The insufficient performance of Pt and Pd benchmark catalysts remains a significant obstacle to the practical application of direct liquid fuel cells.In this study,we report a synthesis of amorphous PdSe/crystalline P...The insufficient performance of Pt and Pd benchmark catalysts remains a significant obstacle to the practical application of direct liquid fuel cells.In this study,we report a synthesis of amorphous PdSe/crystalline Pt nanoparticles(AC-PdPtSe NPs)by chemical leaching of PdPtSe NPs.AC-PdPtSe NPs display significantly enhanced activity and stability for the electrooxidation of ethylene glycol and glycerol,far surpassing that of amorphous-dominant PdPtSe NPs,commercial Pd/C,and Pt/C catalysts.Notably,the integration of crystalline and amorphous domains leverages the advantages of high electrical conductivity and a wealth of active sites,which can substantially accelerate reaction kinetics.Furthermore,detailed investigations reveal that the boundary between the Pt crystalline and PdSe amorphous phases induces a 3%surface tensile strain.The formation of amorphous-crystalline heterointerfaces optimizes the d-band states,thereby strengthening the adsorption and activation of ethylene glycol and glycerol.This study highlights the advance in phase engineering toward the development of highly active noble-metal nanostructures.展开更多
The development of electrocatalysts that both work effectively at industrial current density and resist chloride ion(Cl^(-))corrosion remains a key challenge for hydrogen production from Cl^(-)-rich alkaline water.Her...The development of electrocatalysts that both work effectively at industrial current density and resist chloride ion(Cl^(-))corrosion remains a key challenge for hydrogen production from Cl^(-)-rich alkaline water.Herein,we report a CrO_(x)-engineered nickel-based oxide catalyst(FeCoCrO_(x)/NF)that achieves exceptional activity and stability through a dual-functional interfacial mechanism.Combing in situ Raman spectroscopy,18O isotopic labeling,and electrochemical analysis,we demonstrate that the oxygen evolution reaction follows a lattice oxygen-mediated mechanism.The CrO_(x)layer selectively adsorbs hydroxide ions,forming a dynamic interfacial barrier that electrostatically repels Cl^(-)ingress,thereby mitigating Cl^(-)corrosion.Through enthalpy-based analysis,we demonstrate that electronic redistribution via Cr-O-Fe bonding increases the vacancy formation energy of Fe,thereby suppressing its dissolution.In alkaline electrolyte containing 0.5 M Cl^(-)(1.0 M KOH),the catalyst is operating continuously for 1400 h at an industrial current density of 1000 mA cm^(-2).Furthermore,the catalyst retains 99.5%of its initial activity under fluctuating current density(100-1000 mA cm^(-2)),demonstrating robustness required for industrial electrolyzers.This study establishes a paradigm for designing corrosion-resistant electrocatalysts through the synergistic modulation of interfacial ion selectivity and bulk lattice oxygen activation,advancing the application of green hydrogen production in Cl^(-)-rich alkaline water.展开更多
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
Nickel-based catalysts display promising potential in integrated hydrogen production through methanol electrooxidation(MOR).The unavoidable selfoxidation from Ni(OH)_(2)to NiOOH severely restricts their MOR performanc...Nickel-based catalysts display promising potential in integrated hydrogen production through methanol electrooxidation(MOR).The unavoidable selfoxidation from Ni(OH)_(2)to NiOOH severely restricts their MOR performance.To inspire the progress of MOR before self-oxidation of Ni species by altering reaction pathways,a heterostructured Ni-WO_(2)catalyst is constructed to follow the direct electrooxidation pathway of methanol.Insitu/ex-situ characterization techniques combined with density functional theory calculations reveal the constructed Ni-WO_(2)hetero structure alters the electronic structure of Ni site.It's found Ni-Ni bond in Ni-WO_(2)becomes longer and the electrons transfer from Ni sites to W sites.This results in up shifted d band center of Ni site and its closing to the Fermi energy level,which optimizes the CH_(3)OH adsorption and the deprotonation of*CH_(3)O into*CH_(2)O in potential-determining step.Moreover,the formed asymmetric adsorption sites increase the polarity of the methanol and the intermediate.As expected,CH_(3)OH molecule is highly converted into HCOOH via direct electrooxidation pathway.This obtained Ni-WO_(2)exhibits superior MOR activity with high peak current density of 325.26 mA cm^(-2) and performs long term of 90 h at10 mA cm^(-2) in hydrogen production.This work provides an important guidance for designing efficient Ni-based samples for direct electrooxidation of methanol.展开更多
Multi-components landfill leachate is one type of wastewater that is challenging to deal with.The excellent degrading ability and low secondary pollution of electrochemical oxidation make it a promising technology for...Multi-components landfill leachate is one type of wastewater that is challenging to deal with.The excellent degrading ability and low secondary pollution of electrochemical oxidation make it a promising technology for leachate treatment.However,the commercial application of this method is restricted by some technical barriers such as limited anode activity and intricate operating conditions.To improve the efficiency of electrochemical leachate treatment,many researchers commit to developing efficient electrode and optimizing operation process for eliminating these limitations.This review summarized the recently studied countermeasures for accelerating the performance of electrochemical oxidation of leachate with respect to the electron transfer,active sites and stability of electrode.The performance of electrochemical leachate treatment with different anode and the corresponding underlying mechanisms were summarized and discussed.Besides,the effects of critical parameters including temperature,pH,current density and electrolyte on reaction were discussed.With these in mind,this work offers recommendations for the improvement of electrooxidation performance as well as direction for the design of leachate treatment engineering.展开更多
In direct ethylene glycol fuel cells,advanced anodic electrocatalysts are urgently required to achieve high energy efficiency and optimal fuel utilization for complete ethylene glycol electrooxidation.In this work,bim...In direct ethylene glycol fuel cells,advanced anodic electrocatalysts are urgently required to achieve high energy efficiency and optimal fuel utilization for complete ethylene glycol electrooxidation.In this work,bimetallic PtRh nanodendrites(PtRh NDs)with a three-dimensionally self-supporting structure,abundant(100)crystal facets,and numerous Pt/Rh active sites are synthesized using a simple wet chemical reduction method.The as-synthesized PtRh NDs exhibit outstanding electrocatalytic activity and remarkable selectivity for the ethylene glycol oxidation reaction(EGOR)in alkaline media,significantly enhancing the utilization of ethylene glycol fuel in fuel cells.Theoretical calculations demonstrate that the exposure of(100)crystal faces and the incorporation of Rh atoms play crucial roles in improving the activity and selectivity of EGOR.The present work not only provides an effective method for the synthesis of PtRh NDs with rich(100)crystal faces but also provides new insights into the synergistic effects between the crystal faces and the components in the electrocata lytic process.展开更多
Ni-based materials,widely recognized for their exceptional catalytic properties,experience structural transformations that profoundly influence their performance characteristics and operational stability.To deeply und...Ni-based materials,widely recognized for their exceptional catalytic properties,experience structural transformations that profoundly influence their performance characteristics and operational stability.To deeply understand the reconstruction mechanism of Ni-based catalysts,this review systematically summarizes the advanced strategies tailoring the dynamic reconstruction process,including electrochemical activation,defect engineering,partial etching,ionic doping,and heterostructure construction.Furthermore,we discuss the implications of these surface transformations on catalytic activity,highlighting their role in optimizing reaction pathways and enhancing overall efficiency in various electrooxidation reactions,such as oxygen evolution reaction(OER),urea oxidation reaction(UOR),glycerol oxidation reaction(GOR),hydroxymethylfurfural oxidation reaction(HMFOR),and ammonia oxidation reaction(AOR).By summarizing recent research findings,this review aims to provide a systematical summary of how surface dynamics can be harnessed to improve the design of Ni-based catalysts for a variety of electrooxidation applications,paving the way for advancements in energy conversion and storage technologies.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
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
The electrochemical oxidation of biomass-derived platform molecule 5-hydroxymethylfurfural(HMF)represents a crucial pathway for green transformation into high-value chemicals,yet its reaction pathway selectivity,effic...The electrochemical oxidation of biomass-derived platform molecule 5-hydroxymethylfurfural(HMF)represents a crucial pathway for green transformation into high-value chemicals,yet its reaction pathway selectivity,efficiency,and catalyst stability are strongly dependent on the electrolyte pH environment.Under alkaline conditions,high OH−concentration facilitates preferential aldehyde group oxidation and efficient deprotonation,enabling highly efficient synthesis of 2,5-furandicarboxylic acid,but simultaneously induces HMF self-degradation and complicates product separation.As pH decreases,the reaction mechanism shifts toward enhanced hydroxymethyl oxidation,leading to intermediate accumulation(such as 5-hydroxymethyl-2-furancarboxylic acid,2,5-diformylfuran,and 5-formyl-2-furancarboxylic acid)with challenging selectivity control and significantly slowed reaction kinetics.This review comprehensively examines the systematic differences in HMF oxidation pathways and surface catalytic mechanisms across the full pH range from alkaline to acidic conditions.Addressing the distinct reaction characteristics and core challenges in alkaline,near-neutral,and acidic media,we systematically evaluate design strategies for high-efficiency electrocatalysts and explore reactor design aspects.Future research should focus on process integration(with tailored reactor design)for energy consumption reduction in alkaline systems,targeted synthesis of diverse oxidation products in near-neutral systems,and innovative catalyst development for acidic systems,thereby advancing the efficiency,selectivity,and practical application of HMF electrooxidation technologies across the entire pH spectrum through synergistic optimization of catalyst,reactor,and process.展开更多
The electrocatalytic oxidation of 5-hydroxymethylfurfural(HMF)offers a promising approach for producing high-value chemicals and hydrogen.While cobalt-based oxides are promising catalysts for the HMF oxidation reactio...The electrocatalytic oxidation of 5-hydroxymethylfurfural(HMF)offers a promising approach for producing high-value chemicals and hydrogen.While cobalt-based oxides are promising catalysts for the HMF oxidation reaction(HMFOR),their performance is limited by inefficient oxidation of CoO_(x)to the active CoO_(2)phase.Here,we demonstrate that introducing oxygen vacancies into CoO_(x)significantly enhances its oxidation kinetics.The oxygen vacancy-rich CoO_(x)supported on copper foam(CoO_(x)/CF)achieves an impressive 98%HMF conversion with a Faradaic efficiency of 98.6%at 1.5 V vs.RHE.Operando Raman spectroscopy reveals that oxygen vacancies facilitate the preferential formation ofγ-CoOOH overβ-CoOOH during electrocatalysis,thereby promoting the generation of the active CoO_(2)phase.Combining in situ infrared spectroscopy with density functional theory(DFT)calculations,we unambiguously establish the reaction pathway,which proceeds via the sequence of HMF→5-hydroxymethyl-2-fur ancarboxylic acid(HMFCA)→2-formyl-5-furancarboxylic acid(FFCA)→2,5-furandicarboxylic acid(FDCA),and reveal the pivotal role of the active CoO_(2)species in accelerating hydroxyl radical oxidation.This work not only provides fundamental mechanistic insights into oxygen vacancy-mediated catalyst design but also offers a novel strategy for developing high-performance transition metal oxide electrocatalysts for biomass valorization.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
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
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
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
Electrocatalysts for ethanol oxidation reaction(EOR)are generally limited by their poor durability because of the catalyst poisoning induced by the reaction intermediate carbon monoxide(CO).Therefore,the rapid oxidati...Electrocatalysts for ethanol oxidation reaction(EOR)are generally limited by their poor durability because of the catalyst poisoning induced by the reaction intermediate carbon monoxide(CO).Therefore,the rapid oxidation removal of CO intermediates is crucial to the durability of EOR-based catalysts.Herein,in order to effectively avoiding the catalyst CO poisoning and improve the durability,the graphene-nickel nitride hybrids(AG-Ni_(3)N)were designed for supporting palladium nanoparticles(Pd/AG-Ni_(3)N)and then used for ethanol electrooxidation.The density functional theory(DFT)calculations demonstrated the introduction of AG-Ni_(3)N depresses the CO absorption and simultaneously promotes the adsorption of OH species for CO oxidation removal.The fabricated Pd/AG-Ni_(3)N catalyst distinctively exhibits excellent electroactivity with the mass catalytic activity of 3499.5 m A mg^(-1) on EOR in alkaline media,which is around 5.24 times higher than Pd/C(commercial catalyst).Notably,the Pd/AG-Ni_(3)N hybrids display excellent stability and durability after chronoamperometric measurements with a total operation time of 150,000 s.展开更多
基金supported by the National Natural Science Foundation of China(Nos.52274304,52073199).
文摘The insufficient performance of Pt and Pd benchmark catalysts remains a significant obstacle to the practical application of direct liquid fuel cells.In this study,we report a synthesis of amorphous PdSe/crystalline Pt nanoparticles(AC-PdPtSe NPs)by chemical leaching of PdPtSe NPs.AC-PdPtSe NPs display significantly enhanced activity and stability for the electrooxidation of ethylene glycol and glycerol,far surpassing that of amorphous-dominant PdPtSe NPs,commercial Pd/C,and Pt/C catalysts.Notably,the integration of crystalline and amorphous domains leverages the advantages of high electrical conductivity and a wealth of active sites,which can substantially accelerate reaction kinetics.Furthermore,detailed investigations reveal that the boundary between the Pt crystalline and PdSe amorphous phases induces a 3%surface tensile strain.The formation of amorphous-crystalline heterointerfaces optimizes the d-band states,thereby strengthening the adsorption and activation of ethylene glycol and glycerol.This study highlights the advance in phase engineering toward the development of highly active noble-metal nanostructures.
基金supported by the National Nature Science Foundation of China under Grant No.22269021the Tianshan Talent Project of Xinjiang Uygur Autonomous Region:2023TSYCQNTJ0039the Open project of Key Laboratory in Xinjiang Uygur Autonomous Region of China:2023D04027。
文摘The development of electrocatalysts that both work effectively at industrial current density and resist chloride ion(Cl^(-))corrosion remains a key challenge for hydrogen production from Cl^(-)-rich alkaline water.Herein,we report a CrO_(x)-engineered nickel-based oxide catalyst(FeCoCrO_(x)/NF)that achieves exceptional activity and stability through a dual-functional interfacial mechanism.Combing in situ Raman spectroscopy,18O isotopic labeling,and electrochemical analysis,we demonstrate that the oxygen evolution reaction follows a lattice oxygen-mediated mechanism.The CrO_(x)layer selectively adsorbs hydroxide ions,forming a dynamic interfacial barrier that electrostatically repels Cl^(-)ingress,thereby mitigating Cl^(-)corrosion.Through enthalpy-based analysis,we demonstrate that electronic redistribution via Cr-O-Fe bonding increases the vacancy formation energy of Fe,thereby suppressing its dissolution.In alkaline electrolyte containing 0.5 M Cl^(-)(1.0 M KOH),the catalyst is operating continuously for 1400 h at an industrial current density of 1000 mA cm^(-2).Furthermore,the catalyst retains 99.5%of its initial activity under fluctuating current density(100-1000 mA cm^(-2)),demonstrating robustness required for industrial electrolyzers.This study establishes a paradigm for designing corrosion-resistant electrocatalysts through the synergistic modulation of interfacial ion selectivity and bulk lattice oxygen activation,advancing the application of green hydrogen production in Cl^(-)-rich alkaline water.
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financially supported by the National Natural Science Foundation of China(Nos.U24A2023 and 21571119)the Natural Science Foundation of Shanxi Province(No.202203021221136)+4 种基金"Chunhui Plan"Cooperative Scientific Research Project of Education Ministry(No.HZKY20220510)the Scientific and Technological Innovation Programs of Higher Education Institution in Shanxi(No.2019L0466)the Graduate Education Innovation Project of Shanxi Province(Nos.2023JG093,2024KY421,and 2024XSY43)the Graduate Education Innovation Project of Shanxi Normal University(No.2021XSY038)1331 Engineering of Shanxi Province
文摘Nickel-based catalysts display promising potential in integrated hydrogen production through methanol electrooxidation(MOR).The unavoidable selfoxidation from Ni(OH)_(2)to NiOOH severely restricts their MOR performance.To inspire the progress of MOR before self-oxidation of Ni species by altering reaction pathways,a heterostructured Ni-WO_(2)catalyst is constructed to follow the direct electrooxidation pathway of methanol.Insitu/ex-situ characterization techniques combined with density functional theory calculations reveal the constructed Ni-WO_(2)hetero structure alters the electronic structure of Ni site.It's found Ni-Ni bond in Ni-WO_(2)becomes longer and the electrons transfer from Ni sites to W sites.This results in up shifted d band center of Ni site and its closing to the Fermi energy level,which optimizes the CH_(3)OH adsorption and the deprotonation of*CH_(3)O into*CH_(2)O in potential-determining step.Moreover,the formed asymmetric adsorption sites increase the polarity of the methanol and the intermediate.As expected,CH_(3)OH molecule is highly converted into HCOOH via direct electrooxidation pathway.This obtained Ni-WO_(2)exhibits superior MOR activity with high peak current density of 325.26 mA cm^(-2) and performs long term of 90 h at10 mA cm^(-2) in hydrogen production.This work provides an important guidance for designing efficient Ni-based samples for direct electrooxidation of methanol.
基金financially supported by the Innovative Research Groups of the National Natural Science Foundation of China(No.52121004)the project of National Natural Science Foundation(No.U21A20294)+1 种基金the Scientific Foundation of Hunan Province(Nos.2024RC1012,2022JJ40622)The Technology Innovation Guidance Project of Jiangxi Province,China(Nos.20203BDH80W017,20212BDH81030)。
文摘Multi-components landfill leachate is one type of wastewater that is challenging to deal with.The excellent degrading ability and low secondary pollution of electrochemical oxidation make it a promising technology for leachate treatment.However,the commercial application of this method is restricted by some technical barriers such as limited anode activity and intricate operating conditions.To improve the efficiency of electrochemical leachate treatment,many researchers commit to developing efficient electrode and optimizing operation process for eliminating these limitations.This review summarized the recently studied countermeasures for accelerating the performance of electrochemical oxidation of leachate with respect to the electron transfer,active sites and stability of electrode.The performance of electrochemical leachate treatment with different anode and the corresponding underlying mechanisms were summarized and discussed.Besides,the effects of critical parameters including temperature,pH,current density and electrolyte on reaction were discussed.With these in mind,this work offers recommendations for the improvement of electrooxidation performance as well as direction for the design of leachate treatment engineering.
基金sponsored by the National Natural Science Foundation of China(22272103)the Programs of Science and Technology of Suzhou in China(ZXL2021448 and SYG202137)+4 种基金Science and Technology Innovation Team of Shaanxi Province(2022TD-35 and 2023-CX-TD-27)the Young Scientist Initiative Project of School of Materials Science and Engineering at Shaanxi Normal University(2024YSIP-MSE-SNNU004)the Fundamental Research Funds for the Central Universities(GK202505036)the Technology Innovation Leading Program of Shaanxi in ChinaSanqin Scholars Innovation Teams in Shaanxi Province in China。
文摘In direct ethylene glycol fuel cells,advanced anodic electrocatalysts are urgently required to achieve high energy efficiency and optimal fuel utilization for complete ethylene glycol electrooxidation.In this work,bimetallic PtRh nanodendrites(PtRh NDs)with a three-dimensionally self-supporting structure,abundant(100)crystal facets,and numerous Pt/Rh active sites are synthesized using a simple wet chemical reduction method.The as-synthesized PtRh NDs exhibit outstanding electrocatalytic activity and remarkable selectivity for the ethylene glycol oxidation reaction(EGOR)in alkaline media,significantly enhancing the utilization of ethylene glycol fuel in fuel cells.Theoretical calculations demonstrate that the exposure of(100)crystal faces and the incorporation of Rh atoms play crucial roles in improving the activity and selectivity of EGOR.The present work not only provides an effective method for the synthesis of PtRh NDs with rich(100)crystal faces but also provides new insights into the synergistic effects between the crystal faces and the components in the electrocata lytic process.
基金supported by National Natural Science Foundation of China(Nos.52073199 and 52274304)。
文摘Ni-based materials,widely recognized for their exceptional catalytic properties,experience structural transformations that profoundly influence their performance characteristics and operational stability.To deeply understand the reconstruction mechanism of Ni-based catalysts,this review systematically summarizes the advanced strategies tailoring the dynamic reconstruction process,including electrochemical activation,defect engineering,partial etching,ionic doping,and heterostructure construction.Furthermore,we discuss the implications of these surface transformations on catalytic activity,highlighting their role in optimizing reaction pathways and enhancing overall efficiency in various electrooxidation reactions,such as oxygen evolution reaction(OER),urea oxidation reaction(UOR),glycerol oxidation reaction(GOR),hydroxymethylfurfural oxidation reaction(HMFOR),and ammonia oxidation reaction(AOR).By summarizing recent research findings,this review aims to provide a systematical summary of how surface dynamics can be harnessed to improve the design of Ni-based catalysts for a variety of electrooxidation applications,paving the way for advancements in energy conversion and storage technologies.
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.
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supported by the National Key R&D Program of China(2023YFA1507400)the National Natural Science Foundation of China(Grant No.22325805,22441010,22408203)+2 种基金Beijing Natural Science Foundation(Grant No.JQ22003)the Haihe Laboratory of Sustainable Chemical Transformations(24HHWCSS00007)Tsinghua University Dushi Program,and Sinopec Group(PR20232572).
文摘The electrochemical oxidation of biomass-derived platform molecule 5-hydroxymethylfurfural(HMF)represents a crucial pathway for green transformation into high-value chemicals,yet its reaction pathway selectivity,efficiency,and catalyst stability are strongly dependent on the electrolyte pH environment.Under alkaline conditions,high OH−concentration facilitates preferential aldehyde group oxidation and efficient deprotonation,enabling highly efficient synthesis of 2,5-furandicarboxylic acid,but simultaneously induces HMF self-degradation and complicates product separation.As pH decreases,the reaction mechanism shifts toward enhanced hydroxymethyl oxidation,leading to intermediate accumulation(such as 5-hydroxymethyl-2-furancarboxylic acid,2,5-diformylfuran,and 5-formyl-2-furancarboxylic acid)with challenging selectivity control and significantly slowed reaction kinetics.This review comprehensively examines the systematic differences in HMF oxidation pathways and surface catalytic mechanisms across the full pH range from alkaline to acidic conditions.Addressing the distinct reaction characteristics and core challenges in alkaline,near-neutral,and acidic media,we systematically evaluate design strategies for high-efficiency electrocatalysts and explore reactor design aspects.Future research should focus on process integration(with tailored reactor design)for energy consumption reduction in alkaline systems,targeted synthesis of diverse oxidation products in near-neutral systems,and innovative catalyst development for acidic systems,thereby advancing the efficiency,selectivity,and practical application of HMF electrooxidation technologies across the entire pH spectrum through synergistic optimization of catalyst,reactor,and process.
基金financial support from the National Natural Science Foundation of China(Nos.22308246,22478278)the Central Government Guides the Local Science and Technology Development Special Fund(No.YDZJSX20231A015)the Fundamental Research Program of Shanxi Province(No.202203021212266)。
文摘The electrocatalytic oxidation of 5-hydroxymethylfurfural(HMF)offers a promising approach for producing high-value chemicals and hydrogen.While cobalt-based oxides are promising catalysts for the HMF oxidation reaction(HMFOR),their performance is limited by inefficient oxidation of CoO_(x)to the active CoO_(2)phase.Here,we demonstrate that introducing oxygen vacancies into CoO_(x)significantly enhances its oxidation kinetics.The oxygen vacancy-rich CoO_(x)supported on copper foam(CoO_(x)/CF)achieves an impressive 98%HMF conversion with a Faradaic efficiency of 98.6%at 1.5 V vs.RHE.Operando Raman spectroscopy reveals that oxygen vacancies facilitate the preferential formation ofγ-CoOOH overβ-CoOOH during electrocatalysis,thereby promoting the generation of the active CoO_(2)phase.Combining in situ infrared spectroscopy with density functional theory(DFT)calculations,we unambiguously establish the reaction pathway,which proceeds via the sequence of HMF→5-hydroxymethyl-2-fur ancarboxylic acid(HMFCA)→2-formyl-5-furancarboxylic acid(FFCA)→2,5-furandicarboxylic acid(FDCA),and reveal the pivotal role of the active CoO_(2)species in accelerating hydroxyl radical oxidation.This work not only provides fundamental mechanistic insights into oxygen vacancy-mediated catalyst design but also offers a novel strategy for developing high-performance transition metal oxide electrocatalysts for biomass valorization.
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.
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(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.
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.
基金funded by the National Natural Science Foundation of China(No.91745112)sponsored by Shanghai Rising-Star Program(No.19QA1404100)+1 种基金Financial support from the Science and Technology Commission of Shanghai Municipality(Nos.19DZ2271100 and 18020500800)the support from the Opening Project of PCOSS,Xiamen University,201910。
文摘Electrocatalysts for ethanol oxidation reaction(EOR)are generally limited by their poor durability because of the catalyst poisoning induced by the reaction intermediate carbon monoxide(CO).Therefore,the rapid oxidation removal of CO intermediates is crucial to the durability of EOR-based catalysts.Herein,in order to effectively avoiding the catalyst CO poisoning and improve the durability,the graphene-nickel nitride hybrids(AG-Ni_(3)N)were designed for supporting palladium nanoparticles(Pd/AG-Ni_(3)N)and then used for ethanol electrooxidation.The density functional theory(DFT)calculations demonstrated the introduction of AG-Ni_(3)N depresses the CO absorption and simultaneously promotes the adsorption of OH species for CO oxidation removal.The fabricated Pd/AG-Ni_(3)N catalyst distinctively exhibits excellent electroactivity with the mass catalytic activity of 3499.5 m A mg^(-1) on EOR in alkaline media,which is around 5.24 times higher than Pd/C(commercial catalyst).Notably,the Pd/AG-Ni_(3)N hybrids display excellent stability and durability after chronoamperometric measurements with a total operation time of 150,000 s.
