Low Rh doping accelerated HER/OER bifunctional catalytic activities of nanoflower-like Ni-Co sulfide for greatly boosting overall water splitting.

Facile synthesis of high-efficiency and stable bifunctional electrocatalyst is essential for producing clean hydrogen in energy storage systems. Herein, low Rh-doped flower-like Ni3S2/Co3S4 heterostructures were facilely prepared on porous nickel foam (labeled Rh-Ni3S2/Co3S4/NF) by a hydrothermal method. The correlation of the precursors types with the morphological structures and catalytic properties were rigorously investigated for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in the control groups. The low Rh doping within the catalyst played important role in boosting the catalytic characteristics. The resulting catalyst showed the smaller overpotentials of 197 and 78 mV to drive a current density of 10 mA cm-2 for the OER and HER in alkaline electrolyte, respectively. And the potential only required 1.71 V to drive a current density of 100 mA cm-2 in a water splitting device. It reflects excellent overall water splitting of the home-made Rh-Ni3S2/Co3S4/NF. This strategy shed some constructive light for preparing transition metal sulfide-based electrocatalysts in water splitting devices.

Boosting electrocatalytic hydrogen evolution via partial oxidation of rhenium through cobalt modification in nanoalloy structure.

Although the theoretical electrocatalytic activity of rhenium (Re) for the hydrogen evolution reaction is comparable to that of platinum, the experimental performance of reported rhenium-based electrocatalysts remains unsatisfactory. Herein, we report a highly efficient and stable electrocatalyst composed of rhenium and cobalt (Co) nanoalloy embedded in nitrogen-doped carbon film (Re3Co2@NCF). The Re3Co2@NCF electrocatalyst exhibited remarkable hydrogen evolution performance, with an overpotential as low as 30 ± 3 mV to reach a current density of 10 mA cm-2. In addition, the Re3Co2@NCF demonstrated exceptional stability over several days at a current density of 150 mA cm-2. Theoretical calculations revealed that alloying cobalt with rhenium altered the electronic structure of the metals, causing partial oxidation of the superficial metal atoms. This modification provided a balance for various intermediates' adsorption and desorption, thereby boosting the intrinsic activity of rhenium for hydrogen evolution reaction. This work improves the electrocatalytic performance of rhenium to its theoretical activity, suggesting a promising future for rhenium-based electrocatalysts.

Metal organic framework-assisted copper-modified titania (Cu/TiO2) with abundant exposed active sites and highly accessible pore channels for an enhanced photo-generation of hydrogen.

Metal-doping is a common strategy for establishing active sites on photocatalyst, but appropriately exposing them for maximized atomic utilization remains a great challenge in photocatalytic research. Herein, we propose a metal organic framework (MOF)-assisted approach to synthesis copper-modified titania (Cu-TiO2/Cu) photocatalyst with homogenously distributed and highly accessible active sites in its matrix. Significantly, an MOF precursor, namely NH2-MIL-125, with co-chelation of titania (Ti) and copper (Cu) was subjected to mild calcination, subsequently results in Cu-modified TiO2 with highly accessible channels to its inner surface. These channels provide not only a large reactive surface (>400 m2 g-1); they also enable facile modifying route for the pre-deposited Cu in prior to photoreaction. Specifically, NH3 treatment was applied to partially reduce deposited Cu ions (Cu+ and Cu2+) into Cu nanoparticles, where their interplays realize improved optical properties and charge separation during photoreactions. Furthermore, the NH3-induced Cu nanoparticles could also serve as the adsorptive site for H+, thereby enabling 5629 µmol h-1 g-1 H2 generation over the optimum photocatalyst of Cu20/TiO2/Cu500. Such performance is associated to 35.44 and 1.71-fold improvements compared to pure TiO2 (Cu0/TiO2) and untreated Cu-ion modified TiO2 (Cu20/TiO2), respectively. This work offers a new synthetic strategy for obtaining photocatalyst with evenly distributed and highly accessible active sites, thus improving the commensurability of photocatalytic H2 generation from the industrial perspective.

Integrated doped-Ru electrocatalyst with excellent H adsorption-desorption and active site on hollow tubular structures for boosting efficient hydrogen evolution.

Electrochemical water splitting for hydrogen production is an ideal process for clean energy production. However, highly active and low-cost electrocatalysts are essential and challenging. In this work, a multi-component Cu-based catalyst (Ru-M-C-Cu), synergized with ruthenium (Ru) heteroatom doping, was synthesized via a facile immersion-calcination-immersion method. Based on the cotton biomass substrate, a hollow tubular structure was obtained. By virtue of its distinctive structure and high carbon content, cotton biomass assumed a dual role as a sacrificial template and a reducing agent in the eco-friendly synthesis of electrocatalysts, which was instrumental in the creation of a multi-component system augmented by heteroatom doping. The multi-component system was constructed by in-situ transformation and redox reaction during calcination in an oxygen-free environment. The Ru-M-C-Cu catalyst exhibited a competitive overpotential of 108 mV at a current density of 10 mA cm-2 for alkaline hydrogen evolution reaction (HER). The satisfactory catalytic performance of Ru-M-C-Cu can be attributed to the fact that the Ru-O-Cu catalytic centers enhanced the adsorption and desorption abilities of the Cu-O active sites toward hydrogen. Furthermore, the hollow tubular structure allowed the electrolyte to make full contact with the active sites of the Ru-M-C-Cu catalyst, thus accelerated the HER kinetics. The catalyst showed structural and chemical stability after a 12-hour successive test. Besides, the production cost of Ru-M-C-Cu was significantly reduced by 99.1 % than that of commercial 20 % Pt/C, showing the potential as an alternative catalyst by offering a more accessible and sustainable source. This work provides a new design of sustainable low-budget electrocatalysts with the proposed strategies expected for producing clean and renewable hydrogen energy.

Nickel-based dual single atom electrocatalysts for the nitrate reduction reaction.

Electrochemical nitrate (NO3-) reduction reaction (NO3-RR) to ammonium (NH4+) or nitrogen (N2) provides a green route for nitrate remediation. However, nitrite generation and hydrogen evolution reactions hinder the feasibility of the process. Herein, dual single atom catalysts were rationally designed by introducing Ag/Bi/Mo atoms to atomically dispersed NiNC moieties supported by nitrogen-doped carbon nanosheet (NCNS) for the NO3-RR. Ni single atoms loaded on NCNS (Ni/NCNS) tend to reduce NO3- to valuable NH4+ with a high selectivity of 77.8 %. In contrast, the main product of NO3-RR catalyzing by NiAg/NCNS, NiBi/NCNS, and NiMo/NCNS was changed to N2, giving rise to N2 selectivity of 48.4, 47.1 and 47.5 %, respectively. Encouragingly, Ni/NCNS, NiBi/NCNS, and NiAg/NCNS showed excellent durability in acidic electrolytes, leading to nitrate conversion rates of 70.3, 91.1, and 93.2 % after a 10-h reaction. Simulated wastewater experiments showed that NiAg/NCNS could remove NO3- up to 97.8 % at -0.62 V after 9-h electrolysis. This work afforded a new strategy to regulate the reaction pathway and improve the conversion efficiency of the NO3-RR via engineering the dual atomic sites of the catalysts.

Nanocrystalline transition metal tetraborides as efficient electrocatalysts for hydrogen evolution reaction at the large current density.

While great efforts have been made to improve the electrocatalytic activity of existing materials toward hydrogen evolution reaction (HER), it is also importance for searching new type of nonprecious HER catalysts to realize the practical hydrogen evolution. Herein, we firstly report nanocrystalline transition metal tetraborides (TMB4, TM=W and Mo) as an efficient HER electrocatalyst has been synthesized by a single-step solid-state reaction. The optimized nanocrystalline WB4 exhibits an overpotential as low as 172 mV at 10 mA/cm2 and small Tafel slope of 63 mV/dec in 0.5 M H2SO4. Moreover, the nanocrystalline WB4 outperforms the commercial Pt/C at high current density region, confirming potential applications in industrially electrochemical water splitting. Theoretical study reveals that high intrinsic HER activity of WB4 is originated from its large work function that contributes to the weak hydrogen-adsorption energy. Therefore, this work provides new insights for development of robust nanocrystalline electrocatalysts for efficient HER.

Regulating the electronic structure of Pt SAs-Ni2P for enhanced hydrogen evolution reaction.

The single atom catalysts (SACs) show immense promise as catalytic materials. By doping the single atoms (SAs) of precious metals onto substrates, the atomic utilization of these metals can be maximized, thereby reducing catalyst costs. The electronic structure of precious metal SAs is significantly influenced by compositions of doped substrates. Therefore, optimizing the electronic structure through appropriate doping of substrates can further enhance catalytic activity. Here, Pt single atoms (Pt SAs) are doped onto transition metal sulfide substrate NiS2 (Pt SAs-NiS2) and phosphide substrate Ni2P (Pt SAs-Ni2P) to design and prepare catalysts. Compared to the Pt SAs-NiS2 catalyst, the Pt SAs-Ni2P catalyst exhibits better hydrogen evolution catalytic performance and stability. Under 1 M KOH conditions, the hydrogen evolution mass activity current density of the Pt SAs-Ni2P catalyst reaches 0.225 A mgPt-1 at 50 mV, which is 33 times higher than that of commercial Pt/C catalysts. It requires only 44.9 mV to achieve a current density of 10 mA cm-2. In contrast, for the Pt SAs-NiS2 catalyst, the hydrogen evolution mass activity current density is 0.178 A mgPt-1, requiring 77.8 mV to achieve a current density of 10 mA cm-2. Theoretical calculations indicate that in Pt SAs-Ni2P, the interaction between Pt SAs and the Ni2P substrate causes the Pt d-band center to shift downward, enhancing the H2O desorption and providing optimal H binding sites. Additionally, the hollow octahedral morphology of Ni2P provides a larger surface area, exposing more reactive sites and improving reaction kinetics. This study presents an effective pathway for preparing high-performance hydrogen evolution electrocatalysts by selecting appropriate doped substrates to control the electronic structure of Pt SAs.

Synergistic engineering of heterostructure and oxygen vacancy in cobalt hydroxide/aluminum oxyhydroxide as bifunctional electrocatalysts for urea-assisted hydrogen production.

Designing inexpensive, high-efficiency and durable bifunctional catalysts for urea oxidation reaction (UOR) and hydrogen evolution reaction (HER) is an encouraging tactic to produce hydrogen with reduced energy expenditure. Herein, oxygen vacancy-rich cobalt hydroxide/aluminum oxyhydroxide heterostructure on nickel foam (denoted as Co(OH)2/AlOOH/NF-100) has been fabricated using one step hydrothermal process. Theoretical calculation and experimental results indicate the electrons transfer from Co(OH)2 to highly active AlOOH results in the interfacial charge redistribution and optimization of electronic structure. Abundant oxygen vacancies in the heterostructure could improve the conductivity and simultaneously serve as the active sites for catalytic reaction. Consequently, the optimal Co(OH)2/AlOOH/NF-100 demonstrates excellent electrocatalytic performance for HER (62.9 mV@10 mA cm-2) and UOR (1.36 V@10 mA cm-2) due to the synergy between heterointerface and oxygen vacancies. Additionally, the in situ electrochemical impedance spectrum (EIS) for UOR suggests that the heterostructured catalyst exhibits rapid reaction kinetics, mass transfer and current response. Importantly, the urea-assisted electrolysis composed of the Co(OH)2/AlOOH/NF-100 manifests a low cell voltage (1.48 V @ 10 mA cm-2) in 1 M KOH containing 0.5 M urea. This work presents a promising avenue to the development of HER/UOR bifunctional electrocatalysts.

Silver Nanowire Aerogel Support Promotes Stable Hydrogen Evolution Reaction at High Current Density.

The stability of electrocatalysts during the hydrogen evolution reaction (HER) is vital for efficient production of hydrogen energy. Herein, we demonstrate that silver nanowire aerogel-based support (AABS) could facilitate the construction of HER catalysts with extraordinary long-term stability. A full nanostructure catalyst of nickel phosphide based formed on AABS (Ni2P-Ni5P4@AABS) was prepared to achieve an overpotential of 687 mV (without iR compensation) for HER at the current density of 1 A cm-2 in 0.5 M H2SO4. Excitingly, the stable HER performance was kept for 42 days during the long-term stability (i-t) test at high current density (0.5-1 A cm-2). The excellent HER performance of the Ni2P-Ni5P4@AABS catalyst is attributed to rapid electron transport pathways, numerous more accessible active sites, and support induced enhanced catalytic activity. The support effect was highlighted by a proposed phenomenological two-channel model for electron transport, which provides fresh insights into the design strategy for energy storage and delivery.

Ru Nanoparticles Encapsulated by Defective TiO2 Boost the Hydrogen Oxidation/ Evolution Reaction.

The development of efficient and durable electrocatalysts for the alkaline hydrogen oxidation/evolution reaction is crucial for anion exchange membrane fuel cells/water electrolyzers. However, designing such electrocatalysts poses a challenge due to the need for optimizing various adsorbates. Herein, highly dispersed Ru nanoparticles catalysts is reported encapsulated and supported by defective anatase phase of titanium dioxide (named as Ru NPs/def-TiO2(A)) for boosting hydrogen-cycle electrocatalysis with robust anti-CO-poisoning in alkaline conditions. The Ru NPs/def-TiO2(A) achieves a high-quality activity of 7.65 A mgRu -1, which is 23.2 and 9.5-fold higher than commercial Ru/C and Pt/C in alkaline HOR. Moreover, this catalyst exhibits an outstanding overpotential of 21 mV at 10 mA cm-2 in alkaline HER. Hydrogen underpotential deposition (Hupd) and CO stripping experiments demonstrate that Ru NPs/def-TiO2(A) has the optimized H*, OH*, and CO* adsorption strength, enabling the Ru NPs/def-TiO2(A) catalyst to display excellent and robust HOR/HER performance under alkaline conditions. Using density functional theory calculations, the enhanced HOR performance mechanism for the Ru NPs/def-TiO2(A) catalyst originates from the TiO2 step face in contact with the Ru nanoparticles, indicating that the kinetics of water formation are considerably more favorable at the Ru NPs/def-TiO2(A) interface.

Boosting Acidic Hydrogen Evolution Kinetics Induced by Weak Strain Effect in PdPt Alloy for Proton Exchange Membrane Water Electrolyzers.

Strain engineering is an effective strategy for manipulating the electronic structure of active sites and altering the binding strength toward adsorbates during the hydrogen evolution reaction (HER). However, the effects of weak and strong strain engineering on the HER catalytic activity have not been fully explored. Herein, the core-shell PdPt alloys with two-layer Pt shells (PdPt2L) and multi-layer Pt shells (PdPtML) is constructed, which exhibit distinct lattice strains. Notably, PdPt2L with weak strain effect just requires a low overpotential of 18 mV to reach 10 mA cm-2 for the HER and shows the superior long-term stability for 510 h with negligible activity degradation in 0.5 M H2SO4. The intrinsic activity of PdPt2L is 6.2 and 24.5 times higher than that of PdPtML and commercial Pt/C, respectively. Furthermore, PdPt2L||IrO2 exhibits superior activity over Pt/C||IrO2 in proton exchange membrane water electrolyzers and maintains stable operation for 100 h at large current density of 500 mA cm-2. In situ/operando measurements verify that PdPt2L exhibits lower apparent activation energy and accelerated ad-/desorption kinetics, benefiting from the weak strain effect. Density functional theory calculations also reveal that PdPt2L displays weaker H* adsorption energy compared to PdPtML, favoring for H* desorption and promoting H2 generation.

Rationally Designed Mo/Ru-Based Multi-Site Heterogeneous Electrocatalyst for Accelerated Alkaline Hydrogen Evolution Reaction.

The rational design of multi-site electrocatalysts with three different functions for facile H2O dissociation, H-H coupling, and rapid H2 release is desirable but difficult to achieve. This strategy can accelerate the sluggish kinetics of the hydrogen evolution reaction (HER) under alkaline conditions. To resolve this issue, a Mo/Ru-based catalyst with three different active sites (Ru/Mo2C/MoO2) is rationally designed and its performance in alkaline HER is evaluated. The experimental results and density functional theory calculations revealed that, at the heterogeneous Mo2C/MoO2 interface, the higher valence state of Mo (MoO2) and the lower valence state of Mo (Mo2C) exhibited strong OH- and H-binding energies, respectively, which accelerated H2O dissociation. Moreover, the interfacial Ru possessed an appropriate hydrogen binding energy for H-H coupling and subsequent H2 evolution. Thus, this catalyst significantly accelerated the Volmer step and the Tafel step and, consequently, HER kinetics. This catalyst also demonstrated low overpotentials of 19 and 160 mV at current densities of 10 and 1000 mA cm-2, respectively, in alkaline media and long-term stability superior to that of most state-of-the-art alkaline HER electrocatalysts. This work provides a rational design principle for advanced multi-site catalytic systems, which can realize multi-electron electrocatalytic reactions.

Self-Standing Mo/MoO2 Porous Flake Arrays for Efficient Hydrogen Evolution Reaction in High-pH Media.

The alkaline hydrogen evolution reaction (HER) is limited by scarce proton availability, resulting in slower reaction kinetics compared to those under acidic conditions. Enhancing the local chemical environment of protons on the catalyst surface can improve the intrinsic reaction kinetics. Here, we design a Mo/MoO2 metallic heterojunction that creates an acidic-like environment with a proton-rich surface, significantly enhancing HER performance in alkaline electrolytes, as confirmed by in situ spectroscopy and electrochemical analysis. A self-standing Mo/MoO2 catalytic electrode is fabricated via a controlled pyrolysis-reduction strategy. This electrode exhibits exceptional HER activity, with low overpotentials of 65 mV at 10 mA cm-2 and 315 mV at 500 mA cm-2, a Tafel slope of 38.2 mV dec-1, and stability exceeding 60 h at -300 mA cm-2 in alkaline solution. The porous flake array structure of the Mo/MoO2 heterojunctions enhances the adjacent hydronium (H3O+) concentration, resulting in a ΔGH* value of 0.15 eV and a water dissociation energy barrier of 0.37 eV in an alkaline medium. The successful preparation of a large-area electrode (2 cm × 2 cm) demonstrates the scalability of this approach for fabricating molybdenum-based catalytic electrodes with enhanced HER activity in alkaline environments.

Electronic Structure Modulating of W 18 O 49 Nanospheres by Niobium Doping for Efficient Hydrogen Evolution Reaction.

Developing efficient electrocatalysts to reduce HER overpotential is vital to enhance hydrogen production efficiency and minimize energy consumption. Adjusting the electronic structure of transition metal oxides via elemental doping is a potent strategy to improve the effectiveness of electrocatalysts for hydrogen evolution. In this work, we synthesized a set of niobium-doped tungsten oxides (Nbx-W18O49) under anoxic conditions using a straightforward "one-pot" solvothermal approach. After doping Nb, the oxygen vacancy content inside W18O49 was increased, which induced a synergistic effect with the active sites of tungsten. In acidic environments, the hydrogen evolution activity of the Nb0.6-W18O49 electrocatalyst is second only by 20 wt% Pt/C. It attains a current density of -10 mA cm-2 at an overpotential of 102 mV. By comparison with W18O49, Nb0.4-W18O49 and Nb0.5-W18O49, Nb0.6-W18O49 demonstrates a reduced charge transfer resistance, which significantly enhances its conductivity and the speed of electron movement across interfaces. Coupled with this feature are notably faster HER kinetics. Additionally, it exhibits excellent stability, meaning it maintains its performance and structural integrity over prolonged periods and under various operational conditions. This article provides a new perspective for discovering inexpensive and efficient hydrogen evolution electrocatalyst materials.

Theoretical design and synthesis of Co30Ni60/CC for high selective methanol oxidation assisted energy-saving hydrogen production.

The integration of methanol oxidation reaction (MOR) with hydrogen evolution reaction (HER) represents an advanced approach to hydrogen production technology. Nonetheless, the rational design and synthesis of bifunctional catalysts for both MOR and HER with exceptional activity, stability and selectivity present formidable challenges. In this work, firstly, density functional theory (DFT) was utilized to design and evaluate material models with high performance for both MOR and HER. Secondly, guided by DFT, Co30Ni60/CC (CC, carbon cloth) composites with a leaf-like nanosheet structure were successfully fabricated via electrodeposition. In the MOR process, Ni acts as the predominant active center, while Co amplifies the electrochemically active surface area (ECSA) and enhances the selectivity of methanol oxidation. Conversely, in the HER process, Co serves as the primary active center, with Ni augmenting the charge transfer rate. The electrochemical results demonstrate that Co30Ni60/CC exhibits exceptional performance in both MOR and HER at a current density (j) of 10 mA cm-2, with peak potentials of 1.323 V and -95 mV, respectively. Additionally, it shows remarkable selectivity for the oxidiation of methanol to high value-added formic acid. Thirdly, following a 100 h chronopotentiometry (CP) test, the required potential demonstrates an increase of 4.9 % (MOR) and 8.1 % (HER), signifying the superior stability of Co30Ni60/CC compared to those reported in the literature. The exceptional performance of Co30Ni60/CC can be primarily attributed to that the leaf-like nanosheets structure not only exposes a plethora of active sites but also facilitates electrolyte diffusion, the monolithic structure prepared by electrodeposition enhances its stability, and the transfer of electrons from Co to Ni regulates its electronic structure, as corroborated by X-ray photoelectron spectroscopy (XPS) and density of states (DOS) analyses. Finally, at the same j, the voltage required by the Co30Ni60/CC||Co30Ni60/CC electrolytic cell, powered by an electrochemical workstation, is 198 mV lower than that required for alkaline water-splitting. Meanwhile, at higher j (100 mA cm-2), the electrolytic cell exhibits sustained and stable operation for 150 h, enabling high-efficiency hydrogen production and the synthesis of high value-added formic acid.

Deciphering electrocatalytic hydrogen production in water through a bioinspired water-stable copper(II) complex adorned with (N2S2)-donor sites.

Electrocatalytic hydrogen production stands as a pivotal cornerstone in ushering the revolutionary era of the hydrogen economy. With a keen focus on emulating the significance of hydrogenase-like active sites in sustainable H2 generation, a meticulously designed and water-stable copper(II) complex, [Cl-Cu-LN2S2]ClO4, featuring the N,S-type ligand, LN2S2 (2,2'-((butane-2,3-diylbis(sulfanediyl))bis(methylene))dipyridine), has been crafted and assessed for its prowess in electrocatalytic H2 production in water, leveraging acetic acid as a proton source. The molecular catalyst, adopting a square pyramidal coordination geometry, undergoes -Cl substitution by H2O during electrochemical conditions yielding [H2O-Cu-LN2S2]2+ as the true catalyst, showcases outstanding activity in electrochemical proton reduction in acidic water, achieving an impressive rate of 241.75 s-1 for hydrogen generation. Controlled potential electrolysis at -1.2 V vs. Ag/AgCl for 1.6 h reveals a high turnover number of 73.06 with a commendable Faradic efficiency of 94.2%. A comprehensive analysis encompassing electrochemical, spectroscopic, and analytical methods reveals an insignificant degradation of the molecular catalyst. However, the post-CPE electrocatalyst, present in the solution domain, signifies the coveted stability and effective activity under the specified electrochemical conditions. The synergy of electrochemical, spectroscopic, and computational studies endorses the proton-electron coupling mediated catalytic pathways, affirming the viability of sustainable hydrogen production.

Topologically Close-Packed Frank-Kasper C15 Phase Intermetallic Ir Alloy Electrocatalysts Enables High-Performance Proton Exchange Membrane Water Electrolyzer.

Chemical synthesis of unconventional topologically close-packed intermetallic nanocrystals (NCs) remains a considerable challenge due to the limitation of large volume asymmetry between the components. Here, a series of unconventional intermetallic Frank-Kasper C15 phase Ir2M (M = rare earth metals La, Ce, Gd, Tb, Tm) NCs is successfully prepared via a molten-salt assisted reduction method as efficient electrocatalysts for hydrogen evolution reaction (HER). Compared to the disordered counterpart (A1-Ir2Ce), C15-Ir2Ce features higher Ir-Ce coordination number that leads to an electron-rich environment for Ir sites. The C15-Ir2Ce catalyst exhibits excellent and pH-universal HER activity and requires only 9, 16, and 27 mV overpotentials to attain 10 mA cm-2 in acidic, alkaline, and neutral electrolytes, respectively, representing one of the best HER electrocatalysts ever reported. In a proton exchange membrane water electrolyzer, the C15-Ir2Ce cathode achieves an industrial-scale current density of 1 A cm-2 with a remarkably low cell voltage of 1.7 V at 80 °C and can operate stably for 1000 h with a sluggish voltage decay rate of 50 µV h-1. Theoretical investigations reveal that the electron-rich Ir sites intensify the polarization of *H2O intermediate on C15-Ir2Ce, thus lowering the energy barrier of the water dissociation and facilitating the HER kinetics.

Phase Engineering-Mediated D-Band Center of Ru Sites Promote the Hydrogen Evolution Reaction Under Universal pH Condition.

The rational design of pH-universal electrocatalyst with high-efficiency, low-cost and large current output suitable for industrial hydrogen evolution reaction (HER) is crucial for hydrogen production via water splitting. Herein, phase engineering of ruthenium (Ru) electrocatalyst comprised of metastable unconventional face-centered cubic (fcc) and conventional hexagonal close-packed (hcp) crystalline phase supported on nitrogen-doped carbon matrix (fcc/hcp-Ru/NC) is successfully synthesized through a facile pyrolysis approach. Fascinatingly, the fcc/hcp-Ru/NC displayed excellent electrocatalytic HER performance under a universal pH range. To deliver a current density of 10 mA cm-2, the fcc/hcp-Ru/NC required overpotentials of 16.8, 23.8 and 22.3 mV in 1 M KOH, 0.5 M H2SO4 and 1 M phosphate buffered solution (PBS), respectively. Even to drive an industrial-level current density of 500 and 1000 mA cm-2, the corresponding overpotentials are 189.8 and 284 mV in alkaline, 202 and 287 mV in acidic media, respectively. Experimental and theoretical calculation result unveiled that the charge migration from fcc-Ru to hcp-Ru induced by work function discrepancy within fcc/hcp-Ru/NC regulate the d-band center of Ru sites, which facilitated the water adsorption and dissociation, thus boosting the electrocatalytic HER performance. The present work paves the way for construction of novel and efficient electrocatalysts for energy conversion and storage.

Electronic Metal-Support Interaction Induces Hydrogen Spillover and Platinum Utilization in Hydrogen Evolution Reaction.

The substantial promotion of hydrogen evolution reaction (HER) catalytic performance relies on the breakup of the Sabatier principle, which can be achieved by the alternation of the support and electronic metal support interaction (EMSI) is noticed. Due to the utilization of tungsten disulfides as support for platinum (Pt@WS2), surprisingly, Pt@WS2 demands only 31 mV overpotential to attain 10 mA cm-2 in acidic HER test, corresponding to a 2.5-fold higher mass activity than benchmarked Pt/C. The pH dependent electrochemical measurements associated with H2-TPD and in-situ Raman spectroscopy indicate a hydrogen spillover involved HER mechanism is confirmed. The WS2 support triggers a higher hydrogen binding strength for Pt leading to the increment in hydrogen concentration at Pt sites proved by upshifted d band center as well as lower Gibbs free energy of hydrogen, favourable for hydrogen spillover. Besides, the WS2 shows a comparably lower effect on Gibbs free energy for different Pt layers (-0.50 eV layer-1) than carbon black (-0.88 eV layer-1) contributing to a better Pt utilization. Also, the theoretical calculation suggests the hydrogen spillover occurs on the 3rd Pt layer in Pt@WS2; moreover, the energy barrier is lowered with increment in hydrogen coverage on Pt.

In-Situ Anchoring of Co Single-Atom Synergistically with Cd Vacancy of Cadmium Sulfide for Boosting Asymmetric Charge Distribution and Photocatalytic Hydrogen Evolution.

In the context of reshaping the energy pattern, designing and synthesizing high-performance noble metal-free photocatalysts with ultra-high atomic utilization for hydrogen evolution reaction (HER) still remains a challenge. In a streamlined synthesis process, in-situ single atom anchoring is performed in parallel with HER by irradiating a precursory defect-state CdS/Co suspension (Co-DCdS-Ss) system under simulated sunlight and the in-situ synthesizing single-atom Co photocatalyst (Co5:DCdS) exhibits further improved catalytic performance (60.10 mmol g-1 h-1) compared with Co-DCdS-Ss (18.09 mmol g-1 h-1), reaching an apparent quantum yield of 57.6% at 500 nm and a solar-chemical energy conversion efficiency (SCC) of 6.26% at AM 1.5G. In-depth characterization tests and density functional theory (DFT) calculations prove that the anchoring of Co single atom deepens the asymmetric charge distribution of the two-coordination S atom adjacent to the cadmium vacancy (VCd). The synergy between electron delocalization VCd and Co single atom on the catalyst surface is constructed, which bifunctional sites responsible for boosting water adsorption-dissociation and hydrogen evolution. This study advances the understanding of the underlying mechanisms of synergy between surface defects and metal single atoms and opens a new horizon for the development of advanced materials in the field of photocatalysis.