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 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
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
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
A core shell structured C@MoxTi1-xO2-δnanocrystal with a functionalized interface(C@MTNC-FI)was fabricated via the hydrothermal method with subsequent annealing derived from tetrabutyl orthotitanate.The formation of ...A core shell structured C@MoxTi1-xO2-δnanocrystal with a functionalized interface(C@MTNC-FI)was fabricated via the hydrothermal method with subsequent annealing derived from tetrabutyl orthotitanate.The formation of anatase TiO2 was inhibited by the simultaneous presence of the hydrothermal etching/regrowth process,infiltration of Mo dopants and carbon coating,which endows the C@MTNC-FI with an ultrafine crystalline architecture that has a Mo-functionalized interface and carbon-coated shell.Pt Ru nanoparticles(NPs)were supported on C@MTNC-FI by employing a microwave-assisted polyol process(MAPP).The obtained Pt Ru/C@MTNC-FI catalyst has 2.68 times higher mass activity towards methanol electrooxidation than that of the un-functionalized catalyst(Pt Ru/C@TNC)and 1.65 times higher mass activity than that of Pt Ru/C catalyst with over 25%increase in durability.The improved catalytic performance is due to several aspects including ultrafine crystals of TiO2 with abundant grain boundaries,Mofunctionalized interface with enhanced electron interactions,and core shell architecture with excellent electrical transport properties.This work suggests the potential application of an interface-functionalized crystalline material as a sustainable and clean energy solution.展开更多
Carbon modified TiO_2 nanobelts(TiO_2-C) were synthesized using a hydrothermal growth method,as a support material for palladium(Pd) nanoparticles(Pd/TiO_2-C) to improve the electrocatalytic performance for methanol e...Carbon modified TiO_2 nanobelts(TiO_2-C) were synthesized using a hydrothermal growth method,as a support material for palladium(Pd) nanoparticles(Pd/TiO_2-C) to improve the electrocatalytic performance for methanol electrooxidation by comparison to Pd nanoparticles on bare TiO_2 nanobelts(Pd/TiO_2)and activated carbon(Pd/AC). Cyclic voltammetry characterization was conducted with respect to saturated calomel electrode(SCE) in an alkaline methanol solution, and the results indicate that the specific activity of Pd/TiO_2-C is 2.2 times that of Pd/AC and 1.5 times that of Pd/TiO_2. Chronoamperometry results revealed that the TiO_2-C support was comparable in stability to activated carbon, but possesses an enhanced current density for methanol oxidation at a potential of -0.2 V vs. SCE. The current study demonstrates the potential of Pd nanoparticle loaded on hierarchical TiO_2-C nanobelts for electrocatalytic applications such as fuel cells and batteries.展开更多
Direct liquid fuel cells(DLFCs) have received increasing attention because of their high energy densities,instant recharging abilities, simple cell structure, and facile storage and transport. The main challenge for t...Direct liquid fuel cells(DLFCs) have received increasing attention because of their high energy densities,instant recharging abilities, simple cell structure, and facile storage and transport. The main challenge for the commercialization of DLFCs is the high loading requirement of platinum group metals(PGMs) as catalysts. Atomically dispersed catalysts(ADCs) have been brought into recent focus for DLFCs due to their well-defined active sites, high selectivity, maximal atom-utilization, and anti-poisoning property. In this review, we summarized the structure–property relationship for unveiling the underlying mechanisms of ADCs for DLFCs. More specifically, different types of fuels used in DLFCs such as methanol, formic acid,and ethanol were discussed. At last, we highlighted current challenges, research directions, and future outlooks towards the practical application of DLFCs.展开更多
In situ and simultaneous remediation of a variety of pollutants in sediments remains a challenge.In this study,we report that the combination of electrocoagulation(EC)and electrooxidation(EO)is efficient in the immobi...In situ and simultaneous remediation of a variety of pollutants in sediments remains a challenge.In this study,we report that the combination of electrocoagulation(EC)and electrooxidation(EO)is efficient in the immobilization of phosphorus and heavymetals and in the oxidation of ammonium and toxic organicmatter.The integratedmixed metal oxide(MMO)/Fe anode system allowed the facile removal of ammonium and phosphorus in the overlying water(99% of 10 mg/L NH_(4)^(+)-N and 95% of 10 mg/L P disappeared in 15 and 30 min,respectively).Compared with the controls of the single Fe anode and single MMO anode systems,the dual MMO/Fe anode system significantly improved the removal of phenanthrene and promoted the transition of Pb and Cu from the mobile species to the immobile species.The concentrations of Pb and Cu in the toxicity characteristic leaching procedure extracts were reduced by 99%and 97% after an 8 hr operation.Further tests with four real polluted samples indicated that substantial proportions of acid-soluble fraction Pb and Cu were reduced(30%-31% for Pb and 16%–23% for Cu),and the amounts of total organic carbon and NH_(4)^(+)-N decreased by 56%–71% and 32%–63%,respectively.It was proposed that the in situ electrogenerated Fe(II)at the Fe anode and the active oxygen/chlorine species at the MMO anode are conducive to outstanding performance in the co-treatment of multiple pollutants.The results suggest that the EC/EO method is a powerful technology for the in situ remediation of sediments contaminated with different pollutants.展开更多
Better understanding of electrochemical reaction behaviors of hydrazine electrooxidation at metal phosphides has long been desired and the optimization of reaction kinetics has been proved to be operable.Herein,the de...Better understanding of electrochemical reaction behaviors of hydrazine electrooxidation at metal phosphides has long been desired and the optimization of reaction kinetics has been proved to be operable.Herein,the dehydrogenation kinetics of hydrazine electrooxidation at Ni_(2)P is adjusted by Co as the(Ni_(0.6)Co_(0.4))_(2)P catalyzes HzOR effectively with onset potential of–45 mV and only 113 mV is needed to drive the current density of 50 mA cm^(‒2),showing over 60 mV lower than Ni_(2)P and Co_(2)P.It also delivers the maximum power density of 263.0 mW cm^(-2) for direct hydrazine fuel cell.Detailed experimental results revealed that Co doping not only decreases the adsorption energy of N_(2)H_(4) on Ni sites,lowering the energy barrier for dehydrogenation,but also acts as the active sites in the optimal reaction coordination to boost the reaction kinetics.This work represents a breakthrough in improving the catalytic performance of non‐precious metal electrocatalysts for hydrazine electrooxidation and highlights an energy‐saving electrochemical hydrogen production method.展开更多
The synthesis of ultrasmall metal nanoclusters(NCs) with high catalytic activities is of great importance for the development of clean and renewable energy technologies but remains a challenge. Here we report a facile...The synthesis of ultrasmall metal nanoclusters(NCs) with high catalytic activities is of great importance for the development of clean and renewable energy technologies but remains a challenge. Here we report a facile wet-chemical method to prepare ~1.0 nm Au Pd NCs supported on amine-functionalized carbon blacks. The Au Pd NCs exhibit a specific activity of 5.98 mA cm_(AuPd)^(-2)and mass activity of 5.25 A mg_(auPd)^(-1) for ethanol electrooxidation, which are far better than those of commercial Pd/C catalysts(1.74 mAcm_(AuPd)^(-2) and 0.54 A mg_(Pd)^(-1) ). For formic acid dehydrogenation, the Au Pd NCs have an initial turn over frequency of 49339 h^(-1) at 298 K without any additive, which is much higher than those obtained for most of reported Au Pd catalysts. The reported synthesis may represent a facile and low-cost approach to prepare other ultrasmall metal NCs with high catalytic activities for various applications.展开更多
Carbon supported Pt（Pt/C） electrocatalysts were prepared with glucose as protection agent and NaBH 4 as reductant.The Pt nanoparticles deposited on carbon support presented reduced size and well dispersity attribute...Carbon supported Pt（Pt/C） electrocatalysts were prepared with glucose as protection agent and NaBH 4 as reductant.The Pt nanoparticles deposited on carbon support presented reduced size and well dispersity attributed to the protection effect of glucose.Glucose absorbed on the particle surface was readily removed by water washing without leading to agglomeration of the Pt nanoparticles.The as-prepared Pt/C electrocatalysts showed improved mass activity for methanol electrooxidation compared to the catalyst prepared without glucose protection.The improved performance is attributed to the larger electrochemical active surface area thus increased active sites on the Pt/C elctrocatalysts prepared under the protection of glucose.展开更多
Glucose fuel cells(GFCs)driven by abiotic catalysts are promising green power sources for portable or wearable devices.In this work,a CoO_(x)incorporated carbon nanofiber(CoO_(x)@CNF)catalyst with mixed valences cobal...Glucose fuel cells(GFCs)driven by abiotic catalysts are promising green power sources for portable or wearable devices.In this work,a CoO_(x)incorporated carbon nanofiber(CoO_(x)@CNF)catalyst with mixed valences cobalt oxides have been developed through partial oxidation of pyrolyzed electrospun Co^(2+)/poly acrylonitrile fibers.The cobalt valence modulating could be achieved via regulating the incorporation ratio of cobalt acetate in precursors or the oxidation temperature of the pyrolyzed fibers.Electrocatalytic analyses show that the presence of CoO in CoO_(x)@CNF will provide more active sites for glucose electrooxidation,and thus enhance the electrocatalytic performance significantly.As a result,the glucose fuel cell built with the CoO.@CNF anode containing both CoO and Co_(3)O_(4)delivered a maximum power density of 270μW cm^(-2),which is higher than that of other reported Co_(3)O_(4)based GFCs.This work provides a simple strategy to develop excellent transition metal catalysts for GFCs to expand their applications in portable and wearable energy devices.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 (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.
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.
基金the National Natural Science Foundation of China (Grant Nos. 21273058, 21673064, 51802059 and 21503059)China Postdoctoral Science Foundation (Grant Nos. 2018M631938, 2018T110307 and 2017M621284)+1 种基金Heilongjiang Postdoctoral Fund (LBH-Z17074)Fundamental Research Funds for the Central Universities (Grant No. HIT. NSRIF. 2019040 and 2019041)
文摘A core shell structured C@MoxTi1-xO2-δnanocrystal with a functionalized interface(C@MTNC-FI)was fabricated via the hydrothermal method with subsequent annealing derived from tetrabutyl orthotitanate.The formation of anatase TiO2 was inhibited by the simultaneous presence of the hydrothermal etching/regrowth process,infiltration of Mo dopants and carbon coating,which endows the C@MTNC-FI with an ultrafine crystalline architecture that has a Mo-functionalized interface and carbon-coated shell.Pt Ru nanoparticles(NPs)were supported on C@MTNC-FI by employing a microwave-assisted polyol process(MAPP).The obtained Pt Ru/C@MTNC-FI catalyst has 2.68 times higher mass activity towards methanol electrooxidation than that of the un-functionalized catalyst(Pt Ru/C@TNC)and 1.65 times higher mass activity than that of Pt Ru/C catalyst with over 25%increase in durability.The improved catalytic performance is due to several aspects including ultrafine crystals of TiO2 with abundant grain boundaries,Mofunctionalized interface with enhanced electron interactions,and core shell architecture with excellent electrical transport properties.This work suggests the potential application of an interface-functionalized crystalline material as a sustainable and clean energy solution.
基金supported by FedDev Ontario through the Applied Research and Commercialization (ARC) Initiative and the Natural Sciences and Engineering Research Council of Canada (NSERC) programMicrobonds, Inc. for additional financial support
文摘Carbon modified TiO_2 nanobelts(TiO_2-C) were synthesized using a hydrothermal growth method,as a support material for palladium(Pd) nanoparticles(Pd/TiO_2-C) to improve the electrocatalytic performance for methanol electrooxidation by comparison to Pd nanoparticles on bare TiO_2 nanobelts(Pd/TiO_2)and activated carbon(Pd/AC). Cyclic voltammetry characterization was conducted with respect to saturated calomel electrode(SCE) in an alkaline methanol solution, and the results indicate that the specific activity of Pd/TiO_2-C is 2.2 times that of Pd/AC and 1.5 times that of Pd/TiO_2. Chronoamperometry results revealed that the TiO_2-C support was comparable in stability to activated carbon, but possesses an enhanced current density for methanol oxidation at a potential of -0.2 V vs. SCE. The current study demonstrates the potential of Pd nanoparticle loaded on hierarchical TiO_2-C nanobelts for electrocatalytic applications such as fuel cells and batteries.
基金financial supports from the National Science Foundation under Grant Nos. CBET-1949840 and CMMI-1851674financial support from the Preeminent Postdoctoral Program (P3) of the University of Central Florida。
文摘Direct liquid fuel cells(DLFCs) have received increasing attention because of their high energy densities,instant recharging abilities, simple cell structure, and facile storage and transport. The main challenge for the commercialization of DLFCs is the high loading requirement of platinum group metals(PGMs) as catalysts. Atomically dispersed catalysts(ADCs) have been brought into recent focus for DLFCs due to their well-defined active sites, high selectivity, maximal atom-utilization, and anti-poisoning property. In this review, we summarized the structure–property relationship for unveiling the underlying mechanisms of ADCs for DLFCs. More specifically, different types of fuels used in DLFCs such as methanol, formic acid,and ethanol were discussed. At last, we highlighted current challenges, research directions, and future outlooks towards the practical application of DLFCs.
基金supported by the National Key Research and Development Program of China (Nos. 2020YFC1808502 and2018YFC1802804)the Open Project Program of the Key Laboratory of Environmental Protection & Safety of Communication Foundation Engineering,China Communications Construction Co.,Ltd
文摘In situ and simultaneous remediation of a variety of pollutants in sediments remains a challenge.In this study,we report that the combination of electrocoagulation(EC)and electrooxidation(EO)is efficient in the immobilization of phosphorus and heavymetals and in the oxidation of ammonium and toxic organicmatter.The integratedmixed metal oxide(MMO)/Fe anode system allowed the facile removal of ammonium and phosphorus in the overlying water(99% of 10 mg/L NH_(4)^(+)-N and 95% of 10 mg/L P disappeared in 15 and 30 min,respectively).Compared with the controls of the single Fe anode and single MMO anode systems,the dual MMO/Fe anode system significantly improved the removal of phenanthrene and promoted the transition of Pb and Cu from the mobile species to the immobile species.The concentrations of Pb and Cu in the toxicity characteristic leaching procedure extracts were reduced by 99%and 97% after an 8 hr operation.Further tests with four real polluted samples indicated that substantial proportions of acid-soluble fraction Pb and Cu were reduced(30%-31% for Pb and 16%–23% for Cu),and the amounts of total organic carbon and NH_(4)^(+)-N decreased by 56%–71% and 32%–63%,respectively.It was proposed that the in situ electrogenerated Fe(II)at the Fe anode and the active oxygen/chlorine species at the MMO anode are conducive to outstanding performance in the co-treatment of multiple pollutants.The results suggest that the EC/EO method is a powerful technology for the in situ remediation of sediments contaminated with different pollutants.
文摘Better understanding of electrochemical reaction behaviors of hydrazine electrooxidation at metal phosphides has long been desired and the optimization of reaction kinetics has been proved to be operable.Herein,the dehydrogenation kinetics of hydrazine electrooxidation at Ni_(2)P is adjusted by Co as the(Ni_(0.6)Co_(0.4))_(2)P catalyzes HzOR effectively with onset potential of–45 mV and only 113 mV is needed to drive the current density of 50 mA cm^(‒2),showing over 60 mV lower than Ni_(2)P and Co_(2)P.It also delivers the maximum power density of 263.0 mW cm^(-2) for direct hydrazine fuel cell.Detailed experimental results revealed that Co doping not only decreases the adsorption energy of N_(2)H_(4) on Ni sites,lowering the energy barrier for dehydrogenation,but also acts as the active sites in the optimal reaction coordination to boost the reaction kinetics.This work represents a breakthrough in improving the catalytic performance of non‐precious metal electrocatalysts for hydrazine electrooxidation and highlights an energy‐saving electrochemical hydrogen production method.
基金supported by the National Natural Science Foundation of China (51901083)the Fundamental Research Funds for the Central Universities。
文摘The synthesis of ultrasmall metal nanoclusters(NCs) with high catalytic activities is of great importance for the development of clean and renewable energy technologies but remains a challenge. Here we report a facile wet-chemical method to prepare ~1.0 nm Au Pd NCs supported on amine-functionalized carbon blacks. The Au Pd NCs exhibit a specific activity of 5.98 mA cm_(AuPd)^(-2)and mass activity of 5.25 A mg_(auPd)^(-1) for ethanol electrooxidation, which are far better than those of commercial Pd/C catalysts(1.74 mAcm_(AuPd)^(-2) and 0.54 A mg_(Pd)^(-1) ). For formic acid dehydrogenation, the Au Pd NCs have an initial turn over frequency of 49339 h^(-1) at 298 K without any additive, which is much higher than those obtained for most of reported Au Pd catalysts. The reported synthesis may represent a facile and low-cost approach to prepare other ultrasmall metal NCs with high catalytic activities for various applications.
基金Supported by the National Innovative Research Program for Undergraduates,China(No.2010A33039)the Science and Technology Development Program of Jilin Province,China(No.20100420)
文摘Carbon supported Pt（Pt/C） electrocatalysts were prepared with glucose as protection agent and NaBH 4 as reductant.The Pt nanoparticles deposited on carbon support presented reduced size and well dispersity attributed to the protection effect of glucose.Glucose absorbed on the particle surface was readily removed by water washing without leading to agglomeration of the Pt nanoparticles.The as-prepared Pt/C electrocatalysts showed improved mass activity for methanol electrooxidation compared to the catalyst prepared without glucose protection.The improved performance is attributed to the larger electrochemical active surface area thus increased active sites on the Pt/C elctrocatalysts prepared under the protection of glucose.
基金We gratefully acknowledge to the financial support from the Chongqing Key Laboratory for Advanced MaterialsTechnologies of Clean Energies and Academician Station of Hainan Province(SQ2021PTZ0024).
文摘Glucose fuel cells(GFCs)driven by abiotic catalysts are promising green power sources for portable or wearable devices.In this work,a CoO_(x)incorporated carbon nanofiber(CoO_(x)@CNF)catalyst with mixed valences cobalt oxides have been developed through partial oxidation of pyrolyzed electrospun Co^(2+)/poly acrylonitrile fibers.The cobalt valence modulating could be achieved via regulating the incorporation ratio of cobalt acetate in precursors or the oxidation temperature of the pyrolyzed fibers.Electrocatalytic analyses show that the presence of CoO in CoO_(x)@CNF will provide more active sites for glucose electrooxidation,and thus enhance the electrocatalytic performance significantly.As a result,the glucose fuel cell built with the CoO.@CNF anode containing both CoO and Co_(3)O_(4)delivered a maximum power density of 270μW cm^(-2),which is higher than that of other reported Co_(3)O_(4)based GFCs.This work provides a simple strategy to develop excellent transition metal catalysts for GFCs to expand their applications in portable and wearable energy devices.
