrogen production
from biomass using dark fermentation. Renew. Sustain. Energy Rev. 91,
665e694. https://doi.org/10.1016/j.rser.2018.04.043.
Rafieenia, R., Pivato, A., Lavagnolo, M.C., 2018. Effect of inoculum pre-treatment on
mesophilic hydrogen and methane production from food waste using two-
stage anaerobic digestion. Int. J. Hydrogen Energy 43, 12013e12022. https://
doi.org/10.1016/j.ijhydene.2018.04.170.
Rashid, N., Lee, K., Mahmood, Q., 2011. Bio-hydrogen production by Chlorella vul-
garis under diverse photoperiods. Bioresour. Technol. 102, 2101e2104. https://
doi.org/10.1016/j.biortech.2010.08.032.
Rashid, N., Saif, M., Rehman, U., Memon, S., Ur, Z., Lee, K., Han, J., 2013. Current
status , barriers and developments in biohydrogen production by microalgae.
Renew. Sustain. Energy Rev. 22, 571e579. https://doi.org/10.1016/
j.rser.2013.01.051.
Reddy, N.L., Rao, V.N., Vijayakumar, M., Aminabhavi, T.M., 2019. A review on fron-
tiers in plasmonic nano-photocatalysts for hydrogen production. Int. J.
Hydrogen Energy 44, 10453e10472. https://doi.org/10.1016/
j.ijhydene.2019.02.120.
Reece, S., Esswein, A., Sung, K., Green, Z., Nocera, D., 2011. Compositions, Electrodes,
Methods, and Systems for Water Electrolysis and Other Electrochemical Tech-
niques. https://doi.org/10.1037/t24245-000. US patent 2011/0048962 A1.
Ren, N.Q., Guo, W.Q., Wang, X.J., Xiang, W.S., Liu, B.F., Wang, X.Z., Ding, J., Chen, Z.B.,
2008. Effects of different pretreatment methods on fermentation types and
dominant bacteria for hydrogen production. Int. J. Hydrogen Energy 33,
4318e4324. https://doi.org/10.1016/j.ijhydene.2008.06.003.
Rick, R., Pires, E., Jose, H., Sato, M., Coimbra-arau, C.H., 2013. Overview of hydrogen
production technologies from biogas and the applications in fuel cells. Int. J.
Hydrogen Energy 8, 5215e5225. https://doi.org/10.1016/j.ijhydene.2013.02.057.
Rohrich, K., Wirth, H., Ferney-Voltaire, 2011. Reactor with a Thermal Gradient
Controlled for the Production of Pure Hydrogen. US patent 7943045B2. https://
doi.org/10.1016/j.(73).
Rolf, L., 2011. Method and Apparatus for Generating Hydrogen Gas Using Biomass.
JP patent 2011522951A.
Rongfeng, S., Guihuan, Y., Min, X., Li, S., Haibin, G., Weijie, Z., 2007. Method and
Device for Preparing Synthesized Gas by Biomass Step-wise Rich Oxygen
Gasification. CN patent 101164866A.
Saha, B.C., Iten, L.B., Cotta, M.A., Wu, Y.V., 2005. Dilute acid pretreatment, enzymatic
saccharification, and fermentation of rice hulls to ethanol. Biotechnol. Prog. 21,
816e822. https://doi.org/10.1021/bp049564n.
Sako, K., Ken, S., 2019. Fuel cell watercraft. US patent 10.364.009 B2.
Salem, A.H., Mietzel, T., Brunstermann, R., Widmann, R., 2018. Two-stage anaerobic
fermentation process for bio-hydrogen and bio-methane production from pre-
treated organic wastes. Bioresour. Technol. 265, 399e406.
Sattler, C., Roeb, M., Agrafiotis, C., Thomey, D., 2017. Solar hydrogen production via
sulphur based thermochemical water-splitting. Sol. Energy 156, 30e47. https://
doi.org/10.1016/j.solener.2017.05.060.
Seifert, K., Waligorska, M., Laniecki, M., 2010. Hydrogen generation in photobio-
logical process from dairy wastewater. Int. J. Hydrogen Energy 35, 9624e9629.
https://doi.org/10.1016/j.ijhydene.2010.07.015.
Sengmee, D., Cheirsilp, B., Suksaroge, T.T., Prasertsan, P., 2017. Biophotolysis-based
hydrogen and lipid production by oleaginous microalgae using crude glycerol as
exogenous carbon source. Int. J. Hydrogen Energy 42, 1970e1976. https://
doi.org/10.1016/j.ijhydene.2016.10.089.
Shao, H., Xin, G., Zheng, J., Li, X., Akiba, E., 2012. Nanotechnology in Mg-based
materials for hydrogen storage. Nano Energy 1, 590e601. https://doi.org/
10.1016/j.nanoen.2012.05.005.
Skjånes, K., Rebours, C., Lindblad, P., 2013. Potential for green microalgae to produce
hydrogen, pharmaceuticals and other high value products in a combined pro-
cess. Crit. Rev. Biotechnol. 33, 172e215. https://doi.org/10.3109/
07388551.2012.681625.
Soboh, B., Linder, D., Hedderich, R., 2004. A multisubunit membrane-bound [ NiFe ]
hydrogenase and an NADH-dependent Fe-only hydrogenase in the fermenting
bacterium Thermoanaerobacter tengcongensis. Microbiology 150, 2451e2463.
https://doi.org/10.1099/mic.0.27159-0.
Song, W., Rashid, N., Choi, W., Lee, K., 2011. Biohydrogen production by immobilized
Chlorella sp. using cycles of oxygenic photosynthesis and anaerobiosis. Bio-
resour. Technol. 102, 8676e8681. https://doi.org/10.1016/j.biortech.2011.02.082.
Stolyarevsky, A.Y., 2015. Method of producing hydrogen from biomass. RU patent
2602150C2.
Suguru, T., Akihiro, M., Takamichi, K., Osamu, A., 2018. Electrolytic cell, pp. 1e27. EP
3 330 410 A1, 1e27 1.
Sun, Y., Cheng, J., 2002. Hydrolysis of lignocellulosic materials for ethanol
W.J. Martinez-Burgos, E. de Souza Candeo, A.B. Pedroni Medeiros et al.
production : a review. Bioresour. Technol. 83, 1e11.
Sundararajan, M., Hilllier, I., 2013. 9.21 [Fe]-, [NieFe]-, and [FeeFe]-Hydrogenases.
Compr. Inorg. Chem. II 551e567. https://doi.org/10.1016/B978-0-08-097774-
4.00925-6.
Sydney, E.B., Larroche, C., Novak, A.C., Nouaille, R., Sarma, S.J., Brar, S.K., Letti, L.A.J.,
Soccol, V.T., Soccol, C.R., 2014. Economic process to produce biohydrogen and
volatile fatty acids by a mixed culture using vinasse from sugarcane ethanol
industry as nutrient source. Bioresour. Technol. 159, 380e386. https://doi.org/
10.1016/j.biortech.2014.02.042.
Takahashi, S., Madono, A., Kishi, T., Arimoto, O., 2014. Electrolytic cell, 1, 1e27. In-
ternational application published under the patent cooperation treaty (PCT)
EP3330410A1.
Talluri, S., Raj, S.M., Christopher, L.P., 2013. Consolidated bioprocessing of untreated
switchgrass to hydrogen by the extreme thermophile Caldicellulosiruptor sac-
charolyticus DSM 8903. Bioresour. Technol. 139, 272e279. https://doi.org/
10.1016/j.biortech.2013.04.005.
Tamagnini, P., Leita ~o, E., Oliveira, P., Ferreira, D., Pinto, F., Harris, D.J., Heidorn, T.,
Lindblad, P., 2007. Cyanobacterial hydrogenases: diversity, regulation and ap-
plications. FEMS (Fed. Eur. Microbiol. Soc.) Microbiol. Rev. 31, 692e720. https://
doi.org/10.1111/j.1574-6976.2007.00085.x.
Tan, Z.H., Ouyang, L.Z., Huang, J.M., Liu, J.W., Wang, H., Shao, H.Y., Zhu, M., 2019.
Hydrogen Generation via Hydrolysis of Mg 2 Si 770, pp. 108e115. https://
doi.org/10.1016/j.jallcom.2018.08.122.
Tandon, M., Thakur, V., Tiwari, K.L., 2018a. Comparison of bio-hydrogen production
yield capacity between asynchronous and simultaneous saccharification and
fermentation processes from agricultural residue by mixed anaerobic cultures.
Bioresour. Technol. 247, 1210e1214. https://doi.org/10.1016/
j.biortech.2017.09.053.
Tandon, M., Thakur, V., Tiwari, K.L., Jadhav, S.K., 2018b. Enterobacter ludwigii strain
IF2SW-B4 isolated for bio-hydrogen production from rice bran and de-oiled rice
bran. Environ. Technol. Innov. https://doi.org/10.1002/cbic.201700576.
Tanikkul, P., Juntarakod, P., Pisutpaisal, N., 2018. ScienceDirect Optimization of
biohydrogen production of palm oil mill effluent by ozone pretreatment. Int. J.
Hydrogen Energy 1e9. https://doi.org/10.1016/j.ijhydene.2018.09.063.
Taylor, R., Davenport, R., Talbot, J., Herz, R., Luc, W., Genders, D., Symons, P.,
Brown, L., 2014. Status of the Solar Sulfur Ammonia Thermochemical Hydrogen
Production System for Splitting Water. Energy Procedia 49, 2047e2058. https://
doi.org/10.1016/j.egypro.2014.03.217.
Taylor, C.M., Wenk, J., Mattia, D., 2019. Enhancing the photo-corrosion resistance of
ZnO nanowire photocatalysts. J. Hazard Mater. 378, 120799. https://doi.org/
10.1016/j.jhazmat.2019.120799.
Teli, A., Ficara, E., Malpei, F., 2014. Bio-hydrogen production from cheese whey by
dark fermentation. Chem. Eng. Trans. 37, 613e618. https://doi.org/10.3303/
CET1437103.
Thungklin, P., Reungsang, A., Sittijunda, S., 2011. Hydrogen production from sludge
of poultry slaughterhouse wastewater treatment plant pretreated with micro-
wave. Int. J. Hydrogen Energy 36, 8751e8757. https://doi.org/10.1016/
j.ijhydene.2010.07.073.
€
Tosuner, Z.V., Taylan, G.G., Ozmıhçı, S., 2018. Effects of rice husk particle size on
biohydrogen production under solid state fermentation. Int. J. Hydrogen Energy.
https://doi.org/10.1016/j.ijhydene.2018.10.230.
Vi, L.V.T., Salakkam, A., Reungsang, A., 2017. Optimization of key factors affecting
bio-hydrogen production from sweet potato starch. Energy Procedia 138,
973e978. https://doi.org/10.1016/j.egypro.2017.10.092.
Wan, J., Ning, Y., Shi, X., Jin, D., Li, S., Chen, Y., 2013. Microbial community structure
of anaerobic sludge for hydrogen production under different acid pretreatment
conditions. J. Renew. Sustain. Energy 5. https://doi.org/10.1063/1.4800199.
Wang, J., Wan, W., 2008. Effect of Fe2 þconcentration on fermentative hydrogen
production by mixed cultures. Int. J. Hydrogen Energy 33, 1215e1220. https://
doi.org/10.1016/j.ijhydene.2007.12.044.
Wang, Yin, Y., 2018. Fermentative hydrogen production using various biomass-
based materials as feedstock. Renew. Sustain. Energy Rev. 92, 284e306.
https://doi.org/10.1016/j.rser.2018.04.033.
Wang, H., Fang, M., Fang, Z., Bu, H., 2010. Effects of sludge pretreatments and
organic acids on hydrogen production by anaerobic fermentation. Bioresour.
Technol. 101, 8731e8735. https://doi.org/10.1016/j.biortech.2010.06.131.
Wang, H., Zhi, Z., Wang, J., Ma, S., 2012. Comparison of various pretreatment
methods for biohydrogen production from cornstalk. Bioproc. Biosyst. Eng. 35,
1239e1245. https://doi.org/10.1007/s00449-012-0711-7.
Wei, Z., Zhen, G., Zhaoan, C., Hongbin, L., Xingju, Y., Meifang, J., 2009. Producing
Biohydrogen, by Culturing Platymonas Subcordiformis in Photobioreactor with
Carbon Dioxide and Kangweifang Nutrient Salt to Obtain Algae Liquid, Filling
Algae Liquid in Hydrogen Producing Reactor and Illuminating Algae. CN patent
101275117-A1.
14
Journal of Cleaner Production 286 (2021) 124970
Wei, Z., Meng, P.M., Ying, S., Yang, W., Shuyao, W., Ximing, S., 2020. Preparation
Method and Application of Novel Composite Photocatalyst for Hydrogen Pro-
duction by Photocatalytic Water Photolysis. CN patent 111229326A.
Weimer, A., Perkins, C., Lewandowski, A., Bingham, C., 2006. Metal-Oxide Based
Process For The Generation Of Hydrogen From Water Splitting Utilizing A High
Temperature Solar Aerosol Flow Reactor. US 2006/0188433 A1, 1-26 1.
Weizhi, W., Xinyue, L., Xinxin, W., 2018. A Kind of Hollow Tubular CoSe2Nano
Material and its Preparation Method and Application. CN patent
CN109046394A.
Wold, M.L., 2014. Power Generation System. International Application Published
under the Patent Cooperation Treaty (PCT) WO 2014/145823 Al.
Wong, Y.M., Wu, T.Y., Juan, J.C., 2014. A review of sustainable hydrogen production
using seed sludge via dark fermentation. Renew. Sustain. Energy Rev. 34,
471e482. https://doi.org/10.1016/j.rser.2014.03.008.
Wong, Y.M., Show, P.L., Wu, T.Y., Leong, H.Y., Ibrahim, S., Juan, J.C., 2018. Production
of bio-hydrogen from dairy wastewater using pretreated landfill leachate
sludge as an inoculum. J. Biosci. Bioeng. xx https://doi.org/10.1016/
j.jbiosc.2018.07.012.
Wood, P.K., Offices, L., 2014. Solar metal sulfate-ammonia based thermochemical
water splitting cycle for hydrogen production. US patent 8691068B1.
Wu, J., Ein-mozaffari, F., Upreti, S., 2013a. Bioresource Technology Effect of ozone
pretreatment on hydrogen production from barley straw. Bioresour. Technol.
144, 344e349. https://doi.org/10.1016/j.biortech.2013.07.001.
Wu, J., Ein-Mozaffari, F., Upreti, S., 2013b. Effect of ozone pretreatment on hydrogen
production from barley straw. Bioresour. Technol. 144, 344e349. https://
doi.org/10.1016/j.biortech.2013.07.001.
Xia, A., Cheng, J., Lin, R., Lu, H., Zhou, J., Cen, K., 2013. Comparison in dark hydrogen
fermentation followed by photo hydrogen fermentation and methanogenesis
between protein and carbohydrate compositions in Nannochloropsis oceanica
biomass. Bioresour. Technol. 138, 204e213. https://doi.org/10.1016/
j.biortech.2013.03.171.
Xia, A., Jacob, A., Herrmann, C., Murphy, J.D., 2016. Fermentative bio-hydrogen
production from galactose. Energy 96, 346e354. https://doi.org/10.1016/
j.energy.2015.12.087.
Xiao, B., Liu, J., 2009. Effects of various pretreatments on biohydrogen production
from sewage sludge. Chin. Sci. Bull. 54, 2038e2044. https://doi.org/10.1007/
s11434-009-0100-z.
Xiao, L., Deng, Z., Fung, K.Y., Ng, K.M., 2013. Biohydrogen generation from anaerobic
digestion of food waste. Int. J. Hydrogen Energy 38, 13907e13913. https://
doi.org/10.1016/j.ijhydene.2013.08.072.
Xu, X., Zhang, J., Wang, Shuaijun, Yao, Z., Wu, H., Shi, L., Yin, Y., Wang, Shaobin,
Sun, H., 2019. Photocatalytic reforming of biomass for hydrogen production
over ZnS nanoparticles modified carbon nitride nanosheets. J. Colloid Interface
Sci. 555, 22e30. https://doi.org/10.1016/j.jcis.2019.07.066.
Xueli, C., Zunhong, Y., Xin, G., Fuchen, W., Guangsuo, Y., Haifeng, L., Zhijie, Z.,
Zhenghua, Yifei, W., Xingjun, W., Xiaolei, G., Qinfeng, L., Weifeng, L., Weiwei, Z.,
2007. Method and Device for Preparing Combustion Gas by Gasifying Biomass.
CN patent 101012384A.
Yang, X., Hall, M.B., 2008. Trigger Mechanism for the Catalytic Hydrogen Activation
by Monoiron (Iron - Sulfur Cluster-free) Hydrogenase, vol. 5, pp. 14036e14037.
Yang, H., Shen, J., 2006. Effect of ferrous iron concentration on anaerobic bio-
hydrogen production from soluble starch. Int. J. Hydrogen Energy 31,
2137e2146. https://doi.org/10.1016/j.ijhydene.2006.02.009.
Yang, H., Lin, W., Lecheng, L., 2018. A Kind of Phosphatization Cobalt/nitrogen Mixes
Porous Carbon Composite Catalytic Material and its Preparation Method and
Application. CN patent CN 109289894A 01.
Yaping, J., Weidong, S., Yuanyong, H., Jianlin, R., Ruijie, C., 2020. High-hydrophilicity
G-C3N4And Preparation Method and Application Thereof. CN patent
111318297A.
Yimeng, C., 2018. A Kind of Solar Biomass Energy Hydrogen Energy Combined
Power Generation Device. CN patent CN106185805B.
Yokoi, H., Maki, R., Hirose, J., Hayashi, S., 2002. Microbial production of hydrogen
from starch-manufacturing wastes. Biomass Bioenergy 22, 389e395.
Zhang, W., 2010. Solar Photolysis Water Hydrogen Production Catalyst and Prepa-
ration Method. CN patent 101767023A.
Zhaoyu, W., Yiting, G., Yuyun, W., Dandan, Z., Wentao, C., Mingwen, Z., 2020.
Application of Perovskite Material in Dye-Sensitized Photolysis Water-Splitting
Hydrogen Production.
Zhiznin, S.Z., Vassilev, S., Gusev, A.L., 2019. ScienceDirect Economics of secondary
renewable energy sources with hydrogen generation. Int. J. Hydrogen Energy
44, 11385e11393. https://doi.org/10.1016/j.ijhydene.2019.03.072.
Zhu, H., Be
land, M., 2006. Evaluation of Alternative Methods of Preparing Hydrogen
Producing Seeds from Digested Wastewater Sludge, vol. 31, pp. 1980e1988.
https://doi.org/10.1016/j.ijhydene.2006.01.019.