Electrocatalytic nitric oxide(NO)reduction reaction(NORR)is a promising and sustainable process that can simultaneously realize green ammonia(NH3)synthesis and hazardous NO removal.However,current NORR performances ar...Electrocatalytic nitric oxide(NO)reduction reaction(NORR)is a promising and sustainable process that can simultaneously realize green ammonia(NH3)synthesis and hazardous NO removal.However,current NORR performances are far from practical needs due to the lack of efficient electrocatalysts.Engineering the lattice of metal-based nanomaterials via phase control has emerged as an effective strategy to modulate their intrinsic electrocatalytic properties.Herein,we realize boron(B)-insertion-induced phase regulation of rhodium(Rh)nanocrystals to obtain amorphous Rh_(4)B nanoparticles(NPs)and hexagonal close-packed(hcp)RhB NPs through a facile wet-chemical method.A high Faradaic efficiency(92.1±1.2%)and NH_(3) yield rate(629.5±11.0μmol h^(−1) cm^(−2))are achieved over hcp RhB NPs,far superior to those of most reported NORR nanocatalysts.In situ spectro-electrochemical analysis and density functional theory simulations reveal that the excellent electrocatalytic performances of hcp RhB NPs are attributed to the upshift of d-band center,enhanced NO adsorption/activation profile,and greatly reduced energy barrier of the rate-determining step.A demonstrative Zn-NO battery is assembled using hcp RhB NPs as the cathode and delivers a peak power density of 4.33 mW cm−2,realizing simultaneous NO removal,NH3 synthesis,and electricity output.展开更多
Herein,a tandem electrocatalytic-catalytic method is employed to produce valuable alanine from nitrate and waste polylactic acid(PLA).Initially,two strategies are proposed to enhance the performance of electrocatalyti...Herein,a tandem electrocatalytic-catalytic method is employed to produce valuable alanine from nitrate and waste polylactic acid(PLA).Initially,two strategies are proposed to enhance the performance of electrocatalytic NO_(3)^(-)reduction reaction(NO_(3)^(-)RR):optimizing NO_(3)^(-)adsorption and accelerating water dissociation by modulating the cathode electrocatalyst.Fe-regulated Co nanosheets(Fe_(0.33)-Co(OH)_(2)NSs)have been developed as an efficient electrocatalyst,which demonstrate a remarkable Faradaic efficiency(FE)of 98.2%,with a corresponding yield rate of 10.7 mg h^(-1)cm^(-2)for NO_(3)RR to NH_(3)at-0.1 V vs.RHE.Additionally,~95%FEs of NH_(3)at-200 mA cm^(-2)have been maintained for>430 h in the alkaline solution.Subsequently,in situ technologies have been utilized to elucidate the NO_(3)^(-)RR pathways,the structure transformation of the electrocatalysts,and the effects of Fe-induced work function reduction and electron enrichment at Co sites on electrocatalytic activity.Finally,alanine is synthesized by using PLA and the generated NH_(3)as the raw reactants on the Ru/TiO_(2)catalyst,achieving maximum yield and selectivity of 81.3%and 91.8%,respectively,which provides a novel approach to utilize the nitrogen resource and mitigate plastic pollution.展开更多
The electrochemical conversion of nitrate,a widespread water pollutant,into valuable ammonia represents a green and decentralized approach to ammonia synthesis.However,the sluggish multielectronproton coupling path an...The electrochemical conversion of nitrate,a widespread water pollutant,into valuable ammonia represents a green and decentralized approach to ammonia synthesis.However,the sluggish multielectronproton coupling path and the low reactive species(nitrate and proton)concentration at the catalyst interface inhibit the efficiency of ammonia production from nitrate reduction reaction(NitRR).Herein,we introduce a novel iron-based tandem catalyst encapsulated by reduced graphene oxide(denoted as Fe-rGO),with a superior ammonia production rate of 47.815 mg h^(-1)mg_(ca)^(t-1)and a high Faraday efficiency(FE)of 96.51%at an applied potential of-0.5 V.It also delivers a robust stability with FE above90%under a current density of 250 mA cm^(-2)for 50 h.In situ X-ray absorption spectroscopy reveals that the FeO_(x)is dynamically translated to Fe~0 site concurrently with the enhancement of the NH_(3)production rate,suggesting the Fe^(0) site as hydrogenation active center.The asymmetric distribution of surface charges of rGO not only enriches nitrate ions at the catalytic interface and promotes the hydrogenation process in NitRR,but also protects the iron species and ensures their stability during electrolysis.The Zn-NO_(3)^(-)battery demonstrates an impressive FE of 88.6%,highlighting its exceptional potential for practical applications.展开更多
Electrocatalytic hydrogen peroxide(H_(2)O_(2))production via the two-electron oxygen reduction reaction(2e−ORR)is promising,but non-metal catalysts with high selectivity are lacking.Herein,a high content of pyrrolic N...Electrocatalytic hydrogen peroxide(H_(2)O_(2))production via the two-electron oxygen reduction reaction(2e−ORR)is promising,but non-metal catalysts with high selectivity are lacking.Herein,a high content of pyrrolic N doped carbon(HPNC)with small mesopores is constructed.Over 80%H_(2)O_(2) selectivity at a wide potential of 0.2–0.6 V is achieved.The finite element simulation reveals that small pore-size mesopores are beneficial to O_(2) adsorption.And in-situ characterization proves that HPNC suppresses the breakage of Osingle bondO bond and enhances the stabilization of *OOH intermediates,thus improving the 2e−ORR performance.This work highlights the combination of non-metal active sites and geometry for 2e−ORR electrocatalysis.展开更多
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
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 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
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
Electrocatalysis has emerged as a sustainable approach for the selective oxidation of fatty alcohols to fatty acids,circumventing the environmental concerns associated with conventional routes.However,the low aqueous ...Electrocatalysis has emerged as a sustainable approach for the selective oxidation of fatty alcohols to fatty acids,circumventing the environmental concerns associated with conventional routes.However,the low aqueous solubility of hydrophobic fatty alcohols presents a major challenge.While nickel hydroxide(Ni(OH)_(2))serves as a cost-effective catalyst for alcohol oxidation,its hydrophilic nature limits substrate accessibility and mass transport,causing sluggish kinetics and competing oxygen evolution.Herein,we propose a hydrophobic interface engineering strategy via co-electrodeposition of Ni(OH)_(2)with polytetrafluoroethylene(PTFE),fabricating the composite electrode(ED-Ni(OH)_(2)-PTFE).The optimized electrode achieves 95%Faradaic efficiency for octanoic acid at 1.5 V vs.RHE,with a production rate 2–3 times higher than pristine Ni(OH)_(2).Mechanistic studies combining in situ Raman spectroscopy,fluorescence imaging,and coarse-grained molecular dynamics simulations reveal that PTFE selectively enriches octanol at the electrode-electrolyte interface by modulating interfacial hydrophobicity.A continuous-flow microreactor integrating anodic octanol oxidation with cathodic hydrogen evolution reduces cell voltage by~100 m V,achieving simultaneous fatty acid and hydrogen production.This work highlights the critical role of hydrophobic interfacial microenvironment design in organic electrosynthesis,offering a promising strategy for upgrading fatty alcohols under mild conditions.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
Modulating the adsorption energy of intermediate species via alloying presents a promising approach to enhance the electrocatalytic nitrate reduction to ammonia(NRA).Nonetheless,the synthesis of alloy catalysts that a...Modulating the adsorption energy of intermediate species via alloying presents a promising approach to enhance the electrocatalytic nitrate reduction to ammonia(NRA).Nonetheless,the synthesis of alloy catalysts that are uniformly distributed and structurally stable poses significant challenges.Herein,the CuNi alloy was successfully anchored on oxygen vacancy-rich N-Ti_(3)C_(2)T_(x) through metal-support interactions(MSI).The three-dimensional(3D)wrinkled morphology of N-Ti_(3)C_(2)T_(x) MXene was achieved by employing melamine-formaldehyde spheres(MFs)as self-sacrificial templates,which effectively prevented the restacking of the Ti_(3)C_(2)T_(x) layers,thereby increasing specific surface area and promoting the formation of surface oxygen vacancies.Ti–O–M structure plays a crucial role in inhibiting both particle migration and metal atom diffusion.X-ray photoelectron spectroscopy(XPS)analysis confirms moderate metal-support interactions between the CuNi alloy and N-Ti_(3)C_(2)T_(x),leading to the establishment of stable Ti–O–M bonds and charge redistribution within the Ti-O-M framework.The Cu_(5)Ni_(5)/N-Ti_(3)C_(2)T_(x) sample achieves an impressive Faradaic efficiency(FE)of 97.50%at−0.27 V vs.RHE,alongside the highest NH3 yield rate of 527.44µmol h−1 cm−2.In-situ electrochemical Raman spectroscopy and theoretical calculations reveal that the high intrinsic catalytic activity of NRA can be attributed to the synergistic effects between the CuNi alloy and the interfacial metal-oxygen interactions.This work provides significant perspectives on the design of interfacial metal interactions and the development of durable electrocatalysts.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
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
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
Electrocatalytic CO_(2)reduction(CO_(2)RR)is spurring intensive research interest,where many attentions have been paid to catalyst design and mechanism study.Electrode near-surface microenvironment matters fundamental...Electrocatalytic CO_(2)reduction(CO_(2)RR)is spurring intensive research interest,where many attentions have been paid to catalyst design and mechanism study.Electrode near-surface microenvironment matters fundamentally for reactant mass transfer,water molecule interference,catalyst exposure,and others,yet it has been rarely investigated.In the latest issue of Angew.Chem.Int.Ed.,Han,Kang and coauthors reported a method to regulate the microenvironment on the catalyst surface by adding polyethylene glycol,which remarkably improves the yield of multicarbon products.This strategy of controlling multiple proton-electron coupling processes through molecular chemistry-driven microenvironmental regulation is thought to inspire new idea for addressing the low efficiency challenge of CO_(2)RR.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
The quest for sustainable energy solutions has intensified the search for alternative feedstocks that can supplement or replace fossil fuels. Obtaining fuels or chemicals through the conversion of renewable biomass is...The quest for sustainable energy solutions has intensified the search for alternative feedstocks that can supplement or replace fossil fuels. Obtaining fuels or chemicals through the conversion of renewable biomass is a promising candidate [1,2]. Some noblemetal-based (e.g., Pt, Pd and Rh) catalysts exhibit significant catalytic activity to the conversion reaction of these biomass.展开更多
基金funding support from General Research Fund[Project No.14300525]from the Research Grants Council(RGC)of Hong Kong SAR,Chinafunding support from Natural Science Foundation of China(NSFC)Young Scientists Fund(Project No.22305203)+2 种基金NSFC Projects Nos.22309123,22422303,22303011,22033002,92261112 and U21A20328support from the Hong Kong Branch of National Precious Metals Material Engineering Research Center(NPMM)at City University of Hong Kongsupport from Young Collaborative Research Grant[Project No.C1003-23Y]support from RGC of Hong Kong SAR,China.
文摘Electrocatalytic nitric oxide(NO)reduction reaction(NORR)is a promising and sustainable process that can simultaneously realize green ammonia(NH3)synthesis and hazardous NO removal.However,current NORR performances are far from practical needs due to the lack of efficient electrocatalysts.Engineering the lattice of metal-based nanomaterials via phase control has emerged as an effective strategy to modulate their intrinsic electrocatalytic properties.Herein,we realize boron(B)-insertion-induced phase regulation of rhodium(Rh)nanocrystals to obtain amorphous Rh_(4)B nanoparticles(NPs)and hexagonal close-packed(hcp)RhB NPs through a facile wet-chemical method.A high Faradaic efficiency(92.1±1.2%)and NH_(3) yield rate(629.5±11.0μmol h^(−1) cm^(−2))are achieved over hcp RhB NPs,far superior to those of most reported NORR nanocatalysts.In situ spectro-electrochemical analysis and density functional theory simulations reveal that the excellent electrocatalytic performances of hcp RhB NPs are attributed to the upshift of d-band center,enhanced NO adsorption/activation profile,and greatly reduced energy barrier of the rate-determining step.A demonstrative Zn-NO battery is assembled using hcp RhB NPs as the cathode and delivers a peak power density of 4.33 mW cm−2,realizing simultaneous NO removal,NH3 synthesis,and electricity output.
基金supported by the National Key R&D Program of China(2022YFB4002700)the National Natural Science Foundation of China(22475071)the Shanghai Science and Technology Committee Rising-Star Program(22QA1403400)。
文摘Herein,a tandem electrocatalytic-catalytic method is employed to produce valuable alanine from nitrate and waste polylactic acid(PLA).Initially,two strategies are proposed to enhance the performance of electrocatalytic NO_(3)^(-)reduction reaction(NO_(3)^(-)RR):optimizing NO_(3)^(-)adsorption and accelerating water dissociation by modulating the cathode electrocatalyst.Fe-regulated Co nanosheets(Fe_(0.33)-Co(OH)_(2)NSs)have been developed as an efficient electrocatalyst,which demonstrate a remarkable Faradaic efficiency(FE)of 98.2%,with a corresponding yield rate of 10.7 mg h^(-1)cm^(-2)for NO_(3)RR to NH_(3)at-0.1 V vs.RHE.Additionally,~95%FEs of NH_(3)at-200 mA cm^(-2)have been maintained for>430 h in the alkaline solution.Subsequently,in situ technologies have been utilized to elucidate the NO_(3)^(-)RR pathways,the structure transformation of the electrocatalysts,and the effects of Fe-induced work function reduction and electron enrichment at Co sites on electrocatalytic activity.Finally,alanine is synthesized by using PLA and the generated NH_(3)as the raw reactants on the Ru/TiO_(2)catalyst,achieving maximum yield and selectivity of 81.3%and 91.8%,respectively,which provides a novel approach to utilize the nitrogen resource and mitigate plastic pollution.
基金supported by the National Natural Science Foundation of China(12205300(H.S.),12405377(M.H.L))the Postdoctoral Science Foundation of China(2024M763694(M.H.L))+3 种基金the Natural Science Foundation of Hunan Province(2024JJ4027(H.S.))the Postdoctoral Fellowship Program of CPSF under Grant Number GZB20240859(M.H.L)financial support from the Hunan Normal University Program(grant05311204666)financial support from the 2024 Large Instrument Testing Open Fund of Hunan Normal University(24CSY033,24CSY086)。
文摘The electrochemical conversion of nitrate,a widespread water pollutant,into valuable ammonia represents a green and decentralized approach to ammonia synthesis.However,the sluggish multielectronproton coupling path and the low reactive species(nitrate and proton)concentration at the catalyst interface inhibit the efficiency of ammonia production from nitrate reduction reaction(NitRR).Herein,we introduce a novel iron-based tandem catalyst encapsulated by reduced graphene oxide(denoted as Fe-rGO),with a superior ammonia production rate of 47.815 mg h^(-1)mg_(ca)^(t-1)and a high Faraday efficiency(FE)of 96.51%at an applied potential of-0.5 V.It also delivers a robust stability with FE above90%under a current density of 250 mA cm^(-2)for 50 h.In situ X-ray absorption spectroscopy reveals that the FeO_(x)is dynamically translated to Fe~0 site concurrently with the enhancement of the NH_(3)production rate,suggesting the Fe^(0) site as hydrogenation active center.The asymmetric distribution of surface charges of rGO not only enriches nitrate ions at the catalytic interface and promotes the hydrogenation process in NitRR,but also protects the iron species and ensures their stability during electrolysis.The Zn-NO_(3)^(-)battery demonstrates an impressive FE of 88.6%,highlighting its exceptional potential for practical applications.
文摘Electrocatalytic hydrogen peroxide(H_(2)O_(2))production via the two-electron oxygen reduction reaction(2e−ORR)is promising,but non-metal catalysts with high selectivity are lacking.Herein,a high content of pyrrolic N doped carbon(HPNC)with small mesopores is constructed.Over 80%H_(2)O_(2) selectivity at a wide potential of 0.2–0.6 V is achieved.The finite element simulation reveals that small pore-size mesopores are beneficial to O_(2) adsorption.And in-situ characterization proves that HPNC suppresses the breakage of Osingle bondO bond and enhances the stabilization of *OOH intermediates,thus improving the 2e−ORR performance.This work highlights the combination of non-metal active sites and geometry for 2e−ORR electrocatalysis.
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.
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(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 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.
基金Financial supports from the National Natural Science Foundation(No.21991104 and No.22,278,235)。
文摘Electrocatalysis has emerged as a sustainable approach for the selective oxidation of fatty alcohols to fatty acids,circumventing the environmental concerns associated with conventional routes.However,the low aqueous solubility of hydrophobic fatty alcohols presents a major challenge.While nickel hydroxide(Ni(OH)_(2))serves as a cost-effective catalyst for alcohol oxidation,its hydrophilic nature limits substrate accessibility and mass transport,causing sluggish kinetics and competing oxygen evolution.Herein,we propose a hydrophobic interface engineering strategy via co-electrodeposition of Ni(OH)_(2)with polytetrafluoroethylene(PTFE),fabricating the composite electrode(ED-Ni(OH)_(2)-PTFE).The optimized electrode achieves 95%Faradaic efficiency for octanoic acid at 1.5 V vs.RHE,with a production rate 2–3 times higher than pristine Ni(OH)_(2).Mechanistic studies combining in situ Raman spectroscopy,fluorescence imaging,and coarse-grained molecular dynamics simulations reveal that PTFE selectively enriches octanol at the electrode-electrolyte interface by modulating interfacial hydrophobicity.A continuous-flow microreactor integrating anodic octanol oxidation with cathodic hydrogen evolution reduces cell voltage by~100 m V,achieving simultaneous fatty acid and hydrogen production.This work highlights the critical role of hydrophobic interfacial microenvironment design in organic electrosynthesis,offering a promising strategy for upgrading fatty alcohols under mild conditions.
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upported by the National Natural Science Foundation of China(Nos.U22A20253,52272293,and 52401275)the Fellowship of China Postdoctoral Science Foundation(No.2021M701116).
文摘Modulating the adsorption energy of intermediate species via alloying presents a promising approach to enhance the electrocatalytic nitrate reduction to ammonia(NRA).Nonetheless,the synthesis of alloy catalysts that are uniformly distributed and structurally stable poses significant challenges.Herein,the CuNi alloy was successfully anchored on oxygen vacancy-rich N-Ti_(3)C_(2)T_(x) through metal-support interactions(MSI).The three-dimensional(3D)wrinkled morphology of N-Ti_(3)C_(2)T_(x) MXene was achieved by employing melamine-formaldehyde spheres(MFs)as self-sacrificial templates,which effectively prevented the restacking of the Ti_(3)C_(2)T_(x) layers,thereby increasing specific surface area and promoting the formation of surface oxygen vacancies.Ti–O–M structure plays a crucial role in inhibiting both particle migration and metal atom diffusion.X-ray photoelectron spectroscopy(XPS)analysis confirms moderate metal-support interactions between the CuNi alloy and N-Ti_(3)C_(2)T_(x),leading to the establishment of stable Ti–O–M bonds and charge redistribution within the Ti-O-M framework.The Cu_(5)Ni_(5)/N-Ti_(3)C_(2)T_(x) sample achieves an impressive Faradaic efficiency(FE)of 97.50%at−0.27 V vs.RHE,alongside the highest NH3 yield rate of 527.44µmol h−1 cm−2.In-situ electrochemical Raman spectroscopy and theoretical calculations reveal that the high intrinsic catalytic activity of NRA can be attributed to the synergistic effects between the CuNi alloy and the interfacial metal-oxygen interactions.This work provides significant perspectives on the design of interfacial metal interactions and the development of durable electrocatalysts.
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 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 National Natural Science Foundation of China(22393961,U23A20132,22209007)the Beijing Natural Science Foundation(2232016)+1 种基金the Beijing Nova Program(20240484611)the Fundamental Research Funds for the Central Universities,China(buctrc202029,buctrc202129).
文摘Electrocatalytic CO_(2)reduction(CO_(2)RR)is spurring intensive research interest,where many attentions have been paid to catalyst design and mechanism study.Electrode near-surface microenvironment matters fundamentally for reactant mass transfer,water molecule interference,catalyst exposure,and others,yet it has been rarely investigated.In the latest issue of Angew.Chem.Int.Ed.,Han,Kang and coauthors reported a method to regulate the microenvironment on the catalyst surface by adding polyethylene glycol,which remarkably improves the yield of multicarbon products.This strategy of controlling multiple proton-electron coupling processes through molecular chemistry-driven microenvironmental regulation is thought to inspire new idea for addressing the low efficiency challenge of CO_(2)RR.
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.
文摘The quest for sustainable energy solutions has intensified the search for alternative feedstocks that can supplement or replace fossil fuels. Obtaining fuels or chemicals through the conversion of renewable biomass is a promising candidate [1,2]. Some noblemetal-based (e.g., Pt, Pd and Rh) catalysts exhibit significant catalytic activity to the conversion reaction of these biomass.
