Improved Alkaline Hydrogen Evolution Performance of Dealloying Fe75-xCoxSi12.5B12.5 Electrocatalyst.

The electrocatalytic performance of a Fe65Co10Si12.5B12.5 Fe-based compounds toward alkaline hydrogen evolution reaction (HER) is enhanced by dealloying. The dealloying process produced a large number of nanosheets on the surface of NS-Fe65Co10Si12.5B12.5, which greatly increased the specific surface area of the electrode. When the dealloying time is 3 h, the overpotential of NS-Fe65Co10Si12.5B12.5 is only 175.1 mV at 1.0 M KOH and 10 mA cm-2, while under the same conditions, the overpotential of Fe65Co10Si12.5B12.5 is 215 mV, which is reduced. In addition, dealloying treated electrodes also show better HER performance than un-dealloying treated electrodes. With the increase in Co doping amount, the overpotential of the hydrogen evolution reaction decreases, and the hydrogen evolution activity is the best when the addition amount of Co is 10%. This work not only provides a basic understanding of the relationship between surface activity and the dealloying of HER catalysts, but also paves a new way for doping transition metal elements in Fe-based electrocatalysts working in alkaline media.

WS2 Moiré Superlattices Supporting Au Nanoclusters and Isolated Ru to Boost Hydrogen Production.

Maximizing the catalytic activity of single-atom and nanocluster catalysts through the modulation of the interaction between these components and the corresponding supports is crucial but challenging. Herein, guided by theoretical calculations, a nanoporous bilayer WS2 Moiré superlattices (MSLs) supported Au nanoclusters (NCs) adjacent to Ru single atoms (SAs) (Ru1/Aun-2LWS2) is developed for alkaline hydrogen evolution reaction (HER) for the first time. Theoretical analysis suggests that the induced robust electronic metal-support interaction effect in Ru1/Aun-2LWS2 is prone to promote the charge redistribution among Ru SAs, Au NCs, and WS2 MSLs support, which is beneficial to reduce the energy barrier for water adsorption and thus promoting the subsequent H2 formation. As feedback, the well-designed Ru1/Aun-2LWS2 electrocatalyst exhibits outstanding HER performance with high activity (η10 = 19 mV), low Tafel slope (35 mV dec-1), and excellent long-term stability. Further, in situ, experimental studies reveal that the reconstruction of Ru SAs/NCs with S vacancies in Ru1/Aun-2LWS2 structure acts as the main catalytically active center, while high-valence Au NCs are responsible for activating and stabilizing Ru sites to prevent the dissolution and deactivation of active sites. This work offers guidelines for the rational design of high-performance atomic-scale electrocatalysts.

Unveiling the Cation Dependence in Alkaline Hydrogen Evolution by Differently-Charged Ruthenium/Molybdenum Sulfide Hybrids.

The sluggish kinetics of hydrogen evolution reaction (HER) via water reduction limits the efficiency of alkaline water electrolysis. The HER kinetics is not only intimately related to the catalyst surface structure but also relevant to the cation identity of the electrolyte. The cation dependence also relies on the surface electronic structure and applied potential, but this interrelated effect and its underlying mechanism awaits elucidation. Herein, differently-charged molybdenum sulfide (MoSx) cluster supports ([Mo3S13]2- and [Mo3S7]4+) are utilized to hybridize with the identical metallic Ru centers. The specific electrostatic interaction between MoSx clusters and Ru precursors induces different Ru valences of the hybrids, with a higher valence state for Ru/Mo3S13 endowing a higher activity. The Ru/Mo3S13 and Ru/Mo3S7 exhibited drastically-different cation dependence, in which the charged support determines the local accumulation of cations and resulting water structures. The more negatively-charged Mo3S13 support induces the facile accumulation of cations, especially for less-hydrated K+ cations. The water activation capability by Ru valences and cation accumulation from the support effect in-together determine the cation-dependent alkaline HER activity. This work not only enriches the understanding about the cation-dependent HER mechanism but also shines a light on the rational optimization strategy of electrode/electrolyte interfaces.

Bimetallic Single-Atom Catalysts for Water Splitting.

Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society. The field of catalysis has been revolutionized by single-atom catalysts (SACs), which exhibit unique and intricate interactions between atomically dispersed metal atoms and their supports. Recently, bimetallic SACs (bimSACs) have garnered significant attention for leveraging the synergistic functions of two metal ions coordinated on appropriately designed supports. BimSACs offer an avenue for rich metal-metal and metal-support cooperativity, potentially addressing current limitations of SACs in effectively furnishing transformations which involve synchronous proton-electron exchanges, substrate activation with reversible redox cycles, simultaneous multi-electron transfer, regulation of spin states, tuning of electronic properties, and cyclic transition states with low activation energies. This review aims to encapsulate the growing advancements in bimSACs, with an emphasis on their pivotal role in hydrogen generation via water splitting. We subsequently delve into advanced experimental methodologies for the elaborate characterization of SACs, elucidate their electronic properties, and discuss their local coordination environment. Overall, we present comprehensive discussion on the deployment of bimSACs in both hydrogen evolution reaction and oxygen evolution reaction, the two half-reactions of the water electrolysis process.

Electro-Co-Polymerisation of Polypyrrole-Polyaniline Composites in Ionic Liquids for Metal-Free Hydrogen Evolution Electrodes.

Pure organic films consisting of polypyrrole, polyaniline and a composite of polypyrrole and polyaniline electrodeposited in the ionic liquid EMIM-TFSI onto mesoporous carbon electrodes are tested for their hydrogen evolution reaction capabilities. The use of these intrinsically conducting polymers is seen as a way of stepping away from expensive and rare metallic catalysts. Co-polymerisation of polypyrrole and polyaniline in a 1 : 10 ratio in EMIM-TFSI was found to be doped with the TFSI- anion and be much more active to the hydrogen evolution reaction when compared to pure polymers. Tafel analysis of the composite gave a value of 144 mV/dec indicating that the Volmer step is the rate limiting step. However, stability tests showed an improvement in the composite's overpoential performance for the hydrogen evolution reaction.

Boosting the Production of Hydrogen from an Overall Urea Splitting Reaction Using a Tri-Functional Scandium-Cobalt Electrocatalyst.

The creation of highly efficient and economical electrocatalysts is essential to the massive electrolysis of water to produce clean energy. The ability to use urea reaction of oxidation (UOR) in place of the oxygen/hydrogen evolution process (OER/HER) during water splitting is a significant step toward the production of high-purity hydrogen with less energy usage. Empirical evidence suggests that the UOR process consists of two stages. First, the metal sites undergo an electrochemical pre-oxidation reaction, and then the urea molecules on the high-valence metal sites are chemically oxidized. Here, the use of scandium-doped CoTe supported on carbon nanotubes called Sc@CoTe/CNT is reported and CoTe/CNT as a composite to efficiently promote hydrogen generation from highly durable and active electrocatalysts for the OER/UOR/HER in urea and alkali solutions. Electrochemical impedance spectroscopy indicates that the UOR facilitates charge transfer across the interface. Furthermore, the Sc@CoTe/CNT nanocatalyst has high performance in KOH and KOH-containing urea solutions as demonstrated by the HER, OER, and UOR (215 mV, 1.59, and 1.31 V, respectively, at 10 mA cm-2 in 1 m KOH) and CoTe/CNT shows 195 mV, 1.61 and 1.3 V, respectively. Consequently, the total urea splitting system achieves 1.29 V, whereas the overall water splitting device obtaines 1.49 V of Sc@CoTe/CNT and CoTe/CNT shows 1.54, 1.48 V, respectively. This work presents a viable method of combining HER with UOR for maximally effective hydrogen production.

Degradation of a Bipolar Membrane in a Hybrid Acid/Alkali Electrolyzer Studied by X-ray Computed Tomography.

The use of a bipolar membrane (BPM) in a hybrid acid/alkali electrolyzer is widely considered as a promising energy technology for efficient hydrogen production. The stability of a BPM is often believed to be largely limited by the anion exchange layer (AEL) due to the hydrophilic attack of AEL polymers by hydroxide groups in alkaline. In this study, we employ X-ray computed tomography (CT) to investigate the degradation behaviors of BPM and found that the cation exchange layer (CEL) experiences more pronounced degradation compared with the AEL during water splitting operations. Despite its chemical stability in both acidic and alkaline environments, the CEL is more prone to electrochemical corrosion under the influence of applied voltages. This susceptibility leads to the formation of micropores and a consequent increase in the porosity. The results of this work provide a new perspective on and highlight the complexity of the degradation behaviors of BPMs in hybrid acid/alkali electrolyzers.

Boosting hydrogen evolution performance of nanofiber membrane-based composite photocatalysts with multifunctional carbon dots.

Recent progress in the co-spinning of nanofibers and semiconductor particles offers a promising strategy for the development of photocatalytic devices, solving aggregation and catalyst recovery challenges. However, composite photocatalysts based on nanofiber membranes often suffer from poor conductivity, low hydrophilicity, and easy recombination of photogenerated electron-hole pairs in the semiconductor components. Here, to tackle the aforementioned issues of ZnIn2S4/polyacrylonitrile (ZIS/PAN) nanofiber-based catalysts, we prepared a composite carbon dots/ZnIn2S4/polyacrylonitrile (CZP) nanofiber membrane by blending carbon dots (CDs) with ZIS/PAN using the electrospinning process. The hydrogen evolution performance of the CZP photocatalyst was significantly improved by CDs, which enhanced the hydrophilicity, increased the light absorption, facilitated the transfer of photogenerated electrons, and reduced the recombination of photogenerated electron-hole pairs. Notably, the optimal CZP photocatalyst achieved a hydrogen evolution rate of 2250 µmol g-1h-1, which is about 23 % higher than that of the nanofiber membrane without CDs and 4.55 times higher than that of ZIS particles. The present work successfully improved the CZP nanofiber membrane of photocatalytic hydrogen evolution performance, and the membrane may benefit further device development by eliminating the need for stirring and simplifying the recovery process.

Enhanced Photocatalytic Hydrogen Evolution Activity Driven by the Synergy Between Surface Vacancies and Cocatalysts: Surface Reaction Matters.

The incorporation of defects and cocatalysts is known to be effective in improving photocatalytic activity, yet their coupled contribution to the photocatalytic hydrogen evolution process has not been well-explored. In this study, We demonstrate that the incorporation of S vacancies and NiSe can contribute to the improvement of charge separation efficiency via the formation of a strong electric field within the bulk ZnIn2S4 (ZIS) and on its surface. More importantly, We also demonstrate that the synergy of S vacancies and NiSe benefits the overall hydrogen evolution activity by facilitating the H2O adsorption and dissociation process. This is particularly important for hydrogen evolution taking place under alkaline conditions where the proton concentration is low, allowing ZISv-NiSe (containing abundant S vacancies) to outperform ZIS-NiSe under alkaline conditions. In contrast, under acid conditions, since there are already sufficient amounts of protons available for reaction, the hydrogen evolution activity became governed by the hydrogen adsorption/desorption process rather than the H2O dissociation process. This leads to ZIS-NiSe exhibiting higher activity than ZISv-NiSe due to its more favorable hydrogen adsorption energy. The findings thus provide insights into how defect and cocatalyst modification strategies can be tailor-made to improve hydrogen evolution activity under different pH conditions.

Polyoxometalate-Based Single-Atom Catalyst with Precise Structure and Extremely Exposed Active Site for Efficient H2 Evolution.

Single-atom catalysts with precise structure and extremely high catalytic efficiency remain a fervent focus in the fields of materials chemistry and catalytic science. Herein, a nickel-substituted polyoxometalate (POM) {NiSb6O4(H2O)3[ß-Ni(hmta)SbW8O31]3}15- (NiPOM) with one extremely exposed nickel site [NiO3(H2O)3] was synthesized using the conventional aqueous method. The uniform dispersion of single nickel center with well-defined structure was facilely achieved by anchoring nanosized NiPOM on graphene oxide (GO). The resulting NiPOM/GO can couple with CdS photoabsorber for the construction of low-cost and ultra-efficient hydrogen evolution system. The H2 yield can reach to 2753.27 mmol gPOM-1 h-1, which represents a record value among all the POM-based photocatalytic systems. Remarkablely, an extremely high hydrogen yield of 3647.28 mmol gPOM-1 h-1 was achieved with simultaneous photooxidation of commercial waste plastic, representing the first POM-based photocatalytic system for H2 evolution and waste plastic conversion. This work highlights a straightforward strategy for constructing extremely exposed single-metal site with precise microenvironment by facilely manipulating nanosized molecular cluster to control individual atom.

Insight into the unique role of silver single-atom in atomic-thickness ZnIn2S4/g-C3N4 Van der Waals heterojunction for photocatalytic hydrogen evolution.

The construction of ultra-close 2D atomic-thickness Van der Waals heterojunctions with high-speed charge transfer still faces challenges. Here, we synthesized single-layer ZnIn2S4 and g-C3N4, and introduced silver single atoms to regulate Van der Waals heterojunctions at the atomic level to optimize charge transfer and catalytic activity. At the atomic scale, the impact of detailed structural differences between the two characteristic surfaces of ZnIn2S4 ([Zn-S4] and [In-S4]) on catalytic performance has been first proposed. Experiments combined with the DFT study demonstrate that single atom Ag not only acts as a charge transfer bridge but also regulates the energy band and intrinsic catalytic activity. Benefiting from the enhanced electron delocalization, the synthesized catalyst ZIS/Ag@CN exhibits excellent photocatalytic performance, with a hydrogen production rate of 5.50 mmol·g-1·h-1, which is much higher than the reported Ag-based single-atom catalysts so far. This work provides a new understanding of atomic-level heterojunction interface regulation and modification.

Pristine Wood-Supported Electrodes With Intrinsic Superhydrophilic/Superaerophobic Surface Intensify Hydrogen Evolution Reaction.

Wood, as a renewable material, has been regarded as an emerging substrate for self-supporting electrodes in large-scale water electrolysis due to numerous merits such as rich pore structure, abundant hydroxyl groups, etc. However, poor conductivity of wood can greatly suppress the performance of wood-based electrodes. Carbonization process can improve wood's conductivity, but the loss of hydroxyl groups and the required high energy consumption are the drawbacks of such a process. Here, a facile strategy is developed to prepare pristine wood-supported electrode (Ni-NiP/W) for enhanced hydrogen evolution reaction (HER); this improves electrical conductivity of wood while retaining its excellent intrinsic properties. The preparation process involves the deposition of copper on the untreated wood followed with the loading of Ni-NiP catalyst at room temperature. Encouragingly, the Ni-NiP/W exhibits conductive and inherited pristine wood's superhydrophilic and superaerophobic properties, that effectively boost mass and charge transfer. It demonstrates high activity and excellent stability in acidic, alkali, and seawater conditions as well as high current densities of up to 2000 mA cm-2; particularly a record-low HER overpotential of 206 mV in acidic conditions at 1000 mA cm-2. This work fully unlocks the admiring potential of pristine wood as superior substrate for high-performance electrochemical electrodes.

Zinc Affinity and Hydrogen Evolution Trade-Off for Homogenous Zn Deposition in Reversible Zn Ion Batteries.

Zn ion batteries (ZIBs) are promising for large-scale energy storage but their practical application is plagued by inhomogeneous Zn deposition. Despite much effort, the harm of simultaneous hydrogen evolution reaction (HER) during plating to Zn deposition, has not received sufficient studies. Herein, Sn-modified Cu nanowires (Sn@CuNWs) with Sn-Cu core-shell nanostructure to achieve uniform Zn deposition by zinc affinity-HER tendency trade-off are fabricated. Confirmed by both theoretical calculation and practical characterization, the nanowires with high zinc affinity and large deposition sites facilitate Zn deposition, while the enlarged HER tendency harmful to Zn plating is inhibited by Sn nanoshell. Therefore, the Zn deposited Sn@CuNWs anode delivers a long lifespan of 800 h at 5 mA cm-2, and the full cell exhibits a high capacity of 294.4 mAh g-1 at 5 A g-1 and a high capacity retention of 97.8% after 2500 cycles. This work reveals the importance of HER regulation for reversible Zn deposition, which should be noticed in further research.

Constructing Unsaturated Ru Atom Arrays Confined in Mn Oxides to Boost Neutral Water Reduction.

Recently, Ru single atoms supported on carbon nanomaterials have demonstrated ultrahigh activity for acid hydrogen evolution reaction (HER), however their neutral HER activity remains low due to the sluggish kinetics for both the water dissociation step to generate H* intermediates and subsequent H* recombination in neutral electrolytes. Here, we synthesize ordered low-coordinated Ru atom arrays confined in Mn oxides (i.e., Li4Mn5O12) for concurrently boosting the water dissociation and H* recombination, thus achieving a 6-fold HER activity enhancement than commercial Pt/C in neutral media. Control experiments indicate that low-coordinated Ru atoms with strong affinity to oxygen atoms of water molecules facilitate the water dissociation to rapidly generate H*. More importantly, both electrochemical and theoretic results uncover that the array-like structure allows the activation of two water molecules on two adjacent Ru atoms for enabling direct H*-H* recombination via the Tafel step, while isolated Ru atoms can only activate water one by one for recombining H* via the sluggish Heyrovsky step. Clearly, this work paves new avenues to boosting the electrocatalytic activity by constructing ordered metal atoms assembles with controllable coordination environments.

Alkali Metals Activated High Entropy Double Perovskites for Boosted Hydrogen Evolution Reaction.

An efficient and facile water dissociation process plays a crucial role in enhancing the activity of alkaline hydrogen evolution reaction (HER). Considering the intricate influence between interfacial water and intermediates in typical catalytic systems, meticulously engineered catalysts should be developed by modulating electron configurations and optimizing surface chemical bonds. Here, a high-entropy double perovskite (HEDP) electrocatalyst La2(Co1/6Ni1/6Mg1/6Zn1/6Na1/6Li1/6)RuO6, achieving a reduced overpotential of 40.7 mV at 10 mA cm-2 and maintaining exemplary stability over 82 h in a 1 m KOH electrolyte is reported. Advanced spectral characterization and first-principles calculations elucidate the electron transfer from Ru to Co and Ni positions, facilitated by alkali metal-induced super-exchange interaction in high-entropy crystals. This significantly optimizes hydrogen adsorption energy and lowers the water decomposition barrier. Concurrently, the super-exchange interaction enhances orbital hybridization and narrows the bandgap, thus improving catalytic efficiency and adsorption capacity while mitigating hysteresis-driven proton transfer. The high-entropy framework also ensures structural stability and longevity in alkaline environments. The work provides further insights into the formation mechanisms of HEDP and offers guidelines for discovering advanced, efficient hydrogen evolution catalysts through super-exchange interaction.

Heteroatom Immobilization Engineering toward High-Performance Metal Anodes.

Heteroatom immobilization engineering (HAIE) is becoming a forefront approach in materials science and engineering, focusing on the precise control and manipulation of atomic-level interactions within heterogeneous systems. HAIE has emerged as an efficient strategy to fabricate single-atom sites for enhancing the performance of metal-based batteries. Despite the significant progress achieved through HAIE in metal anodes for metal-based batteries, several critical challenges such as metal dendrites, side reactions, and sluggish reaction kinetics are still present. In this review, we delve into the fundamental principles underlying heteroatom immobilization engineering in metal anodes, aiming to elucidate its role in enhancing the electrochemical performance in batteries. We systematically investigate how HAIE facilitates uniform nucleation of metal in anodes, how HAIE inhibits side reactions at the metal anode-electrolyte interface, and the role of HAIE in promoting the desolvation of metal ions and accelerating reaction kinetics within metal-based batteries. Finally, we discuss various strategies for implementing HAIE in electrode materials, such as high-temperature pyrolysis, vacancy reduction, and molten-salt etching and anchoring. These strategies include selecting appropriate heteroatoms, optimizing immobilization methods, and constructing material architectures. They can be utilized to further refine the performance to enhance the capabilities of HAIE and facilitate its widespread application in next-generation metal-based battery technologies.

MoSe2-Sensitized Water Splitting Assisted by C60-Dendrons on the Basal Surface.

We propose a new class of H2 evolution photocatalyst containing TMD not as a co-catalyst, but as a photosensitizer: MoSe2/C60-dendron nanohybrids, assisted by 1-benzyl-1,4-dihydronicotinamide (BNAH) as a sacrificial donor and Pt nanoparticles as co-catalysts. The 2D/0D mixed-dimensional heterojunction formed by MoSe2 and C60 is highly effective in generating mobile carriers under visible and NIR light irradiation.  This process involves electron extraction from the exciton in MoSe2 to C60, followed by electron transfer to Pt nanoparticles via MV2+, leading to H2 production from water.  Even NIR light, such as 800 nm light corresponding to the A-exciton absorption of MoSe2, can facilitate water splitting.  The EQY of the H2 evolution reaction was estimated to be 0.0027%.

Factorial Optimization of CoCuFe-LDH/Graphene Ternary Composites as Electrocatalysts for Water Splitting.

The layered double hydroxides (LDHs) have demonstrated significant potential as non-noble-metal electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Their unique compositional and structural properties contribute to their efficiency and stability as catalysts. In this study, CoCuFe-LDH composites were grown on graphene (G) via a cost-effective and straightforward one-step hydrothermal process. A 2-level full-factorial model was employed to determine the impact of Co (1.5, 3, and 4.5 mmol) and graphene (10, 30, and 50 mg) concentrations on the onset potential of OER and HER, which were the chosen response variables. OER and HER activity variabilities were assessed in triplicate using Co[3]Cu[3]Fe[3]-LDH/G[30] (central point), which were determined at 0.01% and 0.02%, respectively. Statistical analyses demonstrated that Co[4.5]Cu[3]Fe[3]-LDH/G[10] and Co[1.5]Cu[3]Fe[3]-LDH/G[10] showed the lowest onset potential at 1.52 V and -0.32 V (V vs RHE) for the OER and HER, respectively, suggesting that a high cobalt concentration enhances OER performance, while optimal HER catalysis was achieved with lower cobalt concentrations. Moreover, the trimetallic composites exhibited good stability with negligible loss of catalytic activity over 24 h.

Theoretical Prediction of Enhanced Hydrogen Evolution Reaction Electrocatalysts Based on Tantalum Phosphide.

Ta-based transition metal catalysts have shown significant catalytic activity for the hydrogen evolution reaction (HER) in recent studies. However, the application of tantalum phosphide (TaP) in the HER has not been documented. Herein, a systematic study of TaP catalysts was performed through density functional theory (DFT). The performance of TaP (004) for the HER was predicted. Thermodynamic analyses of Ta-terminated and P-terminated surfaces with adsorbed hydrogen atoms were conducted, and the HER mechanism on TaP (004) surfaces was carefully investigated. Theoretical results revealed that TaP (004) exhibits excellent HER activity (ΔGH* = 0.0456 eV), and both the Ta-terminated and P-terminated surfaces follow the Volmer-Heyrovsky mechanism under acidic conditions, with the Volmer step being the rate-determining step. A mixed surface strategy was also applied to explore the synergistic effects of Ta-terminated and P-terminated surfaces, which enhanced the HER activity. Additionally, the study screened dopants to assess their impact on the HER activity, revealing that doping with S, Ni, Co, Fe, and Cr could improve the HER performance.

Ampere-Level Hydrogen Generation via 1000 H Stable Seawater Electrolysis Catalyzed by Pt-Cluster-Loaded NiFeCo Phosphide.

Seawater electrolysis can generate carbon-neutral hydrogen but its efficiency is hindered by the low mass activity and poor stability of commercial catalysts at industrial current densities. Herein, Pt nanoclusters are loaded on nickel-iron-cobalt phosphide nanosheets, with the obtained Pt@NiFeCo-P electrocatalyst exhibiting excellent hydrogen evolution reaction (HER) activity and stability in alkaline seawater at ampere-level current densities. The catalyst delivers an ultralow HER overpotential of 19.7 mV at -10 mA cm-2 in seawater-simulating alkaline solutions, along with a Pt-mass activity 20.8 times higher than Pt/C under the same conditions, while dropping to 8.3 mV upon a five-fold NaCl concentrated natural seawater. Remarkably, Pt@NiFeCo-P offers stable operation for over 1000 h at 1 A cm-2 in an alkaline brine electrolyte, demonstrating its potential for efficient and long-term seawater electrolysis. X-ray photoelectron spectroscopy (XPS), in situ electrochemical impedance spectroscopy (EIS), and in situ Raman studies revealed fast electron and charge transfer from the NiFeCo-P substrate to Pt nanoclusters enabled by a strong metal-support interaction, which increased the coverage of H* and accelerated water dissociation on high valent Co sites. This study represents a significant advancement in the development of efficient and stable electrocatalysts with high mass activity for sustainable hydrogen generation from seawater.