Electrochemical impedance spectroscopy(EIS)is a widely used technique to monitor the electrical properties of a catalyst under electrocatalytic conditions.Although it is extensively used for research in electrocatalys...Electrochemical impedance spectroscopy(EIS)is a widely used technique to monitor the electrical properties of a catalyst under electrocatalytic conditions.Although it is extensively used for research in electrocatalysis,its effectiveness and power have not been fully harnessed to elucidate complex interfacial processes.Herein,we use the frequency dispersion parameter,n,which is extracted from EIS measurements(C_(s)=af^(n+1),-2<n<-1),to describe the dispersion characteristics of capacitance and interfacial properties of Co_(3)O_(4) before the onset of oxygen evolution reaction(OER)in alkaline conditions.We first prove that the n-value is sensitive to the interfacial electronic changes associated with Co redox processes and surface reconstruction.The n-value decreases by increasing the specific/active surface area of the catalysts.We further modify the interfacial properties by changing different components,i.e.,replacing the proton with deuterium,adding ethanol as a new oxidant,and changing the cation in the electrolyte.Intriguingly,the n-value can identify different influences on the interfacial process of proton transfer,the decrease and blocking of oxidized Co species,and the interfacial water structure.We demonstrate that the n-value extracted from EIS measurements is sensitive to the kinetic isotope effect,electrolyte cation,adsorbate surface coverage of oxidized Co species,and the interfacial water structure.Thus,it can be helpful to differentiate the multiple factors affecting the catalyst interface.These findings convey that the frequency dispersion of capacitance is a convenient and useful method to uncover the interfacial properties under electrocatalytic conditions,which helps to advance the understanding of the interfaceactivity relationship.展开更多
The dispersion mechanism in Al0：27Ga0：73N/GaN heterostructure was investigated using frequencydependent capacitance and conductance measurements.It was found that the significant capacitance and conductance dispersi...The dispersion mechanism in Al0：27Ga0：73N/GaN heterostructure was investigated using frequencydependent capacitance and conductance measurements.It was found that the significant capacitance and conductance dispersion occurred primarily for measurement frequency beyond 100 kHz before the channel cutoff at the interface,suggesting that the vertical polarization electrical field under the gate metal should be closely related with the observed dispersive behavior.According to the Schottky-Read-Hall model,a traditional trapping mechanism cannot be used to explain our result.Instead,a piezoelectric polarization strain relaxation model was adopted to interpret the dispersion.By fitting the obtained capacitance data,the corresponding characteristic time and charge density were determined 10..8 s and 5.26 1012 cm..2 respectively,in good agreement with the conductance data and theoretical prediction.展开更多
基金Swiss National Science Foundation through its PRIM A grant(grant No.PR00P2_193111)the NCCR MARVEL,a National Centre of Competence in Researchfunded by the Swiss National Science Foundation。
文摘Electrochemical impedance spectroscopy(EIS)is a widely used technique to monitor the electrical properties of a catalyst under electrocatalytic conditions.Although it is extensively used for research in electrocatalysis,its effectiveness and power have not been fully harnessed to elucidate complex interfacial processes.Herein,we use the frequency dispersion parameter,n,which is extracted from EIS measurements(C_(s)=af^(n+1),-2<n<-1),to describe the dispersion characteristics of capacitance and interfacial properties of Co_(3)O_(4) before the onset of oxygen evolution reaction(OER)in alkaline conditions.We first prove that the n-value is sensitive to the interfacial electronic changes associated with Co redox processes and surface reconstruction.The n-value decreases by increasing the specific/active surface area of the catalysts.We further modify the interfacial properties by changing different components,i.e.,replacing the proton with deuterium,adding ethanol as a new oxidant,and changing the cation in the electrolyte.Intriguingly,the n-value can identify different influences on the interfacial process of proton transfer,the decrease and blocking of oxidized Co species,and the interfacial water structure.We demonstrate that the n-value extracted from EIS measurements is sensitive to the kinetic isotope effect,electrolyte cation,adsorbate surface coverage of oxidized Co species,and the interfacial water structure.Thus,it can be helpful to differentiate the multiple factors affecting the catalyst interface.These findings convey that the frequency dispersion of capacitance is a convenient and useful method to uncover the interfacial properties under electrocatalytic conditions,which helps to advance the understanding of the interfaceactivity relationship.
基金Project supported by the Fundamental Research Funds for the Central Universities of China (Nos.JUSRP111A42,JUSRP211A37,JUSRP20914,JUSRP11230)the State Key Laboratory of ASIC & System,China (No.11KF003)the Natural Science Foundation of Jiangsu Province,China (No.BK2012110)
文摘The dispersion mechanism in Al0：27Ga0：73N/GaN heterostructure was investigated using frequencydependent capacitance and conductance measurements.It was found that the significant capacitance and conductance dispersion occurred primarily for measurement frequency beyond 100 kHz before the channel cutoff at the interface,suggesting that the vertical polarization electrical field under the gate metal should be closely related with the observed dispersive behavior.According to the Schottky-Read-Hall model,a traditional trapping mechanism cannot be used to explain our result.Instead,a piezoelectric polarization strain relaxation model was adopted to interpret the dispersion.By fitting the obtained capacitance data,the corresponding characteristic time and charge density were determined 10..8 s and 5.26 1012 cm..2 respectively,in good agreement with the conductance data and theoretical prediction.
