Electrochemical CO_(2)reduction into energy-carrying compounds,such as formate,is of great importance for carbon neutrality,which however suffers from high electrical energy input and liquid products crossover.Herein,...Electrochemical CO_(2)reduction into energy-carrying compounds,such as formate,is of great importance for carbon neutrality,which however suffers from high electrical energy input and liquid products crossover.Herein,we fabricated self-supported ultrathin NiCo layered double hydroxides(LDHs)electrodes as anode for methanol electrooxidation to achieve a high formate production rate(5.89 mmol h^(-1)cm^(-2))coupled with CO_(2)electro-reduction at the cathode.A total formate faradic efficiency of both anode for methanol oxidation and cathode for CO_(2)reduction can reach up to 188%driven by a low cell potential of only 2.06 V at 100 mA cm^(-2)in membrane-electrode assembly(MEA).Physical characterizations demonstrated that Ni^(3+)species,formed on the electrochemical oxidation of Ni-containing hydroxide,acted as catalytically active species for the oxidation of methanol to formate.Furthermore,DFT calculations revealed that ultrathin LDHs were beneficial for the formation of Ni^(3+)in hydroxides and introducing oxygen vacancy in NiCo-LDH could decrease the energy barrier of the rate-determining step for methanol oxidation.This work presents a promising approach for fabricating advanced electrodes towards electrocatalytic reactions.展开更多
(1-x)K_(0.5)Na_(0.5)Nb0_(3-x)Bi(Zn_(2/3)Nb_(1/3))0_(3)((1-x)KNN-xBZN,x=0.010,0.015,0.020,0.025,and 0.030)lead-free ceramics were fabricated via a traditional solid-state method.The crystal structure,microstructure,die...(1-x)K_(0.5)Na_(0.5)Nb0_(3-x)Bi(Zn_(2/3)Nb_(1/3))0_(3)((1-x)KNN-xBZN,x=0.010,0.015,0.020,0.025,and 0.030)lead-free ceramics were fabricated via a traditional solid-state method.The crystal structure,microstructure,dielectric,and conductivity behavior of this system were studied.Combined with X-ray diffraction(XRD)patterns,Rietveld refinement,and dielectric spectroscopy,an orthorhombic phase was determined for x=0.010,an orthorhombic-tetragonal mixed phase was identified for x=0.015,and a rhombohedral symmetry appears in 0.020≤x≤0.030.Both 0.98KNN-0.02BZN and 0.975KNN-0.025BZN ceramics exhibit stable permittivity and low dielectric loss tangent(tan)in wide temperature ranges owing to the combination of rhombohedral-tetragonal step-like feature and the diffuse phase transition from tetragonal to cubic.The activation energies of dielectric relaxation and conductivity behavior at high temperatures initially decrease slightly,then drop sharply,and finally decline slowly,which could be attributed to microstructure morphologies and the concentration of oxygen vacancies.展开更多
CaCu_(3)Ti_(4-x)Y_(x)O_(12)(0≤x≤0.12)ceramics were fabricated with conventional solid-state reaction method.Phase structure and microstructure of prepared ceramics were characterized by X-ray diffraction(XRD)and sca...CaCu_(3)Ti_(4-x)Y_(x)O_(12)(0≤x≤0.12)ceramics were fabricated with conventional solid-state reaction method.Phase structure and microstructure of prepared ceramics were characterized by X-ray diffraction(XRD)and scanning electron microscopy(SEM),respectively.The impedance and modulus tests both suggested the existence of two different relaxation behavior,which were attributed to bulk and grain boundary response.In addition,the conductivity and dielectric permittivity showed a step-like behavior under 405 K.Meanwhile,frequency independence of dc conduction became dominant when above 405 K.In CCTO ceramic,rare earth element Y^(3+)ions as an acceptor were used to substitute Ti sites,decreasing the concentration of oxygen vacancy around grainelectrode and grain boundary.The reason to the reduction of dielectric behavior in low frequencies range was associated with the Y doping in CCTO ceramic.展开更多
基金the financial support from the National Nature Science Foundation of China(22078232 and 21938008)the Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘Electrochemical CO_(2)reduction into energy-carrying compounds,such as formate,is of great importance for carbon neutrality,which however suffers from high electrical energy input and liquid products crossover.Herein,we fabricated self-supported ultrathin NiCo layered double hydroxides(LDHs)electrodes as anode for methanol electrooxidation to achieve a high formate production rate(5.89 mmol h^(-1)cm^(-2))coupled with CO_(2)electro-reduction at the cathode.A total formate faradic efficiency of both anode for methanol oxidation and cathode for CO_(2)reduction can reach up to 188%driven by a low cell potential of only 2.06 V at 100 mA cm^(-2)in membrane-electrode assembly(MEA).Physical characterizations demonstrated that Ni^(3+)species,formed on the electrochemical oxidation of Ni-containing hydroxide,acted as catalytically active species for the oxidation of methanol to formate.Furthermore,DFT calculations revealed that ultrathin LDHs were beneficial for the formation of Ni^(3+)in hydroxides and introducing oxygen vacancy in NiCo-LDH could decrease the energy barrier of the rate-determining step for methanol oxidation.This work presents a promising approach for fabricating advanced electrodes towards electrocatalytic reactions.
基金supported by the Natural Science Foundation of Guangxi(Grant Nos.2019GXNSFBA245069,AA138162,GA245006,and AA294014)the Middle-aged and Young Teachers’Basic Ability Promotion Project of Guangxi(Grant No.2019KY0290)+3 种基金the Guilin University of Technology(Grant No.GUTQDJJ20176612037)the High Level Innovation Team and Outstanding Scholar Program of Guangxi Institutesthe Open Research Program of Key Laboratory of RF Circuit and System,Ministry of Educationthe Key Laboratory of Large Scale Integrated Design of Zhejiang.
文摘(1-x)K_(0.5)Na_(0.5)Nb0_(3-x)Bi(Zn_(2/3)Nb_(1/3))0_(3)((1-x)KNN-xBZN,x=0.010,0.015,0.020,0.025,and 0.030)lead-free ceramics were fabricated via a traditional solid-state method.The crystal structure,microstructure,dielectric,and conductivity behavior of this system were studied.Combined with X-ray diffraction(XRD)patterns,Rietveld refinement,and dielectric spectroscopy,an orthorhombic phase was determined for x=0.010,an orthorhombic-tetragonal mixed phase was identified for x=0.015,and a rhombohedral symmetry appears in 0.020≤x≤0.030.Both 0.98KNN-0.02BZN and 0.975KNN-0.025BZN ceramics exhibit stable permittivity and low dielectric loss tangent(tan)in wide temperature ranges owing to the combination of rhombohedral-tetragonal step-like feature and the diffuse phase transition from tetragonal to cubic.The activation energies of dielectric relaxation and conductivity behavior at high temperatures initially decrease slightly,then drop sharply,and finally decline slowly,which could be attributed to microstructure morphologies and the concentration of oxygen vacancies.
基金This work was financially supported by the Natural Science Foundation of China(Grant Nos.11564010,11264010,21061004 and 50962004)by the Natural Science Foundation of Guangxi(Grant No.GA139008).
文摘CaCu_(3)Ti_(4-x)Y_(x)O_(12)(0≤x≤0.12)ceramics were fabricated with conventional solid-state reaction method.Phase structure and microstructure of prepared ceramics were characterized by X-ray diffraction(XRD)and scanning electron microscopy(SEM),respectively.The impedance and modulus tests both suggested the existence of two different relaxation behavior,which were attributed to bulk and grain boundary response.In addition,the conductivity and dielectric permittivity showed a step-like behavior under 405 K.Meanwhile,frequency independence of dc conduction became dominant when above 405 K.In CCTO ceramic,rare earth element Y^(3+)ions as an acceptor were used to substitute Ti sites,decreasing the concentration of oxygen vacancy around grainelectrode and grain boundary.The reason to the reduction of dielectric behavior in low frequencies range was associated with the Y doping in CCTO ceramic.
