This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the correspo...This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the corresponding ester[Fe_(2)(CO)_(6)(μ‑tedt)](2),where tedt=SCH_(2)CH(CH_(2)OOC(5‑C_(3)HNSCH_(3)))S.Further reactions of complex 2 with tri(ptolyl)phosphine(tp)or tris(4‑fluorophenyl)phosphine(fp)gave the phosphine‑substituted derivatives[Fe_(2)(CO)_(5)(tp)(μ‑tedt)](3)and[Fe_(2)(CO)_(5)(fp)(μ‑tedt)](4).The structures of the newly prepared complexes were elucidated by elemental analysis,NMR,IR,and X‑ray photoelectron spectroscopy.Moreover,single‑crystal X‑ray diffraction analysis confirmed their molecular structures,showing that they contain a di‑iron core ligated by a bridged dithiolate bearing a thiazole moiety and terminal carbonyls.The electrochemical and electrocatalytic proton reduction were probed by cyclic voltammetry,revealing that three complexes can catalyze the reduction of protons to H_(2) under the electrochemical conditions.For comparison,complex 4 possessed the best efficiency with a turnover frequency of 23.5 s^(-1)at 10 mmol·L^(-1)HOAc concentration.In addition,the fungicidal activity of these complexes was also investigated in this study.CCDC:2477511,2;2477512,3;2477513,4.展开更多
CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organ...CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organic frameworks(COFs)are porous crystalline materials formed by connecting organic monomers through covalent bonds.They have the characteristics of functional diversity and rich chemical properties.Their advantages,such as high porosity,a wide range of visible light absorption,and excellent charge separation efficiency,give them good potential in CO_(2)capture,separation,and conversion.Currently,Cu is a key metal in the catalytic CO_(2)reduction reaction(CO_(2)RR)for the preparation of high-value-added chemicals.The preparation of highly stable and large-pore Cu-based COFs using COFs as an ideal sacrificial template for loading Cu can be used to develop high-performance electrocatalysts and photocatalysts.In this review,we discuss the latest advancements in this field,including the development of various Cu-based COFs and their applications as catalysts for CO_(2)RR.Here,we mainly introduce the synthesis strategies,some important characterization information,and the applications of electrocatalytic and photocatalytic CO_(2)conversion using these previously reported Cu-based COFs.展开更多
The two-electron electrochemical oxygen reduction reaction(ORR)affords an appealing alternative for on-site production of hydrogen peroxide(H_(2)O_(2)),which can fulfill the demands of various applications even at low...The two-electron electrochemical oxygen reduction reaction(ORR)affords an appealing alternative for on-site production of hydrogen peroxide(H_(2)O_(2)),which can fulfill the demands of various applications even at low concentrations.Under neutral or near-neutral conditions,the electrolyte environment capable of electrochemically synthesizing H_(2)O_(2) exhibits diversity and holds vast potential for practical applications;however,the electrocatalytic performance is limited without desirable electrode materials.In this contribution,methoxylated nickel hydroxides were proposed for high-performance on-site H_(2)O_(2) electrosynthesis in different potassium fertilizer solutions.The methoxylation compared to pristine Ni(OH)_(2) was demonstrated to optimize the electronic structure with favorable adsorption of reaction intermediates,obviously enhancing the activity and selectivity.In 0.10 M K_(2)SO_(4) solution,H_(2)O_(2) production ranged from 28.1 to 153.6 mg h^(-1) cm^(-2) at current densities of-50 to-250 mA cm^(-2),accompanied by Faradaic efficiency values exceeding 88.0%.An integrated system was devised by combining fertilization,disinfection,and irrigation through the coupling of two-electron ORR with agricultural irrigation,utilizing nutrient solutions as the electrolyte for on-site H_(2)O_(2) electrosynthesis.These findings afford a promising avenue for the practical application of 2e-ORR in neutral environments.展开更多
Elucidating the active site formation mechanism of bismuth(Bi)-based catalysts in electrochemical CO_(2)reduction remains challenging for achieving high activity,selectivity,and long-term stability.Here we confirm thr...Elucidating the active site formation mechanism of bismuth(Bi)-based catalysts in electrochemical CO_(2)reduction remains challenging for achieving high activity,selectivity,and long-term stability.Here we confirm through experimental results that Bi-based catalysts containing halogen ions(I^(-),Cl^(-),Br^(-))and SO_(4)^(2-)maintain the system stability,keeping Faraday efficiency of formic acid above90%in the current range of 50-800 mA cm^(-2).In contrast,anions containing S^(2-)and NO_(3)^(-)in the electrolyte can be reduced to produce by-products.These anions and their by-products could poison the active center,leading to increased side reactions and thus significantly reducing the Faraday efficiency of formic acid.The combination of non-in situ and in situ characterization results revealed that the Bi-based catalysts all underwent the transition from the initial state to the Bi/Bi_(2)O_(2)CO_(3)(BOC)intermediate state in high-concentration KHCO_(3) solution,and the different anions could selectively modulate the degree of exposure of specific crystalline surfaces of BOC.At the late stage of the reaction,BOC was completely converted to metal Bi and became the real active center.Combined with in situ IR and DFT calculations,it is further verified that^(*)OCHO is the key intermediate on the metallic Bi surface,which is most favorable for formic acid formation.This study reveals the key mechanism by which anions affect the formation of active sites via modulating the catalyst reconstruction process,which provides an important theoretical basis for the design and optimization of test conditions of Bi-based catalysts.展开更多
This insightful review explores the electrochemical principles and energy potential of electrocatalytic water splitting(EWS).It highlights recent advancements,identifies key challenges,and underscores the pivotal role...This insightful review explores the electrochemical principles and energy potential of electrocatalytic water splitting(EWS).It highlights recent advancements,identifies key challenges,and underscores the pivotal role of EWS in enabling the transition to sustainable energy systems.This work contextualizes the significance of green hydrogen in global decarbonization pathways and examines the historical progression of electrocatalysis.The fundamental thermodynamics and mechanistic pathways governing both the hydrogen and oxygen evolution reactions(HER and OER)are analyzed,highlighting energy barriers and rate-determining steps.Various electrode architectures and electrochemical cell configurations are evaluated,including a comparative assessment of key electrolyzer technologies and their performance characteristics.Furthermore,we critically examine recent advances and persistent limitations across the landscape of electrocatalysts,spanning noble metal-based materials,earth-abundant transition metal compounds,and emerging materials.Design principles and mechanistic insights drawn from electronic structu re modulation,defect engineering,doping strategies,and na noscale morphology control are elucidated to establish robust structure-property-performance relationships.Major challenges including sluggish oxygen evolution kinetics,catalyst degradation mechanisms,and the integration of devices with intermittent renewable energy sources are thoroughly examined.This work also debates advanced strategies such as hybrid photoelectrochemical systems,flexible device architectures,and the direct utilization of non-traditional water sources(e.g.,seawater,wastewater)as promising pathways for future development.Finally,it is specifically distinguished by its critical focus on bridging the gap between fundamental electrocatalysts development and practical system-level integration,addressing the challenges of scalability and deployment under industrially relevant conditions.This comprehensive review provides a strategic outlook and identifies key scientific priorities for optimizing EWS systems toward efficient,robust,and scalable hydrogen generation.展开更多
The efficient electrocatalytic oxidation of glycerol(GLY)is one of the most promising routes for the valorization of GLY.Doping has emerged as a powerful strategy to tailor the electrocatalytic performance of silver n...The efficient electrocatalytic oxidation of glycerol(GLY)is one of the most promising routes for the valorization of GLY.Doping has emerged as a powerful strategy to tailor the electrocatalytic performance of silver nanoclusters(Ag NCs),yet the effects of doping mode(surface vs.core)and the interface environment(e.g.,electrolyte concentration)on the electrocatalytic performance for Ag NCs toward GLY oxidation remain understood.In this work,surface-doped Ag_(4)M_(2)(SR)_(8) and core-doped Ag_(24)M(SR)_(18)(M=Ni,Pd,Pt;SR=SPhMe_(2))NCs were synthesized for electrocatalytic GLY oxidation.The results revealed a strong dependence of selectivity on doping mode and electrolyte concentration:under low KOH concentration,Pd-and Pt-doped Ag_(4)M_(2) NCs exhibited 100%selectivity toward oxalic acid(OA),whereas Pd-and Pt-doped Ag_(24)M NCs delivered>95%selectivity for formic acid(FA).In contrast,under high KOH concentration,Pd-and Pt-doped Ag_(4)M_(2) NCs gave rise to>80%FA,while Pd-and Pt-doped Ag_(24)M NCs produced>45%FA.Mechanism studies indicated that Ni doping predominantly enhanced catalytic activity via lowering the activation barrier of the initial reaction step(GLY→glyceraldehyde),whereas Pd and Pt doping modulated selectivity through reducing the energy barrier of the selective branch step(glyceric acid→OA,OA→FA).High KOH concentration promoted the oxidation by increasing the electrochemical active surface area and facilitating electron transfer of Ag NCs.This study provides clear guidance for designing high-performance Ag-based electrocatalysts for biomass valorization.展开更多
Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O cr...Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O crystal plane orientation and the corresponding adsorbed ^(*)CO species.Herein,we constructed high-index crystal planes(311) in Cu_(2)O(CO-Cu_(2)O) via a facile self-selective CO-induced strategy under a CO atmosphere,which was verified by high-resolution transmission electron microscopy(HR-TEM) and atomic force microscopy(AFM) results.By exploiting the high surface energy of the high index crystal planes,^(*)CO species are stabilized in CO-Cu_(2)O during CO_(2)RR,resulting in exceptional catalytic performance for CO_(2)-to-C_(2)products.In situ infrared spectroscopy revealed that both atop-type(^(*)CO_(atop)) and hollow-type(^(*)CO_(hollow)) adsorption of ^(*)CO species occurred on the CO-Cu_(2)O.The asymmetric C-C coupling energy barrier between ^(*)CO_(atop) and ^(*)CO_(hollow) in(311) crystal plane decreases by 47.8 % compared to the symmetric coupling of ^(*)CO_(atop) in conventional(100) crystal planes.Consequently,the Faradaic efficiency of C_(2) products generated with CO-Cu_(2)O was increased by as high as 100 % compared to that with pristine Cu_(2)O.展开更多
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
Chlorinated antibiotics pose great challenges in efficient removal,while for the first time,this work greatly enhanced their electrocatalytic dechlorination performance by construction of non-noble metal Co_(3)O_(4)/g...Chlorinated antibiotics pose great challenges in efficient removal,while for the first time,this work greatly enhanced their electrocatalytic dechlorination performance by construction of non-noble metal Co_(3)O_(4)/g-C_(3)N_(4) heterojunctions to improve process cost-effectiveness.The Co_(3)O_(4)/g-C_(3)N_(4) heterojunction demonstrated an effective removal of 93.6%thiamphenicol(TAP)within 45 min,with the rate constant(0.0584 min^(-1))that was 2.4 and 2.8 times that of Co_(3)O_(4) and g-C_(3)N_(4) alone,respectively.The formation of heterojunctions facilitated electron transfer,enriched the electron density on Co_(3)O_(4),and enhanced the adsorption of pollutants as well as the desorption of degradation intermediates.The enhanced production of atomic hydrogen(H*)of Co_(3)O_(4)/g-C_(3)N_(4),which increased by 13.6-28.2 times,contributed more to pollutant removal(64.0%),much higher than that of Co_(3)O_(4)(37.3%)and g-C_(3)N_(4)(6.1%).The energy barrier for H_(2) formation on Co_(3)O_(4)/g-C_(3)N_(4)(0.75 eV)was higher than that on Co_(3)O_(4)(-1.84 eV),supporting that it could stabilize H*and inhibit the formation of H_(2).The Co_(3)O_(4)/g-C_(3)N_(4) heterojunction exhibited stable performance with less impact by pH and co-existing ions,and posed effectiveness for the dechlorination of typical chlorinated antibiotics.This study offers an efficient and sustainable strategy for constructing heterojunctions to enhance the performance of non-noble metal catalysts in electrocatalytic dechlorination.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 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
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
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 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
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
Noble metal-based intermetallic compounds(IMCs)with ordered atomic arrangements exhibit remarkable electrocatalytic activity owing to their unique crystal and electronic structures.During the past years,great advance ...Noble metal-based intermetallic compounds(IMCs)with ordered atomic arrangements exhibit remarkable electrocatalytic activity owing to their unique crystal and electronic structures.During the past years,great advance has been made in the development of noble metal-based IMCs.Recently,Lu and coworkers reported ultrathin“amorphous/intermetallic”(A/IMC)heterophase PtPbBi nanosheets(NSs)with a thickness of 2.5±0.3 nm.The oxidative etching effect caused by the coexistence of O_(2)and Br^(-)ions plays a crucial role in the formation of the IMC and unique two-dimensional structure with irregular shapes and curled edges.This study shows that fabricating an A/IMC heterophase structure with a multimetallic composition can effectively enhance the catalytic performances of noble metal-based electrocatalysts.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
High-entropy alloys(HEAs),with multi-principal-element composition,are gaining attention for their structural stability and mechanical properties.Extensive research has focused on using HEAs as electrocatalysts in the...High-entropy alloys(HEAs),with multi-principal-element composition,are gaining attention for their structural stability and mechanical properties.Extensive research has focused on using HEAs as electrocatalysts in the conversion of single-component reactions,such as hydrogen evolution reaction(HER),oxygen evolution reaction(OER),carbon dioxide reduction reaction(CO_(2)RR),etc.However,their potential in the application of synergistic conversion of pollutants(e.g.,carbon dioxide(CO_(2))and nitrogen oxides(NO_(x)))has been largely overlooked.This review overviews HEAs’fundamental concepts and characteristics,and delves into their advantages in transition metals and optimization strategies for the synergistic conversion process.It offers a novel approach for sustainable environmental remediation and resource utilization.展开更多
文摘This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the corresponding ester[Fe_(2)(CO)_(6)(μ‑tedt)](2),where tedt=SCH_(2)CH(CH_(2)OOC(5‑C_(3)HNSCH_(3)))S.Further reactions of complex 2 with tri(ptolyl)phosphine(tp)or tris(4‑fluorophenyl)phosphine(fp)gave the phosphine‑substituted derivatives[Fe_(2)(CO)_(5)(tp)(μ‑tedt)](3)and[Fe_(2)(CO)_(5)(fp)(μ‑tedt)](4).The structures of the newly prepared complexes were elucidated by elemental analysis,NMR,IR,and X‑ray photoelectron spectroscopy.Moreover,single‑crystal X‑ray diffraction analysis confirmed their molecular structures,showing that they contain a di‑iron core ligated by a bridged dithiolate bearing a thiazole moiety and terminal carbonyls.The electrochemical and electrocatalytic proton reduction were probed by cyclic voltammetry,revealing that three complexes can catalyze the reduction of protons to H_(2) under the electrochemical conditions.For comparison,complex 4 possessed the best efficiency with a turnover frequency of 23.5 s^(-1)at 10 mmol·L^(-1)HOAc concentration.In addition,the fungicidal activity of these complexes was also investigated in this study.CCDC:2477511,2;2477512,3;2477513,4.
文摘CO_(2)reduction technology can promote the resource utilization of carbon and help alleviate global warming and energy supply pressure.It is an effective way to achieve energy conversion and utilization.Covalent organic frameworks(COFs)are porous crystalline materials formed by connecting organic monomers through covalent bonds.They have the characteristics of functional diversity and rich chemical properties.Their advantages,such as high porosity,a wide range of visible light absorption,and excellent charge separation efficiency,give them good potential in CO_(2)capture,separation,and conversion.Currently,Cu is a key metal in the catalytic CO_(2)reduction reaction(CO_(2)RR)for the preparation of high-value-added chemicals.The preparation of highly stable and large-pore Cu-based COFs using COFs as an ideal sacrificial template for loading Cu can be used to develop high-performance electrocatalysts and photocatalysts.In this review,we discuss the latest advancements in this field,including the development of various Cu-based COFs and their applications as catalysts for CO_(2)RR.Here,we mainly introduce the synthesis strategies,some important characterization information,and the applications of electrocatalytic and photocatalytic CO_(2)conversion using these previously reported Cu-based COFs.
基金the support from the National Natural Science Foundation of China(22478221)China Postdoctoral Science Foundation(2023M741920 and GZC20231259)+1 种基金Huaneng Group Science and Technology Research Project(HNKJ23-H71)Department of Chemical Engineering-iBHE Cooperation Joint Fund Project(DCE-iBHE-2025-3)。
文摘The two-electron electrochemical oxygen reduction reaction(ORR)affords an appealing alternative for on-site production of hydrogen peroxide(H_(2)O_(2)),which can fulfill the demands of various applications even at low concentrations.Under neutral or near-neutral conditions,the electrolyte environment capable of electrochemically synthesizing H_(2)O_(2) exhibits diversity and holds vast potential for practical applications;however,the electrocatalytic performance is limited without desirable electrode materials.In this contribution,methoxylated nickel hydroxides were proposed for high-performance on-site H_(2)O_(2) electrosynthesis in different potassium fertilizer solutions.The methoxylation compared to pristine Ni(OH)_(2) was demonstrated to optimize the electronic structure with favorable adsorption of reaction intermediates,obviously enhancing the activity and selectivity.In 0.10 M K_(2)SO_(4) solution,H_(2)O_(2) production ranged from 28.1 to 153.6 mg h^(-1) cm^(-2) at current densities of-50 to-250 mA cm^(-2),accompanied by Faradaic efficiency values exceeding 88.0%.An integrated system was devised by combining fertilization,disinfection,and irrigation through the coupling of two-electron ORR with agricultural irrigation,utilizing nutrient solutions as the electrolyte for on-site H_(2)O_(2) electrosynthesis.These findings afford a promising avenue for the practical application of 2e-ORR in neutral environments.
基金funded by the“Pioneer”and“Leading Goose”R&D Program of Zhejiang(No.2023C03017)China Postdoctoral Science Foundation(No.GZC20230373)+5 种基金Zhejiang Provincial Natural Science Foundation of China(No.LQ24B070010)CMA Key Open Laboratory of Transforming Climate Resources to Economy(No.2024004K)Natural Science Foundation of Huzhou City(No.2024YZ19)the National Natural Science Foundation of China(Nos.22202032,22406020 and 22406019)the Key Research and Development Projects of Xinjiang Uygur Autonomous Region,China(No.2022B02031)Joint Fund of the Zhejiang Provincial Natural Science Foundation of China(No.LBMHY25E060009)。
文摘Elucidating the active site formation mechanism of bismuth(Bi)-based catalysts in electrochemical CO_(2)reduction remains challenging for achieving high activity,selectivity,and long-term stability.Here we confirm through experimental results that Bi-based catalysts containing halogen ions(I^(-),Cl^(-),Br^(-))and SO_(4)^(2-)maintain the system stability,keeping Faraday efficiency of formic acid above90%in the current range of 50-800 mA cm^(-2).In contrast,anions containing S^(2-)and NO_(3)^(-)in the electrolyte can be reduced to produce by-products.These anions and their by-products could poison the active center,leading to increased side reactions and thus significantly reducing the Faraday efficiency of formic acid.The combination of non-in situ and in situ characterization results revealed that the Bi-based catalysts all underwent the transition from the initial state to the Bi/Bi_(2)O_(2)CO_(3)(BOC)intermediate state in high-concentration KHCO_(3) solution,and the different anions could selectively modulate the degree of exposure of specific crystalline surfaces of BOC.At the late stage of the reaction,BOC was completely converted to metal Bi and became the real active center.Combined with in situ IR and DFT calculations,it is further verified that^(*)OCHO is the key intermediate on the metallic Bi surface,which is most favorable for formic acid formation.This study reveals the key mechanism by which anions affect the formation of active sites via modulating the catalyst reconstruction process,which provides an important theoretical basis for the design and optimization of test conditions of Bi-based catalysts.
基金Higher Education Commission(HEC)of Pakistan for financial support under grants#377-IPFP-Ⅱ/Batch-1st/SRGP-NAHE/HEC-2022-27 along with ASIP-Support Award Letter#ASIP/R&D/HEC/2024/10006/83387/127。
文摘This insightful review explores the electrochemical principles and energy potential of electrocatalytic water splitting(EWS).It highlights recent advancements,identifies key challenges,and underscores the pivotal role of EWS in enabling the transition to sustainable energy systems.This work contextualizes the significance of green hydrogen in global decarbonization pathways and examines the historical progression of electrocatalysis.The fundamental thermodynamics and mechanistic pathways governing both the hydrogen and oxygen evolution reactions(HER and OER)are analyzed,highlighting energy barriers and rate-determining steps.Various electrode architectures and electrochemical cell configurations are evaluated,including a comparative assessment of key electrolyzer technologies and their performance characteristics.Furthermore,we critically examine recent advances and persistent limitations across the landscape of electrocatalysts,spanning noble metal-based materials,earth-abundant transition metal compounds,and emerging materials.Design principles and mechanistic insights drawn from electronic structu re modulation,defect engineering,doping strategies,and na noscale morphology control are elucidated to establish robust structure-property-performance relationships.Major challenges including sluggish oxygen evolution kinetics,catalyst degradation mechanisms,and the integration of devices with intermittent renewable energy sources are thoroughly examined.This work also debates advanced strategies such as hybrid photoelectrochemical systems,flexible device architectures,and the direct utilization of non-traditional water sources(e.g.,seawater,wastewater)as promising pathways for future development.Finally,it is specifically distinguished by its critical focus on bridging the gap between fundamental electrocatalysts development and practical system-level integration,addressing the challenges of scalability and deployment under industrially relevant conditions.This comprehensive review provides a strategic outlook and identifies key scientific priorities for optimizing EWS systems toward efficient,robust,and scalable hydrogen generation.
基金support from the Jiangsu Natural Science Foundation of China(BK20230329)the National Natural Science Foundation of China(22401147,22361132540,and 22178161)the Russian Science Foundation(23-73-30007).
文摘The efficient electrocatalytic oxidation of glycerol(GLY)is one of the most promising routes for the valorization of GLY.Doping has emerged as a powerful strategy to tailor the electrocatalytic performance of silver nanoclusters(Ag NCs),yet the effects of doping mode(surface vs.core)and the interface environment(e.g.,electrolyte concentration)on the electrocatalytic performance for Ag NCs toward GLY oxidation remain understood.In this work,surface-doped Ag_(4)M_(2)(SR)_(8) and core-doped Ag_(24)M(SR)_(18)(M=Ni,Pd,Pt;SR=SPhMe_(2))NCs were synthesized for electrocatalytic GLY oxidation.The results revealed a strong dependence of selectivity on doping mode and electrolyte concentration:under low KOH concentration,Pd-and Pt-doped Ag_(4)M_(2) NCs exhibited 100%selectivity toward oxalic acid(OA),whereas Pd-and Pt-doped Ag_(24)M NCs delivered>95%selectivity for formic acid(FA).In contrast,under high KOH concentration,Pd-and Pt-doped Ag_(4)M_(2) NCs gave rise to>80%FA,while Pd-and Pt-doped Ag_(24)M NCs produced>45%FA.Mechanism studies indicated that Ni doping predominantly enhanced catalytic activity via lowering the activation barrier of the initial reaction step(GLY→glyceraldehyde),whereas Pd and Pt doping modulated selectivity through reducing the energy barrier of the selective branch step(glyceric acid→OA,OA→FA).High KOH concentration promoted the oxidation by increasing the electrochemical active surface area and facilitating electron transfer of Ag NCs.This study provides clear guidance for designing high-performance Ag-based electrocatalysts for biomass valorization.
基金the financial support from the National Natural Science Foundation of China (Nos.U23A20677,22022610 and 52400137)"Pioneer" and "Leading Goose" R&D Program of Zhejiang (Nos.2022C03146 and 2023C03017)+2 种基金China Postdoctoral Science Foundation (No.2024T170805)Zhejiang Provincial Natural Science Foundation of China (No.LDT23E06015B06)the support of the Research Computing Center in College of Chemical and Biological Engineering at Zhejiang University for assistance with the calculations。
文摘Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O crystal plane orientation and the corresponding adsorbed ^(*)CO species.Herein,we constructed high-index crystal planes(311) in Cu_(2)O(CO-Cu_(2)O) via a facile self-selective CO-induced strategy under a CO atmosphere,which was verified by high-resolution transmission electron microscopy(HR-TEM) and atomic force microscopy(AFM) results.By exploiting the high surface energy of the high index crystal planes,^(*)CO species are stabilized in CO-Cu_(2)O during CO_(2)RR,resulting in exceptional catalytic performance for CO_(2)-to-C_(2)products.In situ infrared spectroscopy revealed that both atop-type(^(*)CO_(atop)) and hollow-type(^(*)CO_(hollow)) adsorption of ^(*)CO species occurred on the CO-Cu_(2)O.The asymmetric C-C coupling energy barrier between ^(*)CO_(atop) and ^(*)CO_(hollow) in(311) crystal plane decreases by 47.8 % compared to the symmetric coupling of ^(*)CO_(atop) in conventional(100) crystal planes.Consequently,the Faradaic efficiency of C_(2) products generated with CO-Cu_(2)O was increased by as high as 100 % compared to that with pristine Cu_(2)O.
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 Natural Science Foundation of China(Nos.U23B20165 and 52170085)National Key R&D Program International Cooperation Project(No.2023YFE0108100)+1 种基金Key Project of Natural Science Foundation of Tianjin(No.21JCZDJC00320)Fundamental Research Funds for the Central Universities,Nankai University.
文摘Chlorinated antibiotics pose great challenges in efficient removal,while for the first time,this work greatly enhanced their electrocatalytic dechlorination performance by construction of non-noble metal Co_(3)O_(4)/g-C_(3)N_(4) heterojunctions to improve process cost-effectiveness.The Co_(3)O_(4)/g-C_(3)N_(4) heterojunction demonstrated an effective removal of 93.6%thiamphenicol(TAP)within 45 min,with the rate constant(0.0584 min^(-1))that was 2.4 and 2.8 times that of Co_(3)O_(4) and g-C_(3)N_(4) alone,respectively.The formation of heterojunctions facilitated electron transfer,enriched the electron density on Co_(3)O_(4),and enhanced the adsorption of pollutants as well as the desorption of degradation intermediates.The enhanced production of atomic hydrogen(H*)of Co_(3)O_(4)/g-C_(3)N_(4),which increased by 13.6-28.2 times,contributed more to pollutant removal(64.0%),much higher than that of Co_(3)O_(4)(37.3%)and g-C_(3)N_(4)(6.1%).The energy barrier for H_(2) formation on Co_(3)O_(4)/g-C_(3)N_(4)(0.75 eV)was higher than that on Co_(3)O_(4)(-1.84 eV),supporting that it could stabilize H*and inhibit the formation of H_(2).The Co_(3)O_(4)/g-C_(3)N_(4) heterojunction exhibited stable performance with less impact by pH and co-existing ions,and posed effectiveness for the dechlorination of typical chlorinated antibiotics.This study offers an efficient and sustainable strategy for constructing heterojunctions to enhance the performance of non-noble metal catalysts in electrocatalytic dechlorination.
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 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 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(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 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Noble metal-based intermetallic compounds(IMCs)with ordered atomic arrangements exhibit remarkable electrocatalytic activity owing to their unique crystal and electronic structures.During the past years,great advance has been made in the development of noble metal-based IMCs.Recently,Lu and coworkers reported ultrathin“amorphous/intermetallic”(A/IMC)heterophase PtPbBi nanosheets(NSs)with a thickness of 2.5±0.3 nm.The oxidative etching effect caused by the coexistence of O_(2)and Br^(-)ions plays a crucial role in the formation of the IMC and unique two-dimensional structure with irregular shapes and curled edges.This study shows that fabricating an A/IMC heterophase structure with a multimetallic composition can effectively enhance the catalytic performances of noble metal-based electrocatalysts.
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 Natural Science Youth Foundation of China(Grant No.22406121)the Shanghai Super Postdoctoral Incentive Program(Grant No.2023329).
文摘High-entropy alloys(HEAs),with multi-principal-element composition,are gaining attention for their structural stability and mechanical properties.Extensive research has focused on using HEAs as electrocatalysts in the conversion of single-component reactions,such as hydrogen evolution reaction(HER),oxygen evolution reaction(OER),carbon dioxide reduction reaction(CO_(2)RR),etc.However,their potential in the application of synergistic conversion of pollutants(e.g.,carbon dioxide(CO_(2))and nitrogen oxides(NO_(x)))has been largely overlooked.This review overviews HEAs’fundamental concepts and characteristics,and delves into their advantages in transition metals and optimization strategies for the synergistic conversion process.It offers a novel approach for sustainable environmental remediation and resource utilization.
