Designing a highly active and stable bifunctional catalyst is essential for achieving superior overall water splitting(OWS).In this study,a three-dimensional(3D)core-shell structure Co_(3)S_(4)/CuS@NiFe LDH nanocoral ...Designing a highly active and stable bifunctional catalyst is essential for achieving superior overall water splitting(OWS).In this study,a three-dimensional(3D)core-shell structure Co_(3)S_(4)/CuS@NiFe LDH nanocoral spheres electrocatalyst was constructed on nickel foam(NF)via an interfacial engineering strategy.This 3D core-shell heterostructure maximizes the exposure of active sites,optimizes the charge transport pathway and accelerates gas release rates.The protective shell strategy of NiFe LDH provides favorable stability,which contributes to inhibiting the electrochemical corrosion of the electrocatalyst and mitigating the toxic effects of Cl^(-) and other microorganisms during the seawater splitting process.Moreover,the introduction of NiFe LDH induces a change in the OER mechanism from an adsorption evolution mechanism(AEM)to a lattice oxygen mechanism(LOM),which improves the intrinsic activity of the catalyst.Consequently,Co_(3)S_(4)/CuS@NiFe LDH demonstrates exceptional performance in the oxygen evolution reaction(OER)(η100=251 mV)and in the hydrogen evolution reaction(HER)(η100=254 mV),alongside remarkable stability over 100 h.For OWS,it exhibits a voltage of 1.46 V at 10 mA/cm^(2) and maintain stability for 100 h.Impressively,Co_(3)S_(4)/CuS@NiFe LDH still possesses outstanding activity and stability in natural alkaline seawater.This work proposes interfacial engineering to construct bifunctional catalysts with core-shell heterostructures,providing instructive guidelines for the design of highly efficient electrocatalysts toward seawater electrolysis.展开更多
The fast solution of linear equations has always been one of the hot spots in scientific computing.A kind of the diagonal matrix splitting iteration methods are provided,which is different from the classical matrix sp...The fast solution of linear equations has always been one of the hot spots in scientific computing.A kind of the diagonal matrix splitting iteration methods are provided,which is different from the classical matrix splitting methods.Taking the decomposition of the diagonal elements for coefficient matrix as the key point,some new preconditioners are constructed.Taking the tri-diagonal coefficient matrix as an example,the convergence domains and optimal relaxation factor of the new method are analyzed theoretically.The presented new iteration methods are applied to solve linear algebraic equations,even 2D and 3D diffusion problems with the fully implicit discretization.The results of numerical experiments are matched with the theoretical analysis,and show that the iteration numbers are reduced greatly.The superiorities of presented iteration methods exceed some classical iteration methods dramatically.展开更多
Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen e...Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen evolution reaction(HER)and the anodic oxygen evolution reaction(OER).Transition metal-based catalysts have garnered significant research interest as promising alternatives to noble-metal catalysts,owing to their low cost,tunable composition,and noble-metal-like catalytic activity.Nevertheless,systematic reviews on their application as bifunctional catalysts for overall water splitting(OWS)are still limited.This review comprehensively outlines the principal categories of bifunctional transition metal electrocatalysts derived from electrospun nanofibers(NFs),including metals,oxides,phosphides,sulfides,and carbides.Key strategies for enhancing their catalytic performance are systematically summarized,such as heterointerface engineering,heteroatom doping,metal-nonmetal-metal bridging architectures,and single-atom site design.Finally,current challenges and future research directions are discussed,aiming to provide insightful perspectives for the rational design of high-performance electrocatalysts for OWS.展开更多
Herein,we have developed a straightforward wet-chemical method to synthesize a series of Pd-based alloy nanowires(NWs),including Pd Pt NWs,Pd Au NWs,Pd Ir NWs,and Pd Ru NWs,which exhibits high mass activity and turnov...Herein,we have developed a straightforward wet-chemical method to synthesize a series of Pd-based alloy nanowires(NWs),including Pd Pt NWs,Pd Au NWs,Pd Ir NWs,and Pd Ru NWs,which exhibits high mass activity and turnover frequency(TOF) for HER,surpassing Pt/C by 4.6-fold and 1.5-fold in acidic and alkaline electrolytes,respectively.It also demonstrates high stability in alkaline electrolyte at a current density of 220 m A/cm^(2) for 280 h,highlighting its potential for practical applications under industrial current conditions.Pd Pt NWs exhibited ultrathin structures with head-to-tail kinks and inherent defects,significantly increasing the density of active sites and precisely tuning the electronic structure,which could accelerate reaction kinetics and boost water-splitting electrocatalytic performance.This study highlights the potential of Pd Pt NWs as highly efficient catalysts,offering outstanding catalytic performance and stability for practical applications.展开更多
This insightful review explores the electrochemical principles and energy potential of electrocatalytic water splitting(EWS).It highlights recent advancements,identifies key challenges,and underscores the pivotal role...This insightful review explores the electrochemical principles and energy potential of electrocatalytic water splitting(EWS).It highlights recent advancements,identifies key challenges,and underscores the pivotal role of EWS in enabling the transition to sustainable energy systems.This work contextualizes the significance of green hydrogen in global decarbonization pathways and examines the historical progression of electrocatalysis.The fundamental thermodynamics and mechanistic pathways governing both the hydrogen and oxygen evolution reactions(HER and OER)are analyzed,highlighting energy barriers and rate-determining steps.Various electrode architectures and electrochemical cell configurations are evaluated,including a comparative assessment of key electrolyzer technologies and their performance characteristics.Furthermore,we critically examine recent advances and persistent limitations across the landscape of electrocatalysts,spanning noble metal-based materials,earth-abundant transition metal compounds,and emerging materials.Design principles and mechanistic insights drawn from electronic structu re modulation,defect engineering,doping strategies,and na noscale morphology control are elucidated to establish robust structure-property-performance relationships.Major challenges including sluggish oxygen evolution kinetics,catalyst degradation mechanisms,and the integration of devices with intermittent renewable energy sources are thoroughly examined.This work also debates advanced strategies such as hybrid photoelectrochemical systems,flexible device architectures,and the direct utilization of non-traditional water sources(e.g.,seawater,wastewater)as promising pathways for future development.Finally,it is specifically distinguished by its critical focus on bridging the gap between fundamental electrocatalysts development and practical system-level integration,addressing the challenges of scalability and deployment under industrially relevant conditions.This comprehensive review provides a strategic outlook and identifies key scientific priorities for optimizing EWS systems toward efficient,robust,and scalable hydrogen generation.展开更多
Despite intensive research on solar-driven photocatalytic overall water splitting(POWS),the overall efficiencies remain insufficient to meet commercial standards.As a central challenge in realizing this technology mai...Despite intensive research on solar-driven photocatalytic overall water splitting(POWS),the overall efficiencies remain insufficient to meet commercial standards.As a central challenge in realizing this technology mainly lies in the precise tuning and rational designing of highly efficient materials and photocatalytic systems,which is paramount for its unlocking scalable,practical applications.However,novel materials fabrication and advanced photocatalytic systems are essential for overcoming intrinsic limitations of conventional catalysts by enabling this green technology to resolve global energy crisis.Therefore,this review critically explores the engineering developments in POWS process and novel photocatalyst designing,via shifting from simple bandgap engineering to more advanced charge carrier dynamics control via utilizing one/two-step photocatalytic excitation system,surface phase junctions i.e.,Z-scheme and S-scheme heterojunctions,surface modification,morphological tuning,and the role of co-catalysts,to control sluggish kinetics,promote oxygen evolution reaction(OER)and suppress undesirable H2/O2,backward reaction with superior visible light absorption capacity to produce remarkable energy production.Moreover,we critically discuss the recent trend of POWS from a materials discovery phase to demanding engineering and mechanistic optimization phase with viable economic viability,which requires bridging the gap between excellent lab-scale performance to stringent stability,cost,and high efficiency demands of industrial-scale solar fuel production.In addition,the currents challenges and future directions are also enclosed in detail for sustainable energy production.展开更多
NiFe layered double hydroxide(NiFe LDH)has emerged as a promising catalyst for the oxygen evolution reaction(OER);however,its hydrogen evolution reaction(HER)activity remains suboptimal due to unfavorable electronic s...NiFe layered double hydroxide(NiFe LDH)has emerged as a promising catalyst for the oxygen evolution reaction(OER);however,its hydrogen evolution reaction(HER)activity remains suboptimal due to unfavorable electronic structures,particularly the d-electron density of metal sites,which impede water dissociation and lead to poor hydrogen adsorption/desorption capabilities.Herein,we introduce an efficient cooperative d-electron density regulation(CDDR)engineering to comprehensively optimize the delectron density of NiFe LDH by grafting MoO_(x) -modified NiFe LDH nanosheets onto porous nickel particles(PNPs).The PNPs facilitate d-electron density modulation along the edges of the nanosheets,while the MoO_(x) species enable d-electron density modulation across the plane of the nanosheets,thus cooperatively constructing enriched d-electron density in NiFe LDH.Theoretical studies validate the CDDR process and reveal that the enriched d-electron density accelerates water dissociation and optimizes the hydrogen adsorption behavior of NiFe LDH.As a result,the engineered catalyst exhibits significantly improved HER activity,achieving an ultra-low overpotential of 38 mV at 10 mA cm^(-2)in 1 M KOH.Additionally,the CDDR-optimized catalyst also exhibits good OER performance,demonstrating excellent bifunctional performance for overall water splitting in both alkaline freshwater and seawater electrolytes.This work presents a novel CDDR strategy for engineering NiFe LDH into efficient HER catalysts without compromising its OER activity,potentially paving the way for the development of active and robust electrocatalysts for sustainable energy applications.展开更多
Amorphous metal-based catalysts are highly promising for water splitting due to their abundance of unsaturated active sites.Herein,we report a one-step,surfactant-free synthesis of amorphous nickel nanoparticles(NPs)e...Amorphous metal-based catalysts are highly promising for water splitting due to their abundance of unsaturated active sites.Herein,we report a one-step,surfactant-free synthesis of amorphous nickel nanoparticles(NPs)encapsulated in nitrogen-doped carbon shells(A-Ni@NC)via pulsed laser ablation in liquid(PLAL).The synergistic integration of the amorphous Ni core and a defect-rich N-doped carbon shell markedly enhanced the catalytic activities for both the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER),with low overpotentials of 182 mV for HER and 288 mV for OER at 10 mA cm^(-2)in 1.0 m KOH.Furthermore,the bifunctional catalyst achieved a current density of 10 mA cm^(-2)at 1.63 V and retained 98.9%of its initial performance after 100 h of operation.The nitrogen-rich carbon shell not only offered abundant active sites and structural protection but also promoted charge transport.Density functional theory(DFT)calculations revealed that N-doping optimized intermediate adsorption energies,while the amorphous Ni core facilitated efficient electron transfer.This green and scalable synthesis strategy provides a promising platform for developing a wide range of transition metal@N-doped carbon hybrid catalysts for sustainable energy conversion applications.展开更多
Bismuth vanadate(BiVO_(4))is regarded as a promising photoanode for photoelectrochemical(PEC)water splitting.Despite its advantage in band gap and visible-light response,the BiVO_(4)exhibits an unsatisfactory achievin...Bismuth vanadate(BiVO_(4))is regarded as a promising photoanode for photoelectrochemical(PEC)water splitting.Despite its advantage in band gap and visible-light response,the BiVO_(4)exhibits an unsatisfactory achieving water splitting due to severe charge recombination.Herein,we elucidate an innovative approach involving the incorporation of single Ru atom with a CoFe-LDH cocatalyst(Ru_(0.51)-CoFe-LDH)and integrating it onto the BiVO_(4)semiconductor substrate.The resulting Ru_(0.51)-CoFe-LDH/BiVO_(4)photoanode film demonstrates commendable charge injection efficiency(76%)and charge collection efficiency(100%).Interestingly,the yield of hydrogen and oxygen increases linearly at a stoichiometric ratio of about 2:1,reaching 158.6 and 67.4μmol after140 min of irradiation,respectively.According to experimental characterization and density functional theory calculation,this remarkable performance results from single Ru atoms triggering the electron rearrangement of Ru_(0.51)-CoFe-LDH to engineer active sites and optimize interfacial energetics.Additionally,the negative shift of Ru_(0.51)-CoFe-LDH band edge gives rise to more conspicuous band bending of the n-n junction formed with BiVO_(4),expediting the separation and transfer of photogenerated electron-hole pairs at the interface.This work furnishes a new preparation perspective for PEC water splitting systems to construct single atoms in the semiconductor substrate.展开更多
Altermagnets represent a newly discovered class of magnetically ordered materials.Among all the candidates,CrSb stands out due to its largest spin splitting energy and highest Néel temperature exceeding 700 K,mak...Altermagnets represent a newly discovered class of magnetically ordered materials.Among all the candidates,CrSb stands out due to its largest spin splitting energy and highest Néel temperature exceeding 700 K,making it promising for room-temperature spintronic applications.Here we have successfully grown high quality CrSb(100)thin film on GaAs(110)substrate by molecular beam epitaxy.Using angle-resolved photoemission spectroscopy,we successfully obtained the three-dimensional electronic structure of the thin film.Moreover,we observed the emergence of the altermagnetic splitting bands corresponding to the calculated results along the low symmetry pathsT-QandP-D.The bands near the Fermi level are only spin splitting bands along theP-Ddirection,with splitting energy reaching as high as 910 meV.This finding provides insights into the magnetic properties of CrSb thin films and paves the way for further studies on their electronic structure and potential applications in spintronics.展开更多
We report the observation of Zeeman splitting in multiple spectral lines emitted by a laser-produced,magnetized plasma(1–3×10^(18)cm^(-3),1–15 eV)in the context of a laboratory astrophysics experiment under a c...We report the observation of Zeeman splitting in multiple spectral lines emitted by a laser-produced,magnetized plasma(1–3×10^(18)cm^(-3),1–15 eV)in the context of a laboratory astrophysics experiment under a controlled magneticfield up to 20T.Nitrogen lines(NII)in the visible range were used to diagnose the magneticfield and plasma conditions.This was performed by coupling our data with(563–574 nm)the Stark–Zeeman line-shape code PPPB.The excellent agreement between experiment and simulations paves the way for a non-intrusive experimental platform to get time-resolved measurements of the local magneticfield in laboratory plasmas.展开更多
CuBi_(2)O_(4)is identified as a promising photocathode in photoelectrochemical(PEC)water splitting systems.However,the PEC performance of CuBi_(2)O_(4)is far from expected due to the limited separation and transport e...CuBi_(2)O_(4)is identified as a promising photocathode in photoelectrochemical(PEC)water splitting systems.However,the PEC performance of CuBi_(2)O_(4)is far from expected due to the limited separation and transport efficiency of photogenerated carriers.To address the above issues,a cost-effective ternary Cu:NiO_(X)/CuBi_(2)O_(4)/CuO composite photocathode was designed.Firstly,a thin Cu:NiO_(X)film was inserted between CuBi_(2)O_(4)and FTO conducting substrate as a hole-selective layer,which promotes the transmission of photogenerated holes to the FTO substrate effectively.Furthermore,the modification of CuO film on the CuBi_(2)O_(4)electrode not only increases the absorption of sunlight and generates more photogenerated carriers,but also constitutes a heterojunction with CuBi_(2)O_(4),creating a built-in electric field,which facilitates the separation of electrons and holes,and accelerates the electrons transfer to electrode–electrolyte interface.The fabricated Cu:NiO_(X)/CuBi_(2)O_(4)/CuO composite photocathode exhibits a surprisingly high photocurrent density of−1.51 mA·cm^(−2)at 0.4 V versus RHE,which is 2.6 times that of the pristine CuBi_(2)O_(4)photocathode.The improved PEC performance is attributed to the synergy effect of the Cu:NiO_(X)hole-selective layer and the CuBi_(2)O_(4)/CuO heterojunction.Moreover,the combination with the BiVO_(4)/CoS,an unbiased overall water splitting was achieved,which has a photocurrent of 0.193 mA·cm^(−2).展开更多
Altermagnets,a class of unconventional antiferromagnets with non-relativistic spin-splitting,offer promising potential for antiferromagnetic spintronic devices.While many altermagnets are limited by either low magneti...Altermagnets,a class of unconventional antiferromagnets with non-relativistic spin-splitting,offer promising potential for antiferromagnetic spintronic devices.While many altermagnets are limited by either low magnetic transition temperatures or weak spin splitting,the recently discovered metal CrSb,with high N′eel temperature(T_(N)=710 K)and significant spin-splitting due to its unique spin space group,provides a robust platform for remarkable tunneling magnetoresistance(TMR)in collinear all-antiferromagnetic tunnel junctions(AATJs).This study systematically investigates the spin-polarized Fermi surface of CrSb and spin-dependent electron transport in CrSb-based AATJs.The CrSb/β-InSe/CrSb junction with a three-monolayer InSe barrier exhibits a TMR ratio of approximately 290%,with energy-dependent analysis revealing TMR ratios that may exceed 850%when considering the shift of the Fermi energy.We also demonstrate the angle-dependent TMR of CrSb-based AATJs by adjusting N′eel vector orientations.Our findings might provide strong theoretical support for CrSb as a versatile building block for all-antiferromagnetic memory devices.展开更多
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 ...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.展开更多
Direct seawater splitting has emerged as a popular and promising research direction for synthesising clean,green,non-polluting,and sustainable hydrogen energy without depending on high-purity water in the face of the ...Direct seawater splitting has emerged as a popular and promising research direction for synthesising clean,green,non-polluting,and sustainable hydrogen energy without depending on high-purity water in the face of the world’s shortage of fossil energy.However,efficient seawater splitting is hindered by slow kinetics caused by the ultra-low conductivity and the presence of bacteria,microorganisms,and stray ions in seawater.Additionally,producing hydrogen on an industrial scale is challenging due to the high production cost.The present review addresses these challenges from the catalyst point of view,namely,that designing catalysts with high catalytic activity and stability can directly affect the rate and effect of seawater splitting.From the ion transfer perspective,designing membranes can block harmful ions,improving the stability of seawater splitting.From the energy point of view,mixed seawater systems and self-powered systems also provide new and low-energy research systems for seawater splitting.Finally,ideas and directions for further research on direct seawater splitting in the future are pointed out,with the aim of achieving low-cost and high-efficiency hydrogen production.展开更多
This study presents a novel method to fabricate metal-decorated,sulfur-doped layered double hydroxides(M/SLDH)through spontaneous redox and sulfurization processes.The developed Ag/SLDH and Pt/SLDH catalysts with abun...This study presents a novel method to fabricate metal-decorated,sulfur-doped layered double hydroxides(M/SLDH)through spontaneous redox and sulfurization processes.The developed Ag/SLDH and Pt/SLDH catalysts with abundant heterogeneous interfaces and hierarchical nanostructures demonstrated outstanding oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)performance,achieving low overpotentials of 212 and 35 mV at 10 mA cm^(-2)in 1 M KOH,respectively.As both anode and cathode in water splitting,they required only 1.47 V to reach 10 mA cm^(-2)and exhibited high structural robustness,maintaining stability at 1000 mA cm^(-2)for 300 h.In-situ Raman analysis revealed that the synergistic effects of metal nanoparticles and S doping significantly promote the transformation into the S-Co1-xFexOOH layer,which serves as the active phase for water oxidation.Additionally,ultraviolet photoelectron spectroscopy(UPS)and density functional theory(DFT)analyses indicated that incorporating metal nanoparticles and S doping increase electron density near the Fermi level and reduce reaction energy barriers,thus enhancing intrinsic OER and HER activities.This study provides a scalable strategy for synthesizing high-performance electrocatalysts for water splitting,with promising potential for broader applications.展开更多
The design of efficient and cost‐effective bifunctional catalysts, which are capable of driving both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), is of paramount importance for advancing...The design of efficient and cost‐effective bifunctional catalysts, which are capable of driving both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), is of paramount importance for advancing overall water splitting. Here, we developed an innovative heterogeneous interface engineering strategy to boost the electrocatalytic performance of overall water splitting. This approach involves the synergistic integration of ultra‐fine CoMoP nanocrystals coupled with three‐ dimensional (3D) porous C3N4/N‐doped carbon (NC) architectures, constructing a distinctive CoMoP/C3N4/NC heterogeneous interface. The CoMoP/C3N4/NC exhibits distinguished overall water splitting performance. To drive the overall water splitting current of 10 mA cm−2, the CoMoP/C3N4/NC||CoMoP/C3N4/NC electrolysis cell only needs an ultralow cell voltage of 1.496 V. The electronic properties and localized coordination environments characterizations, and density functional theory (DFT) calculations elucidate that the improved catalytic activities of CoMoP/C3N4/NC are primarily attributed to the synergistic interfacial coupling between CoMoP/C3N4/NC heterogeneous interface. A novel multi‐site synergistic catalytic mechanism was revealed by the DFT calculations, in which the optimum H* adsorption site on CoMoP/C3N4/NC for HER is on the cobalt atoms in CoMoP with the ultralow Gibbs free energy of hydrogen bonding (ΔGH*) of 0.018 eV, while for the OER, the optimum intermediates adsorption site of the CoMoP/C3N4/NC is on the carbon atoms in C3N4/NC. Besides, the intricately engineered 3D hierarchical porous framework of the CoMoP/C3N4/NC can facilitate the ion and electron transport and improve mass transfer, which gives rise to enhanced water splitting performance.展开更多
The development of efficient catalysts for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is of great significance for the practical application of water splitting in alkaline electrolytes.Transitio...The development of efficient catalysts for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is of great significance for the practical application of water splitting in alkaline electrolytes.Transition metal sulfide electrocatalysts have been widely recognized as efficient catalysts for water splitting in alkaline media.In this work,an original and efficient synthesis strategy is proposed for the fabrication of asymmetric anode(N-(Co-Cu)S_(x))and cathode(N-CoS/Cu_(2)S).Impressively,these electrodes exhibit superior performance,benefiting from the construction of three-dimensional(3D)structures and the electronic structure adjustment caused by N-doping with increased active sites,improved mass/charge transport and enhanced evolution and release of gas bubbles.Hence,N-(Co-Cu)S_(x)anode exhibits excellent OER performance with only 217 mV overpotential at 10 mA·cm^(-2),while N-CoS/Cu_(2)S cathode possesses excellent HER performance with only 67 mV overpotential at 10 mA·cm^(-2).N-(Co-Cu)S_(x)||N-CoS/Cu_(2)S electrolyzer presents a low cell voltage of 1.53 V at 10 mA·cm^(-2)toward overall water splitting,which is superior to most recently reported transition metal sulfide-based catalysts.展开更多
Rapid hole extraction from photoanodes to cocatalysts is a crucial prerequisite for the realization of highly efficient photoelectrochemical(PEC)water splitting.Herein,Mn-doped nickel-iron layered double hydroxides(Mn...Rapid hole extraction from photoanodes to cocatalysts is a crucial prerequisite for the realization of highly efficient photoelectrochemical(PEC)water splitting.Herein,Mn-doped nickel-iron layered double hydroxides(Mn:NiFe-LDHs),as a co-catalyst,were grafted on bismuth vanadate(BVO)for significantly improved charge transfer and stability simultaneously,in addition to the accelerated water oxidation kinetics.The detailed experimental and theoretical analysis collectively verify that Mn doping increases charge density around Ni and Fe sites.The electron-rich Ni sites boost the kinetics of oxygen evolution reaction and promote the hole extraction simultaneously.Moreover,the electrons are transferred from electron-rich Fe sites to V sites,which effectively restrains the dissolution of V^(5+)ions and enhances the stability of BVO photoanodes.Consequently,the resulting Mn:NiFe-LDH/BVO photoanode achieves a remarkable photocurrent density of 5.5 mA cm^(-2)at 1.23 V versus reversible hydrogen electrode(RHE)with excellent stability.The construction of electron-rich oxygen evolution cocatalysts provides a promising strategy to promote the hole extraction and increase the stability for improved PEC performance.展开更多
The stability and electrocatalytic efficiency of transition metal oxides for water splitting is determined by geometric and electronic structure,especially under high current densities.Herein,a newly designed lamella-...The stability and electrocatalytic efficiency of transition metal oxides for water splitting is determined by geometric and electronic structure,especially under high current densities.Herein,a newly designed lamella-heterostructured nanoporous CoFe/CoFe_(2)O_(4) and CeO_(2−x),in situ grown on nickel foam(NF),holds great promise as a high-efficient bifunctional electrocatalyst(named R-CoFe/Ce/NF)for water splitting.Experimental characterization verifies surface reconstruction from CoFe alloy/oxide to highly active CoFeOOH during in situ electrochemical polarization.By virtues of three-dimensional nanoporous architecture and abundant electroactive CoFeOOH/CeO_(2−x) heterostructure interfaces,the R-CoFe/Ce/NF electrode achieves low overpotentials for oxygen evolution(η_(10)=227 mV;η_(500)=450 mV)and hydrogen evolution(η_(10)=35 mV;η_(408)=560 mV)reactions with high normalized electrochemical active surface areas,respectively.Additionally,the alkaline full water splitting electrolyzer of R-CoFe/Ce/NF||R-CoFe/Ce/NF achieves a current density of 50 mA·cm^(−2) only at 1.75 V;the decline of activity is satisfactory after 100-h durability test at 300 mA·cm^(−2).Density functional theory also demonstrates that the electron can transfer from CeO_(2−x) by virtue of O atom to CoFeOOH at CoFeOOH/CeO_(2−x) heterointerfaces and enhancing the adsorption of reactant,thus optimizing electronic structure and Gibbs free energies for the improvement of the activity for water splitting.展开更多
基金supported by the National Natural Science Foundation of China(No.52274304).
文摘Designing a highly active and stable bifunctional catalyst is essential for achieving superior overall water splitting(OWS).In this study,a three-dimensional(3D)core-shell structure Co_(3)S_(4)/CuS@NiFe LDH nanocoral spheres electrocatalyst was constructed on nickel foam(NF)via an interfacial engineering strategy.This 3D core-shell heterostructure maximizes the exposure of active sites,optimizes the charge transport pathway and accelerates gas release rates.The protective shell strategy of NiFe LDH provides favorable stability,which contributes to inhibiting the electrochemical corrosion of the electrocatalyst and mitigating the toxic effects of Cl^(-) and other microorganisms during the seawater splitting process.Moreover,the introduction of NiFe LDH induces a change in the OER mechanism from an adsorption evolution mechanism(AEM)to a lattice oxygen mechanism(LOM),which improves the intrinsic activity of the catalyst.Consequently,Co_(3)S_(4)/CuS@NiFe LDH demonstrates exceptional performance in the oxygen evolution reaction(OER)(η100=251 mV)and in the hydrogen evolution reaction(HER)(η100=254 mV),alongside remarkable stability over 100 h.For OWS,it exhibits a voltage of 1.46 V at 10 mA/cm^(2) and maintain stability for 100 h.Impressively,Co_(3)S_(4)/CuS@NiFe LDH still possesses outstanding activity and stability in natural alkaline seawater.This work proposes interfacial engineering to construct bifunctional catalysts with core-shell heterostructures,providing instructive guidelines for the design of highly efficient electrocatalysts toward seawater electrolysis.
基金The National Natural Science Foundations of China (12202219)the Natural Science Foundations of Ningxia (2024AAC02009, 2023AAC05001)the Ningxia Youth Top Talents Training Project。
文摘The fast solution of linear equations has always been one of the hot spots in scientific computing.A kind of the diagonal matrix splitting iteration methods are provided,which is different from the classical matrix splitting methods.Taking the decomposition of the diagonal elements for coefficient matrix as the key point,some new preconditioners are constructed.Taking the tri-diagonal coefficient matrix as an example,the convergence domains and optimal relaxation factor of the new method are analyzed theoretically.The presented new iteration methods are applied to solve linear algebraic equations,even 2D and 3D diffusion problems with the fully implicit discretization.The results of numerical experiments are matched with the theoretical analysis,and show that the iteration numbers are reduced greatly.The superiorities of presented iteration methods exceed some classical iteration methods dramatically.
基金Supported by the National Natural Science Foundation of China(No.52273056)the Science and Technology Development Program of Jilin Province,China(No.YDZJ202501ZYTS305)。
文摘Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen evolution reaction(HER)and the anodic oxygen evolution reaction(OER).Transition metal-based catalysts have garnered significant research interest as promising alternatives to noble-metal catalysts,owing to their low cost,tunable composition,and noble-metal-like catalytic activity.Nevertheless,systematic reviews on their application as bifunctional catalysts for overall water splitting(OWS)are still limited.This review comprehensively outlines the principal categories of bifunctional transition metal electrocatalysts derived from electrospun nanofibers(NFs),including metals,oxides,phosphides,sulfides,and carbides.Key strategies for enhancing their catalytic performance are systematically summarized,such as heterointerface engineering,heteroatom doping,metal-nonmetal-metal bridging architectures,and single-atom site design.Finally,current challenges and future research directions are discussed,aiming to provide insightful perspectives for the rational design of high-performance electrocatalysts for OWS.
基金the financial support from the National Natural Science Foundation of China (Nos.21805170,22172093)Natural Science Foundation of Shandong Province (Nos.ZR2023QB219,ZR2021QB161)Qingdao Postdoctoral Innovation Project (No.QDBSH20220202031)。
文摘Herein,we have developed a straightforward wet-chemical method to synthesize a series of Pd-based alloy nanowires(NWs),including Pd Pt NWs,Pd Au NWs,Pd Ir NWs,and Pd Ru NWs,which exhibits high mass activity and turnover frequency(TOF) for HER,surpassing Pt/C by 4.6-fold and 1.5-fold in acidic and alkaline electrolytes,respectively.It also demonstrates high stability in alkaline electrolyte at a current density of 220 m A/cm^(2) for 280 h,highlighting its potential for practical applications under industrial current conditions.Pd Pt NWs exhibited ultrathin structures with head-to-tail kinks and inherent defects,significantly increasing the density of active sites and precisely tuning the electronic structure,which could accelerate reaction kinetics and boost water-splitting electrocatalytic performance.This study highlights the potential of Pd Pt NWs as highly efficient catalysts,offering outstanding catalytic performance and stability for practical applications.
基金Higher Education Commission(HEC)of Pakistan for financial support under grants#377-IPFP-Ⅱ/Batch-1st/SRGP-NAHE/HEC-2022-27 along with ASIP-Support Award Letter#ASIP/R&D/HEC/2024/10006/83387/127。
文摘This insightful review explores the electrochemical principles and energy potential of electrocatalytic water splitting(EWS).It highlights recent advancements,identifies key challenges,and underscores the pivotal role of EWS in enabling the transition to sustainable energy systems.This work contextualizes the significance of green hydrogen in global decarbonization pathways and examines the historical progression of electrocatalysis.The fundamental thermodynamics and mechanistic pathways governing both the hydrogen and oxygen evolution reactions(HER and OER)are analyzed,highlighting energy barriers and rate-determining steps.Various electrode architectures and electrochemical cell configurations are evaluated,including a comparative assessment of key electrolyzer technologies and their performance characteristics.Furthermore,we critically examine recent advances and persistent limitations across the landscape of electrocatalysts,spanning noble metal-based materials,earth-abundant transition metal compounds,and emerging materials.Design principles and mechanistic insights drawn from electronic structu re modulation,defect engineering,doping strategies,and na noscale morphology control are elucidated to establish robust structure-property-performance relationships.Major challenges including sluggish oxygen evolution kinetics,catalyst degradation mechanisms,and the integration of devices with intermittent renewable energy sources are thoroughly examined.This work also debates advanced strategies such as hybrid photoelectrochemical systems,flexible device architectures,and the direct utilization of non-traditional water sources(e.g.,seawater,wastewater)as promising pathways for future development.Finally,it is specifically distinguished by its critical focus on bridging the gap between fundamental electrocatalysts development and practical system-level integration,addressing the challenges of scalability and deployment under industrially relevant conditions.This comprehensive review provides a strategic outlook and identifies key scientific priorities for optimizing EWS systems toward efficient,robust,and scalable hydrogen generation.
基金the Taizhou University,Zhejiang,China for funding(No.T20250101215)the Deanship of research and Graduate Studies at King Khalid University for funding this work through Large Research Project(R.G.P.2/398/46).
文摘Despite intensive research on solar-driven photocatalytic overall water splitting(POWS),the overall efficiencies remain insufficient to meet commercial standards.As a central challenge in realizing this technology mainly lies in the precise tuning and rational designing of highly efficient materials and photocatalytic systems,which is paramount for its unlocking scalable,practical applications.However,novel materials fabrication and advanced photocatalytic systems are essential for overcoming intrinsic limitations of conventional catalysts by enabling this green technology to resolve global energy crisis.Therefore,this review critically explores the engineering developments in POWS process and novel photocatalyst designing,via shifting from simple bandgap engineering to more advanced charge carrier dynamics control via utilizing one/two-step photocatalytic excitation system,surface phase junctions i.e.,Z-scheme and S-scheme heterojunctions,surface modification,morphological tuning,and the role of co-catalysts,to control sluggish kinetics,promote oxygen evolution reaction(OER)and suppress undesirable H2/O2,backward reaction with superior visible light absorption capacity to produce remarkable energy production.Moreover,we critically discuss the recent trend of POWS from a materials discovery phase to demanding engineering and mechanistic optimization phase with viable economic viability,which requires bridging the gap between excellent lab-scale performance to stringent stability,cost,and high efficiency demands of industrial-scale solar fuel production.In addition,the currents challenges and future directions are also enclosed in detail for sustainable energy production.
基金financially supported from the National Key Research and Development Program of China(2022YFB3803600)the National Natural Science Foundation of China(52301272,22309168,12564025,and 52472205)+7 种基金the Fundamental Research Funds for the Central Universities(CCNU25ZH006)the National College Student Innovation and Entrepreneurship Training Project(202510513082)the Research Program of HBNU(2025X082 and2025Y145)the Foundation of Hubei Key Laboratory of Photoelectric Materials and Devices(PMD202404)the General Program of Open Project of the State Key Laboratory of Precision Welding and Joining of Materials Structures(MSWJ-25M-18)the Key Research Project of Hubei Provincial Department of Education(No.D20252503)the Key Project of Hubei Provincial Natural Science Foundation of China(2025AFD002)the Foundation of National Laboratory of Solid State Microstructures(M37087)。
文摘NiFe layered double hydroxide(NiFe LDH)has emerged as a promising catalyst for the oxygen evolution reaction(OER);however,its hydrogen evolution reaction(HER)activity remains suboptimal due to unfavorable electronic structures,particularly the d-electron density of metal sites,which impede water dissociation and lead to poor hydrogen adsorption/desorption capabilities.Herein,we introduce an efficient cooperative d-electron density regulation(CDDR)engineering to comprehensively optimize the delectron density of NiFe LDH by grafting MoO_(x) -modified NiFe LDH nanosheets onto porous nickel particles(PNPs).The PNPs facilitate d-electron density modulation along the edges of the nanosheets,while the MoO_(x) species enable d-electron density modulation across the plane of the nanosheets,thus cooperatively constructing enriched d-electron density in NiFe LDH.Theoretical studies validate the CDDR process and reveal that the enriched d-electron density accelerates water dissociation and optimizes the hydrogen adsorption behavior of NiFe LDH.As a result,the engineered catalyst exhibits significantly improved HER activity,achieving an ultra-low overpotential of 38 mV at 10 mA cm^(-2)in 1 M KOH.Additionally,the CDDR-optimized catalyst also exhibits good OER performance,demonstrating excellent bifunctional performance for overall water splitting in both alkaline freshwater and seawater electrolytes.This work presents a novel CDDR strategy for engineering NiFe LDH into efficient HER catalysts without compromising its OER activity,potentially paving the way for the development of active and robust electrocatalysts for sustainable energy applications.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(NRF-2023R1A2C1005419).
文摘Amorphous metal-based catalysts are highly promising for water splitting due to their abundance of unsaturated active sites.Herein,we report a one-step,surfactant-free synthesis of amorphous nickel nanoparticles(NPs)encapsulated in nitrogen-doped carbon shells(A-Ni@NC)via pulsed laser ablation in liquid(PLAL).The synergistic integration of the amorphous Ni core and a defect-rich N-doped carbon shell markedly enhanced the catalytic activities for both the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER),with low overpotentials of 182 mV for HER and 288 mV for OER at 10 mA cm^(-2)in 1.0 m KOH.Furthermore,the bifunctional catalyst achieved a current density of 10 mA cm^(-2)at 1.63 V and retained 98.9%of its initial performance after 100 h of operation.The nitrogen-rich carbon shell not only offered abundant active sites and structural protection but also promoted charge transport.Density functional theory(DFT)calculations revealed that N-doping optimized intermediate adsorption energies,while the amorphous Ni core facilitated efficient electron transfer.This green and scalable synthesis strategy provides a promising platform for developing a wide range of transition metal@N-doped carbon hybrid catalysts for sustainable energy conversion applications.
基金financially supported by the Hunan Provincial Natural Science Foundation for Distinguished Young Scholars(2025JJ20019)the National Key R&D Program of China(2025YFE0107600)。
文摘Bismuth vanadate(BiVO_(4))is regarded as a promising photoanode for photoelectrochemical(PEC)water splitting.Despite its advantage in band gap and visible-light response,the BiVO_(4)exhibits an unsatisfactory achieving water splitting due to severe charge recombination.Herein,we elucidate an innovative approach involving the incorporation of single Ru atom with a CoFe-LDH cocatalyst(Ru_(0.51)-CoFe-LDH)and integrating it onto the BiVO_(4)semiconductor substrate.The resulting Ru_(0.51)-CoFe-LDH/BiVO_(4)photoanode film demonstrates commendable charge injection efficiency(76%)and charge collection efficiency(100%).Interestingly,the yield of hydrogen and oxygen increases linearly at a stoichiometric ratio of about 2:1,reaching 158.6 and 67.4μmol after140 min of irradiation,respectively.According to experimental characterization and density functional theory calculation,this remarkable performance results from single Ru atoms triggering the electron rearrangement of Ru_(0.51)-CoFe-LDH to engineer active sites and optimize interfacial energetics.Additionally,the negative shift of Ru_(0.51)-CoFe-LDH band edge gives rise to more conspicuous band bending of the n-n junction formed with BiVO_(4),expediting the separation and transfer of photogenerated electron-hole pairs at the interface.This work furnishes a new preparation perspective for PEC water splitting systems to construct single atoms in the semiconductor substrate.
基金supported by the National Key R&D Program of China[Grant No.2023YFA1406304(J J)]the National Natural Science Foundation of China[Grant No.12174362(J J)]+2 种基金the Innovation Program for Quantum Science and Technology[Grant No.2021ZD0302803(D L F)]the New Cornerstone Science Foundation(D L F)Beamline 03U of the Shanghai Synchrotron Radiation Facility,which is supported by ME2 project under contract No.11227902 from the National Natural Science Foundation of China。
文摘Altermagnets represent a newly discovered class of magnetically ordered materials.Among all the candidates,CrSb stands out due to its largest spin splitting energy and highest Néel temperature exceeding 700 K,making it promising for room-temperature spintronic applications.Here we have successfully grown high quality CrSb(100)thin film on GaAs(110)substrate by molecular beam epitaxy.Using angle-resolved photoemission spectroscopy,we successfully obtained the three-dimensional electronic structure of the thin film.Moreover,we observed the emergence of the altermagnetic splitting bands corresponding to the calculated results along the low symmetry pathsT-QandP-D.The bands near the Fermi level are only spin splitting bands along theP-Ddirection,with splitting energy reaching as high as 910 meV.This finding provides insights into the magnetic properties of CrSb thin films and paves the way for further studies on their electronic structure and potential applications in spintronics.
基金supported by grants managed by l’Agence Nationale de la Recherche under the Investissements d’Avenir programs Grant Nos. ANR-18-EURE-0014, ANR-10-LABX-0039-PALM, and ANR-22-CE30-0044supported by grants from Japan Society for the Promotion of Science (JSPS) KAKENHI (Grant No. 23K20038)+2 种基金JSPS Core-to-Core program (Grant No. JPJSCCA20230003)carried out within the framework of the EUROfusion Consortium, funded by the European Union via the Euratom Research and Training Programme (Grant Agreement No. 101052200-EUROfusion)operated within the framework of the Enabling Research Project No. AWP24-ENR-IFE.02.CEA-01 “Magnetized ICF”
文摘We report the observation of Zeeman splitting in multiple spectral lines emitted by a laser-produced,magnetized plasma(1–3×10^(18)cm^(-3),1–15 eV)in the context of a laboratory astrophysics experiment under a controlled magneticfield up to 20T.Nitrogen lines(NII)in the visible range were used to diagnose the magneticfield and plasma conditions.This was performed by coupling our data with(563–574 nm)the Stark–Zeeman line-shape code PPPB.The excellent agreement between experiment and simulations paves the way for a non-intrusive experimental platform to get time-resolved measurements of the local magneticfield in laboratory plasmas.
基金supported by the National Natural Science Foundation of China(No.61804039)the University Natural Sciences Research Project of Anhui Province(No.2022AH010096)+1 种基金the Talent Research Fund of Hefei University(No.20RC35)the Natural Science Foundation of Anhui Higher Education Institution of China(No.2023AH040160).
文摘CuBi_(2)O_(4)is identified as a promising photocathode in photoelectrochemical(PEC)water splitting systems.However,the PEC performance of CuBi_(2)O_(4)is far from expected due to the limited separation and transport efficiency of photogenerated carriers.To address the above issues,a cost-effective ternary Cu:NiO_(X)/CuBi_(2)O_(4)/CuO composite photocathode was designed.Firstly,a thin Cu:NiO_(X)film was inserted between CuBi_(2)O_(4)and FTO conducting substrate as a hole-selective layer,which promotes the transmission of photogenerated holes to the FTO substrate effectively.Furthermore,the modification of CuO film on the CuBi_(2)O_(4)electrode not only increases the absorption of sunlight and generates more photogenerated carriers,but also constitutes a heterojunction with CuBi_(2)O_(4),creating a built-in electric field,which facilitates the separation of electrons and holes,and accelerates the electrons transfer to electrode–electrolyte interface.The fabricated Cu:NiO_(X)/CuBi_(2)O_(4)/CuO composite photocathode exhibits a surprisingly high photocurrent density of−1.51 mA·cm^(−2)at 0.4 V versus RHE,which is 2.6 times that of the pristine CuBi_(2)O_(4)photocathode.The improved PEC performance is attributed to the synergy effect of the Cu:NiO_(X)hole-selective layer and the CuBi_(2)O_(4)/CuO heterojunction.Moreover,the combination with the BiVO_(4)/CoS,an unbiased overall water splitting was achieved,which has a photocurrent of 0.193 mA·cm^(−2).
基金supported by the National Natural Science Foundation of China(Grant Nos.T2394475,T2394470,T2394471,and 12174129)the China Postdoctoral Science Foundation(Grant No.2023M741269).
文摘Altermagnets,a class of unconventional antiferromagnets with non-relativistic spin-splitting,offer promising potential for antiferromagnetic spintronic devices.While many altermagnets are limited by either low magnetic transition temperatures or weak spin splitting,the recently discovered metal CrSb,with high N′eel temperature(T_(N)=710 K)and significant spin-splitting due to its unique spin space group,provides a robust platform for remarkable tunneling magnetoresistance(TMR)in collinear all-antiferromagnetic tunnel junctions(AATJs).This study systematically investigates the spin-polarized Fermi surface of CrSb and spin-dependent electron transport in CrSb-based AATJs.The CrSb/β-InSe/CrSb junction with a three-monolayer InSe barrier exhibits a TMR ratio of approximately 290%,with energy-dependent analysis revealing TMR ratios that may exceed 850%when considering the shift of the Fermi energy.We also demonstrate the angle-dependent TMR of CrSb-based AATJs by adjusting N′eel vector orientations.Our findings might provide strong theoretical support for CrSb as a versatile building block for all-antiferromagnetic memory devices.
基金support from the Czech Science Foundation,project EXPRO,No 19-27454Xsupport by the European Union under the REFRESH—Research Excellence For Region Sustainability and High-tech Industries project number CZ.10.03.01/00/22_003/0000048 via the Operational Programme Just Transition from the Ministry of the Environment of the Czech Republic+1 种基金Horizon Europe project EIC Pathfinder Open 2023,“GlaS-A-Fuels”(No.101130717)supported from ERDF/ESF,project TECHSCALE No.CZ.02.01.01/00/22_008/0004587).
文摘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.
基金support by National Key Research and Development Program of China(2022YFB3803502)National Natural Science Foundation of China(52103076)+5 种基金Science and Technology Commission of Shanghai Municipality(23ZR1400300)special fund of Beijing Key Laboratory of Indoor Air Quality Evaluat ion and Control(NO.BZ0344KF21-02)State Key Laboratory of Electrical Insulation and Power Equipment(EIPE22203)JLF is a member of LSRE-LCM–Laboratory of Separation and Reaction Engineering-Laboratory of Catalysis and Materials,supported by national funds through FCT/MCTES(PIDDAC):LSRE-LCM,UIDB/50020/2020(DOI:10.54499/UIDB/50020/2020)UIDP/50020/2020(DOI:10.54499/UIDP/50020/2020)ALiCE,LA/P/0045/2020(DOI:10.54499/LA/P/0045/2020).
文摘Direct seawater splitting has emerged as a popular and promising research direction for synthesising clean,green,non-polluting,and sustainable hydrogen energy without depending on high-purity water in the face of the world’s shortage of fossil energy.However,efficient seawater splitting is hindered by slow kinetics caused by the ultra-low conductivity and the presence of bacteria,microorganisms,and stray ions in seawater.Additionally,producing hydrogen on an industrial scale is challenging due to the high production cost.The present review addresses these challenges from the catalyst point of view,namely,that designing catalysts with high catalytic activity and stability can directly affect the rate and effect of seawater splitting.From the ion transfer perspective,designing membranes can block harmful ions,improving the stability of seawater splitting.From the energy point of view,mixed seawater systems and self-powered systems also provide new and low-energy research systems for seawater splitting.Finally,ideas and directions for further research on direct seawater splitting in the future are pointed out,with the aim of achieving low-cost and high-efficiency hydrogen production.
基金National Programs for NanoKey Project(2022YFA1504002)National Natural Science Foundation of China(22078233)。
文摘This study presents a novel method to fabricate metal-decorated,sulfur-doped layered double hydroxides(M/SLDH)through spontaneous redox and sulfurization processes.The developed Ag/SLDH and Pt/SLDH catalysts with abundant heterogeneous interfaces and hierarchical nanostructures demonstrated outstanding oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)performance,achieving low overpotentials of 212 and 35 mV at 10 mA cm^(-2)in 1 M KOH,respectively.As both anode and cathode in water splitting,they required only 1.47 V to reach 10 mA cm^(-2)and exhibited high structural robustness,maintaining stability at 1000 mA cm^(-2)for 300 h.In-situ Raman analysis revealed that the synergistic effects of metal nanoparticles and S doping significantly promote the transformation into the S-Co1-xFexOOH layer,which serves as the active phase for water oxidation.Additionally,ultraviolet photoelectron spectroscopy(UPS)and density functional theory(DFT)analyses indicated that incorporating metal nanoparticles and S doping increase electron density near the Fermi level and reduce reaction energy barriers,thus enhancing intrinsic OER and HER activities.This study provides a scalable strategy for synthesizing high-performance electrocatalysts for water splitting,with promising potential for broader applications.
基金supported by the National Natural Science Foundation of China(Grant No.12375303)the Natural Science Foundation of Guangdong Province(Grants No.2024A1515030034 and 2023A1515140156).
文摘The design of efficient and cost‐effective bifunctional catalysts, which are capable of driving both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), is of paramount importance for advancing overall water splitting. Here, we developed an innovative heterogeneous interface engineering strategy to boost the electrocatalytic performance of overall water splitting. This approach involves the synergistic integration of ultra‐fine CoMoP nanocrystals coupled with three‐ dimensional (3D) porous C3N4/N‐doped carbon (NC) architectures, constructing a distinctive CoMoP/C3N4/NC heterogeneous interface. The CoMoP/C3N4/NC exhibits distinguished overall water splitting performance. To drive the overall water splitting current of 10 mA cm−2, the CoMoP/C3N4/NC||CoMoP/C3N4/NC electrolysis cell only needs an ultralow cell voltage of 1.496 V. The electronic properties and localized coordination environments characterizations, and density functional theory (DFT) calculations elucidate that the improved catalytic activities of CoMoP/C3N4/NC are primarily attributed to the synergistic interfacial coupling between CoMoP/C3N4/NC heterogeneous interface. A novel multi‐site synergistic catalytic mechanism was revealed by the DFT calculations, in which the optimum H* adsorption site on CoMoP/C3N4/NC for HER is on the cobalt atoms in CoMoP with the ultralow Gibbs free energy of hydrogen bonding (ΔGH*) of 0.018 eV, while for the OER, the optimum intermediates adsorption site of the CoMoP/C3N4/NC is on the carbon atoms in C3N4/NC. Besides, the intricately engineered 3D hierarchical porous framework of the CoMoP/C3N4/NC can facilitate the ion and electron transport and improve mass transfer, which gives rise to enhanced water splitting performance.
基金supported by the Science and Technology Project of Southwest Petroleum University(No.2021JBGS03)the Local Science and Technology Development Fund Projects Guided by the Central Government of China(No.2021ZYD0060)+2 种基金the National Natural Science Foundation of China(Nos.22209143 and 52371241)Guangdong High-level Innovation Institute Project(Nos.2021B0909050001 and 2021CX02L365)Guangdong Basic and Applied Basic Research Foundation(No.2023B1515120095).
文摘The development of efficient catalysts for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is of great significance for the practical application of water splitting in alkaline electrolytes.Transition metal sulfide electrocatalysts have been widely recognized as efficient catalysts for water splitting in alkaline media.In this work,an original and efficient synthesis strategy is proposed for the fabrication of asymmetric anode(N-(Co-Cu)S_(x))and cathode(N-CoS/Cu_(2)S).Impressively,these electrodes exhibit superior performance,benefiting from the construction of three-dimensional(3D)structures and the electronic structure adjustment caused by N-doping with increased active sites,improved mass/charge transport and enhanced evolution and release of gas bubbles.Hence,N-(Co-Cu)S_(x)anode exhibits excellent OER performance with only 217 mV overpotential at 10 mA·cm^(-2),while N-CoS/Cu_(2)S cathode possesses excellent HER performance with only 67 mV overpotential at 10 mA·cm^(-2).N-(Co-Cu)S_(x)||N-CoS/Cu_(2)S electrolyzer presents a low cell voltage of 1.53 V at 10 mA·cm^(-2)toward overall water splitting,which is superior to most recently reported transition metal sulfide-based catalysts.
基金financially supported by the National Natural Science Foundation of China(Nos.52472241,52403108 and 52301285)the Department of Science and Technology of Hubei Province(Nos.2025AFA114 and 2024CSA076)+1 种基金Wuhan Science and Technology Bureau(Nos.2023020201010116 and 2024040801020319)Hubei Provincial Department of Education(No.Q20231703)
文摘Rapid hole extraction from photoanodes to cocatalysts is a crucial prerequisite for the realization of highly efficient photoelectrochemical(PEC)water splitting.Herein,Mn-doped nickel-iron layered double hydroxides(Mn:NiFe-LDHs),as a co-catalyst,were grafted on bismuth vanadate(BVO)for significantly improved charge transfer and stability simultaneously,in addition to the accelerated water oxidation kinetics.The detailed experimental and theoretical analysis collectively verify that Mn doping increases charge density around Ni and Fe sites.The electron-rich Ni sites boost the kinetics of oxygen evolution reaction and promote the hole extraction simultaneously.Moreover,the electrons are transferred from electron-rich Fe sites to V sites,which effectively restrains the dissolution of V^(5+)ions and enhances the stability of BVO photoanodes.Consequently,the resulting Mn:NiFe-LDH/BVO photoanode achieves a remarkable photocurrent density of 5.5 mA cm^(-2)at 1.23 V versus reversible hydrogen electrode(RHE)with excellent stability.The construction of electron-rich oxygen evolution cocatalysts provides a promising strategy to promote the hole extraction and increase the stability for improved PEC performance.
基金sponsored by the National Natural Science Foundation of China(Nos.5210125 and 52375422)the Science Research Project of Hebei Education Department(No.BJK2023058)the Natural Science Foundation of Hebei Province(Nos.E2020208069,B2020208083 and E202320801).
文摘The stability and electrocatalytic efficiency of transition metal oxides for water splitting is determined by geometric and electronic structure,especially under high current densities.Herein,a newly designed lamella-heterostructured nanoporous CoFe/CoFe_(2)O_(4) and CeO_(2−x),in situ grown on nickel foam(NF),holds great promise as a high-efficient bifunctional electrocatalyst(named R-CoFe/Ce/NF)for water splitting.Experimental characterization verifies surface reconstruction from CoFe alloy/oxide to highly active CoFeOOH during in situ electrochemical polarization.By virtues of three-dimensional nanoporous architecture and abundant electroactive CoFeOOH/CeO_(2−x) heterostructure interfaces,the R-CoFe/Ce/NF electrode achieves low overpotentials for oxygen evolution(η_(10)=227 mV;η_(500)=450 mV)and hydrogen evolution(η_(10)=35 mV;η_(408)=560 mV)reactions with high normalized electrochemical active surface areas,respectively.Additionally,the alkaline full water splitting electrolyzer of R-CoFe/Ce/NF||R-CoFe/Ce/NF achieves a current density of 50 mA·cm^(−2) only at 1.75 V;the decline of activity is satisfactory after 100-h durability test at 300 mA·cm^(−2).Density functional theory also demonstrates that the electron can transfer from CeO_(2−x) by virtue of O atom to CoFeOOH at CoFeOOH/CeO_(2−x) heterointerfaces and enhancing the adsorption of reactant,thus optimizing electronic structure and Gibbs free energies for the improvement of the activity for water splitting.
