Cerium and cerium-based oxides are found to be an important element in three-way catalytic converter(TWC).The effective utilization of TWC is found to be reduced due to thermal loading which results in structural defo...Cerium and cerium-based oxides are found to be an important element in three-way catalytic converter(TWC).The effective utilization of TWC is found to be reduced due to thermal loading which results in structural deformation of ceria,Doping Zr^(4+)into the rare earth element can increase the oxygen storage capacity and thermal stability.Hence,an attempt was made to study the oxygen storage capacity and thermal stability of ceria by doping Zr^(4+)and Nd^(3+).Cerium-based nanocrystallite in the composition of Ce_(0.6)Zr_(0.4-x)Nd_(1.3)xO_(2)(0≤x≤0.4)was prepared by sol-gel synthesize technique with citric acid as a gel-forming agent.X-ray diffraction(XRD)result shows that doping Nd^(3+)into ceria lattice forms homogenous solid solution of cubic fluorite structure up to 25%of substitute only.Doping higher amount of Nd^(3+)into ceria lattice leads to the formation of Nd_(2)O_(3).Raman spectrum study confirms that oxygen storage capacity band is present in Ce_(0.6)Zr_(0.4)O2 and Ce_(0.6)Zr_(0.3)Nd_(0.13)O_(2).The oxygen storage capacity was calculated through weight loss of the sample during the second heating cycle with cyclic heating from30 to 800℃in thermogravimetric analysis(TGA).The TGA study reveals that the oxygen storage capacity of Ce_(0.6)Zr_(0.4)O2 decreases after the substitution of Nd^(3+),which is due to the larger ionic radius of Nd^(3+)compared with that of Zr4+and CeO2.展开更多
The application of homogeneous electrocatalytic reactions in energy storage and conversion has driven surging interests of researchers in exploring the reaction mechanisms of molecular catalysts.In this paper,homogene...The application of homogeneous electrocatalytic reactions in energy storage and conversion has driven surging interests of researchers in exploring the reaction mechanisms of molecular catalysts.In this paper,homogeneous electrocatalytic reaction between hydroxymethylferrocene(HMF)and L-cysteine is intensively investigated by cyclic voltammetry and square wave voltammetry for which,the secondorder rate constant(k_(ec))of the chemical reaction between HMF^(+)and L-cysteine is determined via a 1D homogeneous electrocatalytic reaction model based on finite element simulation.The corresponding k_(ec)(1.1(mol·m^(-3))^(-1)·s^(-1))is further verified by linear sweep voltammograms under the same model.Square wave voltammetry parameters including potential frequency(f),increment(Estep)and amplitude(ESW)have been comprehensively investigated in terms of the voltammetric waveform transition of homogeneous electrocatalytic reaction.Specifically,the effect of potential frequency and increment is in accordance with the potential scan rate in cyclic voltammetry and the increase of pulsed potential amplitude results in a conspicuous split oxidative peaks phenomenon.Moreover,the proposed methodology of k_(ec)prediction is examined by hydroxyethylferrocene(HEF)and L-cysteine.The present work facilitates the understanding of homogeneous electrocatalytic reaction for energy storage purpose,especially in terms of electrochemical kinetics extraction and flow battery design.展开更多
文摘Cerium and cerium-based oxides are found to be an important element in three-way catalytic converter(TWC).The effective utilization of TWC is found to be reduced due to thermal loading which results in structural deformation of ceria,Doping Zr^(4+)into the rare earth element can increase the oxygen storage capacity and thermal stability.Hence,an attempt was made to study the oxygen storage capacity and thermal stability of ceria by doping Zr^(4+)and Nd^(3+).Cerium-based nanocrystallite in the composition of Ce_(0.6)Zr_(0.4-x)Nd_(1.3)xO_(2)(0≤x≤0.4)was prepared by sol-gel synthesize technique with citric acid as a gel-forming agent.X-ray diffraction(XRD)result shows that doping Nd^(3+)into ceria lattice forms homogenous solid solution of cubic fluorite structure up to 25%of substitute only.Doping higher amount of Nd^(3+)into ceria lattice leads to the formation of Nd_(2)O_(3).Raman spectrum study confirms that oxygen storage capacity band is present in Ce_(0.6)Zr_(0.4)O2 and Ce_(0.6)Zr_(0.3)Nd_(0.13)O_(2).The oxygen storage capacity was calculated through weight loss of the sample during the second heating cycle with cyclic heating from30 to 800℃in thermogravimetric analysis(TGA).The TGA study reveals that the oxygen storage capacity of Ce_(0.6)Zr_(0.4)O2 decreases after the substitution of Nd^(3+),which is due to the larger ionic radius of Nd^(3+)compared with that of Zr4+and CeO2.
基金the support of National Natural Science Foundation of China, China (Grant No. 22005010)Beijing Municipal Education Commission Research Project (KM202010005012)
文摘The application of homogeneous electrocatalytic reactions in energy storage and conversion has driven surging interests of researchers in exploring the reaction mechanisms of molecular catalysts.In this paper,homogeneous electrocatalytic reaction between hydroxymethylferrocene(HMF)and L-cysteine is intensively investigated by cyclic voltammetry and square wave voltammetry for which,the secondorder rate constant(k_(ec))of the chemical reaction between HMF^(+)and L-cysteine is determined via a 1D homogeneous electrocatalytic reaction model based on finite element simulation.The corresponding k_(ec)(1.1(mol·m^(-3))^(-1)·s^(-1))is further verified by linear sweep voltammograms under the same model.Square wave voltammetry parameters including potential frequency(f),increment(Estep)and amplitude(ESW)have been comprehensively investigated in terms of the voltammetric waveform transition of homogeneous electrocatalytic reaction.Specifically,the effect of potential frequency and increment is in accordance with the potential scan rate in cyclic voltammetry and the increase of pulsed potential amplitude results in a conspicuous split oxidative peaks phenomenon.Moreover,the proposed methodology of k_(ec)prediction is examined by hydroxyethylferrocene(HEF)and L-cysteine.The present work facilitates the understanding of homogeneous electrocatalytic reaction for energy storage purpose,especially in terms of electrochemical kinetics extraction and flow battery design.
