Seawater electrolysis is a promising approach for sustainable energy without relying on precious freshwater.However,the large-scale seawater electrolysis is hindered by low catalytic efficiency and severe anode corros...Seawater electrolysis is a promising approach for sustainable energy without relying on precious freshwater.However,the large-scale seawater electrolysis is hindered by low catalytic efficiency and severe anode corrosion caused by the harmful chlorine.In contrast to the oxygen evolution reaction (OER)and chlorin ion oxidation reaction (ClOR),glycerol oxidation reaction (GOR) is more thermodynamically and kinetically favorable alternative.Herein,a Ru doping cobalt phosphide (Ru-CoP_(2)) is proposed as a robust bifunctional electrocatalyst for seawater electrolysis and GOR,for the concurrent productions of hydrogen and value-added formate.The in situ and ex situ characterization analyses demonstrated that Ru doping featured in the dynamic reconstruction process from Ru-CoP_(2)to Ru-CoOOH,accounting for the superior GOR performance.Further coupling GOR with hydrogen evolution was realized by employing Ru-CoP_(2)as both anode and cathode,requiring only a low voltage of 1.43 V at 100 mA cm^(-2),which was 250 m V lower than that in alkaline seawater.This work guides the design of bifunctional electrocatalysts for energy-efficient seawater electrolysis coupled with biomass resource upcycling.展开更多
The conversion of urea-containing wastewater into clean hydrogen energy has gained increasing attention.However,challenges remain,particularly with sluggish catalytic kinetics and limited long-term stability of urea o...The conversion of urea-containing wastewater into clean hydrogen energy has gained increasing attention.However,challenges remain,particularly with sluggish catalytic kinetics and limited long-term stability of urea oxidation reaction(UOR).Herein,we report the loosely porous CoOOH nano-architecture(CoOOH LPNAs)with hydrophilic surface and abundant oxygen vacancies(Ov)on carbon fiber paper(CFP)by electrochemical reconstruction of the CoP nanoneedles precursor.The resulting three-dimensional electrode exhibited an impressively low potential of 1.38 V at 1000 mA·cm^(−2) and excellent durability for UOR.Furthermore,when tested in an anion exchange membrane(AEM)electrolyzer,it required only 1.53 V at 1000 mA·cm^(−2) for industrial urea-assisted water splitting and operated stably for 100 h without degrada-tion.Experimental and theoretical investigations revealed that rich oxygen vacancies effectively modulate the electronic structure of the CoOOH while creating unique Co3-triangle sites with Co atoms close together.As a result,the adsorption and desorption processes of reactants and intermediates in UOR could be finely tuned,thereby significantly reducing ther-modynamic barriers.Additionally,the superhydrophilic self-supported nanoarray structure facilitated rapid gas bubble release,improving the overall efficiency of the reaction and preventing potential catalyst detachment caused by bubble accumulation,thereby improving both catalytic activity and stability at high current densities.展开更多
Balancing the adsorption of OH⁻and 5-hydroxymethylfurfural(HMF)is crucial in optimizing the competing HMF oxidation reaction and oxygen evolution reaction,especially given the polymerization tendency of HMF in alkalin...Balancing the adsorption of OH⁻and 5-hydroxymethylfurfural(HMF)is crucial in optimizing the competing HMF oxidation reaction and oxygen evolution reaction,especially given the polymerization tendency of HMF in alkaline solutions.Herein,we present an innovative approach for rapidly synthesizing a NiFe bimetallic metalorganic framework(MOF)induced by electron-withdrawing carbon quantum dot(EW-CQD)via electron beam irradiation within 2 min.EW-CQD serve as structural regulators,expanding the NiFe-MOF interlayer spacing,increasing reactive site availability,and more effectively balancing the adsorption of OH6(-) and HMF,thereby significantly boosting the oxidation activity of HMF.The resulting EW-CQD-MOF exhibits a low potential of 1.36 V vs.RHE at 10 mA cm^(-2)and maintains excellent durability over 120 h.Comprehensive in situ characterization elucidates the HMF oxidation reaction pathway,showing high selectivity towards 2,5-furandicarboxylic acid(FDCA)under ambient conditions,with an impressive HMF conversion rate of 94%and FDCA selectivity of 96%within 6 h.These findings underscore the critical role of structural optimization and adsorption balance in catalytic performance enhancement and offer valuable insights for designing high-efficiency catalysts,advancing sustainable catalytic processes.展开更多
Metal-organic frameworks(MOFs)h ave attracted widespread attention due to their large surface area and porous structure.Rationally designing the nanostructures of MOFs to promote their application in ethanol electroox...Metal-organic frameworks(MOFs)h ave attracted widespread attention due to their large surface area and porous structure.Rationally designing the nanostructures of MOFs to promote their application in ethanol electrooxidation is still a challenge.Here,a novel Cu-NCNs(Cu-nitrogen-doped carbon nanotubes)support was synthesized by pyrolysis of melamine(MEL)and Cu-ZIF-8 together,and then,Pd-Au nanoalloys were loaded by sodium borohydride reduction method to prepare PdAu@Cu-NCNs catalysts.The generating mesoporous carbon with high specific surface area and favorable electron and mass transport can be used as a potential excellent carrier for PdAu nanoparticles.In addition,the balance of catalyst composition and surface structure was tuned by controlling the content of Pd and Au.Thus,the best-performed Pd_(2)Au_(2)@Cu-NCN-1000-2(where 1000 means the carrier calcination temperature,and 2 means the calcination constant temperature time)catalyst exhibits better long-term stability and electrochemical activity for ethanol oxidation in alkaline media(4.80 A·mg^(-1)),which is 5.05 times higher than that of commercial Pd/C(0.95 A·mg^(-1)).Therefore,this work is beneficial to further promoting the application of MOFs in direct ethanol fuel cells(DEFCs)and can be used as inspiration for the design of more efficient catalyst support structures.展开更多
The selective electrochemical conversion of glycerol into value-added products is a green and sustainable strategy for the biomass utilization.In this work,Au nanowires(Au-NW)modified with polyethyleneimine(PEI)molecu...The selective electrochemical conversion of glycerol into value-added products is a green and sustainable strategy for the biomass utilization.In this work,Au nanowires(Au-NW)modified with polyethyleneimine(PEI)molecule(Au-NW@PEI)is obtained by an up-bottom post-modification approach.Physical characterization,molecular dynamics simulation and density functional theory demonstrate that the loose-packed PEI monolayer firmly and uniformly distribute on the Au-NW surface due to the strong Au-N interaction.Electrochemical experiments and product analysis display that PEI modification significantly enhance the electro-activity of Au-NW for the glycerol electro-oxidation reaction(GEOR)due to the electronic effect.Meanwhile,the steric hindrance and electrostatic effect of PEI layer make the optimizing adsorption of intermediates possible.Therefore,the selectivity of C3 product glyceric acid over Au-NW@PEI is increased by nearly 20%.The work thus indicates that the rational design of metal-organic interface can effectively elevate the electro-activity and selectivity of Au nanostructures,which may have wide application in biomass development.展开更多
The pressing environmental concerns and the depletion of fossil fuel reserves necessitate a transition toward sustainable energy sources.Ethanol,a renewable biomass-derived fuel,is a promising alternative due to its a...The pressing environmental concerns and the depletion of fossil fuel reserves necessitate a transition toward sustainable energy sources.Ethanol,a renewable biomass-derived fuel,is a promising alternative due to its availability and high energy density.This study investigates the synthesis of gold nanoparticles(Au NPs)via a square-wave pulse deposition technique,aiming to enhance catalytic activity for ethanol electrooxidation.By varying pulse durations,we were able to exert precise control over Au NP size and distribution without stabilizing agents.Characterization using field emission scanning electron microscopy and X-ray diffraction techniques confirmed the formation of clustered nanoparticles of metallic gold phase.Electrochemical characteristics analyses revealed that Au NPs synthesized with a 900 ms pulse duration exhibited the lowest charge transfer resistance and the highest electrochemically active surface area.The electrocatalytic performance test of these Au NPs demonstrated an anodic current density of 2.5 mA cm^-(2)and a Tafel slope of 78 mV dec^(-1),indicating superior catalytic performance and reaction kinetics.Additionally,the Au NPs showed high resistance to poisoning,as evidenced by a low j_(b)/j_(f)ratio of 0.28 and stable chronoamperometric response.These findings underscore the potential of this synthesis method for producing high-performance electrocatalysts utilized in exploiting ethanol's potential as an environmentally friendly energy carrier.展开更多
Constructing the desired long-range dual sites to enhance the C–C bond-cleavage and CO-tolerate ability during ethanol oxidation reaction is of importance for further applications.Herein,the concept of holding atomic...Constructing the desired long-range dual sites to enhance the C–C bond-cleavage and CO-tolerate ability during ethanol oxidation reaction is of importance for further applications.Herein,the concept of holding atomically dispersed NiO_(x)cluster supported on Pt-based high-index facets(NiO_(x)/Pt)is proposed to build O-bridged Pt–Ni dual sites.Strikingly,the obtained NiO_(x)/Pt dual sites show 4.97 times specific activity higher than that of commercial Pt/C(0.35 mA cm^(-2)),as well as outstanding CO-tolerance and durability.The advanced electrochemical in-situ characterizations reveal that the NiO_(x)/Pt can accelerate rapid dehydroxylation and C–C bondcleavage over the Pt–Ni dual sites.Theoretical calculations disclose that the atomically dispersed NiO_(x)species can lower the adsorption/reaction energy barriers of intermediates.This tactic provides a promising methodology on regulating the surface synergistic sites via engineering atomically dispersed oxide site.展开更多
Direct ethanol fuel cells(DEFCs)are a promising alternative to conventional energy sources,offering high energy density,environmental sustainability,and operational safety.Compared to methanol fuel cells,DEFCs exhibit...Direct ethanol fuel cells(DEFCs)are a promising alternative to conventional energy sources,offering high energy density,environmental sustainability,and operational safety.Compared to methanol fuel cells,DEFCs exhibit lower toxicity and a more mature preparation process.Unlike hydrogen fuel cells,DEFCs provide superior storage and transport feasibility,as well as cost-effectiveness,significantly enhancing their commercial viability.However,the stable C-C bond in ethanol creates a high activation energy barrier,often resulting in incomplete electrooxidation.Current commercial platinum(Pt)-and palladium(Pd)-based catalysts demonstrate low C-C bond cleavage efficiency(<7.5%),severely limiting DEFC energy output and power density.Furthermore,high catalyst costs and insufficient activity impede large-scale commercialization.Recent advances in DEFC anode catalyst design have focused on optimizing material composition and elucidating catalytic mechanisms.This review systematically examines developments in ethanol electrooxidation catalysts over the past five years,highlighting strategies to improve C1 pathway selectivity and C-C bond activation.Key approaches,such as alloying,nanostructure engineering,and interfacial synergy effects,are discussed alongside their mechanistic implications.Finally,we outline current challenges and future prospects for DEFC commercialization.展开更多
The electrooxidation of CO on Ru (0001) and RuO2 (100) electrode surfaces were characterized by cyclic voltammetry, AES and RHEED. The CO adlayer was first partially oxidized at 0.8 V, which is controlled by the atta...The electrooxidation of CO on Ru (0001) and RuO2 (100) electrode surfaces were characterized by cyclic voltammetry, AES and RHEED. The CO adlayer was first partially oxidized at 0.8 V, which is controlled by the attack of oxygen species toward the Ru(0001) surface. The remaining CO adlayer oxidation at 0.55 V is related to the combination of CO molecules with oxygen species already located on the surface. In contrast, successive peaks on RuO2(100) at 0.4 V and 0.72 V are observed, which shows that CO molecules can directly react with two different lattice-oxygen on the surface to carbon dioxide.展开更多
Direct borohydride hydrogen peroxide fuel cells(DBHPFCs)are emerging as a transformative technology for sustainable energy conversion.Despite their potential,their efficiency is largely hindered by the limitations of ...Direct borohydride hydrogen peroxide fuel cells(DBHPFCs)are emerging as a transformative technology for sustainable energy conversion.Despite their potential,their efficiency is largely hindered by the limitations of the anode catalyst.In response to this challenge,we have developed a novel series of Co-based heterojunction metal-organic framework(MOF)derivatives,supported on reduced graphene oxide(rGO)-modified nickel foam(NF),to enhance borohydride electrooxidation performance.Our synthesis involves the thermal transformation of a ZIF67-Co(OH)_(2)-rGO/NF precursor within a controlled temperature between 300 and 750℃,yielding distinct phase heterostructures and pristine Co and CoO,verified by X-ray diffraction(XRD)and transmission electron microscopy(TEM)analyses.Additionally,the Ultraviolet photoelectron spectroscopy and theoretical calculation result further validate the formation of the heterojunction and direction of electron transfer along the interface as well as the BH_(4)^(-)adsorption behavior across the heterointerface.Notably,the catalyst annealed at 600℃,designated Co-CoO@C-rGO/NF-600,exhibits an exceptional oxidation current density of 2.5 A cm^(-2)at 0 V vs.Ag/AgCl in an electrolyte containing 2 mol L^(-1)NaOH and 0.4 mol L^(-1)NaBH_(4)Furthermore,the Co-CoO@C-rGO/NF-600 catalyst demonstrates remarkable performance as the anode catalyst in a DBHPFC assembly,achieving a peak power density of 385.73 mW cm^(-2)and demonstrating the enduring operational stability.The superior electrocatalytic performance is primarily attributed to the synergistic effects of Co-CoO nanoparticles rich in active heterointerfaces and the superior electron mobility afforded by the rGO scaffold.These results not only deepen our understanding of anode catalyst design for DBHPFCs but also pave the way for breakthroughs in electrocatalytic technologies,driving forward the quest for sustainable energy solutions.展开更多
Direct methanol fuel cells （DMFCs） are very promising power source for stationary and portable miniatureelectric appliances due to its high efficiency and low emissions of pollutants. As the key material, cata-lysts...Direct methanol fuel cells （DMFCs） are very promising power source for stationary and portable miniatureelectric appliances due to its high efficiency and low emissions of pollutants. As the key material, cata-lysts for both cathode and anode face several problems which hinder the commercialization of DMFCs.In this review, we mainly focus on anode catalysts of DMFCs. The process and mechanism of methanolelectrooxidation on Pt and Pt-based catalysts in acidic medium have been introduced. The influences ofsize effect and morphology on electrocatalytic activity are discussed though whether there is a size effectin MOP, catalyst is under debate. Besides, the non Pt catalysts are also listed to emphasize though Pt isstill deemed as the indispensable element in anode catalyst of DMFCs in acidic medium. Different cata-lyst systems are compared to illustrate the level of research at present. ome debates need to be verifiedwith experimental evidences.展开更多
The factors affecting the electrooxidation of hydroxypivalaldehyde（HPAL） in an undivided cell were studied by using cyclic voltammetry（CV）, linear scan voltammetry（ LSV）, and potentiostatic electrolysis. The ele...The factors affecting the electrooxidation of hydroxypivalaldehyde（HPAL） in an undivided cell were studied by using cyclic voltammetry（CV）, linear scan voltammetry（ LSV）, and potentiostatic electrolysis. The electrocatalytic activity and stability of a PbO2 electrode in sulfuric acid, acetic acid, and phosphoric acid were studied. The selectivity and the current efficiency for producing hydroxypivalic acid were explored with different supporting electrolytes, concentrations of HPAL, and pH values. The results show that higher selectivity and current efficiency for producing hydroxypivalic acid can be achieved when sulfuric acid with a high concentration is used as the supporting electrolyte and the selectivity and the current efficiency can reach 80% and 60%. resvectively.展开更多
采用固体渗硼法和水热法两步合成泡沫镍自支撑Ni_(3)S_(2)-Ni3B/NF电催化剂,通过XRD、SEM、TEM、XPS对催化剂进行结构、形貌及元素价态分析,并在含尿素的碱性电解液中探究其电化学性能。结果表明:由于异质界面优化了电子结构,暴露出丰...采用固体渗硼法和水热法两步合成泡沫镍自支撑Ni_(3)S_(2)-Ni3B/NF电催化剂,通过XRD、SEM、TEM、XPS对催化剂进行结构、形貌及元素价态分析,并在含尿素的碱性电解液中探究其电化学性能。结果表明:由于异质界面优化了电子结构,暴露出丰富的活性位点,Ni_(3)S_(2)-Ni3B/NF催化剂表现出优异的UOR活性,仅需要1.44 V vs RHE电压就能实现300 mA/cm^(2)电流密度;将Ni_(3)S_(2)-Ni3B/NF||Ni_(3)S_(2)-Ni3B/NF HER-UOR双电极系统用于尿素解耦制氢,在1.6 V低电池电压就能提供10 mA/cm^(2)电流密度,在1.6~1.9 V电压范围内能保持超过96%的产氢法拉第效率。展开更多
Glycerol is one of the most important biomass-based platform molecules,massively produced as a by-product in the biodiesel industry.Its high purification cost from the crude glycerol raw material limits its applicatio...Glycerol is one of the most important biomass-based platform molecules,massively produced as a by-product in the biodiesel industry.Its high purification cost from the crude glycerol raw material limits its application and demands new strategies for valorization.Compared to the conventional thermocatalytic strategies,the electrocatalytic strategies can not only enable the selective conversion at mild conditions but also pair up the cathodic reactions for the co-production with higher efficiencies.In this review,we summarize the recent advances of catalyst designs and mechanistic understandings for the electrocatalytic glycerol oxidation(GOR),and aim to provide an overview of the GOR process and the intrinsic structural-activity correlation for inspiring future work in this field.The review is dissected into three sections.We will first introduce the recent efforts of designing more efficient and selective catalysts for GOR,especially toward the production of value-added products.Then,we will summarize the current understandings about the reaction network based on the ex-situ and in-situ spectroscopic studies as well as the theoretical works.Lastly,we will select some representative examples of creating real electrochemical devices for the valorization of glycerol.By summarizing these previous efforts,we will provide our vision of future directions in the field of GOR toward real applications.展开更多
A Pt/CNTs catalyst coated with N‐doped carbon（xNC‐Pt/CNTs） is synthesized by atomic layer dep‐osition（ALD） and applied in methanol electrooxidation reaction. Pt nanoparticles and polyimide（PI） are sequentiall...A Pt/CNTs catalyst coated with N‐doped carbon（xNC‐Pt/CNTs） is synthesized by atomic layer dep‐osition（ALD） and applied in methanol electrooxidation reaction. Pt nanoparticles and polyimide（PI） are sequentially deposited on carbon nanotubes（CNTs） by ALD. After annealing at 600 °C in H2 atmosphere, the PI is carbonized to produce porous N‐doped carbon. Upon coating with a moder‐ately thick layer of N‐doped carbon, the optimized 50 NC‐Pt/CNTs show higher activity, better long‐term stability, and improved CO resistance towards methanol electrooxidation compared with Pt/CNTs and commercial Pt/C（20 wt%）. X‐ray photoelectron spectroscopy characterization result indicates that the Pt–CO bond is weakened after N‐doped carbon coating and CO adsorption on the Pt surface is weakened, leading to superior electrocatalytic performance.展开更多
基金National Natural Science Foundation of China (Nos. 42276035, 22309030)Guangdong Basic and Applied Basic Research Foundation (Nos. 2023A1515012589,2020A1515110473)Key Plat Form Programs and Technology Innovation Team Project of Guangdong Provincial Department of Education (Nos. 2019GCZX002, 2020KCXTD011)。
文摘Seawater electrolysis is a promising approach for sustainable energy without relying on precious freshwater.However,the large-scale seawater electrolysis is hindered by low catalytic efficiency and severe anode corrosion caused by the harmful chlorine.In contrast to the oxygen evolution reaction (OER)and chlorin ion oxidation reaction (ClOR),glycerol oxidation reaction (GOR) is more thermodynamically and kinetically favorable alternative.Herein,a Ru doping cobalt phosphide (Ru-CoP_(2)) is proposed as a robust bifunctional electrocatalyst for seawater electrolysis and GOR,for the concurrent productions of hydrogen and value-added formate.The in situ and ex situ characterization analyses demonstrated that Ru doping featured in the dynamic reconstruction process from Ru-CoP_(2)to Ru-CoOOH,accounting for the superior GOR performance.Further coupling GOR with hydrogen evolution was realized by employing Ru-CoP_(2)as both anode and cathode,requiring only a low voltage of 1.43 V at 100 mA cm^(-2),which was 250 m V lower than that in alkaline seawater.This work guides the design of bifunctional electrocatalysts for energy-efficient seawater electrolysis coupled with biomass resource upcycling.
基金supported by the Applied Basic Research Program of Yunnan Province(202101BE070001-032)Yunnan Major Scientific and Technological Projects(No.202202AG050001).
文摘The conversion of urea-containing wastewater into clean hydrogen energy has gained increasing attention.However,challenges remain,particularly with sluggish catalytic kinetics and limited long-term stability of urea oxidation reaction(UOR).Herein,we report the loosely porous CoOOH nano-architecture(CoOOH LPNAs)with hydrophilic surface and abundant oxygen vacancies(Ov)on carbon fiber paper(CFP)by electrochemical reconstruction of the CoP nanoneedles precursor.The resulting three-dimensional electrode exhibited an impressively low potential of 1.38 V at 1000 mA·cm^(−2) and excellent durability for UOR.Furthermore,when tested in an anion exchange membrane(AEM)electrolyzer,it required only 1.53 V at 1000 mA·cm^(−2) for industrial urea-assisted water splitting and operated stably for 100 h without degrada-tion.Experimental and theoretical investigations revealed that rich oxygen vacancies effectively modulate the electronic structure of the CoOOH while creating unique Co3-triangle sites with Co atoms close together.As a result,the adsorption and desorption processes of reactants and intermediates in UOR could be finely tuned,thereby significantly reducing ther-modynamic barriers.Additionally,the superhydrophilic self-supported nanoarray structure facilitated rapid gas bubble release,improving the overall efficiency of the reaction and preventing potential catalyst detachment caused by bubble accumulation,thereby improving both catalytic activity and stability at high current densities.
基金funded by Shanghai Pujiang Program(21PJD022)Hunan Provincial Natural Science Foundation(2023JJ60522).
文摘Balancing the adsorption of OH⁻and 5-hydroxymethylfurfural(HMF)is crucial in optimizing the competing HMF oxidation reaction and oxygen evolution reaction,especially given the polymerization tendency of HMF in alkaline solutions.Herein,we present an innovative approach for rapidly synthesizing a NiFe bimetallic metalorganic framework(MOF)induced by electron-withdrawing carbon quantum dot(EW-CQD)via electron beam irradiation within 2 min.EW-CQD serve as structural regulators,expanding the NiFe-MOF interlayer spacing,increasing reactive site availability,and more effectively balancing the adsorption of OH6(-) and HMF,thereby significantly boosting the oxidation activity of HMF.The resulting EW-CQD-MOF exhibits a low potential of 1.36 V vs.RHE at 10 mA cm^(-2)and maintains excellent durability over 120 h.Comprehensive in situ characterization elucidates the HMF oxidation reaction pathway,showing high selectivity towards 2,5-furandicarboxylic acid(FDCA)under ambient conditions,with an impressive HMF conversion rate of 94%and FDCA selectivity of 96%within 6 h.These findings underscore the critical role of structural optimization and adsorption balance in catalytic performance enhancement and offer valuable insights for designing high-efficiency catalysts,advancing sustainable catalytic processes.
基金financially supported by the Program for Professor of Special Appointment(Eastern Scholar)at SIHLProject of Shanghai Municipal Science and Technology Commission(No.22DZ2291100)+6 种基金Open Fund of Anhui International Joint Research Center for Nano Carbon-based Materials and Environmental Health(No.NCMEH2022Y02)Gaoyuan Discipline of Shanghai-Materials Science and Engineering,and Shanghai Polytechnic University-Drexel University Joint Research Center for Optoelectronics and Sensingsupported by the Science Fund for Distinguished Young Scholars of Fujian Province(No.2019J06027)the Open Project of Jiangsu Key Laboratory for Carbon-Based Functional Materials&Devices(Soochow University)(No.KS2022)Collaborative Innovation Center of Suzhou Nano Science&Technologythe 111 ProjectJoint International Research Laboratory of Carbon-Based Functional Materials and Devices。
文摘Metal-organic frameworks(MOFs)h ave attracted widespread attention due to their large surface area and porous structure.Rationally designing the nanostructures of MOFs to promote their application in ethanol electrooxidation is still a challenge.Here,a novel Cu-NCNs(Cu-nitrogen-doped carbon nanotubes)support was synthesized by pyrolysis of melamine(MEL)and Cu-ZIF-8 together,and then,Pd-Au nanoalloys were loaded by sodium borohydride reduction method to prepare PdAu@Cu-NCNs catalysts.The generating mesoporous carbon with high specific surface area and favorable electron and mass transport can be used as a potential excellent carrier for PdAu nanoparticles.In addition,the balance of catalyst composition and surface structure was tuned by controlling the content of Pd and Au.Thus,the best-performed Pd_(2)Au_(2)@Cu-NCN-1000-2(where 1000 means the carrier calcination temperature,and 2 means the calcination constant temperature time)catalyst exhibits better long-term stability and electrochemical activity for ethanol oxidation in alkaline media(4.80 A·mg^(-1)),which is 5.05 times higher than that of commercial Pd/C(0.95 A·mg^(-1)).Therefore,this work is beneficial to further promoting the application of MOFs in direct ethanol fuel cells(DEFCs)and can be used as inspiration for the design of more efficient catalyst support structures.
基金sponsored by National Natural Science Foundation of China(No.22202130)China Postdoctoral Science Foundation(No.2022M710088)+3 种基金Science and Technology Innovation Team of Shaanxi Province(Nos.2023-CX-TD-27 and 2022TD-35)Fundamental Research Funds for the Central Universities(Nos.GK202202001 and GK202101005)Open Funds of the State Key Laboratory of Electroanalytical Chemistry(No.SKLEAC202207)the 111 Project(No.B14041)。
文摘The selective electrochemical conversion of glycerol into value-added products is a green and sustainable strategy for the biomass utilization.In this work,Au nanowires(Au-NW)modified with polyethyleneimine(PEI)molecule(Au-NW@PEI)is obtained by an up-bottom post-modification approach.Physical characterization,molecular dynamics simulation and density functional theory demonstrate that the loose-packed PEI monolayer firmly and uniformly distribute on the Au-NW surface due to the strong Au-N interaction.Electrochemical experiments and product analysis display that PEI modification significantly enhance the electro-activity of Au-NW for the glycerol electro-oxidation reaction(GEOR)due to the electronic effect.Meanwhile,the steric hindrance and electrostatic effect of PEI layer make the optimizing adsorption of intermediates possible.Therefore,the selectivity of C3 product glyceric acid over Au-NW@PEI is increased by nearly 20%.The work thus indicates that the rational design of metal-organic interface can effectively elevate the electro-activity and selectivity of Au nanostructures,which may have wide application in biomass development.
基金supported by the National Research and Innovation Agency(BRIN)and Lembaga Pengelola Dana Pendidikan(LPDP)Ministry of Finance,Republic of Indonesia through Riset dan Inovasi Untuk Indonesia Maju(RIIM)scheme batch 2 with contract number 1/PG.02.00.PT/LPPM/IV/2024(110/IV/KS/11/2022).
文摘The pressing environmental concerns and the depletion of fossil fuel reserves necessitate a transition toward sustainable energy sources.Ethanol,a renewable biomass-derived fuel,is a promising alternative due to its availability and high energy density.This study investigates the synthesis of gold nanoparticles(Au NPs)via a square-wave pulse deposition technique,aiming to enhance catalytic activity for ethanol electrooxidation.By varying pulse durations,we were able to exert precise control over Au NP size and distribution without stabilizing agents.Characterization using field emission scanning electron microscopy and X-ray diffraction techniques confirmed the formation of clustered nanoparticles of metallic gold phase.Electrochemical characteristics analyses revealed that Au NPs synthesized with a 900 ms pulse duration exhibited the lowest charge transfer resistance and the highest electrochemically active surface area.The electrocatalytic performance test of these Au NPs demonstrated an anodic current density of 2.5 mA cm^-(2)and a Tafel slope of 78 mV dec^(-1),indicating superior catalytic performance and reaction kinetics.Additionally,the Au NPs showed high resistance to poisoning,as evidenced by a low j_(b)/j_(f)ratio of 0.28 and stable chronoamperometric response.These findings underscore the potential of this synthesis method for producing high-performance electrocatalysts utilized in exploiting ethanol's potential as an environmentally friendly energy carrier.
基金supported by the National Natural Science Foundation of China(22305101)the Natural Science Foundation of Jiangsu Province(BK20231032)+1 种基金the Fundamental Research Funds for the Central Universities(JUSRP123020)Startup Funding at Jiangnan University(1045219032220100).
文摘Constructing the desired long-range dual sites to enhance the C–C bond-cleavage and CO-tolerate ability during ethanol oxidation reaction is of importance for further applications.Herein,the concept of holding atomically dispersed NiO_(x)cluster supported on Pt-based high-index facets(NiO_(x)/Pt)is proposed to build O-bridged Pt–Ni dual sites.Strikingly,the obtained NiO_(x)/Pt dual sites show 4.97 times specific activity higher than that of commercial Pt/C(0.35 mA cm^(-2)),as well as outstanding CO-tolerance and durability.The advanced electrochemical in-situ characterizations reveal that the NiO_(x)/Pt can accelerate rapid dehydroxylation and C–C bondcleavage over the Pt–Ni dual sites.Theoretical calculations disclose that the atomically dispersed NiO_(x)species can lower the adsorption/reaction energy barriers of intermediates.This tactic provides a promising methodology on regulating the surface synergistic sites via engineering atomically dispersed oxide site.
基金supported by the National Natural Science Foundation of China(22472023,22202037)the Jilin Province Science and Technology Development Program(20250102077JC)the Fundamental Research Funds for the Central Universities(2412024QD014,2412023QD019).
文摘Direct ethanol fuel cells(DEFCs)are a promising alternative to conventional energy sources,offering high energy density,environmental sustainability,and operational safety.Compared to methanol fuel cells,DEFCs exhibit lower toxicity and a more mature preparation process.Unlike hydrogen fuel cells,DEFCs provide superior storage and transport feasibility,as well as cost-effectiveness,significantly enhancing their commercial viability.However,the stable C-C bond in ethanol creates a high activation energy barrier,often resulting in incomplete electrooxidation.Current commercial platinum(Pt)-and palladium(Pd)-based catalysts demonstrate low C-C bond cleavage efficiency(<7.5%),severely limiting DEFC energy output and power density.Furthermore,high catalyst costs and insufficient activity impede large-scale commercialization.Recent advances in DEFC anode catalyst design have focused on optimizing material composition and elucidating catalytic mechanisms.This review systematically examines developments in ethanol electrooxidation catalysts over the past five years,highlighting strategies to improve C1 pathway selectivity and C-C bond activation.Key approaches,such as alloying,nanostructure engineering,and interfacial synergy effects,are discussed alongside their mechanistic implications.Finally,we outline current challenges and future prospects for DEFC commercialization.
文摘The electrooxidation of CO on Ru (0001) and RuO2 (100) electrode surfaces were characterized by cyclic voltammetry, AES and RHEED. The CO adlayer was first partially oxidized at 0.8 V, which is controlled by the attack of oxygen species toward the Ru(0001) surface. The remaining CO adlayer oxidation at 0.55 V is related to the combination of CO molecules with oxygen species already located on the surface. In contrast, successive peaks on RuO2(100) at 0.4 V and 0.72 V are observed, which shows that CO molecules can directly react with two different lattice-oxygen on the surface to carbon dioxide.
基金funded by the National Natural Science Foundation of China(No.52402106)the Natural Science Foundation of Heilongjiang Province Jointly Guided Project(No.LH2023B010)the Planning Project of Heilongjiang Province Education Department(No.LJYXL2022-036)。
文摘Direct borohydride hydrogen peroxide fuel cells(DBHPFCs)are emerging as a transformative technology for sustainable energy conversion.Despite their potential,their efficiency is largely hindered by the limitations of the anode catalyst.In response to this challenge,we have developed a novel series of Co-based heterojunction metal-organic framework(MOF)derivatives,supported on reduced graphene oxide(rGO)-modified nickel foam(NF),to enhance borohydride electrooxidation performance.Our synthesis involves the thermal transformation of a ZIF67-Co(OH)_(2)-rGO/NF precursor within a controlled temperature between 300 and 750℃,yielding distinct phase heterostructures and pristine Co and CoO,verified by X-ray diffraction(XRD)and transmission electron microscopy(TEM)analyses.Additionally,the Ultraviolet photoelectron spectroscopy and theoretical calculation result further validate the formation of the heterojunction and direction of electron transfer along the interface as well as the BH_(4)^(-)adsorption behavior across the heterointerface.Notably,the catalyst annealed at 600℃,designated Co-CoO@C-rGO/NF-600,exhibits an exceptional oxidation current density of 2.5 A cm^(-2)at 0 V vs.Ag/AgCl in an electrolyte containing 2 mol L^(-1)NaOH and 0.4 mol L^(-1)NaBH_(4)Furthermore,the Co-CoO@C-rGO/NF-600 catalyst demonstrates remarkable performance as the anode catalyst in a DBHPFC assembly,achieving a peak power density of 385.73 mW cm^(-2)and demonstrating the enduring operational stability.The superior electrocatalytic performance is primarily attributed to the synergistic effects of Co-CoO nanoparticles rich in active heterointerfaces and the superior electron mobility afforded by the rGO scaffold.These results not only deepen our understanding of anode catalyst design for DBHPFCs but also pave the way for breakthroughs in electrocatalytic technologies,driving forward the quest for sustainable energy solutions.
基金supported by the National Natural Science Foundation of China (21633008,21673221)the Jilin Province Science and Technology Development Program (20160622037JC,20170203003SF,and 20170520150JH)+1 种基金the Hundred Talents Program of the Chinese Academy of Sciencesthe Recruitment Program of Foreign Experts (WQ20122200077)
文摘Direct methanol fuel cells （DMFCs） are very promising power source for stationary and portable miniatureelectric appliances due to its high efficiency and low emissions of pollutants. As the key material, cata-lysts for both cathode and anode face several problems which hinder the commercialization of DMFCs.In this review, we mainly focus on anode catalysts of DMFCs. The process and mechanism of methanolelectrooxidation on Pt and Pt-based catalysts in acidic medium have been introduced. The influences ofsize effect and morphology on electrocatalytic activity are discussed though whether there is a size effectin MOP, catalyst is under debate. Besides, the non Pt catalysts are also listed to emphasize though Pt isstill deemed as the indispensable element in anode catalyst of DMFCs in acidic medium. Different cata-lyst systems are compared to illustrate the level of research at present. ome debates need to be verifiedwith experimental evidences.
基金Supported by the National Natural Science Foundation of China(No. 20373020).
文摘The factors affecting the electrooxidation of hydroxypivalaldehyde（HPAL） in an undivided cell were studied by using cyclic voltammetry（CV）, linear scan voltammetry（ LSV）, and potentiostatic electrolysis. The electrocatalytic activity and stability of a PbO2 electrode in sulfuric acid, acetic acid, and phosphoric acid were studied. The selectivity and the current efficiency for producing hydroxypivalic acid were explored with different supporting electrolytes, concentrations of HPAL, and pH values. The results show that higher selectivity and current efficiency for producing hydroxypivalic acid can be achieved when sulfuric acid with a high concentration is used as the supporting electrolyte and the selectivity and the current efficiency can reach 80% and 60%. resvectively.
文摘采用固体渗硼法和水热法两步合成泡沫镍自支撑Ni_(3)S_(2)-Ni3B/NF电催化剂,通过XRD、SEM、TEM、XPS对催化剂进行结构、形貌及元素价态分析,并在含尿素的碱性电解液中探究其电化学性能。结果表明:由于异质界面优化了电子结构,暴露出丰富的活性位点,Ni_(3)S_(2)-Ni3B/NF催化剂表现出优异的UOR活性,仅需要1.44 V vs RHE电压就能实现300 mA/cm^(2)电流密度;将Ni_(3)S_(2)-Ni3B/NF||Ni_(3)S_(2)-Ni3B/NF HER-UOR双电极系统用于尿素解耦制氢,在1.6 V低电池电压就能提供10 mA/cm^(2)电流密度,在1.6~1.9 V电压范围内能保持超过96%的产氢法拉第效率。
文摘Glycerol is one of the most important biomass-based platform molecules,massively produced as a by-product in the biodiesel industry.Its high purification cost from the crude glycerol raw material limits its application and demands new strategies for valorization.Compared to the conventional thermocatalytic strategies,the electrocatalytic strategies can not only enable the selective conversion at mild conditions but also pair up the cathodic reactions for the co-production with higher efficiencies.In this review,we summarize the recent advances of catalyst designs and mechanistic understandings for the electrocatalytic glycerol oxidation(GOR),and aim to provide an overview of the GOR process and the intrinsic structural-activity correlation for inspiring future work in this field.The review is dissected into three sections.We will first introduce the recent efforts of designing more efficient and selective catalysts for GOR,especially toward the production of value-added products.Then,we will summarize the current understandings about the reaction network based on the ex-situ and in-situ spectroscopic studies as well as the theoretical works.Lastly,we will select some representative examples of creating real electrochemical devices for the valorization of glycerol.By summarizing these previous efforts,we will provide our vision of future directions in the field of GOR toward real applications.
基金supported by the National Natural Science Foundation of China (21403272, 21673269)the Natural Science Foundation of Shanxi Province (2015021046)~~
文摘A Pt/CNTs catalyst coated with N‐doped carbon（xNC‐Pt/CNTs） is synthesized by atomic layer dep‐osition（ALD） and applied in methanol electrooxidation reaction. Pt nanoparticles and polyimide（PI） are sequentially deposited on carbon nanotubes（CNTs） by ALD. After annealing at 600 °C in H2 atmosphere, the PI is carbonized to produce porous N‐doped carbon. Upon coating with a moder‐ately thick layer of N‐doped carbon, the optimized 50 NC‐Pt/CNTs show higher activity, better long‐term stability, and improved CO resistance towards methanol electrooxidation compared with Pt/CNTs and commercial Pt/C（20 wt%）. X‐ray photoelectron spectroscopy characterization result indicates that the Pt–CO bond is weakened after N‐doped carbon coating and CO adsorption on the Pt surface is weakened, leading to superior electrocatalytic performance.
