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Hydrogen fuel is a non-toxic and source-abundant energetic system, but for its applications in the industry, several issues related to its storage must be resolved. Compounds like NaBH 4 appear as promising hydrogen sources, while can release the latter rapidly under controllable conditions with the use of heterogeneous catalyst systems. In this work, we synthesized a Ni–CoP catalyst by electrodeposition in a three-step process on carbon paper as support. The materials were characterized via SEM-EDS, XRD, and XPS techniques, while the hydrogen evolution reaction (HER) from alkaline NaBH 4 solutions was tested as a batch experiment. Ni–CoP catalyst showed a high amount of H 2 generated in a short time (∼550 mL in 1 min) and remained at 78 and 54% of its initial performance after respectively 100 and 300 h of a continuous hydrolysis process. Our catalyst revealed exceptional performance and stability at higher temperatures and a long process time, which have been a rare subject of investigation in other reports for NaBH 4 hydrolysis in the past. This work paves a new perspective in studying catalysts for hydrogen generation from borohydrides. [Display omitted] • Ni–CoP catalyst was electrodeposited on a carbon support. • Material characterization proved the formation of desired active layers. • High efficiency and stability of the catalyst for a long-term NaBH 4 hydrolysis was revealed. [ABSTRACT FROM AUTHOR]

Hydrogen (H2) is a new type of renewable energy that can meet people's growing energy needs and is environmentally friendly. In order to improve the industrial application prospects and electrochemical performance of hydrogen evolution catalysts, extensive research on transition metal materials has been carried out. Among the many catalytic materials, cobalt is an element with potential for the hydrogen evolution reaction (HER) due to its abundant reserves, low cost, and small energy barrier for H adsorption. This review classifies the latest research on cobalt-based catalysts according to the types of compound, including cobalt-based sulfides, phosphides, carbides, borides, oxides, etc., and summarizes the latest research progress of cobalt-based compound catalysts in acidic and alkaline media. Strategies to tune the properties of cobalt-based compound catalysts for high catalytic activity for HER are focused on, including structural engineering, defect engineering, and doping, etc. The advantages and limitations of each modified approach are reviewed. Not only that, but also the catalytic activity and advantages of the catalyst are evaluated by using density functional theory (DFT) calculation-related descriptors, activity evaluation parameters, etc. Finally, limitations and challenges of cobalt-based materials for HER are presented, as well as prospects for future research. This paper aims to understand the chemical and physical factors that affect cobalt-based catalysts, and to find directions for future research on cobalt-based catalysts. [ABSTRACT FROM AUTHOR]

Summary: Catalysts with cobalt (Co) and graphitic carbon hybrid structure are receiving significant attention in various electrocatalysis applications because of their stability and high activities. In addition, the size and the well dispersed distribution of metal active site are some of the most important factors for electrocatalyst. In this paper, we successfully synthesized ultra‐small and well dispersed Co nanoparticle on nitrogen‐doped carbon structure (Co/NC) adding and evaporating a Zinc (Zn) and found the optimized ratio of Co and Zn. We used a bottom‐up method to synthesize catalysts with Co on carbon substrate structure from zeolitic imidazolate frameworks (ZIF). Zinc (Zn) was also added and evaporated by pyrolysis. By addition and evaporation of Zn, Co nanoparticle became smaller and more evenly dispersed. As a result, the OER performance was significantly improved than the catalyst without Zn. Also, an optimized catalyst with abundant uniformly dispersed Co was successfully synthesized by appropriately controlling the ratio of Co and Zn comprising the ZIFs. As the ratio of Zn increased, the size and the amount of Co nanoparticles were decreased, and Co nanoparticles were more evenly dispersed. Furthermore, carbon substrate has more porous structure due to the evaporation of Zn atoms. When the Co:Zn ratio was 1:3, Co/NC showed the best electrocatalytic performance due to optimized active sites and large surface area. The optimized Co/NC showed an overpotential of 1.56 V (vs RHE) to acquire a current density of 10 mA cm−2, which is higher activity than commercial RuO2. We also analyzed the material characterization occurred as the ratio of Zn in ZIF increased, revealing the factors enhancing the OER activity. Optimized Co/NC (Co:Zn = 1:3) exhibited improved OER activity and long‐term and cycle stability in the OER. [ABSTRACT FROM AUTHOR]

The hydrogen evolution reaction (HER) is a complex reaction involving many interdependent physicochemical steps. Highly ordered carbon nitride‐based materials, such as Na‐PHI and K‐PHI, display some of the highest activities for H2 evolution among the carbon nitride‐based materials, due to their electronic properties, but also the presence of cyanimide terminations, which favors the charge transfer for the Pt cocatalyst nanoparticles (NPs). For such highly optimized semiconductor structures, the necessity to control and improve other steps of the photocatalytic process becomes essential, in particular the poor electron transfer from the Pt NPs to the protons in solution over the Helmholtz or Stern layer. Taking highly ordered Na‐PHI as a test material, the influence of water‐dissolved alkali cations on the HER is systematically studied and it is experimentally verified that the electron transfer from the Pt NPs to the protons in solution limits the efficiency of heterogeneous carbon nitride‐based catalysts. This paper explains how hydrated alkali cations influence electron transfer and are able to boost the H2 evolution rate of the same Na‐PHI from 2401 up to 5330 µmol h−1 g−1 with an apparent quantum yield of 13% at 420 nm. [ABSTRACT FROM AUTHOR]

As a narrow bandgap semiconductor, transition metal selenides are promising as excellent electrocatalysts for hydrogen evolution reactions (HERs). Herein, using an ultra-thin MOF as the precursor, a Co-doped core–shell shaped NiSe2 based catalyst is successfully constructed by a two-step calcination method as an efficient HER catalyst. Experiments and theoretical calculations indicate that the introduction of Co adjusts the electronic structure of Ni and Se, promoting charge transfer and reducing the energy barrier of the rate-limiting step to accelerate the hydrogen precipitation reaction. In addition, the core–shell structure contributes to mass transport, and the outer carbon layer improves the stability of the catalyst. The optimal catalyst (Ni0.75Co0.25Se2@NC) exhibited satisfactory electrocatalytic activity as evidenced by a low overpotential of −143 mV at a current density of −10 mA cm−2 and a small Tafel slope of 37.5 mV dec−1. This work provides a valuable strategy for fabricating efficient NiSe2 based electrocatalysts for the HER. [ABSTRACT FROM AUTHOR]

In this contribution, a simple method for the screening of photocatalytic activity of catalyst materials is presented. The method is based on two steps: the immobilization of the photocatalyst and the subsequent testing of their photocatalytic activity, using the gas evolution at the solid‐liquid interface. Up to four catalysts can be tested under the same conditions. The observed gas evolution for selected photocatalysts is consistent with trends reported in the literature from conventional photocatalytic reactors. [ABSTRACT FROM AUTHOR]

Hydrogen spillover effect has recently garnered a lot of attention in the field of electrocatalytic hydrogen evolution reactions. A new avenue for understanding the dynamic behavior of atomic migration in which hydrogen atoms moving on a catalyst surface was opened up by the setup of the word "hydrogen spillover." However, there is currently a dearth of thorough knowledge regarding the hydrogen spillover effect. Currently, the advancement of sophisticated characterization procedures offers progressively useful information to enhance our grasp of the hydrogen spillover effect. The understanding of material fabrication for hydrogen spillover effect has erupted. Considering these factors, we made an effort to review most of the articles published on the hydrogen spillover effect and carefully analyzed the aspect of material fabrication. All of our attention has been directed toward the molecular pathway that leads to improve hydrogen evolution reactions performance. In addition, we have attempted to elucidate the spillover paths through the utilization of DFT calculations. Furthermore, we provide some preliminary research suggestions and highlight the opportunities and obstacles that are still to be confronted in this study area. [ABSTRACT FROM AUTHOR]

The development of efficient and low-cost catalysts is of great significance for the future application of the electrocatalytic hydrogen evolution reaction (HER). Herein, a series of Ni,N co-doped Mo2C nanostructures (Nix–Mo2C/N) with different Ni content levels are fabricated. The phase-directing effect of Ni on Mo2C/N is observed, which is in charge of the phase transformation of Mo2C/N from an α- to a β-phase. At the optimized Ni-doping level, biphase Ni15–Mo2C/N exhibits outstanding HER activity under both acidic and alkaline conditions. In particular, under alkaline conditions, Ni15–Mo2C/N delivers an overpotential of only 105.0 mV, accompanied by a low Tafel slope of 44.96 mV dec−1. The performance is comparable to commercial 20% Pt/C and higher than most state-of-the-art Mo2C-based catalysts as well. [ABSTRACT FROM AUTHOR]

Recently, much attention has been focused on the development of photocatalysts for hydrogen evolution. Up to now, efficient hydrogen generation is still greatly challenging due to the restraints of the surface redox reaction rate, and the introduction of a co-catalyst is one of the keys to this problem. Here, dual non-noble co-catalysts NixP and Mn3O4 were proposed and prepared on a g-C3N4/red phosphorus (CNP) hybrid structure with a high light adsorption capability by a two-step photo-deposition method. The photo-excited charge on the composite catalyst separate and transfer from C3N4 to red phosphorous due to a type I heterojunction structure. NixP and Mn3O4 act as reductive and oxidative co-catalysts, respectively. The hydrogen production rate was 5851.3 μmol g−1 h−1, 12.4 times that of pure CNP. The consistent catalytic activity in an actual 25 mL flask for hydrogen evolution over eight hours accumulated 245.08 μmol H2 under solar simulated irradiation. This work provides practical reference for the development of a novel inexpensive photocatalyst system. [ABSTRACT FROM AUTHOR]

Currently, two-dimensional (2D) layered transition metal chalcogenides (TMCs), especially MoS2, are attracting widespread attention in the field of water electrolysis. Unfortunately, the catalytic activity of MoS2 is limited to a few edge sites and by its low conductivity. Herein, MoS2/NiS heterostructures possessing a flower-like morphology were constructed via an accurate thermal treatment process to realize precise interface modification. As expected, through the adjunction of a certain amount of polyvinylpyrrolidone, NiS grew uniformly on the surface of MoS2 nanosheets, thereby forming a large number of visual lattice fringes with a specific interplanar spacing, which promoted a higher electron-transfer efficiency. The better electron-transfer efficiency resulted in a better hydrogen evolution reaction performance, providing an overpotential of 158 mV at 10 mA cm−1, a Tafel slope of 128.1 mV dec−1, and significantly long-term durability. Moreover, density functional theory calculation also showed that the precise interface modification of MoS2/NiS heterostructure exhibited more occupations at the Fermi level, which improved the electrical conductivity. Additionally, the MoS2/NiS catalysts achieved a moderately lower hydrogen adsorption energy (ΔGH*), indicating that it had better catalytic hydrogen evolution performance. This work can be extended to design other catalytic materials and for understanding reactions in the fields of energy conversion through theoretical calculations. [ABSTRACT FROM AUTHOR]

The first Pd2+ containing polyoxoniobate [Pd(cyclam)]5{H3Nb6O19}2 ⋅ 26H2O (I) was prepared at room temperature. In the structure, two hexaniobate clusters are surrounded by a bi‐capped cube formed by Pd2+ centered complexes. This motif is arranged in a layer‐like fashion with crystal water molecules located between cations and anions. Temperature resolved in‐situ X‐ray diffraction experiments demonstrate that successive removal of the crystal water molecules leads to formation of several crystalline intermediate phases. Water sorption investigations show that thermally removed H2O can be successfully reintegrated proceeding via two distinct steps. The catalytic performance for the light‐driven hydrogen evolution reaction (HER) was investigated in a sacrificial system and fluorescein Na+ salt as sensitizer yielding a high value of 90 μmol/h H2. Surprisingly, a composite Pd@Na7[HNb6O19] ⋅ 15H2O is in‐situ formed during the catalytic reaction by cation exchange with simultaneous reduction of Pd2+ nanoparticles decorating the hexaniobate support. The recovered catalyst was even more active producing 157 μmol/h H2 with an apparent quantum efficiency of 1.85 %. Photocatalytic experiments performed with ex‐situ generated Pd nanoparticles deposited on Na7[HNb6O19] ⋅ 15H2O show much lower activities indicating a synergistic effect of the in‐situ generated Pd@Na7[HNb6O19] ⋅ 15H2O catalyst. [ABSTRACT FROM AUTHOR]

A synergistic combination of photoredox and polarity reversal catalysis enabled a hydrogen evolution cross-coupling of silanes with H2O, alcohols, phenols, and silanols, which afforded the corresponding silanols, monosilyl ethers, and disilyl ethers, respectively, in moderate to excellent yields. The dehydrogenative cross-coupling of Si–H and O–H proceeded smoothly with broad substrate scope and good functional group compatibility in the presence of only an organophotocatalyst 4-CzIPN and a thiol HAT catalyst, without the requirement of any metals, external oxidants and proton reductants, which is distinct from the previously reported photocatalytic hydrogen evolution cross-coupling reactions where a proton reduction cocatalyst such as a cobalt complex is generally required. Mechanistically, a silyl cation intermediate is generated to facilitate the cross-coupling reaction, which therefore represents an unprecedented approach for the generation of silyl cation via visible-light photoredox catalysis. [ABSTRACT FROM AUTHOR]

Due to inefficient charge separation and low surface catalytic conversion efficiencies, cocatalysts are required for achieving photocatalytic hydrogen evolution. Being a noble‐metal‐free cocatalyst, metallic 1T‐WS2 with excellent conductivity can function for this reaction. Herein, 1T‐WS2/Zn0.5Cd0.5S is constructed via a simple and feasible grinding approach. The composite containing 7.5 % 1T‐WS2 in 1T‐WS2/Zn0.5Cd0.5S achieves a hydrogen evolution rate of 61.65 mmol g−1 h−1 and an external quantum efficiency of 8.04 % at 420 nm, which is 37 times that of bare Zn0.5Cd0.5S (1.67 mmol g−1 h−1). The electrical conductivity of metallic 1T‐WS2 reduces the transfer impedance at the interface and thus accelerates the non‐radiative energy transfer and electron transport rate. The different Fermi levels of 1T‐WS2 and Zn0.5Cd0.5S form a Schottky junction, which promotes the transfer of photogenerated electrons from Zn0.5Cd0.5S to 1T‐WS2. More importantly, the close interface contact between 1T‐WS2 and Zn0.5Cd0.5S results in strong electron interactions, which is conducive to the spatial separation of photogenerated electrons and holes. This work will further expand the application of 1T‐WS2 in the photocatalytic hydrogen evolution process. [ABSTRACT FROM AUTHOR]

The electrolytic water method is an outstanding hydrogen production process because of its high stability and no restriction. A low-priced and efficient catalyst for electro-deposition of Ni–Co microspheres and nanoclusters on carbon steel (Ni–Co/CS) has been prepared by the dynamic hydrogen bubble template. In the 6 M KOH solution, Ni–Co/CS only requires an overpotential of 48 mV to provide a current density of 50 mA cm−2. At the same time, it also has a large electrochemically active specific surface area (ECSA) and a hydrophilic surface. In addition, the study about the influence of carbon steel (CS) on Ni–Co coatings and the comparison experiment for different base materials has been completed. The results prove that CS is an excellent base material for hydrogen production. It can help the Ni–Co catalyst to have a stable electrolysis in 6 M KOH for 500 h. The above properties of Ni–Co/CS catalyst make it a new choice of hydrogen production by electrolysis of water in practical applications. [ABSTRACT FROM AUTHOR]

Efficient and inexpensive electrocatalysts play an important role in the hydrogen evolution reaction (HER) of electrolytic water splitting. Herein, Ni2P-MoC/coal-based carbon fiber (Ni2P-MoC/C-CF) self-supporting catalysts were obtained by low-temperature phosphorization and high-temperature carbonization. The Mo source and oxidized coal were uniformly dispersed in the carbon support by electrospinning technology. A precursor of Ni was introduced by the impregnation method. The synergistic effect of MoC and Ni2P may reduce the strong hydrogen adsorption capacity of pure MoC and provide a fast hydrogen release process. In addition, the C-CFs prepared by electrospinning can not only prevent the agglomeration of MoC and Ni2P particles at a high temperature but also provide a self-supporting support for the catalyst. As a result, the catalytic performance of the HER was improved greatly, and a low overpotential of 112 mV at 10 mA cm−2 was exhibited stably by the Ni2P-MoC/C-CFs. This work not only converts coal into coal-based carbon materials but also provides a feasible pathway for the rational design of large-scale molded hydrogen electrocatalysts. [ABSTRACT FROM AUTHOR]

The in situ surface reconstitution of a catalyst for hydrogen evolution refers to its structure evolution induced by strong interactions with reaction intermediates during the hydrogen evolution reaction (HER), which eventually leads to the self-optimization of active sites. In consideration of the superior performance that can be achieved by in situ surface reconstitution, more and more attention has been paid to the relationship between active site structure evolution and the self-optimization of HER activity. More and more in situ and/or operando techniques have been explored to track the dynamic structural evolution of HER catalysts in order to clarify the underlying mechanism. This review summarizes recent advances in various types of reconstruction such as the reconfiguration of crystallinity, morphological evolution, chemical composition evolution, phase transition refactoring, surface defects, and interface refactoring in the HER process. Finally, different perspectives and outlooks are offered to guide future investigations. This review is expected to provide some new clues for a deeper understanding of in situ surface reconfiguration in hydrogen evolution reactions and the targeted design of catalysts with desirable structures. [ABSTRACT FROM AUTHOR]

Green hydrogen production via electrocatalytic water splitting paves the way for renewable, clean, and sustainable hydrogen (H2) generation. H2 gas is produced from the cathodic hydrogen evolution reaction (HER), where the reaction is catalyzed primarily from Pt-based catalysts under both acidic and alkaline environments. Lowering the loading of Pt and the search for alternative active catalysts for HER is still an ongoing challenge. Two-dimensional MXenes are effective supports to stabilize and homogenously distribute HER-active electrocatalysts to boost the HER performance. Factors involved in the effectiveness of MXenes for their role in HER include transition metal types and termination groups. Recently, tailoring the conditions during the synthesis of MXenes has made it possible to tune the morphology of MXenes from multilayers to few layers (delaminated), formation of porous MXenes, and those with unique crumpled and rolled structures. Changing the morphology of MXenes alters the surface area, exposed active sites and accessibility of electrolyte materials/ions to these active sites. This review provides insight into the effects of varying morphology of MXenes towards the electrocatalytic HER activity of the MXene itself and MXene composites/hybrids with HER-active catalysts. Synthesis methods to obtain the different MXene morphologies are also summarized. [ABSTRACT FROM AUTHOR]

The use of non-thermal plasma technology in producing green fuels is a much-appreciated environmentally friendly approach. In this study, an Al2O3-supported CrxZnS semiconductor catalyst was tested for hydrogen evolution from hydrogen sulfide (H2S) gas by using a single-layered dielectric barrier discharge (DBD) system. The Al2O3-supported CrxZnS catalyst (x = 0.20, 0.25, and 0.30) was produced by using a co-impregnation method and characterized for its structural and photocatalytic characteristics. The discharge column of the DBD system was filled with this catalyst and fed with hydrogen sulfide and argon gas. The DBD plasma was sustained with a fixed AC source of 10 kV where plasma produced species and UV radiations activated the catalyst to break H2S molecules under ambient conditions. The catalyst (hexagonal-cubic-sphalerite structure) showed an inverse relationship between the band gap and the dopant concentration. The hydrogen evolution decreased with an increase in dopant concentration in the nanocomposite. The Cr0.20ZnS catalyst showed excellent photocatalytic activity under the DBD exposure by delivering 100% conversion efficiency of H2S into hydrogen. The conversion decreased to 96% and 90% in case of Cr0.25ZnS and Cr0.30ZnS, respectively. [ABSTRACT FROM AUTHOR]

A novel Zn−Fe flow battery featuring an Fe3+ reduction reaction (Fe3+RR)‐coupled zinc oxidation, and an Fe2+ oxidation reaction (Fe2+OR)‐coupled hydrogen evolution reaction (HER) system as well, was established. This battery is capable of driving two Fe2+OR‐coupled HER systems in series based on the above Fe2+/Fe3+ cycling, for efficient self‐powered hydrogen evolution. Meanwhile, this Fe2+/Fe3+ cycling enables the preparation of a multifunctional catalyst, Pt‐3@SXNS (siloxene nanosheet), by the Fe2+OR‐promoted dispersion of Pt nanoparticles on SXNS; alternatively, this support could be obtained by Fe3+RR‐assisted exfoliation using Fe3+ from the anolyte of Fe2+OR‐coupled HER. The Pt‐3@SXNS catalyst exhibits excellent catalytic activities toward Fe3+RR in the Zn−Fe flow battery, HER, and Fe2+OR in the electrolyzer, which is attributed to the strong electronic interaction between Pt and Si. This work offers a new strategy for energy storage and low‐cost hydrogen production from acidic wastewater. [ABSTRACT FROM AUTHOR]

Quasi-two-dimensional oxides Sr3Mn2O6 and Sr3FeMnO6 have been synthesized and their bifunctional electrocatalytic activity toward both half-reactions of water-splitting, i.e., oxygen-evolution reaction (OER) and hydrogen-evolution reaction (HER), has been demonstrated. The two materials are isostructural and consist of (Fe/Mn)O5 square-pyramidal units that form two-dimensional layers, separated by strontium ions. This structure type is related to the so-called Ruddlesden-Popper (RP) structure, which typically contains 7 oxygens per formula unit and consists of octahedrally coordinated transition metals. The two materials in this work can be described as oxygen-deficient RP systems. Both compounds show electrocatalytic activity for OER and HER, with Sr3FeMnO6 having a significantly greater performance compared to Sr3Mn2O6. The overpotential required for both OER and HER is considerably lowered for Sr3FeMnO6. This material also shows faster reaction kinetics and greater electrochemically active surface area compared to Sr3Mn2O6. While the activity of Sr3FeMnO6 does not reach those of state-of-the-art catalysts, its bifunctional electrocatalytic performance is remarkable. In addition, it demonstrates the important role of electronegativity in directing functional properties such as electrocatalysis. [ABSTRACT FROM AUTHOR]

Producing hydrogen via water electrolysis could be a favorable technique for energy conversion, but the freshwater shortage would inevitably limit the industrial application of the electrolyzers. Being an inexhaustible resource of water on our planet, seawater can be a promising alternative electrolyte for industrial hydrogen production. However, many challenges are hindering the actual application of seawater splitting, especially the competing reactions relating to chlorine at the anode that could severely corrode the catalysts. The execution of direct seawater electrolysis needs efficient and robust electrocatalysts that can prevent the interference of competing reactions and resist different impurities. In recent years, researchers have made great advances in developing high-efficiency electrocatalysts with improved activity and stability. This review will provide the macroscopic understanding of direct seawater splitting, the strategies for rational electrocatalyst design, and the development prospects of hydrogen production via seawater splitting. The nonprecious metal-based electrocatalysts for stable seawater splitting and their catalytic mechanisms are emphasized to offer guidance for designing the efficient and robust electrocatalyst, so as to promote the production of green hydrogen via seawater splitting. [ABSTRACT FROM AUTHOR]

Defect engineering is an effective strategy to improve the activity of two-dimensional molybdenum disulfide base planes toward electrocatalytic hydrogen evolution reaction. Here, we report a Frenkel-defected monolayer MoS2 catalyst, in which a fraction of Mo atoms in MoS2 spontaneously leave their places in the lattice, creating vacancies and becoming interstitials by lodging in nearby locations. Unique charge distributions are introduced in the MoS2 surface planes, and those interstitial Mo atoms are more conducive to H adsorption, thus greatly promoting the HER activity of monolayer MoS2 base planes. At the current density of 10 mA cm−2, the optimal Frenkel-defected monolayer MoS2 exhibits a lower overpotential (164 mV) than either pristine monolayer MoS2 surface plane (358 mV) or Pt-single-atom doped MoS2 (211 mV). This work provides insights into the structure-property relationship of point-defected MoS2 and highlights the advantages of Frenkel defects in tuning the catalytic performance of MoS2 materials. While material defect sites are active for chemical reactions, it is important to understand how different defect types impact reactivity. Here, authors prepare Frenkel-defected MoS2 monolayers and demonstrate improved performances for H2 evolution electrocatalysis than pristine or doped MoS2. [ABSTRACT FROM AUTHOR]

The reaction of NiCl2, K2(i-mnt) (i-mnt2−= 2,2-dicyanoethylene-1,1-dithiolate) and 1-benzyl-4-amino-pyridinium bromide [BzPyNH2]Br affords a nickel complex, [BzPyNH2]2[Ni(i-mnt)2], a molecular catalyst for electrochemical and photochemical driven hydrogen evolution. As an electrocatalyst, [BzPyNH2]2[Ni(i-mnt)2] can electrocatalyze hydrogen generation from a neutral buffer with a turnover frequency (TOF) of 556 (±3) mol of hydrogen per mole of catalyst per hour (mol H2/mol catalyst/h) at an overpotential (OP) of 837.6 mV. As a photocatalyst, combining with CdS nanorods (CdS NRs) as a photosensitizer, and ascorbic acid (H2A) as a sacrificial electron donor, [BzPyNH2]2[Ni(i-mnt)2] photocatalyzes hydrogen evolution in heterogeneous environments with a turnover number (TON) of 18420 (±5) mol H2 per mol of catalyst during 60 h irradiation. The highest apparent quantum yield (AQY) is ∼10% at 469 nm. Several chemical and physical methods are employed to understand catalytic procedures for H2 production. [ABSTRACT FROM AUTHOR]

Electrochemical hydrogen production is considered as one of the most significant ways to develop clean energy in the future. Herein, the self‐supporting electrocatalyst of MoS2@Ni(Mn)VOX is fabricated on 3D nickel foam (NF) by a facile two‐step electrodeposition approach. The optimal MoS2@Ni(Mn)VOX electrode shows an ultralow overpotential of 61 mV to achieve a current density of 10 mA cm−2 and a Tafel slope of 35.1 mV dec−1 in 1 m KOH, which is superior to NF, MoS2@NF, NiVOX, Ni(Mn)VOX, or MoS2@NiVOX. The uniformly dispersed coral‐shaped heterostructure exposes more active sites and makes the charge transfer rate faster. The outstanding synergistic effect of MoS2 and transition metal oxides of Ni, Mn, and V also contribute to the enhanced activity of the catalyst. Benefiting from these, MoS2@Ni(Mn)VOX shows superior alkaline hydrogen evolution reaction activity and long‐term stability. Herein, a novel catalyst for highly efficient hydrogen evolution in alkaline media is provided. [ABSTRACT FROM AUTHOR]

One consistent challenge of both computational and empirical catalyst screening is ensuring that the variables chosen for the screen are driving the performance analyzed. Here, we compare photocatalytic hydrogen evolution from in situ formed Au and Au/Cu nanoparticles to nanoparticles of the same composition synthesized prior to being used as catalysts, as well as compare them to in situ formed Au and Au/Cu nanoparticles in the presence of exogeneous ligand. For all experiments, we observed that ligand‐terminated nanoparticles performed better than un‐stabilized in situ formed nanoparticles. We tested the generality of this result by studying Co, Ni, and Pd in the same system and also observed that the introduction of nanoparticle ligand leads to enhanced catalytic activity. Taken together, these results suggest 1) nanoparticle ligands can be beneficial, and even necessary, to produce catalysts with sustained activity 2) For computational prediction of these catalysts, factors relating to particle formation and stability need to be considered when both generating predictions as well as interpreting experimental results based on those predictions. [ABSTRACT FROM AUTHOR]

Using photocatalysis to produce hydrogen is a promising research area in the immediate future. This article intends to design photocatalysts of crystalline (amorphous) TiO2/two‐dimensional MoS2 sandwich structure supporting singleatoms (SAs). After the effective mass, electrostatic potential, light absorption spectrum and other related properties were calculated, the analysis shows that catalysts with amorphous sandwich structure has excellent electron‐hole separation ability, and precious metal SAs can adsord onto the amorphous sandwich structure stably. Except for the Pt@Amorphousr‐TiO2/MoS2 sandwich structure single‐atom catalysts (SACs), which is only active towards oxygen evolution, all the other interlayer catalysts are active for both photocatalytic hydrogen evolution and oxygen evolution. [ABSTRACT FROM AUTHOR]

Main observation and conclusion: The efficient production and utilization of hydrogen play an important role in the closed loop of energy conversion. It is an urgent need to find low‐cost and high‐performance replacements for platinum‐based catalysts towards hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER). Herein, bifunctional RuNi alloy nanoparticles embedded in oxygen‐doped carbon were prepared via simple annealing of Ru‐doped Ni‐BTC, the limiting current density of which could reach 2.46 mA/cm2 (close to Pt) in 0.1 mol/L KOH for HOR. And the low overpotentials of only 29 mV in 1 mol/L KOH and 62 mV in 0.5 mol/L H2SO4 were needed to reach the current density of 10 mA/cm2 for HER. The effect of alloying and oxygen‐doped graphene contributed to the excellent activity and stability during hydrogen electrocatalysis. This work provides new ideas for the development of novel types of hydrogen electrocatalysts and enriches the application of MOFs in HOR. [ABSTRACT FROM AUTHOR]

Highly efficient removal of nitrate from eutrophication water has been attracting great attention. Here, we develop a new-type denitrification system that is capable of catalytic nitrate reduction on denitrification catalysts suspended in the reactor, using hydrogen as reductant directly generated from electrocatalytic hydrogen evolution reaction (HER). To improve system's efficiency, Ni3S2 nanosheets coated on Ni foam (Ni3S2-NF) was hydrothermally synthesized and applied as cathode material for HER. Meanwhile, bimetals PdCu nanoparticles dispersed in the channels of activated carbon (PdCu-AC) was also prepared by impregnation method and used as catalysts for nitrate reduction. Under − 1.3 V for HER and using 5%PdCu-AC as catalysts, the denitrification system behaved an optimal nitrate removal, with almost 100% nitrate removal and a dinitrogen selectivity of 64% in 5 h under neutral electrolyte at initial nitrate concentration of 100 mg-N/L. Meanwhile, the catalysts showed satisfactory stability, the system maintained over 95% nitrate removal efficiency and ~ 60% TN removal after 6 times runs at optimal denitrification conditions. [ABSTRACT FROM AUTHOR]

The use of highly-active and robust catalysts is crucial for producing green hydrogen by water electrolysis as we strive to achieve global carbon neutrality. Noble metals like platinum are currently used catalysts in industry for the hydrogen evolution, but suffer from scarcity, high price and unsatisfied performance and stability at large current density, restrict their large-scale implementations. Here we report the synthesis of a type of monolith catalyst consisting of a metal disulfide (e.g., tantalum sulfides) vertically bonded to a conductive substrate of the same metal tantalum by strong covalent bonds. These features give the monolith catalyst a mechanically-robust and electrically near-zero-resistance interface, leading to an excellent hydrogen evolution performance including rapid charge transfer and excellent durability, together with a low overpotential of 398 mV to achieve a current density of 2,000 mA cm−2 as required by industry. The monolith catalyst has a negligible performance decay after 200 h operation at large current densities. In light of its robust and metallic interface and the various choices of metals giving the same structure, such monolith materials would have broad uses besides catalysis. Water electrolysis is a promising hydrogen production technique but is restricted from large-scale application due to poor performance and high cost. Here, the authors report a mechanically stable monolith electrocatalyst that achieves superior hydrogen evolution at large current densities. [ABSTRACT FROM AUTHOR]

NiCl2·6H2O ([Ni(H2O)6]2Cl2) per se does not show electrocatalytic hydrogen evolution reaction activity (HER) in an acidic aqueous medium as well as in neutral water. Interestingly, when [Ni(H2O)6]2+ is present in a polyoxovanadate matrix, for example, in the compound K2[Ni(H2O)6]2[V10O28]·4H2O (1), it exhibits homogeneous electrocatalytic HER activity in an acidic aqueous solution with a turn over frequency of 2.1 s−1 and an effective low overpotential of 127 mV at pH 2.3. Compound 1 is the first nickel-containing polyoxometalate catalyst for hydrogen production via homogeneous electrocatalytic proton reduction without its decomposition under electrochemical conditions of HER. [ABSTRACT FROM AUTHOR]