Energy transfer in covalent organic frameworks for visible-light-induced hydrogen evolution

We report herein the use of covalent organic frameworks (COFs) to facilitate the energy transfer from sensitizer to the active sites for efficient photocatalysis. The results indicate that the photocatalytic efficiency can be apparently enhanced by using the layered COFs. The visible-light-induced hydrogen evolution rate (10.4 mmol g⁻¹ h⁻¹) for Pd⁰/TpPa-1 sensitized by Eosin Y was 10 times higher than that of Pd/C. The enhanced photocatalytic H₂-production activity could be originated from the improvement of the photogenerated electron transfer in conjugated COFs. The important role of COFs in facilitating the transfer of photogenerated electrons was verified by the transient photocurrent response and the luminescence analysis. This research highlights the use of COFs to investigate the energy transfer process.     

Recent advancements of layered double hydroxide heterojunction composites with engineering approach towards photocatalytic hydrogen production: A review

Photocatalytic hydrogen production has been considered as one of the most promising alternatives for providing clean, sustainable, and renewable energy sources. Tremendous investigation and efforts have been devoted to increase the efficiency of the solar to energy conversion of a photocatalyst. Layered double hydroxide (LDH) received scientific attention for its excellent compositional flexibility and controllable morphology, leading to the facile incorporation of the metal species into their layered structure. The unique multi-structure and the tunability of its band gap make LDH more prominent in the field of photocatalysis. This article highlights the recent developments in the fabrication of LDH-based photocatalyst nanocomposites and the engineering approaches for augmenting their photocatalytic hydrogen production efficiency. The thermodynamics and challenges in photocatalytic water splitting are deliberated to understand the pathways to construct efficient semiconductor photocatalysis system. The efficiency enhancement of LDH-based photocatalysts are comprehensively discussed by giving special attention to the heterojunction engineering of type I, type II, p-n junction, Z-scheme, S-scheme, and R-scheme. Fabrication of the hybrid LDH nanocomposites through band gap engineering and metal loading are summarised. The architectural and morphological tuning of LDH-based composite through the construction of the novel core-shell structure and layer-by-layer nanosheets are also demonstrated. Finally, the future recommendations are outlined to provide insights for their development in the photocatalysis field.     

Recent progress in structural development and band engineering of perovskites materials for photocatalytic solar hydrogen production: A review

Photocatalytic water splitting for hydrogen production is a promising technology for the conversion of solar light to clean energy. In this perspective, several semiconductors have been under investigation, but they show less efficiency, selectivity and stability for hydrogen production. Recently, perovskites are most demanding due to their exceptional characteristics such as controlled structure and morphology, adjustable band structure, controlled valence state, adjustable oxidation state and visible light response. This review highlights structural classification of perovskites and band engineering for solar energy assisted photocatalytic hydrogen production. In the main stream, overview and fundamentals of perovskite materials for selective solar to hydrogen conversion are presented. The structural modification and band alteration to stimulate quantum efficiency and stability are specifically demonstrated. Photoactivity enhancement through metals, noble metals, non-metals doping, oxygen vacancies and fermi level adjustments are also deliberated. The role of perovskites with binary semiconductors towards hydrogen production has also been discussed. Up conversion effect of doping luminescent agents (Er, Ho, Eu, Nd) for improved photocatalytic activity by band gap narrowing is also deliberated. Various conventional and non-conventional synthesis methods for perovskites including solid-state, hydrothermal, sol-gel, co-precipitation, spray-freeze drying, microwave assisted, spray pyrolysis, low temperature combustion, pulse laser deposition and wet chemical method for enhanced photocatalytic activity are also demonstrated in this work. Finally, the key challenges and future directions for sustainable energy systems are also included.     

A comprehensive comparative energy and exergy analysis in solar based hydrogen production systems

In the presented paper, energy and exergy analysis is performed for thermochemical hydrogen (H₂) production facility based on solar power. Thermal power used in thermochemical cycles and electricity production is obtained from concentrated solar power systems. In order to investigate the effect of thermochemical cycles on hydrogen production, three different cycles which are low temperature Mg–Cl, H₂SO₄ and UT-3 cycles are compared. Reheat-regenerative Rankine and recompression S–CO₂ Brayton power cycles are considered to supply electricity needed in the Mg–Cl and H₂SO₄ thermochemical cycles. Furthermore, the effects of instant solar radiation and concentration ratio on the system performance are investigated. The integration of S–CO₂ Brayton power cycle instead of reheat-regenerative Rankine enhances the system performance. The maximum exergy efficiency which is obtained in the system with Mg–Cl thermochemical and recompression S–CO₂ Brayton power cycles is 27%. Although the energy and exergy efficiencies decrease with the increase of the solar radiation, they increase with the increase of the concentration ratio. The highest exergy destruction occurred in the solar energy unit.     

Recent development in band engineering of binary semiconductor materials for solar driven photocatalytic hydrogen production

Photocatalytic hydrogen production from water splitting is a promising approach to develop sustainable renewable energy resources and limits the global warming simultaneously. Despite the significant efforts have been dedicated for the synthesis of semiconductor materials, key challenge persists is lower quantum efficiency of a photocatalyst due to charge carrier recombination and inability of utilizing full spectrum of solar light irradiation. In this review, recent developments in binary semiconductor materials and their application for photocatalytic water splitting toward hydrogen production are systematically discoursed. In the main stream, fundamentals and thermodynamic for photocatalytic water splitting and selection of photo-catalysts has been presented. Developments in the binary photocatalysts and their efficiency enhancements though surface sensitization, surface plasmon resonance (SPR) effect, Schoktty barrier and electrons mediation toward enhanced hydrogen production has been deliberated. Different modification approaches including band engineering, coupling of semiconductor catalysts, construction of heterojunction, Z-scheme formation and step-type photocatalytic systems are also discussed. The binary semiconductor materials such as TiO₂, g-C₃N₄, ZnO, ZnS, Fe₂O₃, CdS, WO₃, rGO, V₂O₅ and AgX (Cl, Br and I) are systematically disclosed. In addition, role of sacrificial reagents for efficient photocatalysis through reforming and hole-scavenger are elaborated. Finally, future perspectives for photocatalytic water splitting towards renewable hydrogen production have been suggested.     

Copper(II) phthalocyanine/metal organic framework electrocatalyst for hydrogen evolution reaction application

Copper(II)phthalocyanine-incorporated metal organic framework (CuPc/MOF) composite material was synthesized for application as an electrocatalyst for hydrogen evolution reaction (HER). The composite exhibited excellent electroactivity compared to the unmodified MOF, as confirmed by the diffusion coefficients (D) values of 3.89 × 10⁻⁷ and 1.57 × 10⁻⁶ cm² s⁻¹ for MOF and CuPc/MOF, respectively. The D values were determined from cyclic voltammetry (CV) experiments performed in 0.1 mol L⁻¹ tetrabutylammonium perchlorate/dimethyl sulfoxide (TBAP/DMSO) electrolyte. The Tafel slope determined from the CV data of CuPc/MOF-catalysed HER for 0.450 mol L⁻¹ H₂SO₄, was 176.2 mV dec⁻¹, which was higher than that of the unmodified MOF (158.3 mV dec⁻¹). The charge transfer coefficients of MOF and CuPc/MOF were close to 0.5, signifying the occurrence of a Volmer reaction involving either the Heyrovsky or the Tafel mechanism for hydrogen generation. For both MOF and CuPc/MOF, the exchange current density (i₀) improved with increase in the concentration of the hydrogen source (i.e. 0.033–0.45 mol L⁻¹ H₂SO₄) Nonetheless, the CuPc/MOF composite had a higher i₀ value compared with the unmodified MOF. Thus CuPc/MOF has promise as an efficient electrocatalyst for HER.     

An investigation of structural and hydrogen adsorption properties of microporous metal organic framework (MMOF) materials

Microporous metal organic frameworks (MMOFs) have garnered great attraction as adsorbent materials for on-board hydrogen storage. To enhance hydrogen adsorption, we have carried out a systematic study to synthesize, characterize, and modify crystal structures of a number of MMOFs and to investigate their pore characteristics. In addition, their hydrogen adsorption properties at cryogenic and ambient temperature over a range of pressures are analyzed.     

Recent advances in catalyst-enhanced LiAlH4 for solid-state hydrogen storage: A review

LiAlH₄ is regarded as a potential material for solid-state hydrogen storage because of its high hydrogen content (10.5 wt%). However, its high decomposition temperature, slow dehydrogenation kinetics and irreversibility under moderate condition hamper its wider applications. Mechanical milling treatment and doping with a catalyst or additive has drawn significant ways to improve hydrogen storage properties of LiAlH₄. Microstructure or nanostructure materials were developed by using a ball milling technique and doping with various types of catalysts or additives which had dramatically improved the efficiency of LiAlH₄. However, the state-of-the-art technologies is still far from meeting the expected goal for the applications. In this paper, the overview of the recent advances in catalyst-enhanced LiAlH₄ for solid-state hydrogen storage is detailed. The remaining challenges and the future prospect of LiAlH₄–catalyst system is also discussed. This paper is the first systematic review that focuses on catalyst-enhanced LiAlH₄ for solid-state hydrogen storage.     

Three-field synergy of solar energy for induced the enhancement of the oxidation of acrylonitrile in coordination with the production of hydrogen

In the review of the successful solar thermal electrochemical process (STEP) of acrylonitrile oxidation for the effective wastewater treatment, the process was actually driven by solar two fields - thermofield and electrofield, essentially activated and motivated for both thermochemistry and electrochemistry. In this paper, the synergistic system of solar three fields, induced by the primary photofield, and sub-thermofield and sub-electrofield, was designed and employed firstly for promoted the efficiency of the solar utilization and pollutant oxidation plus hydrogen production. With the correlative action, the three sub-chemical processes were induced by the solar three fields. The action actually conducted a three-field synergy of solar energy with a combination of the thermo-activation, photocatalysis and electrochemistry of the pollutant oxidation. Exemplified by acrylonitrile, the solar oxidation plus hydrogen production was theoretically and experimentally investigated by the single-field, coupled two-fields and coupled three-fields patterns. The results indicated that the coupled three-field pattern achieved high efficiencies in the solar utilization and oxidative reaction plus the hydrogen production, which was superior to ones of the single or two fields. The solar thermofield enables that the activated acrylonitrile was apt to be thermally decomposed, greatly in favor of the subsequent photo- and electrooxidation. The photocatalytic efficiency driven by the single photofield was reached at a rate of 31.01%. The electrolysis efficiency powered by single electrofield gained a rate of 24.56%. For the combination of the solar three-field pattern, the oxidation efficiencies run up to a rates of 32.74%, 38.06%, 55.01% and 76.01% during 60 min at the 25 °C, 40 °C, 60 °C, 75 °C, respectively. Especially, a joint of the coupled field realized the 6.38 times of the COD removal rate of acrylonitrile in comparison with the single field pattern. Due to the easy anodic oxidation of acrylonitrile and operation under the high temperature, the cathodic reduction of water was enhanced for the production of hydrogen in the electrolysis of the less potential plus an addition of photocatalysis. The experimental data and mechanistic analysis significantly revealed that the system achieved such a synergetic action. The full mineralization plus the hydrogen production was attributed to a coupling and matching integration of the solar three fields and subchemistries.     

GIS based multi-criteria decision making for solar hydrogen production sites selection in Algeria

Hydrogen production from renewable energy sources appears to be an interesting solution for reducing greenhouse gas emissions and ensuring the energy security supply. This paper develops an integrated framework to evaluate land suitability for hydrogen production from solar energy site selection that combines multi-criteria decision making (MCDM) with geographical information systems (GIS); an application of the proposed framework for Algerian country. In GIS two types of criteria will be taken: constraints and weighting criteria. Constraints criteria will make it possible to reduce the area of study by discarding those areas that prevent the implementation of installing solar hydrogen production systems. These criteria will be obtained from the legislation (land use, water bodies, waterways, roads, railways, power lines, and also their buffer around them). Weighting criteria will be chosen according to the objective to be reached, in this case they will be the hydrogen demand, potential solar hydrogen production, digital elevation models (DEMs), slope, proximity to roads, railways, and power lines. Through the use of MCDM the criteria mentioned will be weighted in order to evaluate potential sites to locate a solar hydrogen production installation system. Analysis and calculation of the weights of these criteria will be conducted using Analytic Hierarchy Process (AHP). As a result, the final index model was grouped into four categories as “very low suitability”, “low suitability”, “moderate suitability” and “high suitability” with a manual interval classification method. The results indicate that 10.34% (246,272.02 km²), of the study area has very low suitability, 60.75% (1,446,907.65 km²) has low suitability, 6.68% (159,100.3 km²) has moderate suitability and 0.49% (11,669.21 km²) has high suitability for a solar-powered hydrogen production installation system. The other 21.74% (517,790.5 km²) of the study area is not suitable for such projects. The sensitivity analysis highlights that the suitable sites for solar hydrogen production installation system are dependent on the weights of the criteria that influence the decision. The MCDM methodology integrated with GIS is a powerful tool for effective evaluation of the solar-powered hydrogen production sites selection.     

Effect of different substrate concentrations and salinity on hydrogen production from mariculture organic waste (MOW)

In this paper, the influence of substrate concentrations and salinity on hydrogen production from mariculture organic waste (MOW) at mesophilic condition in batch reactors was determined. It was found that the hydrogen yield and hydrogen content were influenced by the initial substrate concentrations and salinity. The optimum concentration for hydrogen production was 20 g/L. The salinity could produce inhibit effect for hydrogen production. The low hydrogen content was detected at high salinity condition. The nutrients changing and metabolites composition could also be significantly influenced by the salinity. The releasing of carbohydrate from MOW could be easily used for hydrogen production, and protein could be accumulated and assimilated during the hydrogen fermentation. The enhancing of salinity was disadvantage for total metabolites accumulation.     

Design recommendations for solar organic Rankine cycle (ORC)-powered reverse osmosis (RO) desalination

This paper deals with the design recommendations for solar reverse osmosis (RO) desalination based on solar organic Rankine cycles (SORC). This technology can be the most energy-efficient technology for seawater and brackish water desalination within the small to medium power output range (up to 500 kW) of the power cycle if the system is properly designed. However, theoretical studies, design proposals and experimental works are very scarce and only very few solar reverse osmosis systems driven by ORC has been either implemented or analysed in the past. In this paper, those systems are outlined and general design recommendations from previous detailed analysis already publish are given for future RO desalination system to be designed based on SORC. Useful information is given about the selection of the working fluid and boundary conditions of the ORC, operation temperature and configuration of the solar field, suited solar collector and thermal energy storage technology, etc. Recommendations are exemplified with well selected numerical cases based on recommended working fluids and solar cycle configuration with proper values of design point parameters. Recommendations given in this paper could be helpful in future initiatives regarding the research and development of this promising solar desalination technology.     

Current trends in structural development and modification strategies for metal-organic frameworks (MOFs) towards photocatalytic H2 production: A review

Photocatalytic H₂ generation using semiconductor photocatalysts is considered as a cost-effective and eco-friendly technology for solar to energy conversion; however, the present photocatalysts have been recognized to depict low efficiency. Currently, porous coordination polymers known as metal-organic frameworks (MOFs) constituting flexible and modifiable porous structure and having excess active sites are considered to be appropriate for photocatalytic H₂ production. This review highlights current progress in structural development of MOF materials along with modification strategies for enhanced photoactivity. Initially, the review discusses the photocatalytic H₂ production mechanism with the concepts of thermodynamics and mass transfer with particular focus on MOFs. Elaboration of the structural categories of MOFs into Type I, Type II, Type III and classification of MOFs for H₂ generation into transition metal based, post-transition metal based, noble-metal based and hetero-metal based has been systematically discussed. The review also critically deliberate various modification approaches of band engineering, improvement of charge separation, efficient irradiation utilization and overall efficiency of MOFs including metal modification, heterojunction formation, Z-scheme formation, by introducing electron mediator, and dye based composites. Also, the MOF synthesized derivatives for photocatalytic H₂ generation are elaborated. Finally, future perspectives of MOFs for H₂ generation and approaches for efficiency improvement have been suggested.     

Recent development in electrocatalysts for hydrogen production through water electrolysis

Hydrogen is a carbon-free alternative energy source for use in future energy frameworks with the advantages of environment-friendliness and high energy density. Among the numerous hydrogen production techniques, sustainable and high purity of hydrogen can be achieved by water electrolysis. Therefore, developing electrocatalysts for water electrolysis is an emerging field with great importance to the scientific community. On one hand, precious metals are typically used to study the two-half cell reactions, i.e., hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). However, precious metals (i.e., Pt, Au, Ru, Ag, etc.) as electrocatalysts are expensive and with low availability, which inhibits their practical application. Non-precious metal-based electrocatalysts on the other hand are abundant with low-cost and eco-friendliness and exhibit high electrical conductivity and electrocatalytic performance equivalent to those for noble metals. Thus, these electrocatalysts can replace precious materials in the water electrolysis process. However, considerable research effort must be devoted to the development of these cost-effective and efficient non-precious electrocatalysts. In this review article, we provide key fundamental knowledge of water electrolysis, progress, and challenges of the development of most-studied electrocatalysts in the most desirable electrolytic solutions: alkaline water electrolysis (AWE), solid-oxide electrolysis (SOE), and proton exchange membrane electrolysis (PEME). Lastly, we discuss remaining grand challenges, prospect, and future work with key recommendations that must be done prior to the full commercialization of water electrolysis systems.     

A review of CO2 sorbents for promoting hydrogen production in the sorption-enhanced steam reforming process

Sorption-enhanced-steam-reforming (SESR) is a thermochemical conversion technology that produces a high-purity hydrogen stream by utilizing in-situ removal of CO₂ with a sorbent. In this paper, the advantages and disadvantages of CaO based sorbents, alkali-metal based sorbents (Na₂ZrO₃, Li₂ZrO₃ and Li₄SiO₄), hydrotalcite based sorbents, bifunctional materials and sorbents prepared from wastes are briefly discussed, and the techniques to improve the sorption properties of these CO₂ sorbents are summarized. In the process of hydrogen production by sorption-enhanced-steam-reforming, the selection of suitable high-temperature CO₂ sorbent is the key to produce high purity hydrogen. Furthermore, the hydrogen-production performance of the above-mentioned sorbents in the SESR process is investigated and summarized. Finally, a future perspective and some suggestions regarding these five types of sorbents are put forward.     

Environmental impacts of a standalone solar water splitting system for sustainable hydrogen production: A life cycle assessment

Hydrogen is broadly utilized in various industries. It can also be considered as a future clean energy carrier. Currently, hydrogen is mainly produced from typical fuels such as coal; however, there exist some other clean alternatives which use water decomposition techniques. Water splitting via the copper-chlorine (Cu–Cl) thermochemical cycle is a superb option for producing clean carbon-free fuel. Here, the life cycle assessment (LCA) technique is used to investigate the environmental consequences of an integrated solar Cu–Cl fuel production facility for large-scale hydrogen production. The impact of varying important input parameters including irradiation level, plant lifetime, and solar-to-hydrogen efficiency on various environmental impacts are investigated next. For instance, an improve in the solar-to-hydrogen efficiency from 15% to 30%, results in a reduction in the GWP from 1.25 to 6.27E-01 kg CO₂ eq. An uncertainty analysis using Monte Carlo simulation is conducted to deal with the study uncertainties. The results of the LCA show that the potential of acidification and global warming potential (GWP) of the current system are 8.27E-03 kg SO₂ eq. and 0.91 kg CO₂ eq./kg H₂, respectively. According to the sensitivity analysis, the plant lifetime has the highest effect on the total GWP of the plant with a range of 0.63–1.88 kg of CO₂ eq./kg H₂. Results comparison with past thermochemical-based studies shows that the GWP of the current integrated system is 7% smaller than that of a solar sulfur-iodine thermochemical cycle.     

Integration of wind turbine with heliostat based CSP/CPVT system for hydrogen production and polygeneration: A thermodynamic comparison

In this study, two wind-solar-based polygeneration systems namely CES-1 and CES-2 are developed, modeled, and analyzed thermodynamically. CES-1 hybridizes a heliostat based CSP system with wind turbines while CES-2 integrates heliostat-based CPVT with wind turbines. This study aims to compare the production and thermodynamics performance of two heliostat based concentrated solar power technologies when hybridized with wind turbines. The systems have been modeled to produce, freshwater, hot water, electricity, hydrogen, and cooling with different cycles/subsystems. While the overall objective of the study is to model two polygeneration systems with improved energy and exergy performances, the performances of two solar technologies are compared. The wind turbine system integrated with the comprehensive energy systems will produce 1.14 MW of electricity and it has 72.2% energy and exergy efficiency. Also, based on the same solar energy input, the performance of the heliostat integrated CPVT system (CES-2) is found to be better than that of the CSP based system (CES-1). The polygeneration thermal and exergy efficiencies for the two systems respectively are 48.08% and 31.67% for CES-1; 59.7% and 43.91% for CES-2. Also, the electric power produced by CES-2 is 280 kW higher in comparison to CES-1.     

Modeling hydrogen adsorption in the metal organic framework (MOF-5, connector): Zn4O(C8H4O4)3

Density functional theory investigation is performed to understand the underlying mechanism of hydrogen adsorption in the MOF-5 by using for first time the connector structure. The analysis of chemical bonds of the connector's atoms shows a good agreement between experimental and theoretical results. In particular, we show that this material has a desorption temperature of 115 K and an initial hydrogen storage capacity around 1.57 wt% which are close to the experimental values. We consider the coupling-energy mechanism to explore the most stable configurations in multiple adsorption sites namely metallic, carboxylic and cyclic sites. Three orientations which are vertical, horizontal and sloping are taking into account. The results show that the metallic and cyclic sites are more stable for multiple hydrogen molecule storage and the system reaches 4.57 wt% as a gravimetric storage capacity which is located in the interval 4.50–5.20 wt% found experimentally. In addition, the desorption temperature is improved significantly.     

An innovative compressed air energy storage (CAES) using hydrogen energy integrated with geothermal and solar energy technologies: A comprehensive techno-economic analysis - different climate areas- using artificial intelligent (AI)

The present study evaluates the optimal design of a renewable system based on solar and geothermal energy for power generation and cooling based on a solar cycle with thermal energy storage and an electrolyzer to produce hydrogen fuel for the combustion chamber. The subsystems include solar collectors, gas turbines, an electrolyzer, an absorption chiller, and compressed air energy storage. The solar collector surface area, geothermal source temperature, steam turbine input pressure, and evaporator input temperature were found to be major determinants. The economic analysis of the system showed that the solar subsystem, steam Rankine cycle, and compressed air energy storage accounted for the largest portions of the cost rate. The exergy analysis of the system demonstrated that the solar subsystem and SRC had the highest contributions to total exergy destruction. A comparative case study was conducted on Isfahan, Bandar Abbas, Mashhad, Semnan, and Zanjan in Iran to evaluate the performance of the proposed system at different ambient temperatures and irradiance levels during the year. To optimize the system and find the optimal objective functions, the NSGA-II algorithm was employed. The contradictory objective functions of the system included exergy efficiency maximization and cost rate minimization. The optimal Exergy round trip efficiency and cost rate were found to be 29.25% and 714.25 ($/h), respectively.     

Field experience study and evaluation for hydrogen production through a photovoltaic system in Ouargla region,Algeria

An experimental study on small-scale for solar hydrogen production system via a Proton Exchange Membrane electrolysis under a desert climatic condition in Ouargla region (South-East of Algeria) has been carried out, the target of this study has been first to evaluate hydrogen production by water analysis and to store the solar energy which has had the form of a hydride-metal hydrogen, after that, to investigate the performance of sophisticated commercial electrolyser (HG-60)powered by photovoltaic panels via the Power Management Unit (PMU) as a power conditioner, this paper has also a mathematical models based on real-time experiments were used to simulate both the photovoltaic system and PEM electrolyser work, along with attempting to direct linking strategy with the same experimental components of photovoltaic panels and commercial electrolyser, it was found through this study, the addition of the number of commercial electrolyser with the bank of four HG-60 stacks in series. More effective considering the improving voltage matching, with power transfer efficiency reach to 99%, also another factor is the photovoltaic panels slope on panel output power and hydrogen productivity are theoretically examined, where the proper selection of optimal tilt angle has an importance for collecting the maximum hydrogen amount, eventually, over the experiment span, the real-amount of hydrogen vented over experiment course is around 92.54l.