摘要：With the ever-pressing issues of global energy demand and environmental pollution,molecular hydrogen has been receiving increasing attention as a clean alternative energy *** hydrogen production,the design and development of high-performance catalysts remains rather *** the compositions and structures of catalyst interfaces have paramount influences on the catalytic performances,the central topic here has always been to design and engineer the interface structures via rational routes so as to boost the activities and stabilities of electrocatalysts on hydrogen evolution reaction(HER).Here in this review,we focus on the design and preparation of multi-scale catalysts specifically catering to HER *** start from the design and structure-activity relationship of catalytic nanostructures,summarize the research progresses related to HER nanocatalysts,and interpret their high activities from the atomistic perspective;then,we review the studies regarding the design,preparation,HER applications and structure-activity relationship of single-atom site catalysts(SASCs),and thereupon discuss the future directions in designing HER-oriented *** the end of this review,we present an outlook on the development trends and faced challenges of catalysts for electrochemical HER.

摘要：The electrolysis of water powered by renewable energy sources offers a promising method of"green hydrogen"production,which is considered to be at the heart of future carbon-neutral energy *** the past decades,researchers have reported a number of hydrogen evolution reaction(HER)electrocatalysts with activity comparable to that of commercial Pt/C,but most of them are tested within a small current density range,typically no more than 500 mA cm^(-2).To realize the industrial application of hydrogen production from water electrolysis,it is essential to develop high-efficiency HER electrocatalysts at high current density(HCD≥500 mA cm^(-2)).Nevertheless,it remains challenging and significant to rational design HCD electrocatalysts for *** this paper,the design strategy of HCD electrocatalysts is discussed,and some HCD electrocatalysts for HER are reviewed in seven categories(alloy,metal oxide,metal hydroxide,metal sulfide/selenide,metal nitride,metal phosphide and other derived electrocatalysts).At the end of this article,we also pro-pose some viewpoints and prospects for the future development and research directions of HCD electrocatalysts for HER.

摘要：hydrogen is a promising sustainable energy to replace fossil fuels owning to its high specific energy and environmental *** water electrolysis has been considered as one of the most prospective technologies for large scale hydrogen *** boost the sluggish kinetics of hydrogen evolution reaction(HER)in alkaline media,abundant materials have been designed and ***,we summarize the key achievements in the development of layered transition-metal hydroxides[TM(OH)x]for efficient alkaline *** on the structure of TM(OH)x,the mechanism of synergistic effect between TM(OH)x and HER active materials is illuminated ***,recent progress of TM(OH)x-based HER catalysts to optimize the synergistic effect are categorized as TM(OH)x and active materials,including species,structure,morphology and interaction ***,TM(OH)x-based overall water splitting electrocatalysts and electrodes are summarized in the design principles for high activity and ***,some of key challenges for further developments and applications of hydrogen production are proposed.

摘要：The hydrogen evolution reaction(HER)is a promising way to produce hydrogen,and the use of non-precious metals with an excellent electrochemical performance is vital for ***-based transition metal catalysts have high activity and stability,which are important in reducing the cost of hydrogen production and promoting the development of the hydrogen production ***,there is a lack of discussion regarding the effect of carbon components on the performance of these *** review of the literature discusses the choice of the carbon components in these catalysts and their impact on catalytic performance,including electronic structure control by heteroatom doping,morphology adjustment,and the influence of self-supporting *** not only analyzes the progress in HER,but also provides guidance for synthesizing high-performance carbon-based transition metal catalysts.

摘要：The development of inexpensive and efficient Pt-free electrocatalysts for the hydrogen evolution reaction(HER)is greatly crucial for water *** carbide(WC)exhibiting a Pt-like electronic structure represents an attractive alternative,although its overall performance is limited by the strong W-H bond that impedes hydrogen ***,we employed an in-situ interface engineering strategy to construct high-performance and cost effective electrocatalysts comprising WC/tungsten phosphide(WP)heterostructures that were anchored on N,P-codoped carbon(WC/WP@NPC)via a one-step pyrolysis of a melamine polyphosphate/WO_(3) hybrid in an inert *** to the crystal structure compatibility and electron-rich property of WP,it optimizes the electronic structure and hydrogen adsorption configuration of WC,thus significantly weakening the W-H bond with a thermoneutral Gibbs free energy of hydrogen adsorption(ΔG_(H^(*)))of−0.05 ***,NPC ensures fast electron transport and structural stability of the WC/WP@NPC ternary *** synergistically lead to outstanding HER performances of the catalyst in acidic and alkaline *** finding offers a new strategy for designing Pt-alternative electrocatalysts with outstanding electrochemical performances for high-efficiency water splitting and other applications.

摘要：The exploration of efficient and earth‐rich electrocatalysts for electrochemical reactions is critical to the implementation of large‐scale green energy conversion and storage ***‐dimensional(2D)materials with distinctive structural and electrochemical properties provide fertile soil for researchers to harvest basic science and emerging applications,which can be divided into metal‐free materials(such as graphene,carbon nitride and black phosphorus)and transition metal‐based materials(such as halogenides,phosphates,oxides,hydroxides,and MXenes).For faultless 2D materials,they usually exhibit poor electrochemical hydrogen evolution reaction(HER)activity because only edge sites can be available while the base surface is chemically *** engineering is an effective strategy to generate active sites in 2D materials for improving electrocatalytic *** review presents feasible design strategies for constructing defect sites(including edge defects,vacancy defects and dopant derived defects)in 2D materials to improve their HER *** essential relationships between defect structures and electrocatalytic HER performance are discussed in detail,providing valuable guidance for rationally fabricating efficient HER *** hydrogen adsorption/desorption energy can be optimized by constructing defect sites at different locations and by adjusting the local electronic structure to form unsaturated coordination states for efficient HER.

摘要：Noble metal-free electrocatalysts with high activity are highly desirable for the large-scale application of hydrogen evolution reaction(HER). Mo_(2) C-based nanomaterials have been proved as a promising alternative to noble metal-based electrocatalysts owing to the Pt-resembled d-band density and optimal intermediates-adsorption ***, the aggregation and excessive growth of crystals often occur during their high-temperature synthesis procedure, leading to low catalytic utilization. In this study, the ultrafine Mo_(2) C/Mo_(2) N heterostructure with large surface and interface confined in the N-doped carbon nanofibers(NCNFs) was obtained by a melamine-assisted method. The synergistic effect of Mo_(2) C/Mo_(2) N heterostructure and plenty active sites exposed on the surface of ultrafine nanocrystals improves the electrocatalytic activity. Meanwhile, the N-CNFs ensure fast charge transfer and high structural stability during reactions. Moreover, the in-situ synthesis method strengthens the interfacial coupling interactions between Mo_(2)C/Mo_(2) N heterostructure and N-CNFs, further enhancing the electronic conductivity and electrocatalytic activity. Owing to these advantages, Mo_(2)C/Mo_(2) N@N-CNFs exhibit excellent HER performance with a low overpotential of 75 mV at a current density of 10 mV cm^(-2) in alkaline solution, superior to the single-phased Mo_(2)C counterpart and recently reported Mo_(2)C/Mo_(2) N-based catalysts. This study highlights a new effective strategy to design efficient electrocatalysts via integrating heterostructure, nanostructure and carbon modification.

摘要：The design and synthesis of high‐performance and low‐cost electrocatalysts for the hydrogen evolution reaction(HER),a key half‐reaction in water electrolysis,are *** to their modest hydrogen adsorption energy,ruthenium(Ru)‐based nanomaterials are considered outstanding candidates to replace the expensive platinum(Pt)‐based HER *** this study,we developed an adsorption‐pyrolysis method to construct nitrogen(N)‐doped graphene aerogel(N‐GA)‐supported ultrafine Ru nanocrystal(Ru‐NC)nanocomposites(Ru‐NCs/N‐GA).The particle size of the Ru‐NCs and the conductivity of the N‐GA substrate can be controlled by varying the pyrolysis *** experiments reveal revealed that 10 wt%Ru‐NCs/N‐GA nanocomposites require overpotentials of only 52 and 36 mV to achieve a current density of 10 mA cm^(−2) in 1 mol/L HClO4 and 1 mol/L KOH electrolytes for HER,respectively,which is comparable to 20 wt%Pt/C *** from the ultrafine size and uniform dispersion of the Ru‐NCs,the synergy between Ru and the highly conductive substrate,and the anchoring effect of the N atom,the Ru‐NCs/N‐GA nanocomposites exhibit excellent activity and durability in the pH‐universal HER,thereby opening a new avenue for the production of commercial HER electrocatalysts.

摘要：Single nanoparticle(NP)collisions technique has been widely employed in ***,the short collision duration of single NPs hinders the further improvement in their electrocatalytic ***,to increase the dynamic collision duration of single NPs in the electron tunneling region,enhanced near-wall hindered diffusion is introduced in the stochastic collision process by coupling a Au ultramicroelectrode(UME)with a confined *** the case of single palladium nanoparticle(Pd NP)collisions for the hydrogen evolution reaction(HER),the hydrodynamic trapping confined in the microchannel effectively permits the activation of the HER on the single Pd *** microchannel-based Au UME is promising in the application of single-NP collisions to energy conversion.

摘要：Designing highly efficient Pt-free electrocatalysts with low overpotential for an alkaline hydrogen evolution reaction(HER)remains a significant ***,a novel and efficient cobalt(Co),ruthenium(Ru)bimetallic electrocatalyst composed of CoRu nanoalloy decorated on the N-doped carbon nanotubes(CoRu@N-CNTs),was prepared by reacting fullerenol with melamine via hydrothermal treatment and followed by *** from the electronic communication between Co and Ru sites,the as-obtained CoRu@N-CNTs catalyst exhibited superior electrocatalytic HER *** deliver a current density of 10 mA·cm^(-2),it required an overpotential of merely 19 mV along with a Tafel slope of 26.19 mV·dec^(-1)in 1 mol·L^(-1)potassium hydroxide(KOH)solution,outperforming the benchmark Pt/C *** present work would pave a new way towards the design and construction of an efficient electrocatalyst for energy storage and conversion.