Structural regulation of Pd-based electrocatalytic hydrodechlorination(EHDC)catalyst for constructing high-efficient cathode materials with low noble metal content and high atom utilization is crucial but still challe...Structural regulation of Pd-based electrocatalytic hydrodechlorination(EHDC)catalyst for constructing high-efficient cathode materials with low noble metal content and high atom utilization is crucial but still challenging.Herein,a support electron inductive effect of Pd-Mn/Ni foam catalyst was proposed via in-situ Mn doping to optimize the electronic structure of the Ni foam(NF),which can inductive regulation of Pd for improving the EHDC performance.The mass activity and current efficiency of Pd-Mn/NF catalyst are 2.91 and 1.34 times superior to that of Pd/NF with 2,4-dichlorophenol as model compound,respectively.The Mn-doped interlayer optimized the electronic structure of Pd by bringing the d-state closer to the Fermi level than Pd on the NF surface,which optimizied the binding of EHDC intermediates.Additionally,the Mn-doped interlayer acted as a promoter for generating H∗and accelerating the EHDC reaction.This work presents a simple and effective regulation strategy for constructing high-efficient cathode catalyst for the EHDC of chlorinated organic compounds.展开更多
Electrocatalytic CO_(2)reduction(ECR)to produce value-added fuels and chemicals using renewable electricity is an emerging strategy to mitigate global warming and decrease reliance on fossil fuels.Among various ECR pr...Electrocatalytic CO_(2)reduction(ECR)to produce value-added fuels and chemicals using renewable electricity is an emerging strategy to mitigate global warming and decrease reliance on fossil fuels.Among various ECR products,liquid oxygenates(Oxys)are especially attractive due to their high energy density,high safety and transportability that could be adapted to the existing infrastructure and transportation system.However,efficiently generating these highly reduced oxygen-containing products by ECR remains challenging due to the complexity of coupled proton and electron transfer processes.In recent years,in-depth studies of reaction mechanisms have advanced the design of catalysts and the regulation of reaction systems for ECR to produce Oxys,Here,by focusing on the production of typical Oxys,such as methanol,acetic acid,ethanol,acetone,n-propanol,and isopropanol,we outline various reaction paths and key intermediates for the electrochemical conversion of CO_(2)into these target products.We also summarize the current research status and recent advances in catalysts based on their elemental composition,and consider recent studies on the change of catalyst geometry and electronic structure,as well as the optimization of reaction systems to increase ECR performance.Finally,we analyze the challenges in the field of ECR to Oxys and provide an outlook on future directions for high-efficiency catalyst prediction and design,as well as the development of advanced reaction systems.展开更多
The electrocatalytic nitrogen oxidation reaction(NOR)is a sustainable approach for converting N_(2)to NO_(3)^(-)under mild conditions.However,it still faces challenges including inefficient N_(2)absorption/activation ...The electrocatalytic nitrogen oxidation reaction(NOR)is a sustainable approach for converting N_(2)to NO_(3)^(-)under mild conditions.However,it still faces challenges including inefficient N_(2)absorption/activation and oxygen evolution competition,sluggish kinetics,low Faradaic efficiency,and limited nitrate yields.In this work,a novel two-dimensional(2D)layered MOF Mn-BCPPy(H_(2)BCPPy=3,5-di(4'-carboxyphenyl)pyridine)has been successfully synthesized.The framework is composed of a rod-manganese motifs and possesses abundant active sites including open metal sites(OMSs)and Lewis base sites(LBSs).The Mn-BCPPy is the first MOF catalyst applied in electrocatalytic NOR which NO_(3)^(-)exhibited relatively high activity with a yield of 99.75μg/(h·mg)and a Faraday efficiency(FE)of 32.09%.Furthermore,it can be used as fluorescent sensor for selectively and sensitively detect nitrofuran antibiotics(NFs).Therefore,this work explores the application of MOF materials in the field of electrocatalytic NOR,which reveals that manganese-based MOFs have great potential prospects.展开更多
Diamond combines many unique properties,including high stability,strong optical dispersion,excellent mechanical strength,and outstanding thermal conductivity.Its structure,surface groups,and electrical conductivity ar...Diamond combines many unique properties,including high stability,strong optical dispersion,excellent mechanical strength,and outstanding thermal conductivity.Its structure,surface groups,and electrical conductivity are also tunable,increasing its functional versatility.These make diamond and its related materials,such as its composites,highly promising for various applications in energy fields.This review summarizes recent advances and key achievements in energy storage and conversion,covering electrochemical energy storage(e.g.,batteries and supercapacitors),electrocatalytic energy conversion(e.g.,CO_(2)and nitrogen reduction reactions),and solar energy conversion(e.g.,photo-(electro)chemical CO_(2)and nitrogen reduction reactions,and solar cells).Current challenges and prospects related to the synthesis of diamond materials and the technologies for their energy applications are outlined and discussed.展开更多
A gold catalyst of Au/pyrenyl‑graphdiyne(Pyr‑GDY)was prepared by anchoring small size of gold nanoparticles(Au NPs)on the surface of Pyr‑GDY for electrocatalytic nitrogen reduction reaction(eNRR),in which Au NPs with ...A gold catalyst of Au/pyrenyl‑graphdiyne(Pyr‑GDY)was prepared by anchoring small size of gold nanoparticles(Au NPs)on the surface of Pyr‑GDY for electrocatalytic nitrogen reduction reaction(eNRR),in which Au NPs with a size of approximately 3.69 nm was evenly distributed on spongy‑like porous Pyr‑GDY.The catalyst exhibited a good electrocatalytic activity for N_(2)reduction in a nitrogen‑saturated electrolyte,with an ammonia yield of 32.1μg·h^(-1)·mg_(cat)^(-1)at-0.3 V(vs RHE),3.5 times higher than that of Au/C(Au NPs anchored on carbon black).In addition,Au/Pyr‑GDY showed a Faraday efficiency(FE)of 26.9%for eNRR,and a good catalysis durability for over 22 h.展开更多
Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have re...Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.展开更多
The semi-hydrogenation of alkynes to alkenes is of great significance in the industrial production of pharmaceutical and fine chemicals.Electrochemical semi-hydrogenation(ECSH)has emerged as a promising alternative to...The semi-hydrogenation of alkynes to alkenes is of great significance in the industrial production of pharmaceutical and fine chemicals.Electrochemical semi-hydrogenation(ECSH)has emerged as a promising alternative to conventional thermochemical hydrogenation.However,its practical application is hindered by low reaction rate and competing hydrogen evolution reaction(HER).In this work,the controllable incorporation of sulfur into the lattice of Pd nanostructures is proposed to develop disordered and electron-deficient Pd-based nanosheets on Ni foam and enhance their ECSH performance of alkynes.Mechanistic investigations demonstrate that the electronic and geometric structures of Pd sites are optimized by lattice sulfur,which tunes the competitive adsorption of H*and alkynes,inherently inhibits the H*coupling and weakens alkene adsorption,thereby promotes the semi-hydrogenation of alkynes and prevents the over-hydrogenation of alkenes.The optimized Pd-based nanosheets exhibit efficient electrocatalytic semi-hydrogenation performance in an H-cell,achieving 97%alkene selectivity,94%Faradaic efficiency,and a reaction rate of 303.7μmol mgcatal.^(-1) h^(-1) using 4-methoxyphenylacetylene as the model substrate.Even in a membrane electrode assembly(MEA)configuration,the optimized Pd-based nanosheets achieves a single-cycle alkyne conversion of 96%and an alkene selectivity of 97%,with continuous production of alkene at a rate of 1901.1μmol mgcatal.^(-1) h^(-1).The potential-and time-independent selectivity,good substrate universality with excellent tolerance to active groups(C–Br/Cl/C]O,etc.)further highlight the potential of this strategy for advanced catalysts design and green chemistry.展开更多
5-Hydroxymethylfurfural(HMF),derived from biomass,is a promising sustainable resource that can be converted into valuable chemical compounds.One such compound,2,5-dihydroxymethylfuran(DHMF),produced through the electr...5-Hydroxymethylfurfural(HMF),derived from biomass,is a promising sustainable resource that can be converted into valuable chemical compounds.One such compound,2,5-dihydroxymethylfuran(DHMF),produced through the electrocatalytic hydrogenation of HMF,is widely used in industrial polymer manufacturing.However,the hydrogenation of high-concentration HMF remains challenging due to the tendency for undesirable dimerization.Acknowledging the critical role of adsorbed hydrogen(H*)in HMF hydrogenation,a series of transition metal-doped dual-cubic Cu electrocatalysts(M-Cu,where M=Mo,Pd,Pt,Au,and Ag)were synthesized to systematically investigate the effect of varying H*reactivity on HMF hydrogenation,A pronounced correlation between DHMF selectivity and H*coverage was observed.Increasing H*coverage can enhance the selectivity for DHMF and prevent undesired dimerization of adsorbed HMF molecules.While elevated H*coverage enhanced DHMF selectivity,excessive coverage adversely impacted Faradaic efficiency due to competing hydrogen evolution reaction.This underscores the critical importance of finely tuning H*coverage.The optimal electrocatalyst,achieved by fine-tuning the doping amount of Pt on Cu,demonstrated a Faradaic efficiency of over 90%for DHMF in highconcentration HMF at-0.3 V,marking the highest record reported to date.展开更多
An ultrathin two-dimensional cerium dioxide(2D-CeO_(2))structure was accomplished using a unique combination of template and ion exchange strategies.When employed in the electrochemical degradation of 17-alpha-ethynyl...An ultrathin two-dimensional cerium dioxide(2D-CeO_(2))structure was accomplished using a unique combination of template and ion exchange strategies.When employed in the electrochemical degradation of 17-alpha-ethynylestradiol(EE2)in aqueous solutions,the as-prepared 2D-CeO_(2) performed considerably better than CeO_(2) nanoparticles(CeO_(2)-NPs)and commercial CeO_(2)(C-CeO_(2)).Structure,morphology and composition of all three materials(i.e.,2D-CeO_(2),CeO_(2)-NPs and C-CeO_(2))were characterized and analyzed comparatively by X-ray diffractometer,transmission electron microscopy,scanning electron microscopy,Raman,electron paramagnetic resonance and X-ray photoelectron spectroscopy.Owing to its 2D structure and abundant active sites,2D-CeO_(2) performed better in the electrochemical degradation system of EE2.The catalytic activity of the material was evaluated while studying the effects of EE2 concentration,various electrolyte amounts,current density,and pH of the solution on the degradation.The results indicate that the reaction rate constant of EE2 on 2D-CeO_(2) was as good as 0.028,and EE2 can be degraded by 97.64%after 140 min under optimized conditions.While the reaction rate constants of CeO_(2)-NPs and C-CeO_(2) were only 0.016 and 0.012,and the degradation rates were 88.65%and 80.41%,respectively.Further,the catalytic performance of 2D-CeO_(2) was examined using cyclic voltammetry,linear scanning voltammetry,electrochemical impedance spectroscopy and chronopotentiometry.In addition,the mechanism of electrocatalysis was investigated through a combination of hydroxyl radical generation and quenching experiments,as well as density functional theory analysis.Overall,this ultrathin 2D-CeO_(2) could be a promising candidate in the field of electrochemical degradation of environmental endocrine disrupting chemicals.展开更多
The escalating demand for sustainable and environmentally benign chemical processes has driven the exploration of biomass as an alternative to non-renewable resources.Electrocatalytic upgrading of biomass-derived alde...The escalating demand for sustainable and environmentally benign chemical processes has driven the exploration of biomass as an alternative to non-renewable resources.Electrocatalytic upgrading of biomass-derived aldehydes plays a crucial role in biomass refining,and has become a frontier of mainstream research.This paper reviews the recent advances on the electrocatalytic oxidation of typical biomass-derived aldehydes(5-hydroxymethylfurfural,furfural,glucose,xylose,vanillin and benzaldehyde,etc.).The research presented in this review covers a wide range of oxidation mechanisms for each aldehyde.It is evident from the current literature that challenges related to the comprehensiveness of mechanistic studies,catalyst stability,and reaction scalability remain,but the rapid progress offers hope for future advancements.Finally,we elucidate the challenges in this domain and provide the perspectives on future developments.This review corroborates the significance of investigating the electrocatalytic oxidation of biomass-derived aldehydes and emphasizes the need for continued research to refine these processes for industrial applications.展开更多
In this paper we report the preparation of nano-dendritic Cu_(2)O/Cu heterojunctions doped with varying concentrations of cobalt through a convenient,energy-consumption-free,and environmentally friendly chemical repla...In this paper we report the preparation of nano-dendritic Cu_(2)O/Cu heterojunctions doped with varying concentrations of cobalt through a convenient,energy-consumption-free,and environmentally friendly chemical replacement method.The analysis results reveal that the incorporation of cobalt in its atomic form enhances the adsorption of nitrate species onto the catalyst surface,whereas doping with metallic cobalt promotes the production of active hydrogen(*H).By adjusting the doping concentration of cobalt,we effectively control its doping form(atomic and metallic states)on the surface of dendritic copper,thereby enabling controllable modulation of the active hydrogen concentration on the catalyst surface.By ensuring sufficient consumption of*H during the NITRR process while avoiding excessively high concentrations that could trigger detrimental hydrogen evolution reaction side reactions,this approach remarkably enhances the selectivity of ammonia synthesis in NITRR.This study offers an effective approach to regulate the*H concentration on the surface of the catalyst through adjusting the metal doping form,thereby improving the performance of ammonia synthesis from NITRR.展开更多
In the context of the global pursuit of sustainable energy,dual-atom catalysts(DACs)have attracted widespread attention due to their unique structural and excellent catalytic performance.Unlike the single-atom catalys...In the context of the global pursuit of sustainable energy,dual-atom catalysts(DACs)have attracted widespread attention due to their unique structural and excellent catalytic performance.Unlike the single-atom catalysts,DACs possess two active metal centers,exhibiting intriguing synergistic effects that significantly enhance their efficiency in various electrochemical reactions.This comprehensive review provides an overview of the recent advances in the field of dual-atom catalysts,focusing on their innovative preparation methods and strategies.It further delves into the intrinsic connections between structure and performance,discussing the applications of DACs in hydrogen evolution reaction,oxygen evolution reaction,oxygen reduction reaction,photocatalysis,carbon dioxide reduction reaction,and batteries.Lastly,a forward-looking perspective addresses the current challenges and outlines future directions.This review aims to deepen our understanding of DACs and stimulate further innovation in advanced catalysts for energy conversion systems.展开更多
Electrocatalytic C—N coupling is an environmentally friendly pathway for reducing CO_(2)emissions,nitrate wastewater treatment,and urea production.CeO_(2)is a commonly used electrocatalyst for urea synthesis,but its ...Electrocatalytic C—N coupling is an environmentally friendly pathway for reducing CO_(2)emissions,nitrate wastewater treatment,and urea production.CeO_(2)is a commonly used electrocatalyst for urea synthesis,but its yield was restricted by the deficiency of active sites and the high barrier for C—N coupling.Herein,we employed transient heating to introduce oxygen vacancies as sites for the deposition of single metal atoms,thereby maximizing the atomic utilization as active sites for urea synthesis.The as-prepared CuFe-V-CeO_(2)electrocatalyst exhibits the outstanding urea yield rate(3553 mg h^(-1)g_(ca)^(t-1).)at-1.5 V versus reversible hydrogen electrode(RHE),surpassing the performance of previously reported electrochemical urea electrocatalysts.Theoretical calculation further revealed the roles of Ce,Cu,and Fe sites in active hydrogen(*H)generation,nitrate treatment,and CO_(2)stabilization,respectively.This work offers a novel and effective pathway for the design of electrocatalysts and developing an efficient C—N coupling system for urea production.展开更多
Addressing the contamination of antibiotics has attracted ever-increasing and imperative attention due to their widespread existence,easy-to-cause drug-resistant bacteria infection,coupled with their intrinsic toxicit...Addressing the contamination of antibiotics has attracted ever-increasing and imperative attention due to their widespread existence,easy-to-cause drug-resistant bacteria infection,coupled with their intrinsic toxicity and hazard to environments and human health.Herein,a novel CC/CoNi-LDH-10%Ce anode material was directly constructed through a simple and rapid electrodeposition strategy,serving as an efficacious electrocatalyst for removing ciprofloxacin(CIP)from aqueous solution.Such novel CC/CoNi-LDH-10%Ce anode delivered a higher charge transfer,relatively abundant oxygen vacancies,and a higher electrochemical active area.The as-fabricated CC/CoNi-LDH-10%Ce electrode achieved a substantially boosted CIP removal efficiency of 52.5%relative to that of pure CC at about 23.9%.Notably,doping an appropriate amount of Ce^(3+)can endow the pristine CC/CoNi-LDH with richer oxygen vacancies and excellent electrocatalytic performance.Additionally,the electrocatalytic oxidation of CIP was attributed to both direct oxidation on the electrode surface and indirect oxidation induced by the generated active species(superoxide radicals and hydroxyl radicals).This study provides a simple,universal and flexible tactic for other researchers in designing and manufacturing avenues of electrodes.展开更多
ZnO-based catalysts have been widely used in hydrogenation reactions,but less attention has been paid to the electrocatalytic hydrogenation process on ZnO electrodes.In this work,the preparation of hydrogen species an...ZnO-based catalysts have been widely used in hydrogenation reactions,but less attention has been paid to the electrocatalytic hydrogenation process on ZnO electrodes.In this work,the preparation of hydrogen species and the associ-ated reduction properties under electrochemi-cal processes in aqueous solutions have been in-vestigated on ZnO and Au/ZnO electrodes.The measurements of cyclic voltammetry(CV),X-ray diffraction,and electron paramagnetic resonance(EPR)confirm the formation of hydro-gen species on the interstitial sites(Hi)or on the oxygen vacancy sites(H_(O)).The hydrogena-tion reaction of p-nitrophenol(pNP)at 40μmol/L occurs on both ZnO and Au/ZnO elec-trodes,and the hydrogenation reduction performance of Au/ZnO electrode is better than that of ZnO electrode.CVs show H_(O)species is much more reactive with pNP than Hi species.Compared with the ZnO electrode,the presence of Au on ZnO promotes the formation of H_(O)species and improves the electro-reduction performance to pNP.These results help us to un-derstand the reaction processes related to the electrochemical hydrogenation on ZnO and Au/ZnO surfaces and shed new light on the design of new catalytic hydrogenation systems.展开更多
Ligand-stabilized metal nanoclusters with atomic precision have garnered significant attention for applications in catalysis,biomedicine,and nanoelectronics due to their tunable structures and unique physicochemical p...Ligand-stabilized metal nanoclusters with atomic precision have garnered significant attention for applications in catalysis,biomedicine,and nanoelectronics due to their tunable structures and unique physicochemical properties[1-3].While transition metals such as Au,Ag,Pt,and Pd dominate the core composition,surface ligands are predominantly limited to phosphines,thiols,alkynes,and carbenes.Among these,N-heterocyclic carbenes(NHCs)have emerged as a superior ligand class due to their dual capacity for strongσ-donation andπ-back bonding,which stabilizes diverse metal oxidation states and enhances metal-ligand interactions.Notably,NHC-protected clusters exhibit exceptional thermal stability attributed to CH-π/π-πinteractions and enlarged HOMO-LUMO gaps compared to thiol or phosphine analogues.Despite progress,synthetic limitations persist due to NHCs'sensitivity under harsh conditions.Current methods rely on direct reduction of metal-carbene precursors or ligand exchange reactions,with heterogeneous NHC-capped systems remaining unexplored.展开更多
The fabrication of bifunctional electrocatalysts for hydrogen and oxygen evolution in aqueous environment has far-reaching significance.Especially,reasonable interface process regulation toward heterogeneous composite...The fabrication of bifunctional electrocatalysts for hydrogen and oxygen evolution in aqueous environment has far-reaching significance.Especially,reasonable interface process regulation toward heterogeneous composites can make full use of the active sites and improve the electrocatalytic activity.In this study,we designed and synthesized NiS_(2)-MoS_(2)-based heterogeneous composites as efficient and stable electrocatalysts for hydrogen and oxygen evolution in alkaline electrolyte.The heterostructure was obtained by one-step hydrothermal ulfurization operation towards polymolybdate-based metal-organic complex.The composition and nanostructures can be tailored by modulating experiment parameter,realizing the phase-controlled synthesis and interface regulation:(1)High-percentage of 1T-MoS_(2)can be achieved via selecting appropriate vulcanization time and thiourea concentration,benifiting for the higher electroconductivity and more active sites;(2)Regular and orderly vulcanization time promotes the gradual growth and aggregation of nanosheets;(3)The existence of nickel hydroxide improves the electrocatalytic stability for oxygen production performance.The optimized heterogeneous interfaces provide sufficient active sites and accelerate electron transfer.Consequently,the optimal heterogeneous nanosheets present low overpotentials of 33 and 122 m V at the catalytic current densities of 10 m A/cm2for HER and OER,respectively.展开更多
High entropy materials(HEMs)are the promising electrocatalysts for anion exchange membrane electrolyser(AEMs)and proton exchange membrane fuel cells(PEMFCs)due to the intriguing cocktail effect,wide design space,tailo...High entropy materials(HEMs)are the promising electrocatalysts for anion exchange membrane electrolyser(AEMs)and proton exchange membrane fuel cells(PEMFCs)due to the intriguing cocktail effect,wide design space,tailorable electronic structure,and entropy stabilization effect.The precise fabrication of HEMs with functional nanostructures provides a crucial avenue to optimize the adsorption strength and catalytic activity for electrocatalysis.This review comprehensively summarizes the development of HEMs,focusing on the principles and strategies of structural design,and the catalytic mechanism towards hydrogen evolution reaction,oxygen evolution reaction and oxygen reduction reaction for the development of high-performance electrocatalysts.The complexity inherent in the interactions between different elements,the changes in the d-band center and the Gibbs free energies during the catalytic progress,as well as the coordination environment of the active sites associated with the unique crystal structure to improve the catalytic performance are discussed.We also provide a perspective on the challenges and future development direction of HEMs in electrocatalysis.This review will contribute to the design and development of HEMs-based catalysts for the next generation of electrochemical applications.展开更多
The efficient electrocatalytic nitrate(NO_(3)^(−))reduction to ammonia(NRA)offers a sustainable alternative for both environmental remediation and ammonia synthesis.Developing advanced electrocatalysts with rationally...The efficient electrocatalytic nitrate(NO_(3)^(−))reduction to ammonia(NRA)offers a sustainable alternative for both environmental remediation and ammonia synthesis.Developing advanced electrocatalysts with rationally designed spatial arrangement of active sites and optimizing the synergetic effect among components are crucial for high efficiency and selectivity.Herein,we present Fe/N active sites decorated on porous carbon nanofibers(CNFs)with encapsulated FeCo nanoparticles(FeCo@CNFs-Fe/N)as electrocatalysts for NRA.The FeCo@CNFs-Fe/N catalyst demonstrates exceptional performance,achieving a high ammonia yield of 498.18μmol/(h·g_(cat)).Meanwhile,the enhanced reduction activity,especially the reduction in overpotential by 0.565 V,is 3–10 times higher than that of FeCo-encapsulated and Fe/N-modified CNFs-based catalysts.The enhanced catalytic activity is attributed to the efficient structure design and optimized spatial distribution of active sites,which enhance the electron transfer rate and decrease the reaction energy barrier.Mechanistic studies reveal that the synergetic effect between encapsulated nanoparticles and surface-modified Fe/N sites plays a crucial role in promoting efficient nitrate adsorption and selective ammonia production.These findings highlight the potential of strategically engineered CNF-based composites for nitrate reduction and other advanced electrocatalytic applications.展开更多
Singlet oxygen(^(1)O_(2)),as an electrophilic oxidant,is essential for the selective water decontamination of pollutants from water.Herein,we showcase a high-performing electrocatalytic filtration system composed of c...Singlet oxygen(^(1)O_(2)),as an electrophilic oxidant,is essential for the selective water decontamination of pollutants from water.Herein,we showcase a high-performing electrocatalytic filtration system composed of carbon nanotubes functionalized with CoFe alloy nanoparticles(CoFeCNT)to selectively facilitate the electrochemical activation of O_(2)to^(1)O_(2).Benefiting from the prominently featured bimetal active sites of CoFeCNT,nearly complete production of^(1)O_(2)is achieved by the electrocatalytic activation of O_(2).Additionally,the proposed system exhibits a consistent pollutant removal efficiency>90%in a flow-through reactor over 48 h of continuous operation without a noticeable decline in performance,highlighting the dependable stability of the system for practical applications.The flow-through configuration demonstrates a striking 8-fold enhancement in tetracycline oxidation compared to a conventional batch reactor.This work provides a molecular level understanding of the oxygen reduction reaction,showing promising potential for the selective removal of emerging organic contaminants from water.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22178388 and 22108306)Taishan Scholars Program of Shandong Province(No.tsqn201909065)Chongqing Science and Technology Bureau(No.cstc2019jscx-gksb X0032).
文摘Structural regulation of Pd-based electrocatalytic hydrodechlorination(EHDC)catalyst for constructing high-efficient cathode materials with low noble metal content and high atom utilization is crucial but still challenging.Herein,a support electron inductive effect of Pd-Mn/Ni foam catalyst was proposed via in-situ Mn doping to optimize the electronic structure of the Ni foam(NF),which can inductive regulation of Pd for improving the EHDC performance.The mass activity and current efficiency of Pd-Mn/NF catalyst are 2.91 and 1.34 times superior to that of Pd/NF with 2,4-dichlorophenol as model compound,respectively.The Mn-doped interlayer optimized the electronic structure of Pd by bringing the d-state closer to the Fermi level than Pd on the NF surface,which optimizied the binding of EHDC intermediates.Additionally,the Mn-doped interlayer acted as a promoter for generating H∗and accelerating the EHDC reaction.This work presents a simple and effective regulation strategy for constructing high-efficient cathode catalyst for the EHDC of chlorinated organic compounds.
基金financial supports from the National Natural Science Foundation of China(52201237)the Talent Introduction Project of Chinese Academy of Sciences(E344011)+4 种基金the Shenzhen High Level Talent Team Project(KQTD2022110109364705)the Joint Research Project of China Merchants Group and SIAT(E2Z1521)the Cross Institute Joint Research Youth Team Project of SIAT(E25427)National Natural Science Foundation of China(52402136)the China Postdoctoral Science Foundation(E325281005)。
文摘Electrocatalytic CO_(2)reduction(ECR)to produce value-added fuels and chemicals using renewable electricity is an emerging strategy to mitigate global warming and decrease reliance on fossil fuels.Among various ECR products,liquid oxygenates(Oxys)are especially attractive due to their high energy density,high safety and transportability that could be adapted to the existing infrastructure and transportation system.However,efficiently generating these highly reduced oxygen-containing products by ECR remains challenging due to the complexity of coupled proton and electron transfer processes.In recent years,in-depth studies of reaction mechanisms have advanced the design of catalysts and the regulation of reaction systems for ECR to produce Oxys,Here,by focusing on the production of typical Oxys,such as methanol,acetic acid,ethanol,acetone,n-propanol,and isopropanol,we outline various reaction paths and key intermediates for the electrochemical conversion of CO_(2)into these target products.We also summarize the current research status and recent advances in catalysts based on their elemental composition,and consider recent studies on the change of catalyst geometry and electronic structure,as well as the optimization of reaction systems to increase ECR performance.Finally,we analyze the challenges in the field of ECR to Oxys and provide an outlook on future directions for high-efficiency catalyst prediction and design,as well as the development of advanced reaction systems.
基金supported by Natural Science Foundation of Shandong Province(ZR2021MB075)Fundamental Research Funds for the Central Universities,Ocean University of China(202461021).
文摘The electrocatalytic nitrogen oxidation reaction(NOR)is a sustainable approach for converting N_(2)to NO_(3)^(-)under mild conditions.However,it still faces challenges including inefficient N_(2)absorption/activation and oxygen evolution competition,sluggish kinetics,low Faradaic efficiency,and limited nitrate yields.In this work,a novel two-dimensional(2D)layered MOF Mn-BCPPy(H_(2)BCPPy=3,5-di(4'-carboxyphenyl)pyridine)has been successfully synthesized.The framework is composed of a rod-manganese motifs and possesses abundant active sites including open metal sites(OMSs)and Lewis base sites(LBSs).The Mn-BCPPy is the first MOF catalyst applied in electrocatalytic NOR which NO_(3)^(-)exhibited relatively high activity with a yield of 99.75μg/(h·mg)and a Faraday efficiency(FE)of 32.09%.Furthermore,it can be used as fluorescent sensor for selectively and sensitively detect nitrofuran antibiotics(NFs).Therefore,this work explores the application of MOF materials in the field of electrocatalytic NOR,which reveals that manganese-based MOFs have great potential prospects.
基金西南大学中央高校基本科研业务费项目(SWU-KT22030)重庆市教育委员会科学技术研究项目(KJQN202300205)Deutsche Forschungsgemeinschaft(DFG,German Research Foundation,457444676).
文摘Diamond combines many unique properties,including high stability,strong optical dispersion,excellent mechanical strength,and outstanding thermal conductivity.Its structure,surface groups,and electrical conductivity are also tunable,increasing its functional versatility.These make diamond and its related materials,such as its composites,highly promising for various applications in energy fields.This review summarizes recent advances and key achievements in energy storage and conversion,covering electrochemical energy storage(e.g.,batteries and supercapacitors),electrocatalytic energy conversion(e.g.,CO_(2)and nitrogen reduction reactions),and solar energy conversion(e.g.,photo-(electro)chemical CO_(2)and nitrogen reduction reactions,and solar cells).Current challenges and prospects related to the synthesis of diamond materials and the technologies for their energy applications are outlined and discussed.
文摘A gold catalyst of Au/pyrenyl‑graphdiyne(Pyr‑GDY)was prepared by anchoring small size of gold nanoparticles(Au NPs)on the surface of Pyr‑GDY for electrocatalytic nitrogen reduction reaction(eNRR),in which Au NPs with a size of approximately 3.69 nm was evenly distributed on spongy‑like porous Pyr‑GDY.The catalyst exhibited a good electrocatalytic activity for N_(2)reduction in a nitrogen‑saturated electrolyte,with an ammonia yield of 32.1μg·h^(-1)·mg_(cat)^(-1)at-0.3 V(vs RHE),3.5 times higher than that of Au/C(Au NPs anchored on carbon black).In addition,Au/Pyr‑GDY showed a Faraday efficiency(FE)of 26.9%for eNRR,and a good catalysis durability for over 22 h.
基金supported by the National Key R&D Program of China(2024YFB4106400)National Natural Science Foundation of China(22209200,52302331)。
文摘Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.
基金financially supported by the National Natural Science Foundation of China(51701127,92163209,12264053)Shenzhen Fundamental Research Program(JCYJ20220811170904003,JCYJ20210324094000001)+6 种基金Shenzhen Peacock Plan(20180703896C)Shenzhen Key Laboratory of 2D Metamaterials for Information Technology(ZDSYS201707271014468)the research projects of Guangdong Provincial Education Office(2024KCXTD064)ZJUHIC start-up fund(02090200-K02013002)Beijing Natural Science Foundation(JQ22004)the Natural Science Foundation of Hangzhou(2024SZRYBB020001)the Scientific Research and Innovation Project of Postgraduate Students in the Academic Degree of Yunnan University(KC-23234366).
文摘The semi-hydrogenation of alkynes to alkenes is of great significance in the industrial production of pharmaceutical and fine chemicals.Electrochemical semi-hydrogenation(ECSH)has emerged as a promising alternative to conventional thermochemical hydrogenation.However,its practical application is hindered by low reaction rate and competing hydrogen evolution reaction(HER).In this work,the controllable incorporation of sulfur into the lattice of Pd nanostructures is proposed to develop disordered and electron-deficient Pd-based nanosheets on Ni foam and enhance their ECSH performance of alkynes.Mechanistic investigations demonstrate that the electronic and geometric structures of Pd sites are optimized by lattice sulfur,which tunes the competitive adsorption of H*and alkynes,inherently inhibits the H*coupling and weakens alkene adsorption,thereby promotes the semi-hydrogenation of alkynes and prevents the over-hydrogenation of alkenes.The optimized Pd-based nanosheets exhibit efficient electrocatalytic semi-hydrogenation performance in an H-cell,achieving 97%alkene selectivity,94%Faradaic efficiency,and a reaction rate of 303.7μmol mgcatal.^(-1) h^(-1) using 4-methoxyphenylacetylene as the model substrate.Even in a membrane electrode assembly(MEA)configuration,the optimized Pd-based nanosheets achieves a single-cycle alkyne conversion of 96%and an alkene selectivity of 97%,with continuous production of alkene at a rate of 1901.1μmol mgcatal.^(-1) h^(-1).The potential-and time-independent selectivity,good substrate universality with excellent tolerance to active groups(C–Br/Cl/C]O,etc.)further highlight the potential of this strategy for advanced catalysts design and green chemistry.
基金supported financially by the Australian Research Council(CE230100032,DP230102027,DP240102575,FT200100062)。
文摘5-Hydroxymethylfurfural(HMF),derived from biomass,is a promising sustainable resource that can be converted into valuable chemical compounds.One such compound,2,5-dihydroxymethylfuran(DHMF),produced through the electrocatalytic hydrogenation of HMF,is widely used in industrial polymer manufacturing.However,the hydrogenation of high-concentration HMF remains challenging due to the tendency for undesirable dimerization.Acknowledging the critical role of adsorbed hydrogen(H*)in HMF hydrogenation,a series of transition metal-doped dual-cubic Cu electrocatalysts(M-Cu,where M=Mo,Pd,Pt,Au,and Ag)were synthesized to systematically investigate the effect of varying H*reactivity on HMF hydrogenation,A pronounced correlation between DHMF selectivity and H*coverage was observed.Increasing H*coverage can enhance the selectivity for DHMF and prevent undesired dimerization of adsorbed HMF molecules.While elevated H*coverage enhanced DHMF selectivity,excessive coverage adversely impacted Faradaic efficiency due to competing hydrogen evolution reaction.This underscores the critical importance of finely tuning H*coverage.The optimal electrocatalyst,achieved by fine-tuning the doping amount of Pt on Cu,demonstrated a Faradaic efficiency of over 90%for DHMF in highconcentration HMF at-0.3 V,marking the highest record reported to date.
基金supported by the National Natural Science Foundation of China(Nos.52201249,52301300 and 22202058)the Science and Technology Project of Hebei Education Department(No.ZC2024156)S&T Program of Qinhuangdao(No.202301A013).
文摘An ultrathin two-dimensional cerium dioxide(2D-CeO_(2))structure was accomplished using a unique combination of template and ion exchange strategies.When employed in the electrochemical degradation of 17-alpha-ethynylestradiol(EE2)in aqueous solutions,the as-prepared 2D-CeO_(2) performed considerably better than CeO_(2) nanoparticles(CeO_(2)-NPs)and commercial CeO_(2)(C-CeO_(2)).Structure,morphology and composition of all three materials(i.e.,2D-CeO_(2),CeO_(2)-NPs and C-CeO_(2))were characterized and analyzed comparatively by X-ray diffractometer,transmission electron microscopy,scanning electron microscopy,Raman,electron paramagnetic resonance and X-ray photoelectron spectroscopy.Owing to its 2D structure and abundant active sites,2D-CeO_(2) performed better in the electrochemical degradation system of EE2.The catalytic activity of the material was evaluated while studying the effects of EE2 concentration,various electrolyte amounts,current density,and pH of the solution on the degradation.The results indicate that the reaction rate constant of EE2 on 2D-CeO_(2) was as good as 0.028,and EE2 can be degraded by 97.64%after 140 min under optimized conditions.While the reaction rate constants of CeO_(2)-NPs and C-CeO_(2) were only 0.016 and 0.012,and the degradation rates were 88.65%and 80.41%,respectively.Further,the catalytic performance of 2D-CeO_(2) was examined using cyclic voltammetry,linear scanning voltammetry,electrochemical impedance spectroscopy and chronopotentiometry.In addition,the mechanism of electrocatalysis was investigated through a combination of hydroxyl radical generation and quenching experiments,as well as density functional theory analysis.Overall,this ultrathin 2D-CeO_(2) could be a promising candidate in the field of electrochemical degradation of environmental endocrine disrupting chemicals.
基金supported by the National Key R&D Program of China(2023YFC3905804)the National Natural Science Foundation of China(22078374,22378434,41920104003)the Scientific and Technological Planning Project of Guangzhou(202206010145)。
文摘The escalating demand for sustainable and environmentally benign chemical processes has driven the exploration of biomass as an alternative to non-renewable resources.Electrocatalytic upgrading of biomass-derived aldehydes plays a crucial role in biomass refining,and has become a frontier of mainstream research.This paper reviews the recent advances on the electrocatalytic oxidation of typical biomass-derived aldehydes(5-hydroxymethylfurfural,furfural,glucose,xylose,vanillin and benzaldehyde,etc.).The research presented in this review covers a wide range of oxidation mechanisms for each aldehyde.It is evident from the current literature that challenges related to the comprehensiveness of mechanistic studies,catalyst stability,and reaction scalability remain,but the rapid progress offers hope for future advancements.Finally,we elucidate the challenges in this domain and provide the perspectives on future developments.This review corroborates the significance of investigating the electrocatalytic oxidation of biomass-derived aldehydes and emphasizes the need for continued research to refine these processes for industrial applications.
文摘In this paper we report the preparation of nano-dendritic Cu_(2)O/Cu heterojunctions doped with varying concentrations of cobalt through a convenient,energy-consumption-free,and environmentally friendly chemical replacement method.The analysis results reveal that the incorporation of cobalt in its atomic form enhances the adsorption of nitrate species onto the catalyst surface,whereas doping with metallic cobalt promotes the production of active hydrogen(*H).By adjusting the doping concentration of cobalt,we effectively control its doping form(atomic and metallic states)on the surface of dendritic copper,thereby enabling controllable modulation of the active hydrogen concentration on the catalyst surface.By ensuring sufficient consumption of*H during the NITRR process while avoiding excessively high concentrations that could trigger detrimental hydrogen evolution reaction side reactions,this approach remarkably enhances the selectivity of ammonia synthesis in NITRR.This study offers an effective approach to regulate the*H concentration on the surface of the catalyst through adjusting the metal doping form,thereby improving the performance of ammonia synthesis from NITRR.
基金supported by the China Postdoctoral Science Foundation(Nos.2021M700981,2022M711787,2021M691759 and 2021TQ0169)Shuimu Tsinghua Scholar program(No.2021SM071)Beijing Natural Science Foundation(No.2224103).
文摘In the context of the global pursuit of sustainable energy,dual-atom catalysts(DACs)have attracted widespread attention due to their unique structural and excellent catalytic performance.Unlike the single-atom catalysts,DACs possess two active metal centers,exhibiting intriguing synergistic effects that significantly enhance their efficiency in various electrochemical reactions.This comprehensive review provides an overview of the recent advances in the field of dual-atom catalysts,focusing on their innovative preparation methods and strategies.It further delves into the intrinsic connections between structure and performance,discussing the applications of DACs in hydrogen evolution reaction,oxygen evolution reaction,oxygen reduction reaction,photocatalysis,carbon dioxide reduction reaction,and batteries.Lastly,a forward-looking perspective addresses the current challenges and outlines future directions.This review aims to deepen our understanding of DACs and stimulate further innovation in advanced catalysts for energy conversion systems.
基金supported by the Hebei Natural Science Foundation(B2024205035)supported by the Fundamental Research Funds for the Central Universities+5 种基金the World-Class Universities(Disciplines)the Characteristic Development Guidance Funds for the Central Universities(1061-B23017010264)supported by the Fundamental Research Funds for the Natural Science Foundation of China(92047201,52102237)the Natural Science Foundation of Jiangsu Province(BK20220006)the National Major Projects of Water Pollution Control and Management Technology(2017ZX07204003)the Postdoctoral Science Foundations of China and Jiangsu Province(2021M690861,2022T150183,2021K065A)。
文摘Electrocatalytic C—N coupling is an environmentally friendly pathway for reducing CO_(2)emissions,nitrate wastewater treatment,and urea production.CeO_(2)is a commonly used electrocatalyst for urea synthesis,but its yield was restricted by the deficiency of active sites and the high barrier for C—N coupling.Herein,we employed transient heating to introduce oxygen vacancies as sites for the deposition of single metal atoms,thereby maximizing the atomic utilization as active sites for urea synthesis.The as-prepared CuFe-V-CeO_(2)electrocatalyst exhibits the outstanding urea yield rate(3553 mg h^(-1)g_(ca)^(t-1).)at-1.5 V versus reversible hydrogen electrode(RHE),surpassing the performance of previously reported electrochemical urea electrocatalysts.Theoretical calculation further revealed the roles of Ce,Cu,and Fe sites in active hydrogen(*H)generation,nitrate treatment,and CO_(2)stabilization,respectively.This work offers a novel and effective pathway for the design of electrocatalysts and developing an efficient C—N coupling system for urea production.
基金the funds granted by the Ningxia Natural Science Foundation(2023AAC05003,2024AAC03048,2024AAC03051)the National Natural Science Foundation of China(22108130,22368039)+1 种基金the Ningxia Key Research&Development Program(2023BDE03001)the Ningxia Overseas Returnee Innovation and Entrepreneurship Project for the financial support。
文摘Addressing the contamination of antibiotics has attracted ever-increasing and imperative attention due to their widespread existence,easy-to-cause drug-resistant bacteria infection,coupled with their intrinsic toxicity and hazard to environments and human health.Herein,a novel CC/CoNi-LDH-10%Ce anode material was directly constructed through a simple and rapid electrodeposition strategy,serving as an efficacious electrocatalyst for removing ciprofloxacin(CIP)from aqueous solution.Such novel CC/CoNi-LDH-10%Ce anode delivered a higher charge transfer,relatively abundant oxygen vacancies,and a higher electrochemical active area.The as-fabricated CC/CoNi-LDH-10%Ce electrode achieved a substantially boosted CIP removal efficiency of 52.5%relative to that of pure CC at about 23.9%.Notably,doping an appropriate amount of Ce^(3+)can endow the pristine CC/CoNi-LDH with richer oxygen vacancies and excellent electrocatalytic performance.Additionally,the electrocatalytic oxidation of CIP was attributed to both direct oxidation on the electrode surface and indirect oxidation induced by the generated active species(superoxide radicals and hydroxyl radicals).This study provides a simple,universal and flexible tactic for other researchers in designing and manufacturing avenues of electrodes.
基金supported by the National Key Re-search and Development Program of China(No.2021YFA1500403)the National Natural Science Foundation of China(No.21773047 and No.U1832180)partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication.
文摘ZnO-based catalysts have been widely used in hydrogenation reactions,but less attention has been paid to the electrocatalytic hydrogenation process on ZnO electrodes.In this work,the preparation of hydrogen species and the associ-ated reduction properties under electrochemi-cal processes in aqueous solutions have been in-vestigated on ZnO and Au/ZnO electrodes.The measurements of cyclic voltammetry(CV),X-ray diffraction,and electron paramagnetic resonance(EPR)confirm the formation of hydro-gen species on the interstitial sites(Hi)or on the oxygen vacancy sites(H_(O)).The hydrogena-tion reaction of p-nitrophenol(pNP)at 40μmol/L occurs on both ZnO and Au/ZnO elec-trodes,and the hydrogenation reduction performance of Au/ZnO electrode is better than that of ZnO electrode.CVs show H_(O)species is much more reactive with pNP than Hi species.Compared with the ZnO electrode,the presence of Au on ZnO promotes the formation of H_(O)species and improves the electro-reduction performance to pNP.These results help us to un-derstand the reaction processes related to the electrochemical hydrogenation on ZnO and Au/ZnO surfaces and shed new light on the design of new catalytic hydrogenation systems.
文摘Ligand-stabilized metal nanoclusters with atomic precision have garnered significant attention for applications in catalysis,biomedicine,and nanoelectronics due to their tunable structures and unique physicochemical properties[1-3].While transition metals such as Au,Ag,Pt,and Pd dominate the core composition,surface ligands are predominantly limited to phosphines,thiols,alkynes,and carbenes.Among these,N-heterocyclic carbenes(NHCs)have emerged as a superior ligand class due to their dual capacity for strongσ-donation andπ-back bonding,which stabilizes diverse metal oxidation states and enhances metal-ligand interactions.Notably,NHC-protected clusters exhibit exceptional thermal stability attributed to CH-π/π-πinteractions and enlarged HOMO-LUMO gaps compared to thiol or phosphine analogues.Despite progress,synthetic limitations persist due to NHCs'sensitivity under harsh conditions.Current methods rely on direct reduction of metal-carbene precursors or ligand exchange reactions,with heterogeneous NHC-capped systems remaining unexplored.
基金financially supported by the National Natural Science Foundation of China(Nos.22271021,21971024)Liao Ning Revitalization Talents Program(No.XLYC1902011)Research Foundation of Education Bureau of Liaoning Province(No.LJKQZ20222290)。
文摘The fabrication of bifunctional electrocatalysts for hydrogen and oxygen evolution in aqueous environment has far-reaching significance.Especially,reasonable interface process regulation toward heterogeneous composites can make full use of the active sites and improve the electrocatalytic activity.In this study,we designed and synthesized NiS_(2)-MoS_(2)-based heterogeneous composites as efficient and stable electrocatalysts for hydrogen and oxygen evolution in alkaline electrolyte.The heterostructure was obtained by one-step hydrothermal ulfurization operation towards polymolybdate-based metal-organic complex.The composition and nanostructures can be tailored by modulating experiment parameter,realizing the phase-controlled synthesis and interface regulation:(1)High-percentage of 1T-MoS_(2)can be achieved via selecting appropriate vulcanization time and thiourea concentration,benifiting for the higher electroconductivity and more active sites;(2)Regular and orderly vulcanization time promotes the gradual growth and aggregation of nanosheets;(3)The existence of nickel hydroxide improves the electrocatalytic stability for oxygen production performance.The optimized heterogeneous interfaces provide sufficient active sites and accelerate electron transfer.Consequently,the optimal heterogeneous nanosheets present low overpotentials of 33 and 122 m V at the catalytic current densities of 10 m A/cm2for HER and OER,respectively.
基金supported by the Guangdong Basic and Applied Basic Research Fund Project(2022A1515140061,No.11000-2344014)Startup Foundation for Postdoctor by Dongguan University of Technology(No.11000-221110149)the High-level Talents Program(contract number 2023JC10L014)of the Department of Science and Technology of Guangdong Province。
文摘High entropy materials(HEMs)are the promising electrocatalysts for anion exchange membrane electrolyser(AEMs)and proton exchange membrane fuel cells(PEMFCs)due to the intriguing cocktail effect,wide design space,tailorable electronic structure,and entropy stabilization effect.The precise fabrication of HEMs with functional nanostructures provides a crucial avenue to optimize the adsorption strength and catalytic activity for electrocatalysis.This review comprehensively summarizes the development of HEMs,focusing on the principles and strategies of structural design,and the catalytic mechanism towards hydrogen evolution reaction,oxygen evolution reaction and oxygen reduction reaction for the development of high-performance electrocatalysts.The complexity inherent in the interactions between different elements,the changes in the d-band center and the Gibbs free energies during the catalytic progress,as well as the coordination environment of the active sites associated with the unique crystal structure to improve the catalytic performance are discussed.We also provide a perspective on the challenges and future development direction of HEMs in electrocatalysis.This review will contribute to the design and development of HEMs-based catalysts for the next generation of electrochemical applications.
基金supported by Shanghai Science and Technology Plan Project(No.23ZR1467000)the Fundamental Research Funds for the Central University(No.22120240354)+1 种基金the National Natural Science Foundation of China(No.22131004)the Leading Scientific Research Project from China National Nuclear Corporation(No.CNNC–CXLM-202205).
文摘The efficient electrocatalytic nitrate(NO_(3)^(−))reduction to ammonia(NRA)offers a sustainable alternative for both environmental remediation and ammonia synthesis.Developing advanced electrocatalysts with rationally designed spatial arrangement of active sites and optimizing the synergetic effect among components are crucial for high efficiency and selectivity.Herein,we present Fe/N active sites decorated on porous carbon nanofibers(CNFs)with encapsulated FeCo nanoparticles(FeCo@CNFs-Fe/N)as electrocatalysts for NRA.The FeCo@CNFs-Fe/N catalyst demonstrates exceptional performance,achieving a high ammonia yield of 498.18μmol/(h·g_(cat)).Meanwhile,the enhanced reduction activity,especially the reduction in overpotential by 0.565 V,is 3–10 times higher than that of FeCo-encapsulated and Fe/N-modified CNFs-based catalysts.The enhanced catalytic activity is attributed to the efficient structure design and optimized spatial distribution of active sites,which enhance the electron transfer rate and decrease the reaction energy barrier.Mechanistic studies reveal that the synergetic effect between encapsulated nanoparticles and surface-modified Fe/N sites plays a crucial role in promoting efficient nitrate adsorption and selective ammonia production.These findings highlight the potential of strategically engineered CNF-based composites for nitrate reduction and other advanced electrocatalytic applications.
基金supported by the Natural Science Foundation of Shanghai(No.23ZR1401300)the National Natural Science Foundation of China(No.52170068).
文摘Singlet oxygen(^(1)O_(2)),as an electrophilic oxidant,is essential for the selective water decontamination of pollutants from water.Herein,we showcase a high-performing electrocatalytic filtration system composed of carbon nanotubes functionalized with CoFe alloy nanoparticles(CoFeCNT)to selectively facilitate the electrochemical activation of O_(2)to^(1)O_(2).Benefiting from the prominently featured bimetal active sites of CoFeCNT,nearly complete production of^(1)O_(2)is achieved by the electrocatalytic activation of O_(2).Additionally,the proposed system exhibits a consistent pollutant removal efficiency>90%in a flow-through reactor over 48 h of continuous operation without a noticeable decline in performance,highlighting the dependable stability of the system for practical applications.The flow-through configuration demonstrates a striking 8-fold enhancement in tetracycline oxidation compared to a conventional batch reactor.This work provides a molecular level understanding of the oxygen reduction reaction,showing promising potential for the selective removal of emerging organic contaminants from water.
