Pt-based materials are the benchmarked catalysts in the cathodic hydrogen evolution reaction(HER)of water splitting;the prohibitive cost and scarcity of Pt immensely impede the commercialization of hydrogen energy.Ru ...Pt-based materials are the benchmarked catalysts in the cathodic hydrogen evolution reaction(HER)of water splitting;the prohibitive cost and scarcity of Pt immensely impede the commercialization of hydrogen energy.Ru has aroused significant concern because of its Pt-like activity and much lower price.However,it’s still a top priority to minimize the Ru loading and pursue the most superior cost performance.展开更多
The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alka...The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.展开更多
Available online Alkaline water electrolysis(AWE)is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure.Noble metal-based electrocatalysts,owing to thei...Available online Alkaline water electrolysis(AWE)is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure.Noble metal-based electrocatalysts,owing to their exceptional hydrogen binding energy,exhibit remarkable catalytic activity and long-term stability in the hydrogen evolution reaction(HER).However,the restricted accessibility and exorbitant cost of noble-metal materials pose obstacles to their extensive adoption in industrial contexts.This review investigates strategies aimed at reducing the dependence on noble-metal electrocatalysts and developing a cost-effective alkaline HER catalyst,while considering the principles of sustainable development.The initial discussion covers the fundamental principle of HER,followed by an overview of prevalent techniques for synthesizing catalysts based on noble metals,along with a thorough examination of recent advancements.The subsequent discussion focuses on the strategies employed to improve noble metalbased catalysts,including enhancing the intrinsic activity at active sites and increasing the quantity of active sites.Ultimately,this investigation concludes by examining the present state and future direction of research in the field of electrocatalysis for the HER.展开更多
Organic nanophotocatalysts are promising candidates for solar fuels production,but they still face the challenge of unfavorable geminate recombination due to the limited exciton diffusion lengths.Here,we introduce a b...Organic nanophotocatalysts are promising candidates for solar fuels production,but they still face the challenge of unfavorable geminate recombination due to the limited exciton diffusion lengths.Here,we introduce a binary nanophotocatalyst fabricated by blending two polymers,PS-PEG5(PS)and PBT-PEG5(PBT),with matched absorption and emission spectra,enabling a Forster resonance energy transfer(FRET)process for enhanced photocatalysis.These heterostructure nanophotocatalysts are processed using a facile and scalable flash nanoprecipitation(FNP)technique with precious kinetic control over binary nanoparticle formation.The resulting nanoparticles exhibit an exceptional photocatalytic hydrogen evolution rate up to 65 mmol g^(-1) h^(-1),2.5 times higher than that single component nanoparticles.Characterizations through fluorescence spectra and transient absorption spectra confirm the hetero-energy transfer within the binary nanoparticles,which prolongs the excited-state lifetime and extends the namely“effective exciton diffusion length”.Our finding opens new avenues for designing efficient organic photocatalysts by improving exciton migration.展开更多
Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this s...Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this study,nanocatalysts with ultralow Pt content,excellent performance,and carbon black as support were prepared through in-situ synthesis.These~2-nm particles uniformly and stably dispersed on carbon black because of the strong s-p-d orbital hybridizations between carbon black and Pt,which suppressed the agglomeration of Pt ions.This unique structure is beneficial for the hydrogen evolution reaction.The catalysts exhibited remarkable catalytic activity for hydrogen evolution reaction,exhibiting a potential of 100 mV at 100 mA·cm^(-2),which is comparable to those of commercial Pt/C catalysts.Mass activity(1.61 A/mg)was four times that of a commercial Pt/C catalyst(0.37 A/mg).The ultralow Pt loading(6.84wt%)paves the way for the development of next-generation electrocatalysts.展开更多
The utilization of nickel-based catalysts as alternatives to expensive platinum-based(Pt-based)materials for the hydrogen evolution reaction in acidic electrolytes has attracted considerable attention due to their pot...The utilization of nickel-based catalysts as alternatives to expensive platinum-based(Pt-based)materials for the hydrogen evolution reaction in acidic electrolytes has attracted considerable attention due to their potential for enabling cost-effective industrial applications.However,the unsatisfied cyclic stability and electrochemical activity limit their further application.In this work,nickel-molybdenum(Ni-Mo)alloy catalysts were successfully synthesized through a comprehensive process including electrodeposition,thermal annealing,and electrochemical activation.Owing to the synergistic interaction of molybdenum trinickelide(Ni_(3)Mo)and molybdenum dioxide(MoO_(2))in Ni-Mo alloy,the catalyst display superior overall electrochemical properties.A low overpotential of 86 mV at 10 mA/cm^(2)and a Tafel slope of 74.0 mV/dec in 0.5 mol/L H_(2)SO_(4)solution can be achieved.Notably,remarkable stability with negligible performance degradation even after 100 h could be maintained.This work presents a novel and effective strategy for the design and fabrication of high-performance,non-precious metal electrocatalysts for acidic water electrolysis.展开更多
Elemental doping is an effective strategy for tuning the band structure of graphite carbon nitride(CN)to enhance its photocatalytic performance.In this study,sodium(Na)and oxygen(O)co-doped carbon nitride(Na/O-CN_(x),...Elemental doping is an effective strategy for tuning the band structure of graphite carbon nitride(CN)to enhance its photocatalytic performance.In this study,sodium(Na)and oxygen(O)co-doped carbon nitride(Na/O-CN_(x),x=1.0,2.0,3.0,4.0)was synthesized via solid-phase reaction of sodium citrate(NaCA)and pure CN powder in the Teflon-sealed autoclave under air conditions at 180℃.Surface area of Na/O-CN_(3.0) is measured to be 18.8 m^(2)/g,increasing by 60.7%compared to that of pure CN(11.7 m^(2)/g).Bandgap energy of Na/O-CN_(3.0) is determined to be 2.68 eV,marginally lower than that of pure CN(2.70 eV),thereby enhancing its capacity for sunlight absorption.Meanwhile,the incorporation of Na and O atoms into Na/O-CN_(x) is found to effectively reduce recombination rates of photogenerated electron-hole pairs.As a result,Na/O-CN_(x) samples exhibit markedly enhanced photocatalytic hydrogen evolution activity under visible light irradiation.Notably,the optimal Na/O-CN_(3.0) sample achieves a photocatalytic hydrogen production rate of 103.2μmol·g^(–1)·h^(–1),which is 8.2 times greater than that of pure CN(11.2μmol·g^(–1)·h^(–1)).Furthermore,a series of Na/O-CN_(x)-yO_(2)(y=0,20%,40%,60%,80%,100%)samples were prepared by modulating the oxygen content within reaction atmosphere.The catalytic performance evaluations reveal that the incorporation of both Na and O atoms in Na/O-CN_(3.0) enhances photocatalytic activity.This study also introduces novel methodologies for synthesis of metal atom-doped CN materials at lower temperature,highlighting the synergistic effect of Na and O atoms in photocatalytic hydrogen production of Na/O-CN_(x) samples.展开更多
Negatively charged open-framework metal sulfides(NOSs),taking advantages of the characteristics of excellent visible light absorption,easily exchanged cations,and abundant active sites,hold significant promise as high...Negatively charged open-framework metal sulfides(NOSs),taking advantages of the characteristics of excellent visible light absorption,easily exchanged cations,and abundant active sites,hold significant promise as highly efficient photocatalysts for hydrogen evolution.However,their applications in photocatalytic hydrogen evolution(PHE)are infrequently documented and the corresponding photocatalytic mechanism has not yet been explored.Herein,we excavated a novel NOS photocatalyst of(Me_(2)NH_(2))_(6)In_(10)S_(18)(MIS)with a three-dimensional(3D)structure,and successfully incorporated divalent Co(Ⅱ)and metal Co(0)into its cavities via the convenient cation exchange-assisted approach to regulate the critical steps of photocatalytic reactions.As the introduced Co(0)allows for more efficient light utilization and adroitly surficial hydrogen desorption,and meanwhile acts as the‘electron pump’for rapid charge transfer,Co(0)-modified MIS delivers a surprising PHE activity in the initial stage of photocatalysis.With the prolonging of illumination,metal Co(0)gradually escapes from MIS framework,resulting in the decline of PHE performance.By stark contrast,the incorporated Co(Ⅱ)can establish a strong interaction with MIS framework,and simultaneously capture photogenerated electrons from MIS to produce Co(0),which constructs a stable photocatalytic system as well as provides additional channels for spatially separating photogenerated carriers.Thus,Co(Ⅱ)-modified MIS exhibits a robust and highly stable PHE activity of~4944μmol/g/h during the long-term photocatalytic reactions,surpassing most of the previously reported In–S framework photocatalysts.This work represents a breakthrough in the study of PHE performance and mechanism of NOS-based photocatalysts,and sheds light on the design of vip confined NOS-based photocatalysts towards high-efficiency solar-to-chemical energy conversion.展开更多
The integration of machine learning and electrocatalysis presents nota ble advancements in designing and predicting the performance of chiral materials for hydrogen evolution reactions(HER).This study utilizes theoret...The integration of machine learning and electrocatalysis presents nota ble advancements in designing and predicting the performance of chiral materials for hydrogen evolution reactions(HER).This study utilizes theoretical calculations and machine learning techniques to assess the HER performance of both chiral and achiral M-N-SWCNTs(M=In,Bi,and Sb)single-atom catalysts(SACs).The stability preferences of metal atoms are dependent on chirality when interacting with chiral SWCNTs.The HER activity of the right-handed In-N-SWCNT is 5.71 times greater than its achiral counterpart,whereas the left-handed In-N-SWCNT exhibits a 5.12-fold enhancement.The calculated hydrogen adsorption free energy for the right-handed In-N-SWCNT reaches as low as-0.02 eV.This enhancement is attributed to the symmetry breaking in spin density distribution,transitioning from C_(2V)in achiral SACs to C_(2)in chiral SACs,which facilitates active site transfer and enhances local spin density.Right-handed M-N-SWCNTs exhibit superiorα-electron separation and transport efficiency relative to left-handed variants,owing to the chiral induced spin selectivity(CISS)effect,with spin-upα-electron density reaching 3.43×10^(-3)e/Bohr^(3)at active sites.Machine learning provides deeper insights,revealing that the interplay of weak spatial electronic effects and appropriate curvature-chirality effects significantly enhances HER performance.A weaker spatial electronic effect correlates with higher HER activity,larger exchange current density,and higher turnover frequency.The curvature-chirality effect undersco res the influence of intrinsic structures on HER performance.These findings offer critical insights into the role of chirality in electrocatalysis and propose innovative approaches for optimizing HER through chirality.展开更多
As hydrogen energy technologies gain momentum,the role of renewable energy in facilitating sustainable hydrogen production is becoming increasingly critical.As a hydrogen production method,water electrolysis has attra...As hydrogen energy technologies gain momentum,the role of renewable energy in facilitating sustainable hydrogen production is becoming increasingly critical.As a hydrogen production method,water electrolysis has attracted much attention from researchers due to its operational simplicity,the high purity of the hydrogen generated,and its potential for achieving zero carbon emissions throughout the process.Numerous studies has been manipulated on platinum(Pt)-based catalysts,which exhibit superior performance in hydrogen evolution reactions.Within this category,Pt nanoclusters stand out due to their unique attributes,such as quantum size effects and unique coordination environments.These features enable them to outperform both Pt metal atoms and nanoparticles in hydrogen evolution reactions regarding activity and stability.Here,we primarily delve into the reaction mechanisms underlying Pt nanocluster-based hydrogen catalysts,with particular emphasis on the interactions between the metal catalysts and their associated support materials.We provide an exhaustive summary of the strategies employed in the synthesis,the structural analyses conducted,and the performance metrics observed for Pt nanocluster catalysts when paired with various supporting materials.In closing,we explore the future potential and challenges facing Pt nanocluster-based catalysts in the context of industrial water electrolysis,along with emerging avenues for their design and optimization.展开更多
Employing multiple metals for synergistic electronic structure regulation emerges as a promising approach to develop highly efficient and robust electrocatalysts for hydrogen evolution at ampere levels.In this study,a...Employing multiple metals for synergistic electronic structure regulation emerges as a promising approach to develop highly efficient and robust electrocatalysts for hydrogen evolution at ampere levels.In this study,a series of Schreibersite-type intermetallic compounds,particularly Mo_(2)Fe_(0.8)Ru_(0.2)P,are synthesized through high-temperature solid-phase synthesis.Experimental results demonstrate that the integration of Ru significantly improves the kinetics of proton adsorption and desorption during the hydrogen evolution reaction(HER).Additionally,density functional theory(DFT)calculations and X-ray absorption near edge structure(XANES)analyses effectively corroborate the pronounced d-orbital hybridization of Fe within the structure,which facilitates the transfer of hydroxide ions and the maintenance of material durability during alkaline HER processes.Remarkably,Mo_(2)Fe_(0.8)Ru_(0.2)P exhibits superior alkaline HER activity,characterized by an overpotential of merely 48 mV at a current density of 10 mA cm^(-2).After prolonged operation of 1000 h at high current densities(1.1 A cm^(-2)),the activity decline remains minimal,under 4%(with overpotential increasing from 258 mV to 268 mV).These results demonstrate the potential of strategically combining metallic elements to design high-performance industrial-grade electrocatalysts.展开更多
The activity of photocatalysts can be significantly regulated by designing micro-scale interfacial heterojunctions. The present study demonstrates the skillful construction of a graphdiyne/Sr_(2)Co_(2)O_(5) S-scheme h...The activity of photocatalysts can be significantly regulated by designing micro-scale interfacial heterojunctions. The present study demonstrates the skillful construction of a graphdiyne/Sr_(2)Co_(2)O_(5) S-scheme heterojunction, exhibiting exceptional stability, excellent proton adsorption, and remarkable photocatalytic activity. On the basis of in-situ XPS and calculation of work function, it is proved that the electron migration path between the interface of graphdiyne and Sr_(2)Co_(2)O_(5) conforms to the S-scheme heterojunction mechanism. The recombination rate of photogenerated carriers is significantly reduced by virtue of the synergistic effect of the internal electric field and band edge bending while preserving the inherent redox ability of the materials. The strong coupling between layered graphdiyne and hierarchical flower-like Sr_(2)Co_(2)O_(5) effectively enhances the specific surface area of graphdiyne/Sr_(2)Co_(2)O_(5) heterojunction, thereby facilitating H2O pre-adsorption. Combined with experiments and DFT calculations, it was found that both graphdiyne and Sr_(2)Co_(2)O_(5) have a direct band gap, which makes their electronic transitions without the assistance of phonons, thus improving the efficiency of solar energy conversion. This study offers insights into the potential application of graphdiyne and metal oxides in the field of photocatalytic hydrogen evolution.展开更多
Hydrogen production coupled with small molecule oxidation derived by renewable energy power has been widely studied as an effective method to reduce energy consumption and prepare added value production.Here,the coppe...Hydrogen production coupled with small molecule oxidation derived by renewable energy power has been widely studied as an effective method to reduce energy consumption and prepare added value production.Here,the copper-cobalt phosphide with a multilevel structure has been designed based on the hard and soft acids and bases theory.The nanocone composed of lamellas presented a sharp tip,which a positive effect on the mass transfer enhanced by a local electric field,and the nanolamellas contain CoP/Cu_(3)P interface provide the highly selective active site for the gluconic acid(GNA)synthesis and hydrogen evolution.The catalyst can drive hydrogen evolution at 5 A·cm^(-2)up to 437 h without active decay,and the electrocatalytic glucose oxidation at anode presents high efficiency due to Cu(I)introduction and the synergetic effect between interfaces.Density functional theory(DFT)calculation shows that water splitting more readily occurs at the CoP,which provides adsorbed H and-OH for hydrogen evolution and glucose oxidation,respectively,and glucose adsorption more readily occurs at the Cu_(3)P,which presents lower conversion energy for high value-added GNA.Efficient hydrogen evolution and glucose conversion indicate its high intrinsic activity and synergetic effect.This work provides a special interface construction strategy for the catalytic conversion of hydrogen and small molecules.展开更多
Alkaline electrolytic hydrogen production has emerged as one of the most practical methods for industrial-scale hydrogen production.However,the initial hydrolysis dissociation in alkaline media impedes the hydrogen ev...Alkaline electrolytic hydrogen production has emerged as one of the most practical methods for industrial-scale hydrogen production.However,the initial hydrolysis dissociation in alkaline media impedes the hydrogen evolution reaction(HER)kinetics of commercial catalysts.To overcome this limitation,this study focuses on the development of a highly efficient electrocatalyst for alkaline HER.Ni-based intermetallic compounds exhibit remarkable catalytic activity for HER,with the NiMo alloy being among the most active catalysts in alkaline environments.Here,we designed and fabricated self-supported multiscale porous NiZn/NiMo intermetallic compounds on a metal foam substrate using a versatile dealloying method.The resulting electrode exhibits excellent HER activity,achieving an overpotential of just 204 mV at 1000 mA/cm^(2),and dem-onstrates robust long-term catalytic stability,maintaining performance at 100 mA/cm^(2) for 400 h in an alkaline electrolyte.Thesefindings underscore the potential of nanosized intermetallic compounds fabricated via a dealloying approach to deliver exceptional catalytic performance for alkaline water electrolysis.展开更多
Understanding the role of cations within the catalysts in the interfacial water behavior at the electrolyte/catalyst interface is of pivotal importance for designing advanced catalysts toward hydrogen evolution reacti...Understanding the role of cations within the catalysts in the interfacial water behavior at the electrolyte/catalyst interface is of pivotal importance for designing advanced catalysts toward hydrogen evolution reaction(HER),which remains obscure and requires deep probing.Herein,we demonstrate the first investigation of interfacial water behavior on the surface of a series of sodium tungsten bronzes(Na_(x)WO_(3),0_(x)WO_(3)/electrolyte interface.Our integrated studies indicate that the Na ions significantly enrich the electronic state of WO_(6)octahedrons in Na_(x)WO_(3),which leads to the regulated electronic and atomic structures,endowing Na_(x)WO_(3)with disordered interfacial water network containing more isolated H_(3)O^(+)and subsequently moderate H^(*)adsorption to speed the Volmer step at the Na_(x)WO_(3)surface,thus boosting the HER.Consequently,the intrinsic HER activities achieved on those Na_(x)WO_(3)are tens of times higher than those on WO_(3).Particularly,it is found that Na concentration x=0.69 endows Na_(x)WO_(3)with the highest intrinsic HER activity,and the resultant Na_(0.69)WO_(3)with a unique porous octahedral structure exhibits a low overpotential of only 64 mV at current density of 10 mA cm^(-2)in acidic electrolyte.This study provides the first insight into the cation-dependent interfacial water behavior induced by the cations within the catalyst and establishes the interfacial water-activity relationship of HER,thus allowing for the design of a more advanced catalyst with efficient interfacial structu res towa rds HER.展开更多
Exploring platinum single-atom electrocatalysts(SACs)is of great significance for effectively catalyzing the hydrogen evolution reaction in order to maximize the utilization of metal atoms.Herein,ruthenium clusters wi...Exploring platinum single-atom electrocatalysts(SACs)is of great significance for effectively catalyzing the hydrogen evolution reaction in order to maximize the utilization of metal atoms.Herein,ruthenium clusters with several atoms(Rux)supported on nitrogen-doped,cost-efficient Black Pearls 2000(Ru_(x)NBP),were synthesized as initial materials via a simple hydrothermal method.Then,[PtCl_(4)]^(2–)ion was reductively deposited on RuxNBP to obtain a Pt SAC(Pt1/RuxNBP).Electrochemical measurements demonstrate the excellent HER performance of Pt_(1)/Ru_(x)NBP with a 5.7-fold increase in mass activity compared to the commercial Pt/C at 20 mV.Moreover,the cell voltage of the proton exchange membrane electrolyzer with Pt_(1)/Ru_(x)NBP is 20 mV lower compared to that with commercial Pt/C at 1.0 A cm^(−2).Physical characterization and density functional theory calculations revealed that the preserved Pt–Cl bond of[PtCl_(4)]^(2–)and the RuxNBP support co-regulate the 5d state of isolated Pt atoms and enhance the catalytic HER capacity of Pt1/RuxNBP.展开更多
Exploring transition metal sulfide electrocatalysts with high-efficiency for hydrogen evolution reaction(HER)is essential to produce H_(2) fuel through water splitting.Herein,novel nickel tungsten sulfide heterojuncti...Exploring transition metal sulfide electrocatalysts with high-efficiency for hydrogen evolution reaction(HER)is essential to produce H_(2) fuel through water splitting.Herein,novel nickel tungsten sulfide heterojunction(NiS-WS_(2))with a nanowoven ball-like structure were directed synthetized by a facile hydrothermal method.The hierarchical Ni S-WS_(2) exhibited excellent HER activity with a relatively small overpotential of 142 and 137 m V at 10 m A/cm^(2) in 0.5 mol/L H_(2)SO_(4) and 1 mol/L KOH,which is much better than that of single NiS and WS_(2).The impressive performance of NiS-WS_(2) heterojunction is owed to the collective synergy of special morphological and more exposed active sites between the crystal interfacial of NiS and WS_(2).In addition,the hierarchical NiS-WS_(2) can facilitate the transport of charge/mass by optimized electronic structure,which further improves the HER activity of electrocatalysts.These outcomes provide a simple method to prospect towards the design and application of heterostructures as efficient electrocatalysts,shedding some light on the development of functional materials in energy chemistry.展开更多
The construction of rare earth(RE)alloy catalysts offers a route to harness the unique electronic structure of RE.Within the alloy,RE can fine-tune the electronic configuration of the active element,such as rhodium(Rh...The construction of rare earth(RE)alloy catalysts offers a route to harness the unique electronic structure of RE.Within the alloy,RE can fine-tune the electronic configuration of the active element,such as rhodium(Rh),via the ligand effect,optimizing the electrochemical reaction pathway.However,the challenging negative reduction potential of RE has impeded the progress in developing RE alloys,particularly nanoalloy catalysts.In this study,Rh_(3)Sc/C and Rh_(3)Y/C nanoalloys were synthesized using a sodium vapor reduction strategy for application as hydrogen evolution reaction(HER)catalysts.Elec-trochemical tests reveal that Rh-RE alloy catalysts exhibit significantly improved electrocatalytic activity in 1 mol/L KOH.Notably,Rh_(3)Y/C demonstrates exceptional HER performance,achieving a low over-potential of only 31 mV at 10 mA/cm^(2),surpassing the 50 mV observed for Rh/C.Furthermore,the current density of Rh_(3)Y/C at an 80 mV overpotential is 3.9 times that of Rh/C.This study sheds light on the remarkable catalytic potential of Rh-RE alloys,paving the way for the future expansion of RE nanoalloy systems.展开更多
As a clean energy source,hydrogen plays a critical role in the global mission to achieve carbon neutrality.Among varied hydrogen production techniques,water electrolysis driven by clean energy,such as solar or wind en...As a clean energy source,hydrogen plays a critical role in the global mission to achieve carbon neutrality.Among varied hydrogen production techniques,water electrolysis driven by clean energy,such as solar or wind energy,is the most promising and viable option,with the advantages of celerity,high efficiency,cleanliness,and sustainability.However,this process necessitates a highly active and durable hydrogen evolution reaction(HER)catalyst to enhance the overall reaction efficiency.This article thoroughly reviews the recent development of electrocatalysts exhibiting high-performance HER.In particular,a comprehensive look at noble metals platinum(Pt),ruthenium(Ru),iridium(Ir),and non-noble metals,including sulfides,carbides,nitrides and phosphides is taken.Synthesis strategies,methods for enhancing performance,and the correlation between structure,composition,and catalytic performance are discussed.We also pay particular attention to density functional theory(DFT)calculations to reveal the mechanisms behind the improvement of HER performance.Finally,the critical challenges associated with electrochemical water splitting and propose coping strategies are presented.展开更多
The development of cost-effective,highly efficient and stable catalysts is critical to promote the industrial alkaline hydrogen evolution reaction(HER).However,single-component catalysts often cannot handle the multip...The development of cost-effective,highly efficient and stable catalysts is critical to promote the industrial alkaline hydrogen evolution reaction(HER).However,single-component catalysts often cannot handle the multiple kinetic steps during hydrogen production.To address this challenge,a heterogeneous catalyst comprising metal Co,CoO and carbon-doped Mo_(2)N(Co–CoO–C/Mo_(2)N/CC)was synthesized by heat treatment of carbon cloth-supported CoMoO_(4) microrods in a mixed reduction atmosphere.The resulting catalyst has rich interfaces,exhibiting excellent initial HER activity with an overpotential of 27 mV at 10 mA·cm^(−2) and a Tafel slope of 37 mV·dec^(−1).Further studies show that the activity and stability of the catalyst can be tailored by the dynamic surface reconfiguration and doping effects.The carbon doping and high crystallinity in Mo_(2)N help to reduce the dissolution of Mo and the surface metal Co is preferentially converted into stable Co(OH)2,thus stabilizing the structure of the catalyst and coordinating various reaction kinetics.In an electrolyzer comprising a heterogeneous Co–CoO–C/Mo_(2)N cathode and NiFe layered double hydroxides(LDH)anode,only 1.58 V is required to achieve a current density of 50 mA·cm^(−2),outperforming Pt/RuO catalysts.After continuous electrolysis for 100 h,the potential increases by merely 19 mV from the initial 1.58 V,indicating excellent stability.This study presents a novel strategy for developing highly active and stable heterogeneous catalysts,offering insights into the dynamic evolution of catalyst structures and laying the groundwork for designing efficient and stable composite catalysts for energy conversion applications.展开更多
基金supported by the Development Project of Youth Innovation Team in Shandong Colleges and Universities(No.2019KJC031)the Natural Science Foundation of Shandong Province(Nos.ZR2019MB064,ZR2021MB122 and ZR2022MB137)the Doctoral Program of Liaocheng University(No.318051608).
文摘Pt-based materials are the benchmarked catalysts in the cathodic hydrogen evolution reaction(HER)of water splitting;the prohibitive cost and scarcity of Pt immensely impede the commercialization of hydrogen energy.Ru has aroused significant concern because of its Pt-like activity and much lower price.However,it’s still a top priority to minimize the Ru loading and pursue the most superior cost performance.
基金financially supported by the project of the National Natural Science Foundation of China(52322203)the Key Research and Development Program of Shaanxi Province(2024GHZDXM-21)。
文摘The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.
基金financial support by the National Natural Science Foundation of China(No.52102241)Doctor of Suzhou University Scientific Research Foundation(Nos.2022BSK019,2020BS015)+2 种基金the Primary Research and Development Program of Anhui Province(No.201904a05020087)the Natural Science Research Project in Universities of Anhui Province in China(Nos.2022AH051386,KJ2021A1114)the Foundation(No.GZKF202211)of State Key Laboratory of Biobased Material and Green Papermaking Qilu University of Technology。
文摘Available online Alkaline water electrolysis(AWE)is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure.Noble metal-based electrocatalysts,owing to their exceptional hydrogen binding energy,exhibit remarkable catalytic activity and long-term stability in the hydrogen evolution reaction(HER).However,the restricted accessibility and exorbitant cost of noble-metal materials pose obstacles to their extensive adoption in industrial contexts.This review investigates strategies aimed at reducing the dependence on noble-metal electrocatalysts and developing a cost-effective alkaline HER catalyst,while considering the principles of sustainable development.The initial discussion covers the fundamental principle of HER,followed by an overview of prevalent techniques for synthesizing catalysts based on noble metals,along with a thorough examination of recent advancements.The subsequent discussion focuses on the strategies employed to improve noble metalbased catalysts,including enhancing the intrinsic activity at active sites and increasing the quantity of active sites.Ultimately,this investigation concludes by examining the present state and future direction of research in the field of electrocatalysis for the HER.
基金supported by National Natural Science Foundation of China(NSFC,22338006,92356301,9235630033 and 22375062)Shanghai Municipal Science and Technology Major Project(21JC1401700)+4 种基金Shanghai Pilot Program for Basic Research(22TQ1400100-10)Fundamental Research Funds for the Central UniversitiesShanghai Pujiang Program(22PJ1402400)“Chenguang Program”supported by Shanghai Education Development Foundation and Shanghai Municipal Education Commission(22CGA32)the Young Elite Scientists Sponsorship Program by CAST(2023QNRC001).
文摘Organic nanophotocatalysts are promising candidates for solar fuels production,but they still face the challenge of unfavorable geminate recombination due to the limited exciton diffusion lengths.Here,we introduce a binary nanophotocatalyst fabricated by blending two polymers,PS-PEG5(PS)and PBT-PEG5(PBT),with matched absorption and emission spectra,enabling a Forster resonance energy transfer(FRET)process for enhanced photocatalysis.These heterostructure nanophotocatalysts are processed using a facile and scalable flash nanoprecipitation(FNP)technique with precious kinetic control over binary nanoparticle formation.The resulting nanoparticles exhibit an exceptional photocatalytic hydrogen evolution rate up to 65 mmol g^(-1) h^(-1),2.5 times higher than that single component nanoparticles.Characterizations through fluorescence spectra and transient absorption spectra confirm the hetero-energy transfer within the binary nanoparticles,which prolongs the excited-state lifetime and extends the namely“effective exciton diffusion length”.Our finding opens new avenues for designing efficient organic photocatalysts by improving exciton migration.
基金financially supported by the National Natural Science Foundation of China(No.5217042069)the Young Elite Scientist Sponsorship Program by China Association for Science and Technology(CAST)(No.YESS20200103)the Fundamental Research Funds for the Central Universities(No.265QZ2022004)。
文摘Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this study,nanocatalysts with ultralow Pt content,excellent performance,and carbon black as support were prepared through in-situ synthesis.These~2-nm particles uniformly and stably dispersed on carbon black because of the strong s-p-d orbital hybridizations between carbon black and Pt,which suppressed the agglomeration of Pt ions.This unique structure is beneficial for the hydrogen evolution reaction.The catalysts exhibited remarkable catalytic activity for hydrogen evolution reaction,exhibiting a potential of 100 mV at 100 mA·cm^(-2),which is comparable to those of commercial Pt/C catalysts.Mass activity(1.61 A/mg)was four times that of a commercial Pt/C catalyst(0.37 A/mg).The ultralow Pt loading(6.84wt%)paves the way for the development of next-generation electrocatalysts.
基金supported by the National Natural Science Foundation of China(22179138).
文摘The utilization of nickel-based catalysts as alternatives to expensive platinum-based(Pt-based)materials for the hydrogen evolution reaction in acidic electrolytes has attracted considerable attention due to their potential for enabling cost-effective industrial applications.However,the unsatisfied cyclic stability and electrochemical activity limit their further application.In this work,nickel-molybdenum(Ni-Mo)alloy catalysts were successfully synthesized through a comprehensive process including electrodeposition,thermal annealing,and electrochemical activation.Owing to the synergistic interaction of molybdenum trinickelide(Ni_(3)Mo)and molybdenum dioxide(MoO_(2))in Ni-Mo alloy,the catalyst display superior overall electrochemical properties.A low overpotential of 86 mV at 10 mA/cm^(2)and a Tafel slope of 74.0 mV/dec in 0.5 mol/L H_(2)SO_(4)solution can be achieved.Notably,remarkable stability with negligible performance degradation even after 100 h could be maintained.This work presents a novel and effective strategy for the design and fabrication of high-performance,non-precious metal electrocatalysts for acidic water electrolysis.
基金National Natural Science Foundation of China(21806023)Natural Science Foundation of Hunan Province(2021JJ40199)+2 种基金Education Department Foundation of Hunan Province(20C0813)Hunan University of Science and Technology Fundamental Research FundsPostgraduate Scientific Research Innovation Project of Hunan Province(CX20240877)。
文摘Elemental doping is an effective strategy for tuning the band structure of graphite carbon nitride(CN)to enhance its photocatalytic performance.In this study,sodium(Na)and oxygen(O)co-doped carbon nitride(Na/O-CN_(x),x=1.0,2.0,3.0,4.0)was synthesized via solid-phase reaction of sodium citrate(NaCA)and pure CN powder in the Teflon-sealed autoclave under air conditions at 180℃.Surface area of Na/O-CN_(3.0) is measured to be 18.8 m^(2)/g,increasing by 60.7%compared to that of pure CN(11.7 m^(2)/g).Bandgap energy of Na/O-CN_(3.0) is determined to be 2.68 eV,marginally lower than that of pure CN(2.70 eV),thereby enhancing its capacity for sunlight absorption.Meanwhile,the incorporation of Na and O atoms into Na/O-CN_(x) is found to effectively reduce recombination rates of photogenerated electron-hole pairs.As a result,Na/O-CN_(x) samples exhibit markedly enhanced photocatalytic hydrogen evolution activity under visible light irradiation.Notably,the optimal Na/O-CN_(3.0) sample achieves a photocatalytic hydrogen production rate of 103.2μmol·g^(–1)·h^(–1),which is 8.2 times greater than that of pure CN(11.2μmol·g^(–1)·h^(–1)).Furthermore,a series of Na/O-CN_(x)-yO_(2)(y=0,20%,40%,60%,80%,100%)samples were prepared by modulating the oxygen content within reaction atmosphere.The catalytic performance evaluations reveal that the incorporation of both Na and O atoms in Na/O-CN_(3.0) enhances photocatalytic activity.This study also introduces novel methodologies for synthesis of metal atom-doped CN materials at lower temperature,highlighting the synergistic effect of Na and O atoms in photocatalytic hydrogen production of Na/O-CN_(x) samples.
基金financial supports provided by the Natural Science Foundation of Fujian Province(No.2024J01195)the National Nature Science Foundation of China(No.21905279)+1 种基金Sanming University(Nos.22YG11 and PYT2201)the Education Scientific Research Project of Youth Teachers in the Education Department of Fujian Province(No.JAT220351).
文摘Negatively charged open-framework metal sulfides(NOSs),taking advantages of the characteristics of excellent visible light absorption,easily exchanged cations,and abundant active sites,hold significant promise as highly efficient photocatalysts for hydrogen evolution.However,their applications in photocatalytic hydrogen evolution(PHE)are infrequently documented and the corresponding photocatalytic mechanism has not yet been explored.Herein,we excavated a novel NOS photocatalyst of(Me_(2)NH_(2))_(6)In_(10)S_(18)(MIS)with a three-dimensional(3D)structure,and successfully incorporated divalent Co(Ⅱ)and metal Co(0)into its cavities via the convenient cation exchange-assisted approach to regulate the critical steps of photocatalytic reactions.As the introduced Co(0)allows for more efficient light utilization and adroitly surficial hydrogen desorption,and meanwhile acts as the‘electron pump’for rapid charge transfer,Co(0)-modified MIS delivers a surprising PHE activity in the initial stage of photocatalysis.With the prolonging of illumination,metal Co(0)gradually escapes from MIS framework,resulting in the decline of PHE performance.By stark contrast,the incorporated Co(Ⅱ)can establish a strong interaction with MIS framework,and simultaneously capture photogenerated electrons from MIS to produce Co(0),which constructs a stable photocatalytic system as well as provides additional channels for spatially separating photogenerated carriers.Thus,Co(Ⅱ)-modified MIS exhibits a robust and highly stable PHE activity of~4944μmol/g/h during the long-term photocatalytic reactions,surpassing most of the previously reported In–S framework photocatalysts.This work represents a breakthrough in the study of PHE performance and mechanism of NOS-based photocatalysts,and sheds light on the design of vip confined NOS-based photocatalysts towards high-efficiency solar-to-chemical energy conversion.
基金the full support of the National Natural Science Foundation of China(62071154,51272052 and50902040)the Natural Science Foundation of Heilongjiang Province of China(LH2020B011 and LH2019B006)the Scientific Research Projects of Basic Scientific Research Operational Expenses of Heilongjiang Provincial Colleges and Universities(2021-KYYWF-0171)。
文摘The integration of machine learning and electrocatalysis presents nota ble advancements in designing and predicting the performance of chiral materials for hydrogen evolution reactions(HER).This study utilizes theoretical calculations and machine learning techniques to assess the HER performance of both chiral and achiral M-N-SWCNTs(M=In,Bi,and Sb)single-atom catalysts(SACs).The stability preferences of metal atoms are dependent on chirality when interacting with chiral SWCNTs.The HER activity of the right-handed In-N-SWCNT is 5.71 times greater than its achiral counterpart,whereas the left-handed In-N-SWCNT exhibits a 5.12-fold enhancement.The calculated hydrogen adsorption free energy for the right-handed In-N-SWCNT reaches as low as-0.02 eV.This enhancement is attributed to the symmetry breaking in spin density distribution,transitioning from C_(2V)in achiral SACs to C_(2)in chiral SACs,which facilitates active site transfer and enhances local spin density.Right-handed M-N-SWCNTs exhibit superiorα-electron separation and transport efficiency relative to left-handed variants,owing to the chiral induced spin selectivity(CISS)effect,with spin-upα-electron density reaching 3.43×10^(-3)e/Bohr^(3)at active sites.Machine learning provides deeper insights,revealing that the interplay of weak spatial electronic effects and appropriate curvature-chirality effects significantly enhances HER performance.A weaker spatial electronic effect correlates with higher HER activity,larger exchange current density,and higher turnover frequency.The curvature-chirality effect undersco res the influence of intrinsic structures on HER performance.These findings offer critical insights into the role of chirality in electrocatalysis and propose innovative approaches for optimizing HER through chirality.
基金the National Key Research and Development Program of China(No.2022YFB4102000)the National Natural Science Foundation of China(NSFC,Nos.22102018 and 52171201)+4 种基金the Huzhou Science and Technology Bureau(No.2022GZ45)the Hefei National Research Center for Physical Sciences at the Microscale(No.KF2021005)the China Postdoctoral Science Foundation-Funded Project(No.2022M710601)the Huzhou Science and Technology Bureau(No.2023GZ02)the Natural Science Foundation of Sichuan Province(No.24NSFSC5779)。
文摘As hydrogen energy technologies gain momentum,the role of renewable energy in facilitating sustainable hydrogen production is becoming increasingly critical.As a hydrogen production method,water electrolysis has attracted much attention from researchers due to its operational simplicity,the high purity of the hydrogen generated,and its potential for achieving zero carbon emissions throughout the process.Numerous studies has been manipulated on platinum(Pt)-based catalysts,which exhibit superior performance in hydrogen evolution reactions.Within this category,Pt nanoclusters stand out due to their unique attributes,such as quantum size effects and unique coordination environments.These features enable them to outperform both Pt metal atoms and nanoparticles in hydrogen evolution reactions regarding activity and stability.Here,we primarily delve into the reaction mechanisms underlying Pt nanocluster-based hydrogen catalysts,with particular emphasis on the interactions between the metal catalysts and their associated support materials.We provide an exhaustive summary of the strategies employed in the synthesis,the structural analyses conducted,and the performance metrics observed for Pt nanocluster catalysts when paired with various supporting materials.In closing,we explore the future potential and challenges facing Pt nanocluster-based catalysts in the context of industrial water electrolysis,along with emerging avenues for their design and optimization.
基金supported by Research Grants of the NRF(2023R1A2C2003823,RS-2024-00405818)funded by the National Research Foundation under the Ministry of Science,ICT&Future,Korea。
文摘Employing multiple metals for synergistic electronic structure regulation emerges as a promising approach to develop highly efficient and robust electrocatalysts for hydrogen evolution at ampere levels.In this study,a series of Schreibersite-type intermetallic compounds,particularly Mo_(2)Fe_(0.8)Ru_(0.2)P,are synthesized through high-temperature solid-phase synthesis.Experimental results demonstrate that the integration of Ru significantly improves the kinetics of proton adsorption and desorption during the hydrogen evolution reaction(HER).Additionally,density functional theory(DFT)calculations and X-ray absorption near edge structure(XANES)analyses effectively corroborate the pronounced d-orbital hybridization of Fe within the structure,which facilitates the transfer of hydroxide ions and the maintenance of material durability during alkaline HER processes.Remarkably,Mo_(2)Fe_(0.8)Ru_(0.2)P exhibits superior alkaline HER activity,characterized by an overpotential of merely 48 mV at a current density of 10 mA cm^(-2).After prolonged operation of 1000 h at high current densities(1.1 A cm^(-2)),the activity decline remains minimal,under 4%(with overpotential increasing from 258 mV to 268 mV).These results demonstrate the potential of strategically combining metallic elements to design high-performance industrial-grade electrocatalysts.
基金supported by the Excellent Youth Program,Ningxia Hui Autonomous Region Natural Science Foundation Project(No.2022AAC05034)the Ningxia Low-Grade Resource High-Value Utilization and Environmental Chemical Integration Technology Innovation Team Project of Chinathe Innovative Team for Transforming Waste Cooking Oil into Clean Energy and High Value-Added Chemicals of China.
文摘The activity of photocatalysts can be significantly regulated by designing micro-scale interfacial heterojunctions. The present study demonstrates the skillful construction of a graphdiyne/Sr_(2)Co_(2)O_(5) S-scheme heterojunction, exhibiting exceptional stability, excellent proton adsorption, and remarkable photocatalytic activity. On the basis of in-situ XPS and calculation of work function, it is proved that the electron migration path between the interface of graphdiyne and Sr_(2)Co_(2)O_(5) conforms to the S-scheme heterojunction mechanism. The recombination rate of photogenerated carriers is significantly reduced by virtue of the synergistic effect of the internal electric field and band edge bending while preserving the inherent redox ability of the materials. The strong coupling between layered graphdiyne and hierarchical flower-like Sr_(2)Co_(2)O_(5) effectively enhances the specific surface area of graphdiyne/Sr_(2)Co_(2)O_(5) heterojunction, thereby facilitating H2O pre-adsorption. Combined with experiments and DFT calculations, it was found that both graphdiyne and Sr_(2)Co_(2)O_(5) have a direct band gap, which makes their electronic transitions without the assistance of phonons, thus improving the efficiency of solar energy conversion. This study offers insights into the potential application of graphdiyne and metal oxides in the field of photocatalytic hydrogen evolution.
基金supported by the National Nature Science Foundation of China(No.22269021)Tianshan Talent Project of Xinjiang Uygur Autonomous Region(No.2023TSYCQNTJ0039)the Open project of Key Laboratory in Xinjiang Uygur Autonomous Region of China(No.2023D04027).
文摘Hydrogen production coupled with small molecule oxidation derived by renewable energy power has been widely studied as an effective method to reduce energy consumption and prepare added value production.Here,the copper-cobalt phosphide with a multilevel structure has been designed based on the hard and soft acids and bases theory.The nanocone composed of lamellas presented a sharp tip,which a positive effect on the mass transfer enhanced by a local electric field,and the nanolamellas contain CoP/Cu_(3)P interface provide the highly selective active site for the gluconic acid(GNA)synthesis and hydrogen evolution.The catalyst can drive hydrogen evolution at 5 A·cm^(-2)up to 437 h without active decay,and the electrocatalytic glucose oxidation at anode presents high efficiency due to Cu(I)introduction and the synergetic effect between interfaces.Density functional theory(DFT)calculation shows that water splitting more readily occurs at the CoP,which provides adsorbed H and-OH for hydrogen evolution and glucose oxidation,respectively,and glucose adsorption more readily occurs at the Cu_(3)P,which presents lower conversion energy for high value-added GNA.Efficient hydrogen evolution and glucose conversion indicate its high intrinsic activity and synergetic effect.This work provides a special interface construction strategy for the catalytic conversion of hydrogen and small molecules.
基金Taishan Scholar Project of Shandong Province(No.tsqn202306226)Natural Science Foundation of Shandong Prov-ince(No.ZR2023ME155)+1 种基金The project of“20 Items of University”of Jinan(No.202228046)Luzhou Municipal Science and Technol-ogy Plan Project(Nos.2024JYJ016 and 2024JYJ018).
文摘Alkaline electrolytic hydrogen production has emerged as one of the most practical methods for industrial-scale hydrogen production.However,the initial hydrolysis dissociation in alkaline media impedes the hydrogen evolution reaction(HER)kinetics of commercial catalysts.To overcome this limitation,this study focuses on the development of a highly efficient electrocatalyst for alkaline HER.Ni-based intermetallic compounds exhibit remarkable catalytic activity for HER,with the NiMo alloy being among the most active catalysts in alkaline environments.Here,we designed and fabricated self-supported multiscale porous NiZn/NiMo intermetallic compounds on a metal foam substrate using a versatile dealloying method.The resulting electrode exhibits excellent HER activity,achieving an overpotential of just 204 mV at 1000 mA/cm^(2),and dem-onstrates robust long-term catalytic stability,maintaining performance at 100 mA/cm^(2) for 400 h in an alkaline electrolyte.Thesefindings underscore the potential of nanosized intermetallic compounds fabricated via a dealloying approach to deliver exceptional catalytic performance for alkaline water electrolysis.
基金financially supported by the National Natural Science Foundation of China(22279069,22179067,22478211 and 22372017)the Major Fundamental Research Program of Natural Science Foundation of Shandong Province(ZR2022ZD10)。
文摘Understanding the role of cations within the catalysts in the interfacial water behavior at the electrolyte/catalyst interface is of pivotal importance for designing advanced catalysts toward hydrogen evolution reaction(HER),which remains obscure and requires deep probing.Herein,we demonstrate the first investigation of interfacial water behavior on the surface of a series of sodium tungsten bronzes(Na_(x)WO_(3),0_(x)WO_(3)/electrolyte interface.Our integrated studies indicate that the Na ions significantly enrich the electronic state of WO_(6)octahedrons in Na_(x)WO_(3),which leads to the regulated electronic and atomic structures,endowing Na_(x)WO_(3)with disordered interfacial water network containing more isolated H_(3)O^(+)and subsequently moderate H^(*)adsorption to speed the Volmer step at the Na_(x)WO_(3)surface,thus boosting the HER.Consequently,the intrinsic HER activities achieved on those Na_(x)WO_(3)are tens of times higher than those on WO_(3).Particularly,it is found that Na concentration x=0.69 endows Na_(x)WO_(3)with the highest intrinsic HER activity,and the resultant Na_(0.69)WO_(3)with a unique porous octahedral structure exhibits a low overpotential of only 64 mV at current density of 10 mA cm^(-2)in acidic electrolyte.This study provides the first insight into the cation-dependent interfacial water behavior induced by the cations within the catalyst and establishes the interfacial water-activity relationship of HER,thus allowing for the design of a more advanced catalyst with efficient interfacial structu res towa rds HER.
文摘Exploring platinum single-atom electrocatalysts(SACs)is of great significance for effectively catalyzing the hydrogen evolution reaction in order to maximize the utilization of metal atoms.Herein,ruthenium clusters with several atoms(Rux)supported on nitrogen-doped,cost-efficient Black Pearls 2000(Ru_(x)NBP),were synthesized as initial materials via a simple hydrothermal method.Then,[PtCl_(4)]^(2–)ion was reductively deposited on RuxNBP to obtain a Pt SAC(Pt1/RuxNBP).Electrochemical measurements demonstrate the excellent HER performance of Pt_(1)/Ru_(x)NBP with a 5.7-fold increase in mass activity compared to the commercial Pt/C at 20 mV.Moreover,the cell voltage of the proton exchange membrane electrolyzer with Pt_(1)/Ru_(x)NBP is 20 mV lower compared to that with commercial Pt/C at 1.0 A cm^(−2).Physical characterization and density functional theory calculations revealed that the preserved Pt–Cl bond of[PtCl_(4)]^(2–)and the RuxNBP support co-regulate the 5d state of isolated Pt atoms and enhance the catalytic HER capacity of Pt1/RuxNBP.
基金financially supported by the National Natural Science Foundation of China(No.52202340)the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(No.2021L266)+1 种基金the Applied Basic Research Project of Shanxi Province(No.20210302124425)the Graduate Science and Technology Innovation Project Foundation of Shanxi Normal University(No.2023XSY065)。
文摘Exploring transition metal sulfide electrocatalysts with high-efficiency for hydrogen evolution reaction(HER)is essential to produce H_(2) fuel through water splitting.Herein,novel nickel tungsten sulfide heterojunction(NiS-WS_(2))with a nanowoven ball-like structure were directed synthetized by a facile hydrothermal method.The hierarchical Ni S-WS_(2) exhibited excellent HER activity with a relatively small overpotential of 142 and 137 m V at 10 m A/cm^(2) in 0.5 mol/L H_(2)SO_(4) and 1 mol/L KOH,which is much better than that of single NiS and WS_(2).The impressive performance of NiS-WS_(2) heterojunction is owed to the collective synergy of special morphological and more exposed active sites between the crystal interfacial of NiS and WS_(2).In addition,the hierarchical NiS-WS_(2) can facilitate the transport of charge/mass by optimized electronic structure,which further improves the HER activity of electrocatalysts.These outcomes provide a simple method to prospect towards the design and application of heterostructures as efficient electrocatalysts,shedding some light on the development of functional materials in energy chemistry.
基金the National Natural Science Foundation of China(22371131)the 111 Project from China(B18030)+5 种基金the Beijing-Tianjin-Hebei Collaborative Innovation Project(19YFSLQY00030)the Outstanding Youth Project of Tianjin Natural Science Foundation(20JCJQJC00130)the Key Project of Tianjin Natural Science Foundation(20JCZDJC00650)the opening fund of Key Laboratory of Rare Earths,Chinese Academy of Sciencesthe Functional Research Funds for the Central Universities,Nankai University(63186005)Tianjin Key Lab for Rare Earth Materials and Applications(ZB19500202).
文摘The construction of rare earth(RE)alloy catalysts offers a route to harness the unique electronic structure of RE.Within the alloy,RE can fine-tune the electronic configuration of the active element,such as rhodium(Rh),via the ligand effect,optimizing the electrochemical reaction pathway.However,the challenging negative reduction potential of RE has impeded the progress in developing RE alloys,particularly nanoalloy catalysts.In this study,Rh_(3)Sc/C and Rh_(3)Y/C nanoalloys were synthesized using a sodium vapor reduction strategy for application as hydrogen evolution reaction(HER)catalysts.Elec-trochemical tests reveal that Rh-RE alloy catalysts exhibit significantly improved electrocatalytic activity in 1 mol/L KOH.Notably,Rh_(3)Y/C demonstrates exceptional HER performance,achieving a low over-potential of only 31 mV at 10 mA/cm^(2),surpassing the 50 mV observed for Rh/C.Furthermore,the current density of Rh_(3)Y/C at an 80 mV overpotential is 3.9 times that of Rh/C.This study sheds light on the remarkable catalytic potential of Rh-RE alloys,paving the way for the future expansion of RE nanoalloy systems.
基金supported by the National Natural Science Foundation of China(No.52102470)。
文摘As a clean energy source,hydrogen plays a critical role in the global mission to achieve carbon neutrality.Among varied hydrogen production techniques,water electrolysis driven by clean energy,such as solar or wind energy,is the most promising and viable option,with the advantages of celerity,high efficiency,cleanliness,and sustainability.However,this process necessitates a highly active and durable hydrogen evolution reaction(HER)catalyst to enhance the overall reaction efficiency.This article thoroughly reviews the recent development of electrocatalysts exhibiting high-performance HER.In particular,a comprehensive look at noble metals platinum(Pt),ruthenium(Ru),iridium(Ir),and non-noble metals,including sulfides,carbides,nitrides and phosphides is taken.Synthesis strategies,methods for enhancing performance,and the correlation between structure,composition,and catalytic performance are discussed.We also pay particular attention to density functional theory(DFT)calculations to reveal the mechanisms behind the improvement of HER performance.Finally,the critical challenges associated with electrochemical water splitting and propose coping strategies are presented.
基金supported by the National Natural Science Foundation of China(Nos.22379116,U2003130 and U2004210)the Outstanding Youth Foundation of Natural Science Foundation of Hubei Province(No.2020CFA099)+1 种基金the Foundation of Science Research Program from Hubei Provincial Department of Education(No.Q20221101)the Innovation group of Key Research and Development Program of Hubei Province(Nos.2021BAA208 and 2022BCA061).
文摘The development of cost-effective,highly efficient and stable catalysts is critical to promote the industrial alkaline hydrogen evolution reaction(HER).However,single-component catalysts often cannot handle the multiple kinetic steps during hydrogen production.To address this challenge,a heterogeneous catalyst comprising metal Co,CoO and carbon-doped Mo_(2)N(Co–CoO–C/Mo_(2)N/CC)was synthesized by heat treatment of carbon cloth-supported CoMoO_(4) microrods in a mixed reduction atmosphere.The resulting catalyst has rich interfaces,exhibiting excellent initial HER activity with an overpotential of 27 mV at 10 mA·cm^(−2) and a Tafel slope of 37 mV·dec^(−1).Further studies show that the activity and stability of the catalyst can be tailored by the dynamic surface reconfiguration and doping effects.The carbon doping and high crystallinity in Mo_(2)N help to reduce the dissolution of Mo and the surface metal Co is preferentially converted into stable Co(OH)2,thus stabilizing the structure of the catalyst and coordinating various reaction kinetics.In an electrolyzer comprising a heterogeneous Co–CoO–C/Mo_(2)N cathode and NiFe layered double hydroxides(LDH)anode,only 1.58 V is required to achieve a current density of 50 mA·cm^(−2),outperforming Pt/RuO catalysts.After continuous electrolysis for 100 h,the potential increases by merely 19 mV from the initial 1.58 V,indicating excellent stability.This study presents a novel strategy for developing highly active and stable heterogeneous catalysts,offering insights into the dynamic evolution of catalyst structures and laying the groundwork for designing efficient and stable composite catalysts for energy conversion applications.
