Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the in...Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the intrinsic activity of Ni and Co catalytic centers.However,the dynamic evolution and atomic-scale synergy between these centers remain elusive.Herein,we fabricated NiCo_(2)O_(4)nanosheets supported on nickel foam,where Ni preferentially occupies tetrahedral sites to regulate the electronic configuration of octahedral Co.Experimental and theoretical results demonstrate that the incorporation of tetrahedral Ni induces low-to-intermediate spin transition in octahedral Co,thereby optimizing eg orbital occupancy and stabilizing active sites.This spin-state engineering establishes Ni-Co synergistic catalytic centers for the selective oxidation of glucose to formate(FA).At higher potential(≥1.4 V vs.RHE),octahedral Co undergoes reconstruction into excessive active CoOOH and CoO_(2)species,resulting in glucose overoxidation to CO_(2)and intensified competitive oxygen evolution.In contrast,at lower potentials(<1.4 V vs.RHE),tetrahedral Ni facilitates electron delocalization across the Ni–O–Co lattice,thereby stabilizing octahedral Co for glucose adsorption and oxidation.Subsequently,a coupled electrocatalytic system was constructed,achieving 80.7%FA yield with 91.3%Faradaic efficiency(FE)at NiCo_(2)O_(4)anode and H2 evolution rate of 696μmol h^(−1)with 99.9%FE at Pt cathode for 2 h under 1.35 V vs.RHE.This work provides a deep insight into spin-state regulation of the catalytic center,offering valuable guidance for rational catalyst design.展开更多
Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electro...Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.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
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
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
The organic pollutants,such as quaternary ammonium compounds,in high salinity flowback water from shale gas extraction may pose a severe risk to public health.Conventional biological technologies have limited effectiv...The organic pollutants,such as quaternary ammonium compounds,in high salinity flowback water from shale gas extraction may pose a severe risk to public health.Conventional biological technologies have limited effectiveness in the treatment of high-salt wastewaters,whereas electrocatalytic oxidation has shown potential for treating organic pollutants in high-salt flowback water.This study developed a carbon nanotubes(CNTs)doped Ru/Ir oxide coated Ti electrode CNTs-(Ru_(x)Ir_(y)O_(2))/Ti,which exhibited enhanced electrocatalytic performance for the treatment of quaternary ammonium compound in high-salt wastewater compared to the control metal oxide coated Ti anode(Ru_(x)Ir_(y)O_(2))/Ti,with pseudofirst-order reaction rate constant improved from 7.36×10^(-3) to 1.12×10^(-2) min−1.Moreover,the CNTs-(Ru_(x)Ir_(y)O_(2))/Ti anode electrocatalytic oxidation system exhibited excellent cycling stability.Mechanism studies indicated that the CNTs-(Ru_(x)Ir_(y)O_(2))/Ti electrode enhanced singlet oxygen(^(1)O_(2))generation,which played a major role in pollutant degradation.Furthermore,the formation of high concentrations of HClO and H_(2)O_(2) further facilitated the generation of ^(1)O_(2).This study may provide an efficient and green technology for the treatment of organic pollutants in high-salt shale gas flowback water.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
Electrocatalytic toluene(TL)oxidation to produce benzoic acid(BAC)process is largely hindered due to sluggish kinetics associated with the transformation of the rate-determining step,because of weak TL adsorption and ...Electrocatalytic toluene(TL)oxidation to produce benzoic acid(BAC)process is largely hindered due to sluggish kinetics associated with the transformation of the rate-determining step,because of weak TL adsorption and high rate-determining step energy barrier for difficult to dehydrogenate.Herein,we report Mn_(x)Ce_(1-x)O_(2)/CNT catalyst for accelerated reaction kinetics.Theoretical and experimental studies indicate that Ce sites promote TL adsorption and polyvalent Mn modulates the electronic structure of Ce sites reducing the rate-determining step energy barrier.This results in increasing^(*)C_(6)H_(5)CH_(2)coverage and effectively accelerating TL oxidation reaction(TOR)kinetics.Excitingly,the Faraday efficiency(FE)and BAC yield of optimized Mn_(0.6)Ce_(0.4)O_(2)/CNT at 2.6 V vs.RHE could reach 85.9%and 653.9 mg h^(-1)cm^(-2),respectively.In addition,the Mn_(0.6)Ce_(0.4)O_(2)/CNT displays a high selectivity of 96.3%for BAC.Combining the TL oxidation reaction with hydrogen evolution reaction,the anion exchange membrane electrolyzer of Mn_(0.6)Ce_(0.4)O_(2)/CNT(+)||Pt/C(-)can reach 100 mA cm^(-2)at the voltage of 3.0 V,in which the BAC yield is 579.4 mg h^(-1)cm^(-2)and the FE is 83.6%.This work achieved high selectivity of TOR at industrial-relevant current densities of 100 mA cm^(-2)at the low voltage for the first time.展开更多
Biomass conversion offers an efficient approach to alleviate the energy and environmental issues.Electrochemical oxidation of 5-hydroxymethylfurfural(HMF)has attracted tremendous attention in the latest few years for ...Biomass conversion offers an efficient approach to alleviate the energy and environmental issues.Electrochemical oxidation of 5-hydroxymethylfurfural(HMF)has attracted tremendous attention in the latest few years for the mild synthesis conditions and high conversion efficiency to obtain 2,5-furan dicarboxylic acid(FDCA),but there still remain problems such as limited yield,short cycle life,and ambiguous reaction mechanism.Despite many reviews highlighting a variety of electrocatalysts for electrochemical oxidation of HMF,a detailed discussion of the structural modulation of catalyst and the underlying catalytic mechanism is still lacking.We herein provide a comprehensive summary of the recent development of electrochemical oxidation of HMF to FDCA,particularly focusing on the mechanism studies as well as the advanced strategies developed to regulate the structure and optimize the performance of the electrocatalysts,including heterointerface construction,defect engineering,single-atom engineering,and in situ reconstruction.Experimental characterization techniques and theoretical calculation methods for mechanism and active site studies are elaborated,and challenges and future directions of electrochemical oxidation of HMF are also prospected.This review will provide guidance for designing advanced catalysts and deepening the understanding of the reaction mechanism beneath electrochemical oxidation of HMF to FDCA.展开更多
Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance ...Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance of various catalysts by tuning their oxidation states,particularly for Cu-based catalysts that can reduce CO_(2) to multiple products.However,the oxidation state of copper(OSCu),especially Cu+,changes during the reaction process,posing significant challenges for both catalyst characterization and performance.In this review,the current understanding of the effect of oxidation states on product selectivity was first discussed.A comprehensive overview of in situ/operando characterization techniques,used to monitor the dynamic evolution of oxidation states during ECR,was then provided.Various strategies for stabilizing oxidation states through modification of catalysts and manipulation of external conditions were discussed.This review aimed to deepen the understanding of oxidation states in ECR and enlighten the development of more efficient electrocatalysts.展开更多
The electrocatalytic urea oxidation reaction(UOR)has emerged as an energy-efficient alternative to the traditional oxygen evolution reaction for hydrogen production,with mechanistic understanding being critical for th...The electrocatalytic urea oxidation reaction(UOR)has emerged as an energy-efficient alternative to the traditional oxygen evolution reaction for hydrogen production,with mechanistic understanding being critical for the rational design of catalysts.This review systematically summarizes recent advances in in situ characterization techniques for elucidating the dynamic reaction mechanisms of UOR.Studies reveal that phase transitions,valence state migration,and electronic structure evolution of catalysts under operational conditions are key factors governing activity and stability.Techniques such as in situ X-ray diffraction,X-ray absorption spectroscopy,Raman spectroscopy,and Fourier-transform infrared spectroscopy enable real-time monitoring of catalyst reconstruction,intermediate evolution,and interfacial adsorption behavior,overcoming the environmental deviations inherent in conventional ex situ characterization.When combined with theoretical calculations,these methods provide direct evidence for identifying active-site configurations,reaction pathways,and rate-determining steps.In addition,special emphasis is placed on multimodal in situ strategies for deciphering synergistic effects in nickel-based catalysts,while current challenges,including non-alkaline systems,real wastewater environments,and multi-metal cooperation mechanisms,are critically discussed.Future research should focus on developing novel in situ approaches for complex systems and establishing a mutually reinforcing framework integrating theoretical prediction and experimental validation,thereby advancing UOR catalyst design from empirical exploration to mechanism-guided optimization.展开更多
Electrochemical reaction is emerging as a powerful approach for glucose detection and biomass conversion.However,it has been rarely explored for glucose detection and biomass conversion into valueadded chemicals.Previ...Electrochemical reaction is emerging as a powerful approach for glucose detection and biomass conversion.However,it has been rarely explored for glucose detection and biomass conversion into valueadded chemicals.Previously reported glucose oxidase reduction(GOR)catalysts exhibit issues such as low activity,limited detection range,poor sensitivity,and overreliance on noble metals.Here,we employ an impregnation method to load transition metal nickel onto carbon nanotubes(CNT)and fabricated Ni/CNT30 catalyst via a discharge process.Ni/CNT30 catalyst exhibits a remarkably high catalytic activity of up to 3336.7μA·cm^(-2)·mmol^(-1)·L,a detection limit of 2.43μmol·L^(-1),outstanding stability,and excellent resistance to impurities and interference,surpassing other noble metal-based and oxide-based materials.Hence,this material provides a new approach for the preparation of glucose sensors to achieve precise mobile measurement of glucose concentration and biofuel cells in future.展开更多
To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretre...To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretreatment was employed to construct a Ta_(2)O_(5)ceramic layer on the Ta12W alloy surface.Subsequently,a slurry spraying-vacuum sintering method was used to prepare a Si-Cr-Ti-Zr coating on the pretreated substrate.Comparative studies were conducted on the microstructure,phase composition,and isothermal oxidation resistance(at 1600℃)of the as-prepared coatings with and without the micro-arc oxidation ceramic layer.The results show that the Ta_(2)O_(5)layer prepared at 400 V is more continuous and has smaller pores than that prepared at 350 V.After microarc oxidation pretreatment,the Si-Cr-Ti-Zr coating on Ta12W alloy consists of three distinct layers:an upper layer dominated by Ti_(5)Si_(3),Ta_(5)Si_(3),and ZrSi;a middle layer dominated by TaSi_(2);a coating/substrate interfacial reaction layer dominated by Ta_(5)Si_(3).Both the Si-Cr-Ti-Zr coatings with and without the Ta_(2)O_(5)ceramic layer do not fail after isothermal oxidation at 1600℃for 5 h.Notably,the addition of the Ta2O5 ceramic layer reduces the high-temperature oxidation rate of the coating.展开更多
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
The electrocatalytic oxidation of glycerol toward formic acid is one of the most promising pathways for transformation and utilization of glycerol.Herein,a series of well-defined Ni_(n)(SR)_(2n) nanoclusters(n=4,5,6;d...The electrocatalytic oxidation of glycerol toward formic acid is one of the most promising pathways for transformation and utilization of glycerol.Herein,a series of well-defined Ni_(n)(SR)_(2n) nanoclusters(n=4,5,6;denoted as Ni NCs)were prepared for the electrocatalytic glycerol oxidation toward formic acid,in which Ni_(6)-PET-50CV afforded the most excellent electrocatalytic performance with a high formic acid selectivity of 93% and a high glycerol conversion of 86%.This was attributed to the lowest charge transfer impedance and the most rapid reaction kinetics.Combined electrochemical measurements and X-ray absorption fine structure measurements revealed that the structures of Ni NCs remained intact after CV scanning pretreatment and electrocatalysis via forming the Ni–O bond.Additionally,the kinetic studies and in-situ Fourier transformed infrared suggested a sequential oxidation mechanism,in which the main reaction steps of glycerol→glyceraldehyde→glyceric acid were very rapid to produce a high selectivity of formic acid even though the low glycerol conversion.This work presents an opportunity to study Ni NCs for the efficient electrocatalytic oxidation of biomass-derived polyhydroxyl platform molecules to produce value-added carboxylic acids.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
Ethylene glycol(EG)is a biomass derivative of polyethylene terephthalate(PET),and its electrocatalytic conversion into high-value chemicals has sparked widespread interest.This study reviews the most recent research d...Ethylene glycol(EG)is a biomass derivative of polyethylene terephthalate(PET),and its electrocatalytic conversion into high-value chemicals has sparked widespread interest.This study reviews the most recent research development in electrocatalysis-based EG to glycolic acid(GA)conversion.Firstly,the strategies and research results of modulating the electronic structure of catalysts for efficient selective GA production from EG are reviewed.Second,by reviewing the data of in-situ Fourier transform infrared spectroscopy and in-situ electrochemically attenuated total reflection surface enhanced infrared absorption spectroscopy,the reaction pathway and catalytic mechanism of EG partial oxidation to GA were clarified.Finally,the design and regulation of catalysts for selective oxidation of EG by electrocatalysis in the future are prospected.展开更多
As an emergent energy carrier,ammonia benefits from a well-established industrial infrastructure for its transportation and production,positioning it as a promising candidate toward a carbon-free energy landscape.With...As an emergent energy carrier,ammonia benefits from a well-established industrial infrastructure for its transportation and production,positioning it as a promising candidate toward a carbon-free energy landscape.Within this context,the electrocatalytic ammonia oxidation reaction(AOR)is pivotal.Platinum(Pt),recognized as the most efficient AOR catalyst,has undergone extensive development over the years,yielding notable advancements across various domains,ranging from elucidating the reaction mechanism to exploring innovative materials.This review begins by elucidating the mechanism of ammonia oxidation,summarizing the evolution of the mechanism and the diverse intermediates identified through various detection methods.Subsequently,it outlines the research progress surrounding different Pt-based catalysts,followed by a discussion on standard protocols for electrochemical ammonia oxidation testing,which facilitates meaningful comparisons across studies and catalyzes the development of more efficient and potent catalysts.Moreover,the review addresses current challenges in ammonia oxidation and outlines potential future directions,providing a comprehensive outlook on the field.展开更多
Photoelectrochemical water oxidation reaction (PEC-WOR) as a sustainable route to produce H_(2)O_(2) is attractive but limited by low activity and poor product selectivity of photoanodes due to limited photogenerated ...Photoelectrochemical water oxidation reaction (PEC-WOR) as a sustainable route to produce H_(2)O_(2) is attractive but limited by low activity and poor product selectivity of photoanodes due to limited photogenerated charge efficiency and unfavorable thermodynamics. Herein, by crystal orientation engineering, the WO_(3) photoanode exposing (200) facets achieves both superior WOR activity (15.4 mA cm^(−2) at 1.76 VRHE) and high selectivity to H_(2)O_(2) (∼70%). Comprehensive experimental and theoretical investigations discover that the high PEC-WOR activity of WO_(3)-(200) is attributed to the rapid photogenerated charge separation/transfer both in bulk and at interfaces of WO_(3)-(200) facet, which reduces the charge transfer resistance. This, coupling with the unique defective hydrogen bonding network at the WO_(3)-(200)/electrolyte interface evidenced by operando PEC Fourier transform infrared spectroscopy, facilitating the outward-transfer of the WOR-produced H^(+), lowers the overall reaction barrier for the PEC-WOR. The superior selectivity of PEC-WOR to H_(2)O_(2) is ascribed to the unique defective hydrogen bonding network alleviated adsorption of ∗OH over the WO_(3)-(200) facet, which specially lowers the energy barrier of the 2-electron pathway, as compared to the 4-electron pathway. This work addresses the significant role of crystal orientation engineering on photoelectrocatalytic activity and selectivity, and sheds lights on the underlying PEC mechanism by understanding the water adsorption behaviors under illumination. The knowledge gained is expected to be extended to other photoeletrochemical reactions.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
基金financially supported by the National Natural Science Foundation of China (22472199)Chinese Universities Scientific Fund (15055009)Central University Guided Funds for Building World-Class Universities (Disciplines) and Advancing Characteristic Development
文摘Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the intrinsic activity of Ni and Co catalytic centers.However,the dynamic evolution and atomic-scale synergy between these centers remain elusive.Herein,we fabricated NiCo_(2)O_(4)nanosheets supported on nickel foam,where Ni preferentially occupies tetrahedral sites to regulate the electronic configuration of octahedral Co.Experimental and theoretical results demonstrate that the incorporation of tetrahedral Ni induces low-to-intermediate spin transition in octahedral Co,thereby optimizing eg orbital occupancy and stabilizing active sites.This spin-state engineering establishes Ni-Co synergistic catalytic centers for the selective oxidation of glucose to formate(FA).At higher potential(≥1.4 V vs.RHE),octahedral Co undergoes reconstruction into excessive active CoOOH and CoO_(2)species,resulting in glucose overoxidation to CO_(2)and intensified competitive oxygen evolution.In contrast,at lower potentials(<1.4 V vs.RHE),tetrahedral Ni facilitates electron delocalization across the Ni–O–Co lattice,thereby stabilizing octahedral Co for glucose adsorption and oxidation.Subsequently,a coupled electrocatalytic system was constructed,achieving 80.7%FA yield with 91.3%Faradaic efficiency(FE)at NiCo_(2)O_(4)anode and H2 evolution rate of 696μmol h^(−1)with 99.9%FE at Pt cathode for 2 h under 1.35 V vs.RHE.This work provides a deep insight into spin-state regulation of the catalytic center,offering valuable guidance for rational catalyst design.
基金the financial support from the National Natural Science Foundation of China(52172110,52472231,52311530113)Shanghai"Science and Technology Innovation Action Plan"intergovernmental international science and technology cooperation project(23520710600)+1 种基金Science and Technology Commission of Shanghai Municipality(22DZ1205600)the Central Guidance on Science and Technology Development Fund of Zhejiang Province(2024ZY01011)。
文摘Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.
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 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the funds granted by the Ningxia Natural Science Foundation(2023AAC05003,2024AAC03048,2024AAC03051)the National Natural Science Foundation of China(22108130,22368039)+1 种基金the Ningxia Key Research&Development Program(2023BDE03001)the Ningxia Overseas Returnee Innovation and Entrepreneurship Project for the financial support。
文摘Addressing the contamination of antibiotics has attracted ever-increasing and imperative attention due to their widespread existence,easy-to-cause drug-resistant bacteria infection,coupled with their intrinsic toxicity and hazard to environments and human health.Herein,a novel CC/CoNi-LDH-10%Ce anode material was directly constructed through a simple and rapid electrodeposition strategy,serving as an efficacious electrocatalyst for removing ciprofloxacin(CIP)from aqueous solution.Such novel CC/CoNi-LDH-10%Ce anode delivered a higher charge transfer,relatively abundant oxygen vacancies,and a higher electrochemical active area.The as-fabricated CC/CoNi-LDH-10%Ce electrode achieved a substantially boosted CIP removal efficiency of 52.5%relative to that of pure CC at about 23.9%.Notably,doping an appropriate amount of Ce^(3+)can endow the pristine CC/CoNi-LDH with richer oxygen vacancies and excellent electrocatalytic performance.Additionally,the electrocatalytic oxidation of CIP was attributed to both direct oxidation on the electrode surface and indirect oxidation induced by the generated active species(superoxide radicals and hydroxyl radicals).This study provides a simple,universal and flexible tactic for other researchers in designing and manufacturing avenues of electrodes.
基金supported by the National Natural Science Foundation of China(Nos.52200186 and 52070025)Chongqing Natural Science Foundation(No.CSTB2024NSCQ-MSX0407)+1 种基金the National Key Research and Development Program of China(No.2019YFC1805502)Chongqing Municipal Human Resources and Social Security Bureau(No.2309013519935095).
文摘The organic pollutants,such as quaternary ammonium compounds,in high salinity flowback water from shale gas extraction may pose a severe risk to public health.Conventional biological technologies have limited effectiveness in the treatment of high-salt wastewaters,whereas electrocatalytic oxidation has shown potential for treating organic pollutants in high-salt flowback water.This study developed a carbon nanotubes(CNTs)doped Ru/Ir oxide coated Ti electrode CNTs-(Ru_(x)Ir_(y)O_(2))/Ti,which exhibited enhanced electrocatalytic performance for the treatment of quaternary ammonium compound in high-salt wastewater compared to the control metal oxide coated Ti anode(Ru_(x)Ir_(y)O_(2))/Ti,with pseudofirst-order reaction rate constant improved from 7.36×10^(-3) to 1.12×10^(-2) min−1.Moreover,the CNTs-(Ru_(x)Ir_(y)O_(2))/Ti anode electrocatalytic oxidation system exhibited excellent cycling stability.Mechanism studies indicated that the CNTs-(Ru_(x)Ir_(y)O_(2))/Ti electrode enhanced singlet oxygen(^(1)O_(2))generation,which played a major role in pollutant degradation.Furthermore,the formation of high concentrations of HClO and H_(2)O_(2) further facilitated the generation of ^(1)O_(2).This study may provide an efficient and green technology for the treatment of organic pollutants in high-salt shale gas flowback water.
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supported by the National Natural Science Foundation of China(52272222)the Taishan Scholar Young Talent Program(tsqn201909114,tsqn201909123)the University Youth Innovation Team of Shandong Province(202201010318)。
文摘Electrocatalytic toluene(TL)oxidation to produce benzoic acid(BAC)process is largely hindered due to sluggish kinetics associated with the transformation of the rate-determining step,because of weak TL adsorption and high rate-determining step energy barrier for difficult to dehydrogenate.Herein,we report Mn_(x)Ce_(1-x)O_(2)/CNT catalyst for accelerated reaction kinetics.Theoretical and experimental studies indicate that Ce sites promote TL adsorption and polyvalent Mn modulates the electronic structure of Ce sites reducing the rate-determining step energy barrier.This results in increasing^(*)C_(6)H_(5)CH_(2)coverage and effectively accelerating TL oxidation reaction(TOR)kinetics.Excitingly,the Faraday efficiency(FE)and BAC yield of optimized Mn_(0.6)Ce_(0.4)O_(2)/CNT at 2.6 V vs.RHE could reach 85.9%and 653.9 mg h^(-1)cm^(-2),respectively.In addition,the Mn_(0.6)Ce_(0.4)O_(2)/CNT displays a high selectivity of 96.3%for BAC.Combining the TL oxidation reaction with hydrogen evolution reaction,the anion exchange membrane electrolyzer of Mn_(0.6)Ce_(0.4)O_(2)/CNT(+)||Pt/C(-)can reach 100 mA cm^(-2)at the voltage of 3.0 V,in which the BAC yield is 579.4 mg h^(-1)cm^(-2)and the FE is 83.6%.This work achieved high selectivity of TOR at industrial-relevant current densities of 100 mA cm^(-2)at the low voltage for the first time.
基金National Natural Science Foundation of China(22272150,22302177)Major Program of Zhejiang Provincial Natural Science Foundation of China(LD22B030002)+2 种基金Zhejiang Provincial Ten Thousand Talent Program(2021R51009)Public Technology Application Project of Jinhua City(2022-4-067)Self Designed Scientific Research of Zhejiang Normal University(2021ZS0604)。
文摘Biomass conversion offers an efficient approach to alleviate the energy and environmental issues.Electrochemical oxidation of 5-hydroxymethylfurfural(HMF)has attracted tremendous attention in the latest few years for the mild synthesis conditions and high conversion efficiency to obtain 2,5-furan dicarboxylic acid(FDCA),but there still remain problems such as limited yield,short cycle life,and ambiguous reaction mechanism.Despite many reviews highlighting a variety of electrocatalysts for electrochemical oxidation of HMF,a detailed discussion of the structural modulation of catalyst and the underlying catalytic mechanism is still lacking.We herein provide a comprehensive summary of the recent development of electrochemical oxidation of HMF to FDCA,particularly focusing on the mechanism studies as well as the advanced strategies developed to regulate the structure and optimize the performance of the electrocatalysts,including heterointerface construction,defect engineering,single-atom engineering,and in situ reconstruction.Experimental characterization techniques and theoretical calculation methods for mechanism and active site studies are elaborated,and challenges and future directions of electrochemical oxidation of HMF are also prospected.This review will provide guidance for designing advanced catalysts and deepening the understanding of the reaction mechanism beneath electrochemical oxidation of HMF to FDCA.
基金supported by the National Natural Science Foundation of China(No.52221004)the Shenzhen Science and Technology Program(No.RCJC20221008092758099)+1 种基金the Shenzhen Pengrui Young Faculty Program of Shenzhen Pengrui Foundation(No.SZPR2023004)the Guangdong Higher Education Institutions Innovative Research Team of Urban Water Cycle and Ecological Safety(No.2023KCXTD053).
文摘Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance of various catalysts by tuning their oxidation states,particularly for Cu-based catalysts that can reduce CO_(2) to multiple products.However,the oxidation state of copper(OSCu),especially Cu+,changes during the reaction process,posing significant challenges for both catalyst characterization and performance.In this review,the current understanding of the effect of oxidation states on product selectivity was first discussed.A comprehensive overview of in situ/operando characterization techniques,used to monitor the dynamic evolution of oxidation states during ECR,was then provided.Various strategies for stabilizing oxidation states through modification of catalysts and manipulation of external conditions were discussed.This review aimed to deepen the understanding of oxidation states in ECR and enlighten the development of more efficient electrocatalysts.
文摘The electrocatalytic urea oxidation reaction(UOR)has emerged as an energy-efficient alternative to the traditional oxygen evolution reaction for hydrogen production,with mechanistic understanding being critical for the rational design of catalysts.This review systematically summarizes recent advances in in situ characterization techniques for elucidating the dynamic reaction mechanisms of UOR.Studies reveal that phase transitions,valence state migration,and electronic structure evolution of catalysts under operational conditions are key factors governing activity and stability.Techniques such as in situ X-ray diffraction,X-ray absorption spectroscopy,Raman spectroscopy,and Fourier-transform infrared spectroscopy enable real-time monitoring of catalyst reconstruction,intermediate evolution,and interfacial adsorption behavior,overcoming the environmental deviations inherent in conventional ex situ characterization.When combined with theoretical calculations,these methods provide direct evidence for identifying active-site configurations,reaction pathways,and rate-determining steps.In addition,special emphasis is placed on multimodal in situ strategies for deciphering synergistic effects in nickel-based catalysts,while current challenges,including non-alkaline systems,real wastewater environments,and multi-metal cooperation mechanisms,are critically discussed.Future research should focus on developing novel in situ approaches for complex systems and establishing a mutually reinforcing framework integrating theoretical prediction and experimental validation,thereby advancing UOR catalyst design from empirical exploration to mechanism-guided optimization.
基金supported by the National Natural Science Foundation of China(22408225 and 22478241)the Postdoctoral Fellowship Program of CPSF(GZC20240999).
文摘Electrochemical reaction is emerging as a powerful approach for glucose detection and biomass conversion.However,it has been rarely explored for glucose detection and biomass conversion into valueadded chemicals.Previously reported glucose oxidase reduction(GOR)catalysts exhibit issues such as low activity,limited detection range,poor sensitivity,and overreliance on noble metals.Here,we employ an impregnation method to load transition metal nickel onto carbon nanotubes(CNT)and fabricated Ni/CNT30 catalyst via a discharge process.Ni/CNT30 catalyst exhibits a remarkably high catalytic activity of up to 3336.7μA·cm^(-2)·mmol^(-1)·L,a detection limit of 2.43μmol·L^(-1),outstanding stability,and excellent resistance to impurities and interference,surpassing other noble metal-based and oxide-based materials.Hence,this material provides a new approach for the preparation of glucose sensors to achieve precise mobile measurement of glucose concentration and biofuel cells in future.
基金National Natural Science Foundation of China(52071274)Key Research and Development Projects of Shaanxi Province(2023-YBGY-442)Science and Technology Nova Project-Innovative Talent Promotion Program of Shaanxi Province(2020KJXX-062)。
文摘To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretreatment was employed to construct a Ta_(2)O_(5)ceramic layer on the Ta12W alloy surface.Subsequently,a slurry spraying-vacuum sintering method was used to prepare a Si-Cr-Ti-Zr coating on the pretreated substrate.Comparative studies were conducted on the microstructure,phase composition,and isothermal oxidation resistance(at 1600℃)of the as-prepared coatings with and without the micro-arc oxidation ceramic layer.The results show that the Ta_(2)O_(5)layer prepared at 400 V is more continuous and has smaller pores than that prepared at 350 V.After microarc oxidation pretreatment,the Si-Cr-Ti-Zr coating on Ta12W alloy consists of three distinct layers:an upper layer dominated by Ti_(5)Si_(3),Ta_(5)Si_(3),and ZrSi;a middle layer dominated by TaSi_(2);a coating/substrate interfacial reaction layer dominated by Ta_(5)Si_(3).Both the Si-Cr-Ti-Zr coatings with and without the Ta_(2)O_(5)ceramic layer do not fail after isothermal oxidation at 1600℃for 5 h.Notably,the addition of the Ta2O5 ceramic layer reduces the high-temperature oxidation rate of the coating.
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The electrocatalytic oxidation of glycerol toward formic acid is one of the most promising pathways for transformation and utilization of glycerol.Herein,a series of well-defined Ni_(n)(SR)_(2n) nanoclusters(n=4,5,6;denoted as Ni NCs)were prepared for the electrocatalytic glycerol oxidation toward formic acid,in which Ni_(6)-PET-50CV afforded the most excellent electrocatalytic performance with a high formic acid selectivity of 93% and a high glycerol conversion of 86%.This was attributed to the lowest charge transfer impedance and the most rapid reaction kinetics.Combined electrochemical measurements and X-ray absorption fine structure measurements revealed that the structures of Ni NCs remained intact after CV scanning pretreatment and electrocatalysis via forming the Ni–O bond.Additionally,the kinetic studies and in-situ Fourier transformed infrared suggested a sequential oxidation mechanism,in which the main reaction steps of glycerol→glyceraldehyde→glyceric acid were very rapid to produce a high selectivity of formic acid even though the low glycerol conversion.This work presents an opportunity to study Ni NCs for the efficient electrocatalytic oxidation of biomass-derived polyhydroxyl platform molecules to produce value-added carboxylic acids.
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.
文摘Ethylene glycol(EG)is a biomass derivative of polyethylene terephthalate(PET),and its electrocatalytic conversion into high-value chemicals has sparked widespread interest.This study reviews the most recent research development in electrocatalysis-based EG to glycolic acid(GA)conversion.Firstly,the strategies and research results of modulating the electronic structure of catalysts for efficient selective GA production from EG are reviewed.Second,by reviewing the data of in-situ Fourier transform infrared spectroscopy and in-situ electrochemically attenuated total reflection surface enhanced infrared absorption spectroscopy,the reaction pathway and catalytic mechanism of EG partial oxidation to GA were clarified.Finally,the design and regulation of catalysts for selective oxidation of EG by electrocatalysis in the future are prospected.
基金the National Key Research and Development Program of China(No.2022YFB4102000)the National Natural Science Foundation of China(Nos.22102018 and 52171201)+5 种基金the Huzhou Science and Technology Bureau(No.2022GZ45)the China Postdoctoral Science Foundation-Funded Project(No.2022M710601)the Huzhou Science and Technology Bureau(No.2023GZ02)the Natural Science Foundation of Sichuan Province(No.24NSFSC5779)the National Natural Science Foundation of China(Nos.22322201 and 22278067)the Natural Science Foundation of Sichuan Province(No.2023NSFSC0094)。
文摘As an emergent energy carrier,ammonia benefits from a well-established industrial infrastructure for its transportation and production,positioning it as a promising candidate toward a carbon-free energy landscape.Within this context,the electrocatalytic ammonia oxidation reaction(AOR)is pivotal.Platinum(Pt),recognized as the most efficient AOR catalyst,has undergone extensive development over the years,yielding notable advancements across various domains,ranging from elucidating the reaction mechanism to exploring innovative materials.This review begins by elucidating the mechanism of ammonia oxidation,summarizing the evolution of the mechanism and the diverse intermediates identified through various detection methods.Subsequently,it outlines the research progress surrounding different Pt-based catalysts,followed by a discussion on standard protocols for electrochemical ammonia oxidation testing,which facilitates meaningful comparisons across studies and catalyzes the development of more efficient and potent catalysts.Moreover,the review addresses current challenges in ammonia oxidation and outlines potential future directions,providing a comprehensive outlook on the field.
基金supported by the National Natural Science Foundation of China(22478211,22179067)the Major Fundamental Research Program of Natural Science Foundation of Shandong Province(ZR2022ZD10).
文摘Photoelectrochemical water oxidation reaction (PEC-WOR) as a sustainable route to produce H_(2)O_(2) is attractive but limited by low activity and poor product selectivity of photoanodes due to limited photogenerated charge efficiency and unfavorable thermodynamics. Herein, by crystal orientation engineering, the WO_(3) photoanode exposing (200) facets achieves both superior WOR activity (15.4 mA cm^(−2) at 1.76 VRHE) and high selectivity to H_(2)O_(2) (∼70%). Comprehensive experimental and theoretical investigations discover that the high PEC-WOR activity of WO_(3)-(200) is attributed to the rapid photogenerated charge separation/transfer both in bulk and at interfaces of WO_(3)-(200) facet, which reduces the charge transfer resistance. This, coupling with the unique defective hydrogen bonding network at the WO_(3)-(200)/electrolyte interface evidenced by operando PEC Fourier transform infrared spectroscopy, facilitating the outward-transfer of the WOR-produced H^(+), lowers the overall reaction barrier for the PEC-WOR. The superior selectivity of PEC-WOR to H_(2)O_(2) is ascribed to the unique defective hydrogen bonding network alleviated adsorption of ∗OH over the WO_(3)-(200) facet, which specially lowers the energy barrier of the 2-electron pathway, as compared to the 4-electron pathway. This work addresses the significant role of crystal orientation engineering on photoelectrocatalytic activity and selectivity, and sheds lights on the underlying PEC mechanism by understanding the water adsorption behaviors under illumination. The knowledge gained is expected to be extended to other photoeletrochemical reactions.
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.
