Biomass Conversion and Biorefinery

https://doi.org/10.1007/s13399-020-00965-x

REVIEW ARTICLE

Critical challenges in biohydrogen production processes

from the organic feedstocks
Ahmed I. Osman 1,2 & Tanmay J. Deka 1 & Debendra C. Baruah 3 & David W. Rooney 1

Received: 28 May 2020 / Revised: 12 August 2020 / Accepted: 14 August 2020

# The Author(s) 2020

Abstract
The ever-increasing world energy demand drives the need for new and sustainable renewable fuel to mitigate problems associated
with greenhouse gas emissions such as climate change. This helps in the development toward decarbonisation. Thus, in recent
years, hydrogen has been seen as a promising candidate in global renewable energy agendas, where the production of
biohydrogen gains more attention compared with fossil-based hydrogen. In this review, biohydrogen production using organic
waste materials through fermentation, biophotolysis, microbial electrolysis cell and gasification are discussed and analysed from
a technological perspective. The main focus herein is to summarise and criticise through bibliometric analysis and put forward the
guidelines for the potential future routes of biohydrogen production from biomass and especially organic waste materials. This
research review claims that substantial efforts currently and, in the future, should focus on biohydrogen production from
integrated technology of processes of (i) dark and photofermentation, (ii) microbial electrolysis cell (MEC) and (iii) gasification
of combined different biowastes. Furthermore, bibliometric mapping shows that hydrogen production from biomethanol and the
modelling process are growing areas in the biohydrogen research that lead to zero-carbon energy soon.

Keywords Biohydrogen . Fermentation . Bio-photolysis . Biowaste . Waste to energy . Microbial electrolysis cell . Gasification .
Climate change

Nomenclature LCA Life cycle assessment

ATP Adenosine triphosphate MEC Microbial electrolysis cell
BOD Biological oxygen demand NG Natural gas
Chl Chlorophyll a+b OLR Organic loading rate
CCWP Concentrated cheese whey permeate PNSB Purple non-sulphur bacteria
COD Chemical oxygen demand PF Photofermentation
DF Dark fermentation SCW Second cheese whey
GHG Greenhouse gas SRT Solid retention time
HRT Hydraulic retention time TS Total solid
HPR Hydrogen production rate VSS Volatile suspended solids
HC Hydrocarbon VS Volatile solid
H2SO4 Sulphuric acid WGSR Water gas shift reaction
WoS Web of Science

* Ahmed I. Osman
[email protected]
1 Introduction
1
School of Chemistry and Chemical Engineering, Queen’s University
Belfast, Belfast, Northern Ireland BT9 5AG, UK The depletion of fossil-based fuel sources along with their
2
Chemistry Department, Faculty of Science-Qena, South Valley increasing use day by day has created big concerns related
University, Qena 83523, Egypt to greenhouse gas (GHG) emissions and global warming.
3
Energy Conservation Laboratory, Department of Energy, Tezpur Increasing levels of CO2, which is a patent GHG emission
University, Sonitpur 784028, India and associated with burning fossil fuel sources, were found
 Biomass Conv. Bioref.

to exceed 409 ppm [1–3], which is aiding to the global tem- processes (NG reforming, biomass and coal gasification, wa-
perature increase [4, 5]. Moreover, growing industrial and ter electrolysis and others), there are requirements for better
economic development of the modern world is also demand- reliability and operating flexibility, a reduction in the capital
ing more sources of clean energy for the near future. The costs and a significant enhancement in the plant efficiencies
increasing gap between the growing energy demand and nec- [17]. Herein, we assessed the routes of biohydrogen produc-
essary energy supply due to at the rising human population tion derived from different organic waste materials and
has sparked a huge interest in new biofuel research as well as highlighted the key factors affecting the yield of biohydrogen.
production in recent times [6]. Therefore, from the perspective Furthermore, through bibliometric mapping, we suggest steps
of alternative energy sources, renewable energy sectors like and future guidelines from the gaps in the literature for the
solar, hydro, wind and biofuels like biodiesel, bioethanol and optimisation of hydrogen production from organic waste
biohydrogen are finding its use in current development streams. Overall, this critical review is aimed at helping the
agendas across the world. Recently, hydrogen production by academics working in the biohydrogen production research
water electrolysis has gained global attention as one of the area along with the industrial application and roll-out of a
most promising and eco-friendly energy alternatives. H2 is zero-carbon economy. It will also focus on themes that face
found to have a high energy content of around 122 kJ/g, about the development and potential transformation of the
2.75 times higher than other HC fuels [7, 8]. It also possesses biohydrogen market and its future.
wide versatility in its production as well as its applications
ranging from fuel-cells to biofertilisers and biofuels. H2 pro-
duced from biological sources is known as bio-H2. Hydrogen
produces no harmful greenhouse gases upon combustion but 2 Review methodology
only water. Therefore, it is considered one of the energy
sources to have the potential to replace part of the convention- Web of Science (WoS) was utilised herein to obtain the data
al fossil-based fuels shortly [9]. within the core collection database and then the exported data
As far the production is concerned, fossil fuel is responsible files; some Boolean operator logic was implemented in the
for the majority of hydrogen production, out of which 60% is search to find suitable publications and identify evidence gaps
produced from dedicated primary hydrogen-producing facili- in the knowledge and research concerning the biohydrogen
ties. It is also reported that around 71.27% of hydrogen is topic. A broad timespan of biohydrogen research covering
produced from natural gas (NG), 27.27% from coal, 0.7% all available year option in the time frame of 1970–2020 is
from petroleum and the remaining 0.7% from water electrol- shown in Fig. 1. The bibliometric mapping generated from the
ysis [10–12]. Notably, the hydrogen production from fossil WoS core collection is shown in Fig. 1. The overall number of
reformation is neither renewable nor carbon neutral as the data which was 1539 was exported to the VOSviewer soft-
production process involves high numbers of GHG footprints ware. Herein, we used the co-occurrence as the type of anal-
[4]. H2 production is also achieved with water gas shift reac- ysis and all keywords included and the fractional counting
tion (WGSR), thermal decomposition, catalytic oxidation, method employed. We have direct clusters in Fig. 1 linking
steam gasification, pyrolysis and autothermal reforming [13, specific keywords to general areas such as biohydrogen pro-
14]. The recent popularity of waste-to-energy studies also cre- duction. This approach enabled us to visualise the most dis-
ates an impact on research related to hydrogen production tinguished keywords in publications in the last 50 years for
utilising waste materials effectively. Biohydrogen is produced biohydrogen production. For example, keywords like dark
from different organic wastes, thereby solving the issue of fermentation, water and ethanol production along with ligno-
waste disposal and energy generation at the same time. cellulosic biomass were the most frequently occurring key-
Organic waste can be defined as the waste materials that are words. Other common related keywords to the biohydrogen
biodegradable and originates from plants or animals which production are hydrolysis, pyrolysis, gasification, enzymatic
can be broken into CO2, methane or simple organic molecules hydrolysis, biodiesel production, sludge, microalgae, waste-
[15]. Organic wastes like industrial waste, municipal sewage water, anaerobic digestion, photo-fermentation, glucose, su-
sludge, solid waste, agricultural residues and poultry waste, percritical water and saccharification. Furthermore, the WoS
manure, have the potential to be used for bioenergy produc- search showed other keywords associated with the production
tion [16]. conditions such as pre-treatment, pH, light and temperature.
However, recent publications suggested further investiga- On the other hand, new keywords have been introduced to
tions are required on the production of H2 using organic waste biohydrogen production recently such as methanol, model-
materials. The concept of using waste materials from different ling, storage, fuel-cells, energy recovery, organic waste, bio-
biological sources to produce environment-friendly reactors, light intensity, methanogenesis along with the
biohydrogen can be potentially helpful to tackle the ongoing techno-economic and life cycle assessment (LCA) studies.
environmental challenges, while for all H 2 production This implies that areas such as hydrogen production from
Biomass Conv. Bioref.

Fig. 1 The bibliometric mapping of biohydrogen production in the last 50 years

methanol need further investigations along with modelling, biohydrogen production processes along with their ener-
techno-economic analysis and other research areas. gy conversion efficiencies. Energy conversion efficiency
can be defined as the ratio between the useful output of
an energy conversion machine/process and energy input
3 Production of biohydrogen from organic [25]. In this section, these processes of biohydrogen
waste through biological methods production are discussed. Figure 2 shows the different
biological processes involved in biohydrogen produc-
Although most of the hydrogen production currently is tion. Biohydrogen production with dark fermentation,
based on fossil fuels, efforts to produce biohydrogen MEC and biomass gasification possesses high process
from different bioresiduals such as wastewater or organ- efficiency, and biomass is the common feedstock in all
ic wastes are seen to be increasing [18]. Currently, the of the aforementioned processes. Again, photofermenta-
most popular, widely discussed and developed processes tion and biophotolysis can be seen dependant on solar
of biohydrogen production using organic waste material energy for the production of biohydrogen. Different pro-
are (a) biofermentation (dark fermentation and cess parameters are associated with all these processes,
photofermentation), (b) biophotolysis (direct and indi- which have their own importance. Every process has its
rect), (c) bioelectrochemical system such as microbial certain specification and operating conditions along with
electrolysis cells (MEC) and (d) gasification [19, 20]. advantages and disadvantages which are discussed
Table 1 shows the recent status of the different below.
 Biomass Conv. Bioref.

Table 1 Status of available

biohydrogen production Production process Feedstock Maturity Energy conversion efficiency [Ref.]
technologies (%)

Dark fermentation Biomass Long term 4.3 [21]

Photo fermentation Biomass + sunlight Long term 5.1 [21]
Bio photolysis Sunlight + water Long term 2.7–4.0 [22]
Microbial electrolysis Biomass + Long term 11.3 [23]
cells electricity
Biomass gasification Biomass Commercial 88.1 [24]

3.1 Fermentation Unlike dark fermentation, photofermentation uses photo-

synthetic bacteria that use sunlight to produce CO2 and H2
Fermentation can be defined as the process of energy from organic molecules under anaerobic conditions [28].
generation involving an endogenous electron acceptor For improving the yield of biohydrogen, studies related to
from the oxidation of organic waste materials using a the integration of both the two fermentation processes can
number of different microorganisms. The results of fer- also be found. Figure 3 shows the two types of
mentation depend on the applied catalyst (isolated enzyme biofermentation processes used for H2 production.
or microorganism producer) and used organic substrate
(mostly carbohydrate or protein), along with the process
3.1.1 Dark fermentation
parameters. The character of the fermentation process can
be either aerobic or anaerobic [26]. Fermentation of or-
Dark fermentation has become one of the well-known tech-
ganic waste materials using microorganisms under anaer-
nologies for biohydrogen production, which enables the mi-
obic conditions is a good way to produce H2 along with
croorganisms to produce H2 in a dark anaerobic condition
other organic alcohols/acids as by-products. Depending
[29]. However, with the formation of many by-products, the
on the necessity of light for the microorganisms, the
low H2 yield on substrates is a major disadvantage. Equations
biofermentation can be divided into two types: (a) dark
1 and 2 show the main reactions that are involved in the dark
fermentation and (b) photo fermentation. Dark fermenta-
fermentation process of hydrogen production. Equation 1
tion is the process of fermentation carried out in dark
shows the reaction for H2 production as a result of the proton
anaerobic conditions, where breakdown of cellulosic or-
reduction by generated electrons from C-source degradation.
ganic feedstock results in the production of biological
[NiFe]-hydrogenase and [FeFe]-hydrogenase are generally in-
hydrogen along with organic acids and alcohols [27].
volved in such process of H2 formation [30]. A maximum H2

Fig. 2 Overview of the biological biohydrogen production processes

Biomass Conv. Bioref.

Fig. 3 a Dark fermentation and b

photofermentaion processes
during the hydrogen production
from organic waste or wastewater

yield of 4 mol H2/mol glucose can be seen to be achievable in usually have a low H2 yield compared with other waste
the dark fermentation process practically, though Eq. 2 shows due to the high presence of protein or lipid [33].
a theoretical yield of 12 mol H2/mol glucose [31]. Higher The pre-treatment is a crucial step in biohydrogen research.
yields can be achieved in thermophilic fermentations. This Table 2 shows various studies related to pre-treatment
low yield in dark fermentation is mainly happening due to methods, like physical (high temperature, ultrasonication and
the production of other by-products such as acetic acid, microwave), mechanical (milling and grinding), enzymatic,
propionic acid and butyric acid. Equation 3 shows the acetic radiation and hydrothermal pre-treatment for the improvement
acid pathway, where the reaction of glucose and two water of H2 yield [49–51]. Different types of substrates need differ-
molecules produce acetic acid (CH 3COOH). Similarly, ent pre-treatment methods, which can enhance the production
propionic acid can be found to be produced along with acetic efficiency of hydrogen. Pre-treatment of dairy manure can be
acid from glucose, as shown in Eq. 4. Again, Eq. 5 shows the done mainly with three different methods: (a) acid (0.2% w/w
production of butyric acid from glucose reacting with six wa- HCI solution) treatment, (b) alkali (0.2% w/w NaOH solution)
ter molecules [32]. In all the three pathways, CO2 and H2 are treatment and (c) 2 h infrared oven treatment [33, 35]. In the
seen to be produced in different quantities. case of sewage sludge, 15-min boiling at around 100 °C com-
pletes the pre-treatment [36]. Pre-treatment of rice straw for
2Hþ þ 2e− ↔H2 ð1Þ hydrogen production was found with boiling at 80–100 °C
C6 H12 O6 þ 6H2 O→6CO2 þ 12H2 ð2Þ [37], and in another case, treatment with alkali solution (1%
w/w) was found with cellulose hydrolysis after cutting and
C6 H12 O6 þ 2H2 O→2CH3 COOH þ 2CO2 þ 4H2 ð3Þ
grinding (2 mm size) [41]. Distillery wastewater was also
(Acetic acid pathway) found to be pre-treated with pH neutralisation, centrifugation
and sterilisation [39]. Food waste was found to be pre-treated
C6 H12 O6 →CH3 COOH þ CH3 CH2 COOH þ CO2 þ H2 ð4Þ in many ways. Sieving and 6 h boiling at around 100 °C of
food waste hydrolysate for hydrogen production were report-
(Propionic acid pathway)
ed by Han et al. [42]. Kim et al. [43] mentioned pre-treatment
C6 H12 O6 þ 6H2 O→2CH3 CH2 CH2 COOH þ 2CO2 of food waste and sludge mixture with 30-min heating (at
120 °C), alkalisation (3 M NaOH) and acidification (3 M
þ 2H2 ð5Þ
HCl). Kitchen mill shredding was also applied as a pre-
(Butyric acid pathway) treatment method to food waste combined with 5% glycerol
Several types of waste with different chemical compo- [44].
sitions are seen used as a substrate to produce H2 in the The H2 yield of 1130 mmol/g COD was reported for plain
dark fermentation process. Among those, the most wide- palm oil, while an improvement of 2760 and 1880 mmol/g
ly used waste includes agricultural wastes (viz. COD was found for surfactant (Tween 80) and enzyme
rice/wheat/corn straw, animal manure), various wastewa- (Optimase BG) pre-treatment, respectively [52]. Efficient H2
ter types (viz. distillery wastewater, cheese whey efflu- production with lignocellulosic materials like sugarcane ba-
ent, palm oil mill effluent), food waste, municipal sew- gasse rice/corn/wheat straw and corn stalk from agricultural
age waste and sewage sludge [33]. The sugar or waste needs pre-treatment as mentioned in several different
carbohydrate-rich waste substrates tend to produce more studies [53, 54]. An increase in 47.3% of biohydrogen pro-
H2 compared with lipid or protein-rich substrates. A lin- duction was seen for pre-treatment of rice husk with a com-
ear correlation between H2 production and the proportion mercial enzyme (Celluclast 1.5 L) compared with that of rice
of carbohydrate-rich waste substrate was also found [34]. husk without pre-treatment (321 mL H2/g rice husk) [54].
Waste like sewage sludge and palm oil mill effluent Similarly, 35% high H2 yield (155 mL H2/g VS) was seen in
Table 2 Comparison of biohydrogen production from wastes with the dark fermentation process

Substrate Pre-treatment process Microorganism pH Temperature H2 yield (mL/g VS) [Ref.]

(°C)

Dairy manure HCl (0.2%) treatment, boiling/infrared radiation Mixed culture 5.0 36.0 ± 1 31.5 [35]
Sewage sludge 100 °C boiling (for 15 min) Mixed culture 7.0 37.0 11.2 [36]
Sewage sludge + poplar leaves 20.8
Sewage sludge + flower waste 32.0
Sewage sludge + ryegrass 51.0
Rice straw 80–100 °C boiling Activated sewage sludge 4.0–5.5 35.0 14.5 + 0.3 [37]
Food waste+ sewage sludge +3% 100 °C heat shock (for 30 min) Mixed culture 5.5 35.0 179.3 [38]
crude glycerol
Distillery wastewater Neutralisation (to pH 6.7 with KOH), 5000 rpm centrifugation, sterilisation Mixed culture 5.0 37.0 1.6 ± 0.3* [39]
Cassava wastewater Sieving, 95 °C boiling (for 15 mins) Mixed culture 5.5 37.0 39.8** [40]
Rice straw Cutting and grinding (2 mm size), 1.0% alkali pre-treatment, cellulose Clostridium pasteurianum 7.5 37.0 ± 2 2.6*** [41]
hydrolysis (47.6 mL/g released
sugar)
Food waste hydrolysate Sieving, 100 °C boiling (for 6 h) A. awamori, A. oryzae 4.0–4.6 37.0 219.9 (39.1 mL/g food [42]
waste)
Food waste + sludge 120 °C heating (for 30 mins), alkalisation (3 M NaOH), acidification (3 M HCl) - 5.5 ± 0.1 37.0 13.8 [43]
Food waste +5% crude glycerol Kitchen mill shredding Mixed culture 5.0–5.5 35.0 ± 1 180.0 [44]
Sugarcane bagasse H2SO4 (2%) in solid-to-liquid and mass ratio 1:15, 121 °C sterilisation (for 1 h) Enterobacter aerogenes 6.8 30.0 1000.0**** [45]
Brewery wastewater Dilution with distilled water, pH adjustment with HCL and NaOH Klebsiella pneumoniae 5.5 35.0 ± 1 1.7***** [46]
Glucose – Thermotoga neapolitana 6.5 70.0 1.7***** [47]
Wheat straw Overnight soaking in acetic acid, steam explosion at 190 °C (for 10 min), Caldicellulosiruptor 6.5 ± 0.1 70.0 134.0****** [48]
enzymatic hydrolysis for 72 h saccharolyticus

*mL/mL wastewater; **mL/g- COD; ***L/L hydrolysate

****mL/L hydrolysate; *****mol H2 mol−1 glucose; ******mmol H2/L
Biomass Conv. Bioref.
Biomass Conv. Bioref.

the case of cornstalk pre-treated with lime compared with that pH 5.5 and methanogenic inhibitor from mixed microalgae
of the untreated stalk (115 mL H2/g VS) [55]. Song et al. [56] biomass (Scendesmus and Chlorella).
studied biohydrogen production from an aquatic weed, Production of biohydrogen by dark fermentation is accom-
Alternanthera philoxeroides, pre-treated with 1% H2SO4 at plished by various microorganisms that are capable of
135 °C for 15 min, using Enterobacter aerogenes ZJU1. converting a wide range of organic waste substrates. Based
The optimum H2 production was found to increase by on different living temperatures, these microorganisms are
59.9% to reach production of 62.2 mL/g with pre-treatment classified as thermophiles (45–65 °C), mesophiles (25–
compared with 38.9 mL/g VS for the raw material, without 45 °C) and psychrophiles (0–25 °C). The commonly used
pre-treatment. That low hydrogen yield may be due to the mesophilic cultures for H2 production are Clostridium and
utilisation of different feedstocks (115 mL H2/g VS). Shao Enterobacter (Clostridium beijerinckii, Clostridium
et al. [57] used dilute acid (1% H2SO4)-pre-treated duckweed butyricum, Enterobacter aerogenes and Enterobacter
biomass for H2 production using dark fermentation. They asburiae); while the most reported thermophilic one is
found a maximum H2 yield of 169.30 mL/g dry weight under Thermoanaerobium (Thermoanaerobacterium
a temperature condition of 35 °C and an initial pH value of thermosaccharolyticum) [35]. Again, depending on their
7.0. Acid pre-treatment (0.2% HCl) of dairy manure was also growth of metabolism in the presence of oxygen, they are
seen improving the H2 yield by 36%; further 6.8 and 4.5% divided as facultative (e.g. E. cloacae, Enterobacter
improvement in H2 production from dairy manure was report- aerogenes, Citrobacter intermedius and Escherichia coli) or
ed for base pre-treatment (0.2% NaOH) solution and infrared obligate bacteria (e.g. C. paraputrificum, Ruminococcus albus
oven pre-treatment, respectively [35]. Thus, it can be seen that and Clostridium beijerinckii) [13, 64]. Facultative bacteria are
pre-treatment of substrates is highly recommended for good the organisms that make ATP by aerobic respiration (in the
yield of biohydrogen in dark fermentation. presence of oxygen) and are also capable of anaerobic respi-
Another important parameter for the dark fermentation ration or fermentation (in the absence of oxygen). On the
biohydrogen yield is the pH environment value. pH level contrary, obligate bacteria are unable to produce ATP (in the
in the dark fermentation process is found to influence the absence of oxygen) and cannot live in the presence of oxygen.
metabolic pathway and microorganism activity of the mi- Enterobacter and Clostridium are two species of gram-
croorganisms and thereby affect the substrate degradation positive bacteria for large-scale production of hydrogen for
and production efficiency. The pH levels at the start of their ability of fast-growing and forming endospores. Lactic
operation and during the process were seen carefully main- bacteria like Klebsiella pneumoniae, Cellulomonas and some
tained in many dark fermentation studies [58–60]. Using thermophilic archaea like Thermotoga neapolitana and
dark fermentation of cheese whey wastewater, the highest Caldicellulosiruptor saccharolyticus were also found show-
biohydrogen production was found at pH 5.5 and pH 6.5 ing good results for H2 production through dark fermentation
for thermophilic and mesophilic conditions, respectively [65].
[59]. Xing et al. [35] studied a wide variation in pH be- HRT (hydraulic retention time) acts as one of the important
tween 4.0 and 12.0 for fermentation of dairy manure. At parameters for proper fermentation of substrate and efficient
pH 5.0, they found the highest biohydrogen yield of H2 production. The stability of the reactor and utilisation effi-
31.5 mL/g VS. A pH below 4.0 and above 12.0 showed ciency of the feedstock depends on HRT. Santiago et al. [66]
no biohydrogen production. found that HRT and solid retention time (SRT) have a great
Hydrogenotrophic methanogens act as one of the major impact on the biohydrogen production and associated sub-
H2-consuming microorganisms which reduced the H2 yield products from organic solid waste (OSW) using a dark fer-
by consuming H2 to produce methane. Therefore, inhibiting mentation process. A 16 h of HRT and 55 h of SRT were
the production of hydrogenotrophic methanogens, which acts found to be the optimum conditions to maximise the
as an H2-consuming microorganism, is one of the major steps biohydrogen production. HRT was found as the main
for dark fermentation. Pre-treatment of inoculum is considered influencing parameter in the whole process. The substrate hy-
for enriching H2-producing bacteria and suppressing H2-con- drolysis rate increased with decreasing HRT time. Moreover,
suming methanogens. Since methanogens are strictly anaero- substrate hydrolysis-ssolubilisation process time got reduced
bic microorganisms, aeration around the reactor can inhibit the with an increase in SRT and a decrease in HRT. Fatty acid
methanogen production and thereby increase the H2 yield production was found maximum with long SRT and HRT of
[61]. The impact of pH in the growth of methanogen is another 60 h and 48 h, respectively. Lu et al. [67] studied the effects of
important aspect of biohydrogen yield. It has been reported HRT and concentration of substrate on the HPR (hydrogen
that methanogens are capable of producing methane by con- production rate) from glucose in a pilot-scale bioreactor of
suming H2 under an optimal pH range of 7–8 and optimal 3 m3 with three sequential chambers of 1 m3 each. A HRT
hydraulic retention time (HRT) of 15–20 days [62]. Kumar of 24 h and substrate concentration of 30 g/L with a maximum
et al. [63] attained a hydrogen yield of 29.5 mL/g VS with HPR of 100.2 mol/m3-d were found optimal for the reactor.
 Biomass Conv. Bioref.

The production of biohydrogen using dark fermentation of which include the Rhodobacter species (Rhodobacter
two different cheese deproteinisation diary waste streams capsulatus, Rhodobacter sphaeroides, Rhodovulum palustris
SCW (second cheese whey) and CCWP (concentrated cheese and Rhodopseudomonas sulfidophilum) [72]. Some other bac-
whey permeate) was studied by Colombo et al. [68]. With an teria used in H2 production using nitrogenase and ATP pro-
increasing OLR (organic loading rate), H2 production was duction are Chlorobium vibrioforme, Allochromatium
seen increasing to 3.47 NL H2/d and 5.07 NL H2/d for SCW vinosum, Desulfuromonas acetoxidans, Thiocapsa
and CCWP, respectively. Similarly, organic acid yield was roseopersicina and Chloroflexus aurantiacus [13].
also found higher with increasing OLR (14.6 g/L/d and Hydrogenase and nitrogenase are two different enzymes that
12.6 g/L /d for SCW and CCWP, respectively). Table 2 de- help these bacteria to produce H2 from organic acids using
scribes different studies of biohydrogen production from solar energy [73]. Nitrogenase are found to be the main en-
wastes using a dark fermentation pathway. It can be seen that zymes responsible for H2 production in limited-O2 conditions.
combined fermentation of different substrates leads to an in- NH3 is generally produced from N2 by nitrogenase (in large-
creased biohydrogen yield. Moreover, pre-treatment process- scale production), but in absence of N2, ATP is used along
es such as acid treatment, base treatment, heat treatment and with redundancy by nitrogenase to generate H2 [13], as shown
pH neutralisation have shown a significant impact on the yield in Eq. 8.
of biohydrogen. Most of the studies were found to utilise a
mixed culture process for good results. ð2Hþ þ 2e− þ 4 ATP→H2 þ 4ADP þ PiÞ: ð8Þ

3.1.2 Photofermentation Several studies can be found regarding photofermentive H2

production in recent years. Mirza et al. [74] found a wide
The production of H2 with photofermentation involves de- range of 148–513 mL H2/L photofermentive biohydrogen
composition of organic acids with the aid of light-dependant, production using raw sugarcane bagasse with the help of
sulphur and non-sulphur purple bacteria. A group of bacteria PNSB (purple non-sulphur bacteria) isolated from the paddy
having the ability to do photosynthesis is known as purple rice field Rhodobacter capsulatus-PK. A maximum yield of
sulphur bacteria. Again, purple non-sulphur bacteria 96 mol H2/mol sugar was achieved with initial pH 7.0 ± 0.2
(PNSB), commonly known as photobacteria, are a group of and 10% (v/v) inoculum size, at a temperature of 30 ± 2.0 °C
photoheterotrophic bacteria capable of degrading several car- along with a light intensity of 120–150 W/m2. The production
bon substrates like carbohydrate, organic matter, biowastes of 671 mL/L of H2 from glucose was also found with this
and organic acids for the production of H2 [69]. Equations 6 process. For cost reduction of temperature control during sum-
and 7 show the reaction involved with the production of H2 by mer, Rhodobacter capsulatus-PK was found as a good candi-
photofermentive process from glucose and acetic acid, respec- date for photofermentive bio-H2production. García-Sánchez
tively. Oxidation of organic acids, like acetic acid, propionic et al. [75] used Rhodopseudomonas pseudopalustris to pro-
acid, butyric acid, lactic acid and malic acid, by duce H 2 by tequila vinasses (VT) photofermentation.
photofermentive bacteria, produces H2 and CO2. Therefore, Compared with synthetic medium, they found a double H2
to obtain a higher H2 yield, the two-stage dark fermentation yield with VT. With the replacement of H2 by N2 compared
process is often followed by a photofermentation process [70]. with unchanged headspace, three-time growth was seen in
The energy needed for the growth of microorganisms is gath- R. pseudopalustris up to 4.5 g/L, and the H2 yield also in-
ered from the production of adenosine triphosphate (ATP) creased to 860 mL H2/L. Laurinavichene et al. [39] used
using light through photophosphorylation [4]. Batch or con- PNS bacteria and anaerobic saccharolytic consortium to per-
tinuous photofermentation process can be obtained using an form sequential dark photofermentation, which resulted in
artificial source of light or solar illumination as shown in Fig. 17.6 L/L of distillery waste of maximum H2 yield. Machado
3b. et al. [76] investigated the influence of milk whey permeate
and glucose on the H2 yield using PNS bacteria Rhodobacter
C6 H12 O6 þ 6 H2 O→6 CO2 þ 12 H2 ð6Þ capsulatus and Rhodopseudomonas palustris through co-cul-
2CH3 COOH þ 4H2 O→8H2 þ 4CO2 ð7Þ ture. The maximum H2 yield was found to be 287.39 ±
5.75 mmol of H2/L day. Keskin and Hallenbeck [77] used
The photofermentation process offers the possibility of beet two major sugar mill waste—black strap and beet molas-
high H2 production from a wide variety of substrates including ses for biohydrogen production using photofermentation. The
wastewaters (such as olive mill wastewater, dairy wastewater, H2 yield found from pure beet sucrose, black strap and beet
brewery wastewater) and wastes rich in organic acids (such as molasses are 14 H2/mol sucrose, 8 H2/mol sucrose and
dark fermentation effluent, agricultural waste after hydrolysis) 10.5 mol H2/mol sucrose, respectively. A comparative study
[33, 71]. The best H2-producing microorganism for the of different parameters involved in photofermetive
photofermentation is PNS (purple non-sulphur bacteria), biohydrogen production process is shown in Table 3. The
Table 3 Comparison of biohydrogen production with photofermentation
Biomass Conv. Bioref.

Substrate Pre-treatment process Microorganism pH Temperature Light H2 yield [Ref.]

(°C) (W/m2)

DF effluent of - R.capsulatus B10, R. sphaeroides B-3059 7.0 30.0 30.0 3.2 mL/mL [39]
distillery wastewater
wastewater
Rotten apple batch Crushing, sieve screening Mixed culture 7.1 30.5 24.0 112.0 mL/g TS [78]
Palm oil mill effluent - Rhodopseudomonas palustris 5.5 30.0 ± 1 55.3 2.3 mL H2/mL [79]
POME
DF effluent of Centrifugation, Vacuum filtration Rhodopseudomonas BHU 01 6.8 34.0 8.5 755.0 mL/L [45]
sugarcane bagasse hydrolysate
DF effluent of corn - Mixed culture 7.0 ± 0.08 30.0 23.7 4.7 m3/m3-d [80]
stover
Sugar beet molasses Addition of buffer, pH R. sphaeroides O.U.001 7.5 30.0 114.0 9.4 mol/mol sucrose [81]
adjustment, sterilisation R. capsulatus YO3 10.6 mol/mol
sucrose
R. capsulatus DSM 1710 12.7 mol/mol
sucrose
Rhodopseudomonas palustris DSM 127 19.0 mol/mol
sucrose
Cornstalk pith Enzyme cellulase hydrolysis (at Mixed culture 7.0 30.0 15.8 2.6 mol/mol sugar [82]
50 °C) consumed
Chlorella Acid (1% H2SO4) treatment, Clostridium butyricum 7.0 ± 0.1 30.0 ± 1 47.4 388.0 ± 42.1 mL/g [83]
pyrenoidosa + heating at 135 °C (for 15 min) VS
cassava starch
Cellulose - Cellulomonas fimi ATCC 484, Rhodopseudomonas palustris CGA009 - 30.0 40.0 3.8 mol H2/mol [84]
glucose
Brewery wastewater Pre-treated with banana peel Rhodobacter sphaeroides 158 DSM 7.4 30.0 ± 2 126.0 408.3 mL H2 L−1. [85]
Cornstalk pith - Rhodospirillum rubrum, Rhodopseudmonas capsulata, Rhodopseudomonas 7.3 ± 0.5 30.0 15.8 211.9 mL/L-medium [86]
pulastris, Rhodobacter sphaeroides and Rhodobacter capsulatus
Agar embedded - Heat-treated hot-spring sludge 7.4 37.0 39.5 226.2 mL H2/g TS [87]
molasses
Corn stover powder Rhodobacter sphaeroides, Rhodospirillum rubrum, Rhodobacter capsulatus 6.5 30.0 47.4–55.3 62.3 ± 0.8 mL/g VS [88]
and Rhodopseudomonas palustris
 Biomass Conv. Bioref.

Table 4 Comparison of biohydrogen production by microalgae and cyanobacteria

Microalgae/cyanobacteria Production conditions pH T (°C) Light H2 yield [Ref.]

(W/m2)

C. reinhardtii cbn 1–48 (spectral Tris-acetate-phosphate medium, 7.2 25.0 ± 2 426.6 40.2 mL/kg DCW [92]
selective activation of PSI) 5% CO2, dark anaerobic
adaptation
C. reinhardtii Dang 137+ (magnesium deprived) TAP medium 7.7 25.0 34.1 6.0 mmol/L [93]
Chlorella sp. IOAC707S (phosphorous deprived) TAP-seawater medium 7.2 28.0 10.7 38.0 mL/L [94]
Lyngbya sp. (benzoate as a carbon source Basal medium, 600 mg/l benzoate 7.4 32.0 31.6 17.1 μmol H2/g Chl [95]
at late exponential phase a/h
Nostoc PCC 7120 ΔhupW BG110 medium, supplied with a 8.0 30.0 18.8 6.2 ml/L/h [22]
mixture of red and white light,
altering 100% Ar and Ar/N2
(20/80)
C. reinhardtii (CC124) Sulphur-free TAP medium 7.7 - 64.0 1.3 ± 0.1 mL/L/h [96]
C. reinhardtii CC-425 strain (phosphorus and sulphur TAP medium, TAP-sulphur - - 121.6 0.8 μmol/mg Chl /h [97]
deprived)

temperature variation clearly shows that the optimum operat- electrons derived from Eq. 9 are transferred through PS II
ing temperature range of photofermentation lies between 28 and PS I to a potentially sufficient amount for ferredoxin
and 32 °C. Further, the highest H2 yield with (Fd) reduction. The reduced Fd then is used for the reduction
photofermentation can be seen with a neutral pH value of hydrogenase enzyme NADP+ to NADPH, which is respon-
(around 7) in most of the cases [89]. Moreover, the light in- sible for the production of H2, as shown in Eq. 10 [13].
tensity and HRT play a very important role in the H2 yield in
photofermentation. Because of the slow metabolic activity of 2H2 O þ light energy→O2 þ 4Hþ þ 4e− ð9Þ
PNSB in photofermentation, usually longer HRT can be seen 2Hþ þ 2FdðreÞ↔H2 þ 2FdðoxÞ ð10Þ
compared with dark fermentation [33]. Moreover, light source
plays a very important role in the growth of microorganisms
as well as the H2 yield in photofermentation, which can be
3.2.2 Indirect biophotolysis
easily seen in Table 3.
Indirect biophotolysis involves a two-step photosynthetic con-
3.2 Biophotolysis version of light energy to carbohydrates as a form of chemical
energy. As shown in Eq. 11, in the first step, using light energy
Biophotolysis or water-splitting photosynthesis is the pro- O2 and carbohydrate (starch and glycogen in green algae and
cess in which by using oxygenic photosynthetic microor- cyanobacteria, respectively) are produced [91]. By limiting N2
ganisms like cyanobacteria and green microalgae, H2 can during Eq. 10, an increase in carbohydrate yield and reduction
be produced with only sunlight and water. For this process, in O2 amount can be achieved, which subsequently is advan-
FeFe-hydrogenase is needed for the green microalgae ap- tageous for high H2 yield. The second step involves the con-
plication and heterocystous cyanobacteria nitrogenase version of carbohydrate to CO2 and H2 with light energy un-
finds its use [13]. Biophotolysis H2 production can be di- der an anaerobic condition with less O2, as shown in Eq. 12
vided into two ways: (a) direct biophotolysis and (b) indi- and Eq.13. [73].
rect biophotolysis.
6CO2 þ 12H2 O þ light energy→C6 H12 O6 þ 6O2 : ð11Þ
3.2.1 Direct biophotolysis C6 H12 O6 þ 2H2 O→4H2 þ 2CH3 COOH þ 2CO2 : ð12Þ
2CH3 COOH þ 4H2 O þ light energy→8H2 þ 4CO2 ð13Þ
In the direct biophotolysis, photosynthetic microorganisms
like green algae and cyanobacteria absorb 400–700 nm solar Many recent research studies can be found producing
radiation for their cell growth [90]. After accepting solar radi- biohydrogen from green algae and cyanobacteria as shown
ation, the microorganisms can evolve hydrogen through nitro- in Table 4. Kossalbayev et al. [98] studied the biohydrogen
genase or hydrogenase. In direct biophotolysis, water splitting yield using four different cyanobacteria strains: (a)
occurs with a light energy of 680 nm wavelength to produce Desertifilum sp. IPPAS B-1220, (b) Synechocystis sp. PCC
protons, electrons and oxygen as shown in Eq. 9. The 6803, (c) Phormidium corium B-26 and (d) Synechococcus
Biomass Conv. Bioref.

Fig. 4 Schematic diagram of two-chamber and single-chamber MEC (microbial electrolysis cells)

sp. I12. Within 120 dark hours, Synechocystis sp. PCC 6803 chambers, commonly a proton exchange membrane is used.
was seen to have a high H2 accumulation of 0.037 μmol H2/ Other recently developed membranes include a charge-mosaic
mg Chl/h. Again, at 166 h of light incubation, Desertifilum sp. membrane, cation/anion exchange membrane and bipolar
IPPAS B-1220 was seen to produce 0.229 μmol H2/mg Chl/h. membrane [102]. In the two-chamber MEC, the anode cham-
Hoshino et al. [92] investigated the H2 and O2 yield through ber is filled with the organic wastewater, while the cathode
the implementation of PS I light in Chlamydomonas chamber can be filled with different solutions (like moderate
reinhardtii mutant strains. In a continuous 18 h PS I light acidified water, phosphate-buffered solution, bicarbonate
supply, H2 production was seen at 220 dm3/kg and 176 dm3/ buffers and salt solutions) [103, 104]. The main working pro-
kg for cbn 1–48 (a mutant with a chlorophyll-b deficiency) cess in both the MEC types is the same. Electrons get gener-
and VHLR-S4 (a mutant with high light tolerance), respective- ated by the oxidation of organic matter in the anode, which are
ly. The highest H2 production of 366 dm3/kg was seen in cbn transported to the anode. Then, they are transported to the
1–48 under 1.5 h light and dark iteration with PS I-light. cathode where upon combining with protons, H2 gets gener-
Esquível et al. [99] also studied the H 2 yield with ated [33].
biophotolysis by Chlamydomonas reinhardtii wild and mu- The initial MEC systems comprised of two chambers
tant strains. Kosourov et al. [100] found a maximum of avoiding interference of electrodes, which produced high-
9.4 μmol/mg chlorophyll/h H2 yield with a 7.7 pH by using purity H2 [105]. MEC acts as an anaerobic system sensitive
C. reinhardtii. Huesemann et al. [101] studied H2 production to oxygen. Equations 14–16 show the production of H2 using
using Plectonema boryanum (nonheterocystous nitrogen- MEC for acetate. In addition to a potential generated by mi-
fixing cyanobacterium) under continuous illumination, where croorganisms (− 0.300 V), MEC needs a small external
the maximum H2 production rate was found as 0.18 mL/ potential of more than 0.110 V for the production of H2
mg day with a 1 mM initial nitrate concentration under [106]. The external power source use of the battery is gener-
100 μmol/m2 light intensity. ally considered, but the use of renewable power generated
from solar, wind, MFCs and waste heat can be seen [19, 107].
3.3 Bioelectrochemical system
Anode : CH3 COOH þ 2H2 O→2CO2 þ 8e− þ 8Hþ ð14Þ
Bioelectrochemical system of H2 production from a wide va- Cathode : 8e− þ 8Hþ →4H2 ð15Þ
riety of substrates using microbial electrolysis cells (MEC) is a Overall : CH3 COOH þ 2H2 O→2CO2 þ 4H2 ð16Þ
new technology getting popularity in recent years. MEC tech-
nology is also known as biocatalysed electrolysis cells or Many different substrates were found in use for MEC to
electrofermentation [13]. As shown in Fig. 4, the MEC system produce H2. Some common pure chemical substrates used are
has two electrodes, cathode and anode, which can either be butyrate, glucose, acetate and glycol. However, different
placed in the same single chamber (single-chamber MEC) or waste streams like poultry farming wastewater [108, 109],
be separately placed in two individual chambers (two-cham- domestic wastewater [105, 110, 111], waste activated sludge
ber MEC). In the two-chamber MEC, to separate the two [112–114] and industrial wastewater [115, 116] are used in
 Biomass Conv. Bioref.

Table 5 A comparison study of working parameters of MEC

Type of waste Type of MEC reactor Temperature (°C) pH External H2 yield [Ref.]
voltage (V) (L/L/d)

Domestic wastewater 6 two-chamber cassettes 13.5 ± 1.2–21.0 ± 1.2 7.0 ± 0.4 (influent), 1.1 0.02 L/L/d [105]
(Pilot-scale) MEC 6.7 ± 0.2 (effluent)
Swine manure wastewater Two-chamber MEC 25.0 ± 2 7.0 1.2 5.1* [108]
Waste activated sludge Single-chamber MEC 20.0 7.0 ± 0.2 0.6 90.6** [113]
Effluent from DF sugar beet Two-chamber MEC 25.0 7.2 0.4 306.0*** [115]
juice wastewater
Food processing wastewater Single-chamber MEC 30.0 7.3 0.7 0.4 [116]
(FP)
Chemical industrial wastewater 6.4 0.6
(IN)
Cornstalk wastewater Two-chamber MEC 25.0 ± 2 7.0 1.0 3.9**** [119]

*mmol/g COD; **mL/g VSS; ***mL/g COD; ****mL/L/d

MEC. Tenca et al. [116] found a higher H2 yield for methanol- biohydrogen production processes. Again, an increasing H2
rich industrial wastewater compared with food processing yield with increasing external applied voltage was reported in
wastewater, but the food processing wastewater was found the literature [108, 113].
to have high H2 selectivity of around 86% compared with that In MEC, certain microorganisms which are capable of
of industrial chemical wastewater. Improvement in the H2 transferring electrons from the chamber to anode are used,
yield can be seen in many studies with MEC coupled with known as electrogens. Shewanella spp. and Geobacter spp.
anaerobic digestion and/or dark fermentation [114, 115, 117, are two popular electrogenic groups, out of which Shewanella
118]. Huang et al. [117] studied the H2 production from food oneidensis and Geobacter sulfurreducens are the most
waste from anaerobic digestion coupled with the single- discussed species [122]. Acetobacterium woodii,
chamber MEC. They found 511.02 mL H2/g VS of the H2 Ochrobactrum anthropic, Sphingomonas strain DJ,
yield from the continuous AD-MEC process which was much Rhodopseudomonas palustris and Rhodoferax ferrireducens
higher than the AD H2 yield (49.39 mL H2/g VS). Dhar et al. are some other exoelectrogenic species reported in recent
[115] studied the H2 yield from sugar beet juice using an in- studies [33, 122–124]. Rago et al. [125] found a high H2 yield
tegrated MEC dark fermentation process. Overall H2 yield (2.6 L H 2 /L R E A C T O R /d) with alkaline MEC, using
with the integrated process was found to be 25% of initial Alkalibacter sp. as exoelectrogen.
chemical oxygen demand (COD) (6 mol H2/mol hexoseadded)
which is much higher than that of dark fermentation alone
(13% of initial COD). Li et al. [118] also found a maximum 4 Biohydrogen production
H2 yield of 387.1 mL H2/g corn stalk with the integrated dark through gasification
fermentation MEC process, which was around thrice that from
dark fermentation alone with 20 g/L of corn stalk input and 7.0 Gasification of biowaste is another way of producing bio-H2. In
initial pH value. Lu et al. [114] also found twice H2 yield with gasification, syngas (a mixture of CO, CO2, H2 and CH4) and
waste activated sludge coupled with MEC (Table 5). several by-products (tar, char, light HCs) are produced by partial
Raw materials, temperature, pH and operating voltage play oxidation of organic materials at high temperature and pressure
an important role in determining the H2 yield in MEC. [126]. Even though gasification is not a biological process, it is
However, with MEC, it has been noticed that operating tem- effective for organic waste conversion to hydrogen. The concen-
peratures from 0 can be used in producing biohydrogen from tration of H2 produced during gasification can be improved by
wastewater without having significant effects on the yield. An optimisation of operating parameters. Equations 17–23 show the
H2 yield of 0.015 L/L/d was found with domestic wastewater main reactions involved during gasification.
within an operating temperature range of 13 to 21 °C [105].
Heidrich et al. [120] found improvement in exoelectrogen 2C þ O2→2CO ð17Þ
activities with temperature while studying MEC with domes- C þ O2→CO2 ð18Þ
tic wastewater within 1–22 °C. Patil et al. [121] also demon-
strated operating MEC with wastewater within 0 to 45 °C. C þ H2 O→CO þ H2 ð19Þ
Better performance was seen within 10 °C to 20 °C, thereby
showing the advantages of MEC over other fermentative C þ CO2 →2CO ð20Þ
Biomass Conv. Bioref.

C þ 2H2 →CH4 ð21Þ Table 6 Advantages and challenges with biohydrogen production with
biological methods
CO þ H2 O→CO2 þ H2 ð22Þ
CH4 þ H2 O→CO þ 3H2 ð23Þ H2 production Advantages Challenges
processes
Gasification of different types of waste materials like sew- Dark fermentation ➢ The utilisation of a ➢ Separation of H2
age sludge, municipal solid waste, agricultural and forest bio- diverse, wide variety needed from CO2+H2
mass, animal manure and food waste has been seen as a pop- of different wastes. mixture after
ular technology to produce hydrogen [33]. Prasertcharoensuk ➢ H2 production rate is production.
high. ➢ BOD level in the
et al. [127] studied the effect of parameters on hydrogen pro- ➢ Reactor effluent is high.
duction through lignocellulosic biomass waste gasification. configuration is ➢ Pre-treatment is neces-
H 2 content in the syngas was found increasing up to simple. sary for lignocellulosic
67 mol% with pyrolysis temperature higher than 800 °C and waste.
0.5–1 cm3 particle size. Su et al. [128] studied the effects of Photofermentation ➢ High COD removal ➢ An external source of
rate. light is required
temperature (400–450 °C), food additive (NaHCO3, NaCl and ➢ High H2 yield. ➢ H2 production rate is
NaOH) and reaction time (20–60 min) on the supercritical low.
water gasification of food waste. They found a maximum H2 ➢ The need for low light
yield of 12.73 mol/kg with NaOH as a catalytic agent. Zhang conversion efficiency.
➢ Not suitable for other
et al. [129] found 28.9% H2 content from food waste with an
wastes except
anaerobic digestion and gasification integrated process. VFA-rich waste.
Chang et al. [130] found a maximum of 29.72 g H2/kg sub- Biophotolysis ➢ Use of renewable ➢ A customized
strate and 19.78 g H2/kg substrate H2 yield with bagasse gas- energy. photobioreactor is
ification and waste mushroom gasification, respectively. Shie ➢ High light H2 required.
conversion efficiency ➢ H2 yield is low
et al. [131] studied plasma gasification of lignocellulosic mu-
(microalgae with ➢ External light source is
nicipal solid waste for H2 production. The effect of different FeFe hydrogenase). required.
factors like biomass type, reaction temperature, feed size, cat- MEC ➢ H2 yield is high. ➢ H2 production rate is
alyst type and SB (steam-to-biomass) ratio on the H2 produc- ➢ High COD removal low.
tion in a steam gasification process is discussed by rate. ➢ The need for external
➢ Suitable working voltage.
Parthasarathy and Narayanan [132]. Nanda et al. [133] studied
under room ➢ A catalyst is needed for
supercritical water gasification of different agro-food residues temperature. the electrode.
and fruit wastes like a banana peel, Aloe vera rind, lemon peel,
coconut shell, sugarcane bagasse, pineapple peel and orange
peel. During the production of biodiesel, glycerol is produced
in large quantities as a by-product. Recently, Osman et al.
used glycerol along with the alumina foil waste using to be 14.2 ± 0.2 mL/g VSS, and H2 production rate was
photocatalysis to produce a steady state of 4.2 millimole H2 0.1 3 mL/g VSS h [135]. It was found that for
g/TiO2 hr., which is a promising result of multifunctional photofermentation, the maximum H 2 yield was 642 ±
cheap photocatalytic materials for the production of green 22 mL, and the maximum H2 production rate 77.78 mL/
biohydrogen [134]. L/h, with an initial pH of 7 [136]. In another case, the
effect of adding corn stalk enzymatic hydrolysate H2 yield
was found to increase up to 1287.06 mL H2/g TOC, and
the maximum H 2 production rate was found to be
5 Challenges with biohydrogen production 10.23 mL/h [137]. Kossalbayev et al. [98] found a maxi-
through biological methods mum H 2 yield of 0.348 μmol H 2 /mg Chl/h with
Desertifilum sp. IPPAS B-1220. Moreover, energy con-
Several studies have been made so far for enhancing the version efficiency with biophotolysis was found to be
economic feasibility of the H2 production process via bi- around 2.4–4% [22]. Jayabalan et al. [138] found a max-
ological methods. Although these processes have different imum H 2 production rate of 4.38 ± 0.11 mmol/L/D
advantages, there are many key challenges also which from the sugar industry wastewater using MEC. A H2
need to be addressed in future studies [4, 13, 33]. production rate of 3.48 L/L/d and an H 2 yield of
Table 6 describes the different advantages and challenges 511.02 mL H2 g−1 VS was reported from food waste an-
associated with these processes. As shown in Table 6, the aerobic digestion coupled with MEC [117].
biohydrogen production processes vary from process to Water electrolysis is another way of producing hydrogen
process. The maximum yield of H2 production was found from water using electricity. To produce 1 kg H2, around 9 L
 Biomass Conv. Bioref.

of water is needed and 8 kg of O2 occurs as a by-product in carbon electricity and low-carbon H2, as well as using elec-
this process. The hydrogen produced with water electrolysis trolysis, which accounts for only 2% of the global hydrogen
has a purity of 99.99 vol% (strongly depending on the type of production now. Economically, H2 production from natural
electrolysis (AEL, PEM, etc.)) [139]. Yuzer et al. [140] found gas is the cheapest method in most of the countries around
a maximum hydrogen production rate of 11.4 mmol/h with the the world, such as in the Middle East which costs (1$/kg H2).
use of a bipolar membrane. They found the highest energy On the other hand, electrolysis cost is 10–40$/MWh along
efficiency of 82% and an exergy efficiency of 68% with the with full load hours of 3000–6000, so it can compete with
anion exchange membrane. Chakik et al. [141] found a max- natural gas coupled with CCSU (carbon capture storage and
imum efficiency of 99.13% with a production rate of 2.34 mL/ utilisation). Interestingly, countries that import natural gas and
min using a Zn95%Cr5% electrode in 20 g/L NaOH solution at have available sources of renewables or nuclear power could
0.45 A, 5 V. Kovač et al. [142] studied H2 production with a easily find electrolysis as an attractive option. However, the
rate of 1.138 g/h from the electrolysis of alkaline water using production of H2-based fuel using hydrogen as a feedstock is
solar energy. not economically feasible at the moment.
Bio-H2 production through the biological methods, for Overall, electrolysis is a promising route where the efficien-
instance, dark fermentation, can produce H2 without light cy of the electrolyser ranges from 60 to 80%, while for other
along with in photofermentation, and photosynthetic bac- green hydrogen routes such as dark fermentation,
teria can use a wide range of spectral energy. However, photofermentation, biophotolysis and microbial electrolysis
the energy conversion efficiency, in general, is low with cells, their energy conversion efficiencies are low which are
4.3 and 5.11% for dark and photofermentaion processes, 4.3, 5.11, 4.0 and 11.3%, respectively [21–23]. This is as a
respectively [21]. The major challenges herein are the low result of the complex structure of the biomass that requires
bio-H2 production rate and yield and the high cost of the complicated processing procedures during the production of
raw feedstocks; thus, using organic waste materials helps green bio-H2. Also, finding the cheap feedstock of biomass is
to address this issue. crucial herein. For instance, to meet the theoretical H2 produc-
Overall, hydrogen can be produced from various sources, tion demand in the USA, which is 60 MtH2, this would require
with potential supply from renewable electricity, nuclear pow- nearly 100% of its biomass resources. However, by employing
er and lignocellulosic biomass. However, it is currently dom- PV or wind power, only 1% or 6% will be required [143]. The
inated by using fossil-based fuels. From biomass sources, H2 factors that affect the costing of H2 production from electrolysis
production comes mainly from anaerobic digestion, fermenta- are the cost for the electricity, capital expenditure requirements,
tion or gasification routes. While the former route is mature, it conversion efficiency and annual operating hours.
only processes specific feedstocks (food waste, sewage sludge
and crops waste). While fermentation can utilise and process
the non-edible cellulosic part of lignocellulosic biomass, gas- 6 Conclusion
ification can process the whole portion of the biomass, but the
technology is still not fully mature worldwide. H2 production For the future of the zero-carbon economy, biohydrogen is
mostly comes from natural gas and coal, while during its pro- considered a promising candidate for fossil fuel replacement
duction globally, a greenhouse gas in the form of CO2 is due to its zero-carbon emission. This review study provides a
released which is equivalent to the combined generated annual brief critical technological discussion and analysis of the pro-
CO2 emissions of the UK and Indonesia with an energy con- cesses that are used in biohydrogen production from organic
sumption of 275 million tonnes of oil equivalent (2% of total biowastes along with the factors responsible for the efficient
worldwide energy demand) [10]. Thus, carbon capture and H2 yield. Herein, raw materials, processing and production
storage (CCS) is crucial when producing H2 from fossil- techniques and environmental influences of biohydrogen pro-
based fuels along with maximising our way of producing H2 duction have been reviewed. Wide varieties of biowaste ma-
from clean electricity. Currently, the International Energy terials, such as wastewaters, forest and agricultural residues,
Agency (IEA) reported that the technical potential of produc- food wastes and municipal and sewage wastes, have been
ing hydrogen from renewable electricity is expensive. utilised in biohydrogen production. Regarding the high H2
However, it is expected to decrease by 30% by 2030 due to yield and feedstock availability, dark fermentation,
the scaling up of H2 production along with progress in renew- photofermentation and gasification showed clear promising
ables technology that comes with a reduction in the costing. results. The combined fermentation processes also have
Three major technologies could benefit from that: shown promising results in different studies. Pre-treatment
electrolysers (splitting water using electricity to produce H2), of the substrate, pH, temperature and hydraulic retention time
fuel cells and refuelling equipment. With the progress in solar (HRT) are crucial factors in regulating the optimum
photovoltaic and wind renewable energy technologies along biohydrogen production route. The MEC method showed
with batteries, renewable electricity could provide both low- promising results with a good yield of biohydrogen using
Biomass Conv. Bioref.

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given by the EPSRC project “Advancing Creative Circular Economies active and synergistic Pt/Mo2C/Al2O3 catalyst for water-gas shift
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to thank Charlie Farrell and Patrick McNicholl who assisted in the proof- 16. Dhanya BS, Mishra A, Chandel AK, Verma ML (2020)
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