The hydrogen evolution reaction(HER)holds fundamental impor-tance for advancing renewable energy technologies.HER kinetics in alkaline media is significantly slower than in acidic environments,highlighting the importa...The hydrogen evolution reaction(HER)holds fundamental impor-tance for advancing renewable energy technologies.HER kinetics in alkaline media is significantly slower than in acidic environments,highlighting the importance of developing highly active alkaline elec-trocatalysts.展开更多
As a core component in the electrochemical water splitting system,the cathode catalyst is capable of boosting the kinetics of the hydrogen evolution reaction(HER),while the scarcity and expenditure of current noble me...As a core component in the electrochemical water splitting system,the cathode catalyst is capable of boosting the kinetics of the hydrogen evolution reaction(HER),while the scarcity and expenditure of current noble metal-based electrocatalysts seriously restrict the large-scale commercial development of hydrogen manufacturing devices.Here,we present a robust and controllable self-assembly method for the spatial construction of three-dimensional(3D)porous ternary nanoarchitectures comprising Ti3C2Tx MXene,MoS2nanosheets,and graphene(MX/MoS2/G).This bottom-up strategy contributes to the intriguing structural features of the resulting nanoarchitectures,including 3D crosslinked porous networks,ultrathin walls,plentiful exposed reactive sites,and numerous efficient electron channels.As a consequence,the optimized MX/MoS2/G electrocatalyst depicts superior electrocatalytic HER performance in terms of a competitive onset potential,a small Tafel slope,a large electrochemically active surface area,and exceptional durability,which significantly outperforms the bare MXene,MoS2,graphene,as well as binary MXene/graphene and MoS2/graphene electrocatalysts.展开更多
Transition metal sulfides(TMSs)are primitive composition of biocatalysts that are active for molecular hydrogen production.The development of non-precious TMSs with appropriate spatial ordering has great potentials to...Transition metal sulfides(TMSs)are primitive composition of biocatalysts that are active for molecular hydrogen production.The development of non-precious TMSs with appropriate spatial ordering has great potentials to contribute high-level hydrogen generation.Herein,super-hybrid transition metal sulfide nanoarrays of NiS nanoparticle/WS2nanosheet/Ni3S4nanoparticle(Super-NiS/WS2/Ni3S4)with high spatial ordering and abundant plane-and edge-type WS2-NiS and WS2-M3S4heterointerfaces were elaborately constructed though manipulating the sequential dissociation of phosphotungstic acid(PW12)as W precursor and nickel foam as Ni precursor in one pot.When evaluated for the electrocatalytic hydrogen evolution reaction(HER),the Super-NiS/WS2/Ni3S4only required overpotentials of 57,95,and 151 mV to drive HER in alkaline,acid,and neutral media,respectively,and presented favorable reaction kinetics and test stability.The theoretical and experimental results verify the adsorption and dissociation of water molecules are preferential on WS2-plane-related heterointerfaces.The Gibbs free energy(ΔGH*)analysis indicated the WS2-plane-NiS interface is thermodynamically optimal for HER.Moreover,the collaborations of the abundant plane-and edge-type active interfaces,the open nanosheet-based vertical array,and the phosphorus doping in Super-NiS/WS2/Ni3S4strengthen mass transport and electron transfer in electrocatalysis.The polyoxometalates-based synthetic strategy will inspire the new vision for the rational design and construction of advanced functional materials.展开更多
Low conductivity,slow ion-diffusion,and limited reactive sites are common problems in electrocatalysts and electrode materials.In this study,a complex NiTe-CoTe heterojunction with abundant Te vacancies embedded in N,...Low conductivity,slow ion-diffusion,and limited reactive sites are common problems in electrocatalysts and electrode materials.In this study,a complex NiTe-CoTe heterojunction with abundant Te vacancies embedded in N,P,and F co-doped hollow carbon nanorods(NiTe1-x-CoTe1-x/NPFC)was fabricated via a simple ionic liquid-assisted hydrothermal method and calcination.NiTe1-x-CoTe1-x/NPFC shows excellent activity(80.1 and 108.4 mV overpotentials at 10/100 mA cm-1)for the hydrogen evolution reaction in 1.0 M KOH solution.Moreover,NiTe1-x-CoTe1-x/NPFC exhibits an excellent energy density of 57.9 Wh kg-1at an extremely high power density of 15.90 kW kg-1in a flexible solid-state supercapacitor,revealing its outstanding performance.Mechanistic insights from synchrotron XANES,in situ spectroscopy,and DFT calculations elucidate the interfacial electron transfer pathways,dynamic water dissociation behavior during HER,reversible phase transition mechanisms during energy storage,and the optimization of OH-/H*adsorption energy.Overall,this study will facilitate the design of telluride heterojunctions with tellurium-rich vacancies as well as N,P,and F doped carbon composites,which can be applied to other electrode materials and electrocatalysts.展开更多
Regulating the critical process of proton migration from water dissociation for boosting alkaline hydrogen evolution reaction(HER)remains a challenge.Herein,we propose an electrostatic attraction strategy to achieve t...Regulating the critical process of proton migration from water dissociation for boosting alkaline hydrogen evolution reaction(HER)remains a challenge.Herein,we propose an electrostatic attraction strategy to achieve the migration of a highly efficient hydrogen species to Pt sites over Pt/Co@NC,which is obtained through a facile calcination and electrodeposition method.It exhibits an outstanding geometric activity(η10=31 m V),which surpasses the commercial 20 wt%Pt/C(η10=37 mV).Moreover,the mass activity of Pt/Co@NC is 5.6 A mgPt-1 at-50 mV vs.RHE,which is 2.23 times higher than that of 20 wt%Pt/C.Experimental and theoretical results indicate that the work function of the outer carbon layer,which is changed by the introduction of the inner cobalt core,plays a crucial role in reversing the direction of electron migration between the carbon layer and Pt.The negatively charged Ptδ-can spontaneously attract positively charged protons via the electrostatic interaction effect,thereby achieving the directional migration of hydrogen species.This work presents a strategy for designing advanced alkaline HER electrocatalysts by the electrostatic effect.展开更多
Hydrazine-assisted water electrolysis is a promising route for hydrogen production,and efficient bifunctional electrodes for the anodic hydrazine oxidation reaction(HzOR)and the cathodic hydrogen evolution reaction(HE...Hydrazine-assisted water electrolysis is a promising route for hydrogen production,and efficient bifunctional electrodes for the anodic hydrazine oxidation reaction(HzOR)and the cathodic hydrogen evolution reaction(HER)simplify the devices and enhance the technological advantage.However,suffering from the incompatible adsorption of different intermediates and the sluggish reaction kinetics,the design of effective and durable bi-functional electrodes still faces challenges.Herein,a Lewis acid(WOx)of powerful electron-accepting ability stabilized single-atom Ir catalyst(Ir-SA@WOx),intriguing strong metalsupport interaction(SMSI),is demonstrated to efficiently activate H2O and N2H4molecules.Ir-SA@WOxshows exceptional activity for both HER and HzOR(26.31 and 44.79 A mgIr-1at-100 mV),surpassing commercial Pt/C and Ir/C by factors of 41.8 and 27.6,respectively.A hydrazine-assisted water electrolyzer fabricated with Ir-SA@WOxachieves a current density of 100 mA cm-2at an ultra-low cell voltage of 0.313 V and electricity consumption of merely 0.75 kWh m-3H2,significantly lower than conventional water electrolysis systems(1.852 V,4.43 kWh m-3H2).In situ infrared absorption spectroscopy and theoretical calculations elucidate that the SMSI in Ir-SA@WOxreconstructs the electronic structure to facilitate the activation of the rigid water at the catalyst/electrolyte interface into free species,also optimizes H*adsorption and accelerates dehydrogenation kinetics of the potential-determining step of N2H3*-toN2H2*at Ir-sites,thereby realizing high activity for both HER and HzOR.This work illustrates the tailoring of electronic structures via the SMSI effect for catalytic-activity enhancement,guiding the design of advanced bi-functional catalysts for energy-efficient hydrogen production.展开更多
Nickel-based materials are highly remarkable as promising transition metal catalysts for the electrochemical hydrogen evolution reaction(HER)in alkaline electrolytes.However,their electrochemical performance is limite...Nickel-based materials are highly remarkable as promising transition metal catalysts for the electrochemical hydrogen evolution reaction(HER)in alkaline electrolytes.However,their electrochemical performance is limited by an unfavorable d-band energy(Ed)level.Herein,we showcase an effective lattice-strain strategy to modulate the Ed of Ni sites for achieving optimal alkaline HER kinetics.A specially designed mold spore carbon(MSC)-confined Ni/NiO catalyst with lattice compressive strain(denoted as s-Ni/NiO@MSC)is synthesized through a facile salt-assisted pyrolysis method.Based on X-ray absorption fine structure(XAFS)analysis and density functional theory(DFT)calculations,the intrinsic heteroatoms(N,P,and S)in MSC serve as anchoring sites to enhance the electronic interaction between Ni and the carbon matrix,thereby facilitating water adsorption.Furthermore,the lattice compressive strain at unsaturated Ni sites promotes electron redistribution and shortening Ni-Ni bonds,which further regulates the Ni Edto balance the adsorption/desorption capacities of water and key intermediates(H*and OH*).As a result,s-Ni/NiO@MSC displays enhanced alkaline HER performance,requiring a low potential of 81 mV to achieve 10 mA cm-2while maintaining stability for over 100 h at 100 mA cm−2.This study not only provides effective insights for the construction of carbon-confined nickel catalysts but also offers an important reference for optimizing the alkaline HER kinetics through the rational regulation of the d-band center of transition metals by a lattice strain strategy.展开更多
The development of a high-performance pH-universal electrocatalyst for hydrogen evolution reaction(HER)is a vital step toward hydrogen economy but remains a major challenge.Herein,the Pd,Cu,and Ni three elements were ...The development of a high-performance pH-universal electrocatalyst for hydrogen evolution reaction(HER)is a vital step toward hydrogen economy but remains a major challenge.Herein,the Pd,Cu,and Ni three elements were confined in a nanoparticle via the microemulsion method.Morphology and structural analysis reveal that PdCuNi nanoparticles are nearly spherical in shape with slight aggregation,and are mainly composed of metallic Pd and Cu,as well as Ni oxide.The electrochemical tests show that PdCuNi exhibits favorable HER catalytic activity in acid(η10:45 mV;Tafel slopes:33 mV/dec)and neutral(η10:71 mV;Tafel slopes:87 mV/dec)media,and alkaline(η10:66 mV;Tafel slopes:116 mV/dec)media.The mechanism analysis implies that the synergistic effect of Pd,Cu,and Ni can improve the inherent conductivity of the catalyst and accelerate the charge transfer process.Furthermore,over 30 h long-term stability has been achieved without significant attenuation.This work provides a strategy for developing versatile and robust multimetallic catalysts towards pH-universal HER.展开更多
This study aimed to develop efficient and stable non-precious metal electrocatalysts for the hydrogen evolution reaction(HER),addressing the limitations of current catalysts such as insufficient activity and high cost...This study aimed to develop efficient and stable non-precious metal electrocatalysts for the hydrogen evolution reaction(HER),addressing the limitations of current catalysts such as insufficient activity and high cost.A self-supported CeS/NiS/Ni3N/SSM electrocatalyst with abundant heterointerfaces was successfully constructed on a stainless steel mesh(SSM)via an electrodeposition combined with hightemperature solid-gas phase sulfidationitridation strategy.X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS)analyses confirm the successful introduction of CeS and the strong electronic interaction among the three phases of CeS,NiS,and Ni3N.The doping of Ce induces a redistribution of interface charges,forming electron-deficient Ni centers and optimizing the hydrogen adsorption energy.Scanning electron microscopy(SEM)and transmission electron microscopy(TEM)characterizations reveal that the introduction of CeS transforms the smooth agglomerated particles of NiS/Ni3N into a hierarchical porous structure composed of nanoclusters,significantly increasing the electrochemically active area and constructing clear heterointerfaces,which facilitates the exposure of active sites and mass transfer processes.Density functional theory calculations further indicate that the CeS/NiS/Ni3N heterostructure exhibits a hydrogen adsorption Gibbs free energy(ΔGH*)close to zero(-0.16 eV),significantly superior to that of single components,thereby optimizing the reaction kinetics.The results demonstrate that CeS/NiS/Ni3N/SSM delivers outstanding HER performance in 1 mol/L KOH,requiring an overpotential of only 73.6 mV to achieve the 10 mA/cm2 current density,with a Tafel slope of 87.6 mV/dec,and maintains excellent stability for at least 48 h.This work illustrates that constructing heterointerfaces with simultaneous electronic modulation and structural optimization provides an effective pathway for designing high-performance non-precious metal electrocatalysts.展开更多
The noble metal-based catalysts for hydrogen evolution reaction(HER)and oxygen reduction reaction(ORR)in alkaline electrolytes still confront fundamental challenges in balancing activity,durability,and metal utilizati...The noble metal-based catalysts for hydrogen evolution reaction(HER)and oxygen reduction reaction(ORR)in alkaline electrolytes still confront fundamental challenges in balancing activity,durability,and metal utilization efficiency,which severely impedes the industrial application of hydrogen energy.Herein,we design a hybrid catalyst by hosting dual-scale Pt sites(single atoms and nanoparticles)into a two-dimensional(2D)Pd network,enabling strong electronic coupling and efficient metal utilization.Owing to the self-assembled 2D Pd networks composed of coplanar Pd nanoparticles,which provide abundant anchoring sites for heteroatoms and nanochannels for mass transfer,and the coexistence of multiple active sites by controlling the ratio of Pt single atoms to nanoparticles,the optimized hybrid catalyst(Pt/Pd-5 nanomesh)exhibits exceptional HER activity(20 and 125 mV at 10 and 100 mA cm-2)and ORR activity(a mass activity of 1.66 A mg-PG1Mand a specific activity of 2.70 mA cm-2).In zinc-air batteries,Pt/Pd-5 nanomesh delivers an open-circuit voltage of 1.49 V and maintains stability for 300 h at10 m A cm-2.Combined experimental and computational studies confirm that the synergistic effects between the 2D Pd matrix and multiple Pt active sites not only optimize interfacial water dissociation in HER but also promote the conversion of*O→*OH species during ORR.Furthermore,the complementary characteristics of distinct active sites enable multifunctional cooperativity.This synergistic strategy between the matrix and metal sites may provide a guideline for developing efficient,robust,and multifunctional electrocatalysts.展开更多
The hydrogen evolution reaction(HER)is crucial for hydrogen production and sustainable energy storage.Molybdenum disulfide(MoS2),a representative transition metal dichalcogenides(TMDs),shows potential as an HER cat...The hydrogen evolution reaction(HER)is crucial for hydrogen production and sustainable energy storage.Molybdenum disulfide(MoS2),a representative transition metal dichalcogenides(TMDs),shows potential as an HER catalyst but suffers from limited performance due to poor charge transfer and interfacial effects.Here,we report a salt-assisted chemical vapor deposition(CVD)method for synthesizing high-quality tungsten ditelluride(WTe2)with tunable morphologies using alkali halides(NaCl,KCl and LiCl).The prepared WTe2 nanoribbons and hexagonal nanosheets exhibit morphology-dependent electrical conductivity,with nanosheets showing superior performance.To evaluate WTe2 as a contact electrode,WTe2−MoS2 heterostructures were fabricated and compared with graphene-MoS2 counterparts.The WTe2−MoS2 heterostructure exhibits a superior Tafel slope of 111.57 mV/dec and an overpotential of 298 mV at-10 mA/cm2,significantly outperforming graphene-based electrodes.This improvement is attributed to the excellent conductivity of WTe2 and reduced interfacial Schottky barriers.Moreover,we systematically investigate the influence of WTe2 thickness on HER performance and assess the electrochemical durability and structural stability of the heterostructure,further confirming the effectiveness of WTe2 as a contact electrode for enhancing the HER activity of MoS2.This study offers a novel approach for enhancing the HER performance of MoS2 through controlled WTe2 growth and application as a contact electrode.Our findings provide valuable insights into the synthesis of high-quality WTe2 and broaden the potential applications of two-dimensional materials in energy catalysis.展开更多
Metal sulfide(MS)photocatalysts hold unique features of narrow-bandgap range,high light absorption coefficient,and suitable band structures,offering significant potential for efficient visible-light photocatalytic hyd...Metal sulfide(MS)photocatalysts hold unique features of narrow-bandgap range,high light absorption coefficient,and suitable band structures,offering significant potential for efficient visible-light photocatalytic hydrogen evolution(PHE)via water splitting.However,the low electronic dimensionality of the traditional MS photocatalyst generally decreases the transfer and migration efficiency of the photogenerated charge carriers.In addition,severe intrinsic photocorrosion issue also severely reduces the photostability,hindering the practical application of PHE at scale.In this regard,the advanced design concept of MS photocatalysts,focusing on the high electronic dimensionality construction and efficient photocorrosion inhibition,is of great importance.This review firstly introduces the basic mechanisms of PHE,followed by an in-depth discussion of the fundamental distinction between structural dimensionality and electronic dimensionality,highlighting the superiority of 3D electronic connectivity in enabling isotropic charge migration and shallow defect states.Afterward,the MS photocatalysts with 3D electronic dimensionality and solutions to photocorrosion are systematically summarized,with a special emphasis on the emerging paradigm of advanced“controllable-photocorrosion,”which strategically utilizes the corrosion process to create active sites rather than merely suppressing it.Finally,the current unsolved challenges of MS photocatalysts are comprehensively discussed.展开更多
Large-scale hydrogen production via water electrolysis faces a freshwater shortage.Direct seawater electrolysis offers a solution but encounters new challenges.Herein,we report a feasible strategy to both prevent meta...Large-scale hydrogen production via water electrolysis faces a freshwater shortage.Direct seawater electrolysis offers a solution but encounters new challenges.Herein,we report a feasible strategy to both prevent metal hydroxides deposition and boost the hydrogen evolution reaction by adding a chelating agent,EDTA-Na4,that chelates with Mg2+/Ca2+,thus inhibiting their deposition and gathering them near the cathode surface,resulting in breaking the ordered hydrogen bond networks of interfacial water and reducing the activation energy of water dissociation.Furthermore,hydrolysis of–COO- also promoted water dissociation to produce more active*H and*OH near the electrode surface that in turn serves as a diffusion medium for*OH,accelerating mass transfer and enabling seawater electrolysis to exhibit a stable performance,which operates continuously at 100 mA cm-2@2.20 V and 200 mA cm-2@2.58 V for 400 h in the symmetric electrolyzer and 500 mA cm-2@2.29 V for over 500 h in the asymmetric electrolyzer.This study provides a new perspective to address the issues of stable and scalable direct seawater electrolysis for practical green hydrogen production.展开更多
Alkaline water electrolysis holds great promise for environmental remediation and sustainable energy conversion,yet its efficiency is hampered by the sluggish kinetics of the hydrogen evolution reaction(HER).Ru-based ...Alkaline water electrolysis holds great promise for environmental remediation and sustainable energy conversion,yet its efficiency is hampered by the sluggish kinetics of the hydrogen evolution reaction(HER).Ru-based single-atom catalysts(SACs),with atomically dispersed active sites,offer enhanced catalytic performance.However,the development of Ru SACs is hindered by aggregation at high loadings and an obscured structure-activity relationship.In this work,we engineer Ru SACs supported on P,N self-doped carbon(PNC)derived from mushroom substrate residue through precise regulation of Ru content.This catalyst achieves stable Ru dispersion at loadings up to 2 wt%,thereby forming well-defined RuN3P1coordination structures.Density functional theory calculations reveal that the asymmetric Ru-N3P1 coordination modulates the electronic structure of Ru single atoms,facilitating both kinetically favorable water dissociation and thermodynamically balanced hydrogen adsorption,leading to superior HER activity.The optimized RuSAs/PNC-2wt%catalyst delivers exceptional alkaline HER performance,achieving an overpotential as low as 38 m V at 10 mA cm-2 and remarkable stability maintained over 325 h,attributed to its high density of accessible active sites and facilitated electron transfer kinetics.This study provides an effective strategy for constructing high-loading SACs and establishes a quantitative structure-activity relationship,guiding the design of advanced electrocatalysts for sustainable energy conversion.展开更多
The chemical bonds at heterogeneous interfaces can optimize the hydrogen adsorption free energy(ΔGH*)by reconfiguring the electronic structure,while an in-depth understanding of the hydrogen adsorption configurati...The chemical bonds at heterogeneous interfaces can optimize the hydrogen adsorption free energy(ΔGH*)by reconfiguring the electronic structure,while an in-depth understanding of the hydrogen adsorption configuration is key to identifying the optimal active sites for enhancing hydrogen evolution performance.Here,we synthesize a wide-pH hydrogen evolution reaction(HER)-active Ni3ZnC0.7/WC heterostructure electrocatalyst uniformly anchored on a carbon framework through a one-step calcination method.Experimental and theoretical results demonstrate that Ni-W bridge bonds within the Ni3ZnC0.7/WC heterointerfaces can induce strong electronic interactions,which help to facilitate electron transfer and optimize theΔGH*,thereby enabling extremely excellent catalytic activity.Consequently,owing to its enhanced inherent activity and favorable electrical conductivity,Ni3ZnC0.7/WC exhibits exceptional catalytic performance for HER(94 and 173 mV at 10 mA/cm2)in alkaline and acidic conditions.Additionally,it can maintain durability for at least 565 h under acidic conditions and 582 h under alkaline conditions,respectively,validating its excellent catalytic stability across a broad pH range.This research provides a new perspective and theoretical basis for designing efficient and stable HER electrocatalysts through interface chemical bond engineering.展开更多
CoCo-Prussian blue analogue nanocubes were firstly synthesized via a co-precipitation method and subsequently converted into CoSe2nanocubes through a high-temperature selenization.The core-shell-structured CoSe2...CoCo-Prussian blue analogue nanocubes were firstly synthesized via a co-precipitation method and subsequently converted into CoSe2nanocubes through a high-temperature selenization.The core-shell-structured CoSe2@MoS2electrocatalyst was then fabricated via a hydrothermal process.The resulting material exhibits outstanding hydrogen evolution reaction performances in both acidic and alkaline electrolytes,achieving overpotentials of 229 and 247 mV at the current density of 10 mA cm-2,respectively,with the corresponding Tafel slopes of 79 and 115 mV dec-1.Notably,the CoSe2@MoS2catalyst maintains a high catalytic activity after extended cycles.The enhanced catalytic activity and durability are primarily ascribed to the core-shell architecture,wherein MoS2nanosheets uniformly anchored on the surface of CoSe2nanocubes effectively suppress the self-agglomeration of MoS2nanosheets,thus providing abundant active sites.展开更多
Strain engineering,interfacial electronic modulation,and bubble management are three powerful descriptors for advancing high-current-density water splitting,yet they are rarely integrated within a single electrode des...Strain engineering,interfacial electronic modulation,and bubble management are three powerful descriptors for advancing high-current-density water splitting,yet they are rarely integrated within a single electrode design.Here,we realize their convergence by constructing amorphous-crystalline(AC)phosphorus-doped NiFe2O4 with heterophase interfaces directly constructed on thiocyanate-etched stainless steel(KSS)(denoted KNP-350-AC).The mismatched phases generate~1.5%in-plane tensile strain that reshapes the d-band configuration of Ni/Fe sites through modulation of the local electronic structure.Meanwhile,strong metal-support interaction modulates the work function and establishes a built-in electric field(BEF),enabling favorable interfacial charge redistribution and optimized adsorption energetics of reaction intermediates,as confirmed by ultraviolet photoelectron spectroscopy(UPS)and density functional theory(DFT).Simultaneously,the rough KSS framework introduces superaerophobic microtextures that accelerate bubble detachment under industrial-level current densities.These coupled effects allow the KNP-350-AC electrode to achieve a hydrogen evolution reaction(HER)overpotential of 280 m V@500 mA cm-2,together with remarkable durability in both alkaline freshwater and seawater.This integrated triple-modulation strategy provides a robust pathway for developing practical HER electrocatalysts for large-scale hydrogen production.展开更多
Platinum(Pt)single‐atom catalyst(SAC)shows great promise for hydrogen evolution reaction(HER),but faces a huge challenge in activity enhancement due to the isolated single‐atom sites.Fabricating support with partial...Platinum(Pt)single‐atom catalyst(SAC)shows great promise for hydrogen evolution reaction(HER),but faces a huge challenge in activity enhancement due to the isolated single‐atom sites.Fabricating support with partially amorphous(pa)structures to realize the synergetic interaction in neighboring single atoms could facilitate H2O dissociation and optimize H*adsorption.However,the electrocatalytic mechanism of SAC achieved by tailoring the different amorphous contents of the support has not been clearly explored yet.Herein,neighboring Pt SAs confined in NiFe LDH(Pt@pa‐NiFe LDH‐24)were successfully synthesized via a localized amorphization and impregnation strategy,resulting in significantly boosted HER performance.Experiments and calculations demonstrate that the Pt SAs can accelerate the adsorption/desorption of H2O and effectively promote the Volmer step of the partially amorphous substrate.Benefiting from this,the optimized Pt@pa‐NiFe LDH‐24 exhibits enhanced intrinsic activity,exhibiting a lower overpotential(η10:40 mV)than the commercial Pt/C catalyst.This partial amorphization strategy sheds new light on supporting noble metal single‐atom catalysts for designing efficient HER catalysts in water electrolysis.展开更多
Photocatalytic hydrogen production from water splitting is a promising strategy for sustainable and clean energy generation.However,the design of low-cost,highly active photocatalysts remains a critical challenge.In t...Photocatalytic hydrogen production from water splitting is a promising strategy for sustainable and clean energy generation.However,the design of low-cost,highly active photocatalysts remains a critical challenge.In this study,covalent organic frameworks(COFs)were loaded onto the surface of Cd0.9Cu0.1S to fabricate COF/Cd0.9Cu0.1S heterojunction.As a photocatalyst for hydrogen evolution,the optimized 10COF/Cd0.9Cu0.1S sample achieved a hydrogen evolution rate of 3398.3μmol h-1g-1,representing 2.3-fold and 3398.3-fold enhancements compared with pristine Cd0.9Cu0.1S(1523.3μmol h-1g-1)and COF(almost nothing),respectively.The addition of Co2+as a co-catalyst is a key factor in enhancing performance.Comprehensive photocatalytic tests,in situ X-ray photoelectron spectroscopy,and transient absorption spectroscopy revealed that the charge-transfer process follows an S-scheme mechanism.The covalent interaction between COF and Cd0.9Cu0.1S,coupled with favorable band alignment,induces a built-in electric field at the heterojunction interface,thereby accelerating charge separation and suppressing recombination.This work provides an effective strategy for constructing efficient organic-inorganic heterojunctions,offering new insights into photocatalytic water splitting.展开更多
Symmetry-broken single-atom catalysts(SACs)are pivotal due to their asymmetric electronic environments,which enhance the activity of the hydrogen evolution reaction(HER).This study investigated how symmetry breaking i...Symmetry-broken single-atom catalysts(SACs)are pivotal due to their asymmetric electronic environments,which enhance the activity of the hydrogen evolution reaction(HER).This study investigated how symmetry breaking in SACs affects HER performance using density functional theory(DFT)and variable selection machine learning(ML).The study revealed a nearly volcano-shaped correlation between the degree of spin density symmetry breaking(D asym)and HER activity,with catalysts at the base of the volcano showing enhanced HER activity.Spin density symmetry breaking facilitates the enrichment of unpaired electrons on the active sites and reduces HER energy barriers,resulting in up to a 40-fold enhancement in HER performance of symmetry-broken SACs compared to symmetric SACs.The ML model accurately identified key descriptors,such as symmetry breaking and electronic transfer effects,allowing spin density symmetry breaking on M-N3C-SWCNTs to be further condensed into an effect term with a structure-property relationship.A weaker symmetry breaking effect and a stronger electron transfer enhance HER performance.ML-guided analysis highlighted a spin selection-related Volmer-Heyrovsky pathway with a dual activation mechanism involving surface atom displacement and para-activation.These findings offer critical insights into the design of advanced HER catalysts by elucidating the interplay between symmetry-breaking properties and catalytic behavior.展开更多
基金supported by the National Natural Science Foundation of China(22375079,22161021,22379057,and 22265012)Jiangxi Provincial Natural Science Foundation(20224ACB214001,20242BAB26033,20232ACB213009,20242BAB26046,and 20243BCE51069)C.-T.H.acknowledges the support of Jiangxi Provincial Government(0224/09039001).
摘要The hydrogen evolution reaction(HER)holds fundamental impor-tance for advancing renewable energy technologies.HER kinetics in alkaline media is significantly slower than in acidic environments,highlighting the importance of developing highly active alkaline elec-trocatalysts.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.22209037 and 52472092)。
摘要As a core component in the electrochemical water splitting system,the cathode catalyst is capable of boosting the kinetics of the hydrogen evolution reaction(HER),while the scarcity and expenditure of current noble metal-based electrocatalysts seriously restrict the large-scale commercial development of hydrogen manufacturing devices.Here,we present a robust and controllable self-assembly method for the spatial construction of three-dimensional(3D)porous ternary nanoarchitectures comprising Ti3C2Tx MXene,MoS2nanosheets,and graphene(MX/MoS2/G).This bottom-up strategy contributes to the intriguing structural features of the resulting nanoarchitectures,including 3D crosslinked porous networks,ultrathin walls,plentiful exposed reactive sites,and numerous efficient electron channels.As a consequence,the optimized MX/MoS2/G electrocatalyst depicts superior electrocatalytic HER performance in terms of a competitive onset potential,a small Tafel slope,a large electrochemically active surface area,and exceptional durability,which significantly outperforms the bare MXene,MoS2,graphene,as well as binary MXene/graphene and MoS2/graphene electrocatalysts.
基金supported by the financial supports from the National Natural Science Foundation of China(No.52301016)research projects from Department of Science and Technology of Shandong Province(Nos.2023HWYQ-043,ZR2023ME014,ZR2023QE033)+2 种基金The grant of Youth Innovation Team of Shandong Province(No.2022KJ030)the support of Key Technologies R&D Program of CNBM(No.2023SJYL05)the support of Ji’nan AICC。
摘要Transition metal sulfides(TMSs)are primitive composition of biocatalysts that are active for molecular hydrogen production.The development of non-precious TMSs with appropriate spatial ordering has great potentials to contribute high-level hydrogen generation.Herein,super-hybrid transition metal sulfide nanoarrays of NiS nanoparticle/WS2nanosheet/Ni3S4nanoparticle(Super-NiS/WS2/Ni3S4)with high spatial ordering and abundant plane-and edge-type WS2-NiS and WS2-M3S4heterointerfaces were elaborately constructed though manipulating the sequential dissociation of phosphotungstic acid(PW12)as W precursor and nickel foam as Ni precursor in one pot.When evaluated for the electrocatalytic hydrogen evolution reaction(HER),the Super-NiS/WS2/Ni3S4only required overpotentials of 57,95,and 151 mV to drive HER in alkaline,acid,and neutral media,respectively,and presented favorable reaction kinetics and test stability.The theoretical and experimental results verify the adsorption and dissociation of water molecules are preferential on WS2-plane-related heterointerfaces.The Gibbs free energy(ΔGH*)analysis indicated the WS2-plane-NiS interface is thermodynamically optimal for HER.Moreover,the collaborations of the abundant plane-and edge-type active interfaces,the open nanosheet-based vertical array,and the phosphorus doping in Super-NiS/WS2/Ni3S4strengthen mass transport and electron transfer in electrocatalysis.The polyoxometalates-based synthetic strategy will inspire the new vision for the rational design and construction of advanced functional materials.
基金supported by Startup Fund for Advanced Talents of Putian University(Grant No.2023128)Research Projects of Putian University(Grant No.2024176)+1 种基金Industrial Technology Research Institute of Circular Economy of Putian(Grant No.2023GJGZ001)the Natural Science Foundation of Fujian Province(Grant Nos.2022J011165 and 2024J08079)。
摘要Low conductivity,slow ion-diffusion,and limited reactive sites are common problems in electrocatalysts and electrode materials.In this study,a complex NiTe-CoTe heterojunction with abundant Te vacancies embedded in N,P,and F co-doped hollow carbon nanorods(NiTe1-x-CoTe1-x/NPFC)was fabricated via a simple ionic liquid-assisted hydrothermal method and calcination.NiTe1-x-CoTe1-x/NPFC shows excellent activity(80.1 and 108.4 mV overpotentials at 10/100 mA cm-1)for the hydrogen evolution reaction in 1.0 M KOH solution.Moreover,NiTe1-x-CoTe1-x/NPFC exhibits an excellent energy density of 57.9 Wh kg-1at an extremely high power density of 15.90 kW kg-1in a flexible solid-state supercapacitor,revealing its outstanding performance.Mechanistic insights from synchrotron XANES,in situ spectroscopy,and DFT calculations elucidate the interfacial electron transfer pathways,dynamic water dissociation behavior during HER,reversible phase transition mechanisms during energy storage,and the optimization of OH-/H*adsorption energy.Overall,this study will facilitate the design of telluride heterojunctions with tellurium-rich vacancies as well as N,P,and F doped carbon composites,which can be applied to other electrode materials and electrocatalysts.
基金financially supported by the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(23KJB610003)the Natural Science Foundation of Jiangsu Province(BK20240339)+2 种基金the Science and Technology Support Plan for Youth Innovation of Colleges and Universities of Shandong Province of China(No.2023KJ104)the National Natural Science Foundation of China(No.52202092)the Natural Science Foundation of Shandong Province(No.ZR2022QE076)。
摘要Regulating the critical process of proton migration from water dissociation for boosting alkaline hydrogen evolution reaction(HER)remains a challenge.Herein,we propose an electrostatic attraction strategy to achieve the migration of a highly efficient hydrogen species to Pt sites over Pt/Co@NC,which is obtained through a facile calcination and electrodeposition method.It exhibits an outstanding geometric activity(η10=31 m V),which surpasses the commercial 20 wt%Pt/C(η10=37 mV).Moreover,the mass activity of Pt/Co@NC is 5.6 A mgPt-1 at-50 mV vs.RHE,which is 2.23 times higher than that of 20 wt%Pt/C.Experimental and theoretical results indicate that the work function of the outer carbon layer,which is changed by the introduction of the inner cobalt core,plays a crucial role in reversing the direction of electron migration between the carbon layer and Pt.The negatively charged Ptδ-can spontaneously attract positively charged protons via the electrostatic interaction effect,thereby achieving the directional migration of hydrogen species.This work presents a strategy for designing advanced alkaline HER electrocatalysts by the electrostatic effect.
基金financially supported by National Natural Science Foundation of China(22279069,22478211 and 22372017)。
摘要Hydrazine-assisted water electrolysis is a promising route for hydrogen production,and efficient bifunctional electrodes for the anodic hydrazine oxidation reaction(HzOR)and the cathodic hydrogen evolution reaction(HER)simplify the devices and enhance the technological advantage.However,suffering from the incompatible adsorption of different intermediates and the sluggish reaction kinetics,the design of effective and durable bi-functional electrodes still faces challenges.Herein,a Lewis acid(WOx)of powerful electron-accepting ability stabilized single-atom Ir catalyst(Ir-SA@WOx),intriguing strong metalsupport interaction(SMSI),is demonstrated to efficiently activate H2O and N2H4molecules.Ir-SA@WOxshows exceptional activity for both HER and HzOR(26.31 and 44.79 A mgIr-1at-100 mV),surpassing commercial Pt/C and Ir/C by factors of 41.8 and 27.6,respectively.A hydrazine-assisted water electrolyzer fabricated with Ir-SA@WOxachieves a current density of 100 mA cm-2at an ultra-low cell voltage of 0.313 V and electricity consumption of merely 0.75 kWh m-3H2,significantly lower than conventional water electrolysis systems(1.852 V,4.43 kWh m-3H2).In situ infrared absorption spectroscopy and theoretical calculations elucidate that the SMSI in Ir-SA@WOxreconstructs the electronic structure to facilitate the activation of the rigid water at the catalyst/electrolyte interface into free species,also optimizes H*adsorption and accelerates dehydrogenation kinetics of the potential-determining step of N2H3*-toN2H2*at Ir-sites,thereby realizing high activity for both HER and HzOR.This work illustrates the tailoring of electronic structures via the SMSI effect for catalytic-activity enhancement,guiding the design of advanced bi-functional catalysts for energy-efficient hydrogen production.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.52302235 and 52462013)the Open Fund of Anhui Provincial Key Laboratory of Advanced Catalysis and Energy Materials(Grant Nos.ZD2024A04 and ZD2025A04).
摘要Nickel-based materials are highly remarkable as promising transition metal catalysts for the electrochemical hydrogen evolution reaction(HER)in alkaline electrolytes.However,their electrochemical performance is limited by an unfavorable d-band energy(Ed)level.Herein,we showcase an effective lattice-strain strategy to modulate the Ed of Ni sites for achieving optimal alkaline HER kinetics.A specially designed mold spore carbon(MSC)-confined Ni/NiO catalyst with lattice compressive strain(denoted as s-Ni/NiO@MSC)is synthesized through a facile salt-assisted pyrolysis method.Based on X-ray absorption fine structure(XAFS)analysis and density functional theory(DFT)calculations,the intrinsic heteroatoms(N,P,and S)in MSC serve as anchoring sites to enhance the electronic interaction between Ni and the carbon matrix,thereby facilitating water adsorption.Furthermore,the lattice compressive strain at unsaturated Ni sites promotes electron redistribution and shortening Ni-Ni bonds,which further regulates the Ni Edto balance the adsorption/desorption capacities of water and key intermediates(H*and OH*).As a result,s-Ni/NiO@MSC displays enhanced alkaline HER performance,requiring a low potential of 81 mV to achieve 10 mA cm-2while maintaining stability for over 100 h at 100 mA cm−2.This study not only provides effective insights for the construction of carbon-confined nickel catalysts but also offers an important reference for optimizing the alkaline HER kinetics through the rational regulation of the d-band center of transition metals by a lattice strain strategy.
基金supported in part by the National Natural Science Foundation of China(No.22406050)the Natural Science Foundation of Henan Province(Nos.232300420369,242300420533)。
摘要The development of a high-performance pH-universal electrocatalyst for hydrogen evolution reaction(HER)is a vital step toward hydrogen economy but remains a major challenge.Herein,the Pd,Cu,and Ni three elements were confined in a nanoparticle via the microemulsion method.Morphology and structural analysis reveal that PdCuNi nanoparticles are nearly spherical in shape with slight aggregation,and are mainly composed of metallic Pd and Cu,as well as Ni oxide.The electrochemical tests show that PdCuNi exhibits favorable HER catalytic activity in acid(η10:45 mV;Tafel slopes:33 mV/dec)and neutral(η10:71 mV;Tafel slopes:87 mV/dec)media,and alkaline(η10:66 mV;Tafel slopes:116 mV/dec)media.The mechanism analysis implies that the synergistic effect of Pd,Cu,and Ni can improve the inherent conductivity of the catalyst and accelerate the charge transfer process.Furthermore,over 30 h long-term stability has been achieved without significant attenuation.This work provides a strategy for developing versatile and robust multimetallic catalysts towards pH-universal HER.
基金Project supported by the Natural Science Foundation of Inner Mongolia Autonomous Region(2025MS02002,2024MS02004)the Key Research and Development and Achievement Transformation Program of Inner Mongolia Autonomous Region(2025YFHH0096)Graduate Scientific Research Innovation Project of Inner Mongolia(KC2025055B)。
摘要This study aimed to develop efficient and stable non-precious metal electrocatalysts for the hydrogen evolution reaction(HER),addressing the limitations of current catalysts such as insufficient activity and high cost.A self-supported CeS/NiS/Ni3N/SSM electrocatalyst with abundant heterointerfaces was successfully constructed on a stainless steel mesh(SSM)via an electrodeposition combined with hightemperature solid-gas phase sulfidationitridation strategy.X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS)analyses confirm the successful introduction of CeS and the strong electronic interaction among the three phases of CeS,NiS,and Ni3N.The doping of Ce induces a redistribution of interface charges,forming electron-deficient Ni centers and optimizing the hydrogen adsorption energy.Scanning electron microscopy(SEM)and transmission electron microscopy(TEM)characterizations reveal that the introduction of CeS transforms the smooth agglomerated particles of NiS/Ni3N into a hierarchical porous structure composed of nanoclusters,significantly increasing the electrochemically active area and constructing clear heterointerfaces,which facilitates the exposure of active sites and mass transfer processes.Density functional theory calculations further indicate that the CeS/NiS/Ni3N heterostructure exhibits a hydrogen adsorption Gibbs free energy(ΔGH*)close to zero(-0.16 eV),significantly superior to that of single components,thereby optimizing the reaction kinetics.The results demonstrate that CeS/NiS/Ni3N/SSM delivers outstanding HER performance in 1 mol/L KOH,requiring an overpotential of only 73.6 mV to achieve the 10 mA/cm2 current density,with a Tafel slope of 87.6 mV/dec,and maintains excellent stability for at least 48 h.This work illustrates that constructing heterointerfaces with simultaneous electronic modulation and structural optimization provides an effective pathway for designing high-performance non-precious metal electrocatalysts.
基金supported by the National Natural Science Foundation of China(52571251,U21A20174,and 52201019)the Science and Technology Innovation Talent Team Project of Shanxi Province(202304051001010)+1 种基金the Central Government Guidance Funds for Local Science and Technology Development Projects(YDZJSX2025D019)the Natural Science Foundation of Shanxi Province(202203021212244,202303021221045).
摘要The noble metal-based catalysts for hydrogen evolution reaction(HER)and oxygen reduction reaction(ORR)in alkaline electrolytes still confront fundamental challenges in balancing activity,durability,and metal utilization efficiency,which severely impedes the industrial application of hydrogen energy.Herein,we design a hybrid catalyst by hosting dual-scale Pt sites(single atoms and nanoparticles)into a two-dimensional(2D)Pd network,enabling strong electronic coupling and efficient metal utilization.Owing to the self-assembled 2D Pd networks composed of coplanar Pd nanoparticles,which provide abundant anchoring sites for heteroatoms and nanochannels for mass transfer,and the coexistence of multiple active sites by controlling the ratio of Pt single atoms to nanoparticles,the optimized hybrid catalyst(Pt/Pd-5 nanomesh)exhibits exceptional HER activity(20 and 125 mV at 10 and 100 mA cm-2)and ORR activity(a mass activity of 1.66 A mg-PG1Mand a specific activity of 2.70 mA cm-2).In zinc-air batteries,Pt/Pd-5 nanomesh delivers an open-circuit voltage of 1.49 V and maintains stability for 300 h at10 m A cm-2.Combined experimental and computational studies confirm that the synergistic effects between the 2D Pd matrix and multiple Pt active sites not only optimize interfacial water dissociation in HER but also promote the conversion of*O→*OH species during ORR.Furthermore,the complementary characteristics of distinct active sites enable multifunctional cooperativity.This synergistic strategy between the matrix and metal sites may provide a guideline for developing efficient,robust,and multifunctional electrocatalysts.
基金support from the National Natural Science Foundation of China(No.22175060).
摘要The hydrogen evolution reaction(HER)is crucial for hydrogen production and sustainable energy storage.Molybdenum disulfide(MoS2),a representative transition metal dichalcogenides(TMDs),shows potential as an HER catalyst but suffers from limited performance due to poor charge transfer and interfacial effects.Here,we report a salt-assisted chemical vapor deposition(CVD)method for synthesizing high-quality tungsten ditelluride(WTe2)with tunable morphologies using alkali halides(NaCl,KCl and LiCl).The prepared WTe2 nanoribbons and hexagonal nanosheets exhibit morphology-dependent electrical conductivity,with nanosheets showing superior performance.To evaluate WTe2 as a contact electrode,WTe2−MoS2 heterostructures were fabricated and compared with graphene-MoS2 counterparts.The WTe2−MoS2 heterostructure exhibits a superior Tafel slope of 111.57 mV/dec and an overpotential of 298 mV at-10 mA/cm2,significantly outperforming graphene-based electrodes.This improvement is attributed to the excellent conductivity of WTe2 and reduced interfacial Schottky barriers.Moreover,we systematically investigate the influence of WTe2 thickness on HER performance and assess the electrochemical durability and structural stability of the heterostructure,further confirming the effectiveness of WTe2 as a contact electrode for enhancing the HER activity of MoS2.This study offers a novel approach for enhancing the HER performance of MoS2 through controlled WTe2 growth and application as a contact electrode.Our findings provide valuable insights into the synthesis of high-quality WTe2 and broaden the potential applications of two-dimensional materials in energy catalysis.
基金supported by the National Natural Science Foundation of China(22469007,22202053,52304326,22309037,22305055,52362010,22462006,22462008)the Start-up Research Foundation of Hainan University(KYQD(ZR)-21065,XJ2500008500)+2 种基金the Collaborative Innovation Center of Tropical Marine Science and Technology,Hainan University(XTCX2022HYC21,XTCX2022HYC05)the first batch of“Nanhai New Star”industrial innovation talent platform project(NHXXRCXM202309006)the specific research fund of The Innovation Platform for Academicians of Hainan Province.
摘要Metal sulfide(MS)photocatalysts hold unique features of narrow-bandgap range,high light absorption coefficient,and suitable band structures,offering significant potential for efficient visible-light photocatalytic hydrogen evolution(PHE)via water splitting.However,the low electronic dimensionality of the traditional MS photocatalyst generally decreases the transfer and migration efficiency of the photogenerated charge carriers.In addition,severe intrinsic photocorrosion issue also severely reduces the photostability,hindering the practical application of PHE at scale.In this regard,the advanced design concept of MS photocatalysts,focusing on the high electronic dimensionality construction and efficient photocorrosion inhibition,is of great importance.This review firstly introduces the basic mechanisms of PHE,followed by an in-depth discussion of the fundamental distinction between structural dimensionality and electronic dimensionality,highlighting the superiority of 3D electronic connectivity in enabling isotropic charge migration and shallow defect states.Afterward,the MS photocatalysts with 3D electronic dimensionality and solutions to photocorrosion are systematically summarized,with a special emphasis on the emerging paradigm of advanced“controllable-photocorrosion,”which strategically utilizes the corrosion process to create active sites rather than merely suppressing it.Finally,the current unsolved challenges of MS photocatalysts are comprehensively discussed.
基金the support from the National Key Research and Development Program of China(2023YFB4005000)the Joint Fund of Liaoning Binhai Laboratory(LBLF-2023-04)+3 种基金Dalian Science and Technology Talent Innovation Support Plan(2022RY09)Innovation Research Fund of Dalian Institute of Chemical Physics(DICP I202318)National Natural Science Foundation of China(22478384)the UK EPSRC(EP/W03784X/1)。
摘要Large-scale hydrogen production via water electrolysis faces a freshwater shortage.Direct seawater electrolysis offers a solution but encounters new challenges.Herein,we report a feasible strategy to both prevent metal hydroxides deposition and boost the hydrogen evolution reaction by adding a chelating agent,EDTA-Na4,that chelates with Mg2+/Ca2+,thus inhibiting their deposition and gathering them near the cathode surface,resulting in breaking the ordered hydrogen bond networks of interfacial water and reducing the activation energy of water dissociation.Furthermore,hydrolysis of–COO- also promoted water dissociation to produce more active*H and*OH near the electrode surface that in turn serves as a diffusion medium for*OH,accelerating mass transfer and enabling seawater electrolysis to exhibit a stable performance,which operates continuously at 100 mA cm-2@2.20 V and 200 mA cm-2@2.58 V for 400 h in the symmetric electrolyzer and 500 mA cm-2@2.29 V for over 500 h in the asymmetric electrolyzer.This study provides a new perspective to address the issues of stable and scalable direct seawater electrolysis for practical green hydrogen production.
基金supported by the Guizhou Provincial Science and Technology Projects(NO.ZKZD2023004)the National Natural Science Foundation of China(NO.22568017)+3 种基金the Key Laboratory of Carbon-based Energy Molecular Chemical Utilization Technology in Guizhou Province(NO.2023008)the Guizhou Science and Technology Platform Foundation(NO.ZSYS 2025-033)the One Hundred Person Project of Guizhou Province(NO.GCC 2023013)the Scientific and Technological Innovation Talents Team Project of Guizhou Province(NO.CXTD2023029)。
摘要Alkaline water electrolysis holds great promise for environmental remediation and sustainable energy conversion,yet its efficiency is hampered by the sluggish kinetics of the hydrogen evolution reaction(HER).Ru-based single-atom catalysts(SACs),with atomically dispersed active sites,offer enhanced catalytic performance.However,the development of Ru SACs is hindered by aggregation at high loadings and an obscured structure-activity relationship.In this work,we engineer Ru SACs supported on P,N self-doped carbon(PNC)derived from mushroom substrate residue through precise regulation of Ru content.This catalyst achieves stable Ru dispersion at loadings up to 2 wt%,thereby forming well-defined RuN3P1coordination structures.Density functional theory calculations reveal that the asymmetric Ru-N3P1 coordination modulates the electronic structure of Ru single atoms,facilitating both kinetically favorable water dissociation and thermodynamically balanced hydrogen adsorption,leading to superior HER activity.The optimized RuSAs/PNC-2wt%catalyst delivers exceptional alkaline HER performance,achieving an overpotential as low as 38 m V at 10 mA cm-2 and remarkable stability maintained over 325 h,attributed to its high density of accessible active sites and facilitated electron transfer kinetics.This study provides an effective strategy for constructing high-loading SACs and establishes a quantitative structure-activity relationship,guiding the design of advanced electrocatalysts for sustainable energy conversion.
基金supported by the National Natural Science Foundation of China(No.22179074,52572110,U22A20144)Scientific Research Program Funded by Shaanxi Provincial Education Department(Program No.25JC014)+2 种基金the Key Research and Development Program of Shaanxi Province(2024GX-YBXM-434)the International S&T Cooperation Foundation of Shaanxi Province(2025GHGHJD-002)the Key Program for International S&T Cooperation Projects of Shaanxi Province(2023GHZD-08)。
摘要The chemical bonds at heterogeneous interfaces can optimize the hydrogen adsorption free energy(ΔGH*)by reconfiguring the electronic structure,while an in-depth understanding of the hydrogen adsorption configuration is key to identifying the optimal active sites for enhancing hydrogen evolution performance.Here,we synthesize a wide-pH hydrogen evolution reaction(HER)-active Ni3ZnC0.7/WC heterostructure electrocatalyst uniformly anchored on a carbon framework through a one-step calcination method.Experimental and theoretical results demonstrate that Ni-W bridge bonds within the Ni3ZnC0.7/WC heterointerfaces can induce strong electronic interactions,which help to facilitate electron transfer and optimize theΔGH*,thereby enabling extremely excellent catalytic activity.Consequently,owing to its enhanced inherent activity and favorable electrical conductivity,Ni3ZnC0.7/WC exhibits exceptional catalytic performance for HER(94 and 173 mV at 10 mA/cm2)in alkaline and acidic conditions.Additionally,it can maintain durability for at least 565 h under acidic conditions and 582 h under alkaline conditions,respectively,validating its excellent catalytic stability across a broad pH range.This research provides a new perspective and theoretical basis for designing efficient and stable HER electrocatalysts through interface chemical bond engineering.
基金funded by the Suzhou Huapu Intelligent Technology Co.,Ltd.,China.
摘要CoCo-Prussian blue analogue nanocubes were firstly synthesized via a co-precipitation method and subsequently converted into CoSe2nanocubes through a high-temperature selenization.The core-shell-structured CoSe2@MoS2electrocatalyst was then fabricated via a hydrothermal process.The resulting material exhibits outstanding hydrogen evolution reaction performances in both acidic and alkaline electrolytes,achieving overpotentials of 229 and 247 mV at the current density of 10 mA cm-2,respectively,with the corresponding Tafel slopes of 79 and 115 mV dec-1.Notably,the CoSe2@MoS2catalyst maintains a high catalytic activity after extended cycles.The enhanced catalytic activity and durability are primarily ascribed to the core-shell architecture,wherein MoS2nanosheets uniformly anchored on the surface of CoSe2nanocubes effectively suppress the self-agglomeration of MoS2nanosheets,thus providing abundant active sites.
基金supported by the Science and Technology Innovation Program of Hunan Province(2025RC9005)the National Natural Science Foundation of China(W2533046)+1 种基金the Fundamental Research Funds for the Central Universitiesthe Guangxi Science and Technology Program(AD25069070)。
摘要Strain engineering,interfacial electronic modulation,and bubble management are three powerful descriptors for advancing high-current-density water splitting,yet they are rarely integrated within a single electrode design.Here,we realize their convergence by constructing amorphous-crystalline(AC)phosphorus-doped NiFe2O4 with heterophase interfaces directly constructed on thiocyanate-etched stainless steel(KSS)(denoted KNP-350-AC).The mismatched phases generate~1.5%in-plane tensile strain that reshapes the d-band configuration of Ni/Fe sites through modulation of the local electronic structure.Meanwhile,strong metal-support interaction modulates the work function and establishes a built-in electric field(BEF),enabling favorable interfacial charge redistribution and optimized adsorption energetics of reaction intermediates,as confirmed by ultraviolet photoelectron spectroscopy(UPS)and density functional theory(DFT).Simultaneously,the rough KSS framework introduces superaerophobic microtextures that accelerate bubble detachment under industrial-level current densities.These coupled effects allow the KNP-350-AC electrode to achieve a hydrogen evolution reaction(HER)overpotential of 280 m V@500 mA cm-2,together with remarkable durability in both alkaline freshwater and seawater.This integrated triple-modulation strategy provides a robust pathway for developing practical HER electrocatalysts for large-scale hydrogen production.
基金financially supported by the project of the National Natural Science Foundation of China(Grant Nos.52201019,52571251,U21A20174,and 52001222)the Science and Technology Innovation Talent Team Project of Shanxi Province(Grant No.202304051001010)+2 种基金the Central Government Guidance Funds for Local Science and Technology Development Projects(Grant No.YDZJSX2025D019)the Natural Science Foundation of Shanxi Province(Grant Nos.202203021212244 and 202303021221045)the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(Grant No.STIP,2022L036).
摘要Platinum(Pt)single‐atom catalyst(SAC)shows great promise for hydrogen evolution reaction(HER),but faces a huge challenge in activity enhancement due to the isolated single‐atom sites.Fabricating support with partially amorphous(pa)structures to realize the synergetic interaction in neighboring single atoms could facilitate H2O dissociation and optimize H*adsorption.However,the electrocatalytic mechanism of SAC achieved by tailoring the different amorphous contents of the support has not been clearly explored yet.Herein,neighboring Pt SAs confined in NiFe LDH(Pt@pa‐NiFe LDH‐24)were successfully synthesized via a localized amorphization and impregnation strategy,resulting in significantly boosted HER performance.Experiments and calculations demonstrate that the Pt SAs can accelerate the adsorption/desorption of H2O and effectively promote the Volmer step of the partially amorphous substrate.Benefiting from this,the optimized Pt@pa‐NiFe LDH‐24 exhibits enhanced intrinsic activity,exhibiting a lower overpotential(η10:40 mV)than the commercial Pt/C catalyst.This partial amorphization strategy sheds new light on supporting noble metal single‐atom catalysts for designing efficient HER catalysts in water electrolysis.
基金financially supported by the National Natural Science Foundation of China(Grant No.22268003)Yunnan Fundamental Research Projects(Grant No.202305AF150116)。
摘要Photocatalytic hydrogen production from water splitting is a promising strategy for sustainable and clean energy generation.However,the design of low-cost,highly active photocatalysts remains a critical challenge.In this study,covalent organic frameworks(COFs)were loaded onto the surface of Cd0.9Cu0.1S to fabricate COF/Cd0.9Cu0.1S heterojunction.As a photocatalyst for hydrogen evolution,the optimized 10COF/Cd0.9Cu0.1S sample achieved a hydrogen evolution rate of 3398.3μmol h-1g-1,representing 2.3-fold and 3398.3-fold enhancements compared with pristine Cd0.9Cu0.1S(1523.3μmol h-1g-1)and COF(almost nothing),respectively.The addition of Co2+as a co-catalyst is a key factor in enhancing performance.Comprehensive photocatalytic tests,in situ X-ray photoelectron spectroscopy,and transient absorption spectroscopy revealed that the charge-transfer process follows an S-scheme mechanism.The covalent interaction between COF and Cd0.9Cu0.1S,coupled with favorable band alignment,induces a built-in electric field at the heterojunction interface,thereby accelerating charge separation and suppressing recombination.This work provides an effective strategy for constructing efficient organic-inorganic heterojunctions,offering new insights into photocatalytic water splitting.
摘要Symmetry-broken single-atom catalysts(SACs)are pivotal due to their asymmetric electronic environments,which enhance the activity of the hydrogen evolution reaction(HER).This study investigated how symmetry breaking in SACs affects HER performance using density functional theory(DFT)and variable selection machine learning(ML).The study revealed a nearly volcano-shaped correlation between the degree of spin density symmetry breaking(D asym)and HER activity,with catalysts at the base of the volcano showing enhanced HER activity.Spin density symmetry breaking facilitates the enrichment of unpaired electrons on the active sites and reduces HER energy barriers,resulting in up to a 40-fold enhancement in HER performance of symmetry-broken SACs compared to symmetric SACs.The ML model accurately identified key descriptors,such as symmetry breaking and electronic transfer effects,allowing spin density symmetry breaking on M-N3C-SWCNTs to be further condensed into an effect term with a structure-property relationship.A weaker symmetry breaking effect and a stronger electron transfer enhance HER performance.ML-guided analysis highlighted a spin selection-related Volmer-Heyrovsky pathway with a dual activation mechanism involving surface atom displacement and para-activation.These findings offer critical insights into the design of advanced HER catalysts by elucidating the interplay between symmetry-breaking properties and catalytic behavior.