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
Hollow structuring has been identified as an effective strategy to enhance the cycling stability of electrodes for rechargeable batteries due to the outstanding volume expansion buffering efficiency,which motivates ar...Hollow structuring has been identified as an effective strategy to enhance the cycling stability of electrodes for rechargeable batteries due to the outstanding volume expansion buffering efficiency,which motivates ardent pursuing on the synthetic approaches of hollow materials.Herein,an intriguing route,combining solid precursor transition and Ostwald ripening(SPTOR),is developed to craft nano single-crystal(SC)-constructed MnCO_(3) submicron hollow spindles homogeneously encapsulated in a reduced graphene oxide matrix(MnCO_(3) SMHSs/rGO).It is noteworthy that the H-bonding interaction between Mn_(3)O_(4) nanoparticles(NPs)and oxygen-containing groups on GO promotes uniform anchoring of Mn_(3)O_(4) NPs on GO,mild reductant ascorbic acid triggers the progressive solid-to-solid transition from Mn_(3)O_(4) NPs to MnCO_(3) submicron solid spindles(SMSSs)in situ on GO,and the Ostwald ripening process induces the gradual dissolution of interior polycrystals of MnCO_(3) SMSSs and subsequent recrystallization on surface SCs of MnCO_(3) SMHSs.Remarkably,MnCO_(3) SMHSs/rGO delivers a 500th lithium storage capacity of 2023 mAh g^(-1) at 1000 mAg^(-1),which is 10 times higher than that of MnCO_(3) microspheres/rGO fabricated from a conventional Mn^(2+)salt precursor(202 mAh g^(-1)).The ultrahigh capacity and ultralong lifespan of MnCO_(3) SMHSs/rGO can be primarily attributed to the superior reaction kinetics and reversibility combined with exceptional interfacial and capacitive lithium storage capability,enabled by the fast ion/electron transfer,large specific surface area,and robust electrode pulverization inhibition efficacy.Moreover,fascinating in-depth lithium storage reactions of MnCO_(3) are observed such as the oxidation of Mn^(2+)in MnCO_(3) to Mn^(3+)in charge process after long-term cycles and the further lithiation of Li_(2)CO_(3) in discharge process.As such,the Carbon Energy.SPTOR approach may represent a viable strategy for crafting various hollow functional materials with metastable nanomaterials as precursors.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General Research Project of Zhejiang Provincial Department of Education,Grant/Award Number:Y202250766National Natural Science Foundation of China,Grant/Award Numbers:21905208,22250410263Natural Science Foundation of Zhejiang Province,Grant/Award Numbers:LY23B030001,LZ18E030001。
文摘Hollow structuring has been identified as an effective strategy to enhance the cycling stability of electrodes for rechargeable batteries due to the outstanding volume expansion buffering efficiency,which motivates ardent pursuing on the synthetic approaches of hollow materials.Herein,an intriguing route,combining solid precursor transition and Ostwald ripening(SPTOR),is developed to craft nano single-crystal(SC)-constructed MnCO_(3) submicron hollow spindles homogeneously encapsulated in a reduced graphene oxide matrix(MnCO_(3) SMHSs/rGO).It is noteworthy that the H-bonding interaction between Mn_(3)O_(4) nanoparticles(NPs)and oxygen-containing groups on GO promotes uniform anchoring of Mn_(3)O_(4) NPs on GO,mild reductant ascorbic acid triggers the progressive solid-to-solid transition from Mn_(3)O_(4) NPs to MnCO_(3) submicron solid spindles(SMSSs)in situ on GO,and the Ostwald ripening process induces the gradual dissolution of interior polycrystals of MnCO_(3) SMSSs and subsequent recrystallization on surface SCs of MnCO_(3) SMHSs.Remarkably,MnCO_(3) SMHSs/rGO delivers a 500th lithium storage capacity of 2023 mAh g^(-1) at 1000 mAg^(-1),which is 10 times higher than that of MnCO_(3) microspheres/rGO fabricated from a conventional Mn^(2+)salt precursor(202 mAh g^(-1)).The ultrahigh capacity and ultralong lifespan of MnCO_(3) SMHSs/rGO can be primarily attributed to the superior reaction kinetics and reversibility combined with exceptional interfacial and capacitive lithium storage capability,enabled by the fast ion/electron transfer,large specific surface area,and robust electrode pulverization inhibition efficacy.Moreover,fascinating in-depth lithium storage reactions of MnCO_(3) are observed such as the oxidation of Mn^(2+)in MnCO_(3) to Mn^(3+)in charge process after long-term cycles and the further lithiation of Li_(2)CO_(3) in discharge process.As such,the Carbon Energy.SPTOR approach may represent a viable strategy for crafting various hollow functional materials with metastable nanomaterials as precursors.
