Current challenges and future technology in photofermentation-driven biohydrogen production by utilizing algae and bacteria

Biohydrogen is perceived as the versatile fuel of the future, having the ability to replace fossil fuels in many industrial and commercial sectors and offering the promise of fulfilling future renewable energy demands. Among various options available for the generation of biohydrogen, photofermentation with the help of microbes and algae is one of the most eye-catching approaches due to its relative efficiency, cost economics, and reduced environmental impacts. Generation of biohydrogen by dark fermentation, microbial electrolysis cell as well as photofermentation, along with their bioprocesses, already have been discussed in earlier literature. Photofermentation offers advantages of both biophotolysis (utilization of light energy) and dark fermentation (utilization of organic waste materials as substrate). Many researchers have been reported successful biohydrogen production from photofermentation-based techniques, however not much information is available regarding the considerable gap in industrial and economic challenges in the production of biohydrogen at the commercial level through photofermentation. Efforts have been made in this review to provide updated information on various new technologies being used in this sector, such as the integration of photofermentation with dark fermentation, the use of recombinant DNA technology, and the use of bionanotechnology to improve biohydrogen production through the utilization of various waste. Various challenges in this sector, as well as future perspectives, have been meticulously addressed in order to explore the future of green biohydrogen production for a sustainable future.     

Dark fermentative biohydrogen production using pretreated Scenedesmus obliquus biomass under an integrated paradigm of biorefinery

In recent times, biohydrogen production from microalgal feedstock has garnered considerable research interests to sustainably replace the fossil fuels. The present work adapted an integrated approach of utilizing deoiled Scenedesmus obliquus biomass as feedstock for biohydrogen production and valorization of dark fermentation (DF) effluent via biomethanation. The microalgae was cultivated under different CO₂ concentration. CO₂-air sparging of 5% v/v supported maximum microalgal growth and carbohydrate production with CO₂ fixation ability of 727.7 mg L^?1 d^?1. Thereafter, lipid present in microalgae was extracted for biodiesel production and the deoiled microalgal biomass (DMB) was subjected to different pretreatment techniques to maximize the carbohydrate recovery and biohydrogen yield. Steam heating (121 °C) in coherence with H₂SO₄ (0.5 N) documented highest carbohydrate recovery of 87.5%. DF of acid-thermal pretreated DMB resulted in maximum H₂ yield of 97.6 mL g^?1 VS which was almost 10 times higher as compared to untreated DMB (9.8 mL g^?1 VS). Subsequent utilization of DF effluent in biomethanation process resulted in cumulative methane production of 1060 mL L^?1. The total substrate energy recovered from integrated biofuel production system was 30%. The present study envisages a microalgal biorefinery to produce biohydrogen via DF coupled with concomitant CO₂ sequestration.     

Sustainable biohydrogen production by Chlorella sp. microalgae: A review

The use of fossil fuels is causing a huge environmental impact due to the emission of air pollutants, greenhouse gases, and other ground and water contaminants; also, these fuels are depleting; the world is facing an energy crisis in the years to come if no preventive actions are done. Renewable energies are arising as promising technologies that will complement and even replace conventional fuels shifting the global energy matrix to a cleaner and eco-friendly future. Microalgal biohydrogen is one of those emerging technologies that is showing positive results. This work provides an overview of the key parameters to produce hydrogen from microalgae especially from the genus Chlorella. Current status of chemical and biological hydrogen producing technologies is presented, along with the main metabolic processes for this purpose in microalgae, their characteristic enzymes, several strategies to induce hydrogen production, the key operation parameters and finally providing some remarks about scaling-up and industrial-scale applications.     

New cyanobacterial strains for biohydrogen production

Under certain conditions, cyanobacteria can switch from photosynthesis to hydrogen production, which is a good energy carrier. However, the biological diversity of hydrogen-releasing cyanobacteria has a great unexplored potential. This study is aimed to investigate the ability of new strains of cyanobacteria Cyanobacterium sp. IPPAS B-1200, Dolichospermum sp. IPPAS B-1213, and Sodalinema gerasimenkoae IPPAS B-353 to release H₂ and to evaluate the effects of photosystem II inhibitor 3-(3,4-dichlorphenyl)-1,1-dimethylurea (DCMU) on H₂ production under light and dark conditions. The results showed that cultures treated with DCMU produced several times more H₂ than untreated cells. The highest rate of H₂ photoproduction of 4.24 μmol H₂ (mg Chl a h)^?1 was found in a Dolichospermum sp. IPPAS B-1213 culture treated with 20 μM DCMU.     

Improvement of biohydrogen production from brewery wastewater: Evaluation of inocula,support and reactor

This work explores the production of biohydrogen from brewery wastewater using as inoculum a culture produced by natural fermentation of synthetic wastewater and Klebsiella pneumoniae isolated from the environment. Klebsiella pneumoniae showed good performance as inoculum, as evaluated using assays of between 9 and 16 cycles, with durations of 12 and 24 h, carbohydrate concentrations from 2.79 to 7.22 g L⁻¹, and applied volumetric organic loads from 2.6 to 12.6 g carbohydrate L⁻¹ day⁻¹. The best results were achieved with applied volumetric organic loads of 12.6 g carbohydrate L⁻¹ day⁻¹ and cycle length of 12 h, resulting in mean volumetric productivity of 0.88 L H₂ L⁻¹ day⁻¹, maximum molar flow of 10.80 mmol H₂ h⁻¹, and mean yield of 0.70 mol H₂ mol⁻¹ glucose consumed. The biogas H₂ content was between 18 and 42%, while the mean organic compounds removal and carbohydrate conversion efficiencies were 23 and 81%, respectively. The inoculum produced by natural fermentation was not viable.     

A review on pretreatment methods,photobioreactor design and metabolic engineering approaches of algal biomass for enhanced biohydrogen production

The development of alternative fuels has been promoted by the extreme fossil fuel consumption brought on by urbanisation and deteriorating pollution. Due to its high energy and combustible qualities, biohydrogen has been perceived as a potential fuel substitute in dealing with issues related to the rising emission of greenhouse gases and global warming. As a source of carbon sequestration and sustainable renewable energy, biohydrogen synthesis by algae species has been prevalent in research scale. This review focuses on the novel and recent metabolic approaches for enhanced algal based biohydrogen production. Pretreatment methods available and scaling techniques used for enhancing the biohydrogen productivity using algal species have been elaborated in the review. Algal characteristics that make them suitable alternative for biohydrogen production are discussed briefly. Various pretreatment methods such as physical, chemical, biological and thermal are elaborated. In addition, the factors involved in influencing the biohydrogen productivity and the metabolic engineering approaches for modifying the pathway in algae are highlighted. Scaling up of process using different types of photobioreactors such as tubular, flat panel, airlift and stirred tank are reported that briefs about merits and demerits of each photobioreactor.     

HRT control as a strategy to enhance continuous hydrogen production from sugarcane juice under mesophilic and thermophilic conditions in AFBRs

The objective of this study was to evaluate the effects of hydraulic retention time (HRT) (8–1 h) on H₂ production from sugarcane juice (5000 mg COD L⁻¹) in mesophilic (30 °C, AFBR-30) and thermophilic (55 °C, AFBR-55) anaerobic fluidized bed reactors (AFBRs). At HRTs of 8 and 1 h in AFBR-30, the H₂ production rates were 60 and 116 mL H₂ h⁻¹ L⁻¹, the hydrogen yields were 0.60 and 0.10 mol H₂ mol⁻¹ hexose, and the highest bacterial diversities were 2.47 and 2.34, respectively. In AFBR-55, the decrease in the HRT from 8 to 1 h increased the hydrogen production rate to 501 mL H₂ h⁻¹ L⁻¹ at the HRT of 1 h. The maximum hydrogen yield of 1.52 mol H₂ mol⁻¹ hexose was observed at the HRT of 2 h and was associated with the lowest bacterial diversity (0.92) and highest bacterial dominance (0.52).     

Integrated process to produce biohydrogen from wheat straw by enzymatic saccharification and dark fermentation

In this study, different pretreatment methods, including lyophilization, hydrothermal pretreatment, and ultrasound combined with dilute alkali post-cooking, were investigated to enhance the efficiency of enzymatic saccharification and biohydrogen production of the wheat straw. All pretreatment methods could effectively remove lignin and hemicellulose while retaining cellulose, further enhancing the biomass accessibility for subsequently enzymatic saccharification and biohydrogen production. A reducing sugar concentration of 13.18 g/L was acquired when wheat straw was treated with ultrasound and dilute alkali cooking (R_U). The sequential fermentative hydrogen yield of the substrate R_U was 133.6 mL/g total solids (TS), which was 5.6-fold larger than that of the raw material (23.9 mL/g TS). The study confirmed that ultrasound combined with dilute alkali cooking was an effective method, which not only provided significant guideline for improving biohydrogen production but also presented helpful direction for the efficient pretreatment of other lignocellulosic biomass.     

Hydrofluoroolefin-based mixed refrigerant for enhanced performance of hydrogen liquefaction process

Hydrogen has the highest gravimetric energy density of all fuels; however, it has a low volumetric energy density, unfavorable for storage and transportation. Hydrogen is usually liquefied to meet the bulk transportation needs. The exothermic interconversion of its spin isomers is an additional activity to an already energy-intensive process. The most significant temperature drop occurs in the precooling cycle (between ?150 °C and up to ?180 °C) and consumes more than 50% of the required energy. To reduce the energy consumption and improve the exergy efficiency of the hydrogen liquefaction process, a new high-boiling component, Hydrofluoroolefin (HFO-1234yf), is added to the precooled mixed refrigerant. As a result, the specific energy consumption of precooling cycle reduces by 41.8%, from 10.15 kWh/kg_LH2 to 5.90 kWh/kg_LH2, for the overall process. The exergy efficiency of the proposed case increases by 43.7%; however, the total equipment cost is also the highest. The inflated cost is primarily due to the added ortho-to-para hydrogen conversion reactor, boosting the para-hydrogen concentration. From the perspective of bulk storage and transportation of liquid hydrogen, the simplicity of design and low energy consumption build a convincing case for considering the commercialization of the process.     

Evaluating influences of impurities on hydrogen production in the reaction of Si with water using Si sludge

Hydrogen has attracted much attention as a next-generation energy resource. Among various technologies, one of the promising approaches for hydrogen production is the use of the reaction between Si and water, which does not require any heat, electricity, and light energy as an input. Notwithstanding the usefulness of Si as a prospective raw material of hydrogen production, the manufacturing process of Si requires a significant amount of energy. Therefore, as an alternative to pure Si, this study used a wasted Si sludge, generated though the manufacturing process of Si wafer, for the direct reuse. Thus, the Si-water reaction for the hydrogen generation was investigated in comparison with pure Si and Si sludge by employing X-ray absorption near edge structure (XANES) to evaluate the feasibility of hydrogen production with the use of Si sludge and to identify the influence of impurities contained in Si sludge. As a result, hydrogen was not produced with the use of Si sludge because of containing Al compound as the impurity. Through the XANES analysis, the formation of SiO(OH)₂ was found as core-shell structure, which potentially would hinder the hydrogen generation.     

Interplay between hydrogen production and photosynthesis in a green alga expressing an active photosystem I-hydrogenase chimera

We have previously created and expressed a chimeric polypeptide joining the PsaC subunit of Photosystem I (PSI) to the HydA2 hydrogenase of Chlamydomonas reinhardtii and demonstrated that it assembles into the PSI complex and feeds electrons directly to the hydrogenase domain, allowing for prolonged photobiological hydrogen production. Here we describe a new PSI-hydrogenase chimera using HydA1, the more abundant and physiologically active endogenous hydrogenase of this alga. When the PsaC-HydA1 polypeptide was expressed in a C. reinhardtii strain lacking endogenous hydrogenases, it was assembled into active PSI-HydA1 complexes that were accumulated at a level ～75% that of PSI, which is ～5 times higher than the PSI-HydA2 chimera. Hydrogen production by the chimera could be restored after complete inactivation by oxygen without requiring new synthesis of PSI or the PsaC-HydA1 polypeptide, demonstrating that the complex could be repaired in vivo. The PSI-HydA1 chimera reduces ferredoxin in vivo to such an extent that it can drive the Calvin-Benson-Bassham cycle, leading to high O₂ production rates, and eventually resulting in inactivation of the hydrogenase; use of media that drastically diminished CO₂ fixation and an O₂-scavenging material allowed H₂ production for at least 4 days.     

Molten salt synthesis of high-entropy alloy AlCoCrFeNiV nanoparticles for the catalytic hydrogenation of p-nitrophenol by NaBH4

High-entropy alloy (HEA) AlCoCrFeNiV nanoparticles were prepared from oxide precursors using a molten salt synthesis method without an electrical supply. The oxide precursor was directly reduced by CaH₂ reducing agent in molten LiCl at 600°C-700°C or molten LiCl–CaCl₂ at 500°C-550°C. When the reduction was conducted at 700°C, a face-centered cubic (FCC) structure produced, as identified by X-ray diffraction analysis. With lower reduction temperatures, the FCC structure was absent, replaced by a body-centered cubic (BCC) structure. With a reduction temperature of 550°C, the resulting sample was composed of highly pure HEA AlCoCrFeNiV nanoparticles with a BCC structure of 15 nm. Analyses by scanning electron microscopy/transmission electron microscopy with energy-dispersive X-ray spectroscopy confirmed the formation of homogeneous HEA AlCoCrFeNiV with a nanoscale morphology. In the hydrogenation reaction of p-nitrophenol by NaBH₄, the AlCoCrFeNiV nanoparticles (produced at 550°C) exhibited a catalytic activity with ～90% conversion and 16 kJ/mol activation energy.     

Leachate valorization in anaerobic biosystems: Towards the realization of waste-to-energy concept via biohydrogen,biogas and bioelectrochemical processes

Leachate generated in landfills is considered as a hazardous waste stream due to its composition and needs adequate treatment for environmental protection purposes. Nonetheless, a contemporary technology should not only be able to deal with its degradation, but at the same time, recover energy in various forms. Such valorization approaches with priority on these dual-aims are potentially those that rely on anaerobic biosystems. In the literature, processes considered on that matter include fermentative, digestive and bioelectrochemical set-ups to deliver energy-carriers such as biohydrogen (DF), biogas (AD) and electricity (BES), respectively. Moreover, to enhance the global efficiency of leachate utilization, it has been recently trending to develop integrated options by combining these systems (DF, AD, BES) into a cascade scheme. In this review, it is intended to give an insight to the research activities realized in these fields and show possible directions towards the better exploitation of leachate feedstock under anaerobic conditions.     

Hydrogen-rich syngas production by gasification of Urea-formaldehyde plastics in supercritical water

Supercritical water is a promising medium to convert plastics into hydrogen and other recyclable products efficiently. In previous research, supercritical water gasification characteristics investigations focus on thermoplastics instead of thermoset plastics due to its chemical, thermal and mechanical stability. Urea-formaldehyde (UF) plastics were selected as a typical kind of thermoset plastics for investigation in this paper and quartz tubes were used as the reactor in order to avoid the potential catalytic effect of metal reactor wall. Conversion characteristic were studied and the influence of different operating parameters such as temperature, reaction time, feedstock mass fraction and pressure were investigated respectively. The molar fraction of hydrogen could reach about 70% in 700 °C. Products in gas phase and solid phase were analyzed, and properties, chemical structures and inhibition mechanism of thermoset plastics was analyzed after comparing with polystyrene (PS) plastics. The result showed that increase of high temperature and long reaction time could promote gasification process, meanwhile the increase in the feedstock mass fraction would result in suppression of the gasification process. Finally, kinetic study of UF was carried out and the activation energy and pre-exponential factor of the Arrhenius equation were calculated as 30.09 ± 1.62 kJ/mol and 0.1199 ± 0.0049 min⁻¹, respectively.     

Transition metal/carbon nanoparticle composite catalysts as platinum substitutes for bioelectrochemical hydrogen production using microbial electrolysis cells

Various metal nanoparticle catalysts supported on Vulcan XC-72 and carbon-nanomaterial-based catalysts were fabricated and compared and assessed as substitutes of platinum in microbial electrolysis cells (MECs). The metal-nanoparticle-loaded cathodes exhibited relatively better hydrogen production and electrochemical properties than cathodes coated with carbon nanoparticles (CNPs) and carbon nanotubes (CNTs) did. Catalysts containing Pt (alone or mixed with other metals) most effectively produced hydrogen in terms of overall conversion efficiency, followed by Ni alone or combined with other metals in the order: Pt/C (80.6%) > PtNi/C (76.8%) > PtCu/C (72.6%) > Ni/C (73.0%) > Cu/C (65.8%) > CNPs (47.0%) > CNTs (38.9%) > plain carbon felt (38.7%). Further, in terms of long-term catalytic stability, Ni-based catalysts degraded to a lesser extent over time than did the Cu/C catalyst (which showed the maximum degradation). Overall, the hydrogen generation efficiency, catalyst stability, and current density of the Ni-based catalysts were almost comparable to those of Pt catalysts. Thus, Ni is an effective and inexpensive alternative to Pt catalysts for hydrogen production by MECs.     

Improving inter-plant integration of syngas production technologies by the recycling of CO2 and by-product of the Fischer-Tropsch process

This paper deals with the emission reduction in synthesis-gas production by better integration and increasing the energy efficiency of a high-temperature co-electrolysis unit combined with the Fischer-Tropsch process. The investigated process utilises the by-product of Fischer-Tropsch, as an energy source and carbon dioxide as a feedstock for synthesis gas production. The proposed approach is based on adjusting process streams temperatures with the further synthesis of a new heat exchangers network and optimisation of the utility system. The potential of secondary energy resources was determined using plus/minus principles and simulation of a high-temperature co-electrolysis unit. The proposed technique maximises the economic and environmental benefits of inter-unit integration. Two scenarios were considered for sharing the high-temperature co-electrolysis and the Fischer-Tropsch process. In the first scenario, by-products from the Fischer-Tropsch process were used as fuel for a high-temperature co-electrolysis. Optimisation of secondary energy sources and the synthesis of a new heat exchanger network reduce fuel consumption by 47% and electricity by 11%. An additional environmental benefit is reflected in emission reduction by 25,145 tCO₂/y. The second scenario uses fossil fuel as a primary energy source. The new exchanger network for the high-temperature co-electrolysis was built for different energy sources. The use of natural gas resulted in total annual costs of the heat exchanger network to 1,388,034 USD/y, which is 1%, 14%, 116% less than for coal, fuel oil and LPG, respectively. The use of natural gas as a fuel has the lowest carbon footprint of 7288 tCO₂/y. On the other hand, coal as an energy source has commensurable economic indicators that produce 2 times more CO₂, which can be used as a feedstock for a high-temperature co-electrolysis. This work shows how in-depth preliminary analysis can optimise the use of primary and secondary energy resources during inter-plant integration.     

Hydrogen production using chemical looping technology: A review with emphasis on H2 yield of various oxygen carriers

Natural H₂ in useful quantities is negligible, which makes hydrogen unsuitable as an energy resource compared to other fuels. H₂ production by solar, biological, or electrical sources needs more energy than obtained by combusting it. Lower generation of pollutants and better energy efficiency makes hydrogen a potential energy carrier. Hydrogen finds potential applications in automobile and energy production. However, the cost of producing hydrogen is extremely high. Chemical-looping technology for H₂ generation has caught widespread attention in recent years. This work, presents some recent findings and provides a comprehensive overview of different chemical looping techniques such as chemical looping reforming, syngas chemical looping, coal direct chemical looping, and chemical looping hydrogen generation method for H₂ generation. The above processes are discussed in terms of the relevant chemical reactions and the associated heat of reactions to ascertain the overall endothermicity or exothermicity of the H₂ production. We have compared the H₂ yield data of different Fe/Ni, spinel and perovskites-based oxygen carriers (OC) reported in previous literature. This review is the first comprehensive study to compare the H₂ yield data of all the previously reported oxygen carriers as a function of temperature and redox cycles. In addition, the article summarizes the characteristics and reaction mechanisms of various oxygen carrier materials used for H₂ generation. Lastly, we have reviewed the application of Density Function Theory (DFT) to study the effect of various dopant addition on the efficiency of H₂ production of the oxygen carriers and discussed ASPEN simulations of different chemical looping techniques.     

Environmental sustainability assessment of large-scale hydrogen production using prospective life cycle analysis

The need for a rapid transformation to low-carbon economies has rekindled hydrogen as a promising energy carrier. Yet, the full range of environmental consequences of large-scale hydrogen production remains unclear. Here, prospective life cycle analysis is used to compare different options to produce 500 Mt/yr of hydrogen, including scenarios that consider likely changes to future supply chains. The resulting environmental and human health impacts of such production levels are further put into context with the Planetary Boundaries framework, known human health burdens, the impacts of the world economy, and the externality-priced production costs that embody the environmental impact. The results indicate that climate change impacts of projected production levels are 3.3–5.4 times higher than the allocated planetary boundary, with only green hydrogen from wind energy staying below the boundary. Human health impacts and other environmental impacts are less severe in comparison but metal depletion and ecotoxicity impacts of green hydrogen deserve further attention. Priced-in environmental damages increase the cost most strongly for blue hydrogen (from ～2 to ～5 USD/kg hydrogen), while such true costs drop most strongly for green hydrogen from solar photovoltaic (from ～7 to ～3 USD/kg hydrogen) when applying prospective life cycle analysis. This perspective helps to evaluate potentially unintended consequences and contributes to the debate about blue and green hydrogen.     

Biomass gasification coupled with producer gas cleaning,bottling and HTS catalyst treatment for H2-rich gas production

The aim of the present study is to demonstrate the production of hydrogen-rich fuel gas from J. curcas residue cake. A comprehensive experimental study for the production of hydrogen rich fuel gas from J. curcas residue cake via downdraft gasification followed by high temperature water gas shift catalytic treatment has been carried out. The gasification experiments are performed at different equivalence ratios and performance of the process is reported in terms of producer gas composition & its calorific value, gas production rate and cold gas efficiency. The producer gas is cleaned of tar and particulate matters by passing it through venturi scrubber followed by sand bed filter. The clean producer gas is then compressed at 0.6 MPa and bottled into a gas cylinder. The bottled producer gas and a simulated mixture of producer gas are then subjected to high temperature shift (HTS) catalytic treatment for hydrogen enriched gas production. The effect of three different operating parameters GHSV, steam to CO ratio and reactor temperature on the product gas composition and CO conversion is reported. From the experimental study it is found that, the presence of oxygen in the bottled producer gas has affected the catalyst activity. Moreover, higher concentration of oxygen concentration in the bottled producer gas leads to the instantaneous deactivation of the HTS catalyst.