Low-overpotential layered hydroxides(LDHs)with high theoretical capacity are promising electrodes for supercapaterry and oxygen evolution reaction;however,the low electronic conductivity and insufficient active sites ...Low-overpotential layered hydroxides(LDHs)with high theoretical capacity are promising electrodes for supercapaterry and oxygen evolution reaction;however,the low electronic conductivity and insufficient active sites of bulk LDHs increase the internal resistance and reduce the capacity and oxygen-production efficiency of electrodes.Herein,we prepared a polyaniline-coated Ni-Co-layered double hydroxide intercalated with MoO_(4)^(2−)(M-LDH@PANI)composite electrode using a two-step method.As the amount of MoO_(4)^(2−)in the LDH increases,acicular microspheres steadily evolve into flaky microspheres with a high surface area,providing more active electrochemical sites.Moreover,the amorphous PANI coating of M-LDH boosts the electronic conductivity of the composite electrode.Accordingly,the M-LDH@PANI at an appropriate level of MoO_(4)^(2−)exhibits significantly enhanced energy storage and catalytic performance.Experimental analyses and theoretical calculations reveal that a small amount of MoO_(4)^(2−)is conducive to the expansion of LDH interlayer spacing,while an excessive amount of MoO_(4)^(2−)combines with the H atoms of LDH,thus competing with OH^(−),resulting in reduced electrochemical performance.Moreover,M-LDH flaky microspheres can efficiently modulate deprotonation energy,greatly accelerating surface redox reactions.This study provides an explanation for an unconventional mechanism,and a method for the modification of LDH-based materials for anion intercalation.展开更多
Transition metal chalcogenides(TMCs)are recognized as pre-catalysts,and their(oxy)hydroxides derived from electrochemical reconstruction are the active species in the water oxidation.However,understanding the role of ...Transition metal chalcogenides(TMCs)are recognized as pre-catalysts,and their(oxy)hydroxides derived from electrochemical reconstruction are the active species in the water oxidation.However,understanding the role of the residual chalcogen in the reconstructed layer is lacking in detail,and the corresponding catalytic mechanism remains controversial.Here,taking Cu_(1-x)Co_(x)S as a platform,we explore the regulating effect and existence form of the residual S doped into the reconstructive layer for oxygen evolution reaction(OER),where a dual-path OER mechanism is proposed.First-principles calculations and operando~(18)O isotopic labeling experiments jointly reveal that the residual S in the reconstructive layer of Cu_(1-x)Co_(x)S can wisely balance the adsorbate evolution mechanism(AEM)and lattice oxygen oxidation mechanism(LOM)by activating lattice oxygen and optimizing the adsorption/desorption behaviors at metal active sites,rather than change the reaction mechanism from AEM to LOM.Following such a dual-path OER mechanism,Cu_(0.4)Co_(0.6)S-derived Cu_(0.4)Co_(0.6)OSH not only overcomes the restriction of linear scaling relationship in AEM,but also avoids the structural collapse caused by lattice oxygen migration in LOM,so as to greatly reduce the OER potential and improved stability.展开更多
Prolonging the lifespan of oxygen catalysts in Zn-air batteries was urgently required for the potential commercialization.Herein,two interactional active species were integrated into porous N-doped carbon microspheres...Prolonging the lifespan of oxygen catalysts in Zn-air batteries was urgently required for the potential commercialization.Herein,two interactional active species were integrated into porous N-doped carbon microspheres(Co-Fe-Ru/PNCS)to act as bifunctional oxygen electrocatalysts.Due to the electron transfer from Ru to Co/Fe element,the high value state of Ru could promote OER performance and reduce the charge voltage of the battery.An extended cycle stability of 200 h was achieved in Co-Fe-Ru/PNCS-based battery.Moreover,the quasi in-situ potentiodynamic sweep of air-electrode in battery cell confirmed it was the incorporation of Ru that avoided the passivation of Co/Fe-based nanoparticles.Accordingly,this novel electrocatalyst may provide a new strategy of designing durable bifunctional oxygen electrocatalyst for Zn-air batteries.展开更多
文摘Low-overpotential layered hydroxides(LDHs)with high theoretical capacity are promising electrodes for supercapaterry and oxygen evolution reaction;however,the low electronic conductivity and insufficient active sites of bulk LDHs increase the internal resistance and reduce the capacity and oxygen-production efficiency of electrodes.Herein,we prepared a polyaniline-coated Ni-Co-layered double hydroxide intercalated with MoO_(4)^(2−)(M-LDH@PANI)composite electrode using a two-step method.As the amount of MoO_(4)^(2−)in the LDH increases,acicular microspheres steadily evolve into flaky microspheres with a high surface area,providing more active electrochemical sites.Moreover,the amorphous PANI coating of M-LDH boosts the electronic conductivity of the composite electrode.Accordingly,the M-LDH@PANI at an appropriate level of MoO_(4)^(2−)exhibits significantly enhanced energy storage and catalytic performance.Experimental analyses and theoretical calculations reveal that a small amount of MoO_(4)^(2−)is conducive to the expansion of LDH interlayer spacing,while an excessive amount of MoO_(4)^(2−)combines with the H atoms of LDH,thus competing with OH^(−),resulting in reduced electrochemical performance.Moreover,M-LDH flaky microspheres can efficiently modulate deprotonation energy,greatly accelerating surface redox reactions.This study provides an explanation for an unconventional mechanism,and a method for the modification of LDH-based materials for anion intercalation.
基金supported by the Science and Technology Research Program of Chongqing Municipal Education Commission(KJQN202200550)the Natural Science Foundation Joint Fund for Innovation and Development of Chongqing Municipal Education Commission(CSTB2022NSCQ-LZX0077)+4 种基金the National Natural Science Foundation of China(No.52100065)the Science and Technology Research Program of Natural Science Foundation of Chongqing(cstc2021ycjh-bgzxm0037)the Science and Technology Research Program of Chongqing Municipal Education Commission(KJZD-M202200503)the Chongqing Innovation Research Group Project(No.CXQT21015)the Doctor Start/Talent Introduction Program of Chongqing Normal University(No.02060404/2020009000321)。
文摘Transition metal chalcogenides(TMCs)are recognized as pre-catalysts,and their(oxy)hydroxides derived from electrochemical reconstruction are the active species in the water oxidation.However,understanding the role of the residual chalcogen in the reconstructed layer is lacking in detail,and the corresponding catalytic mechanism remains controversial.Here,taking Cu_(1-x)Co_(x)S as a platform,we explore the regulating effect and existence form of the residual S doped into the reconstructive layer for oxygen evolution reaction(OER),where a dual-path OER mechanism is proposed.First-principles calculations and operando~(18)O isotopic labeling experiments jointly reveal that the residual S in the reconstructive layer of Cu_(1-x)Co_(x)S can wisely balance the adsorbate evolution mechanism(AEM)and lattice oxygen oxidation mechanism(LOM)by activating lattice oxygen and optimizing the adsorption/desorption behaviors at metal active sites,rather than change the reaction mechanism from AEM to LOM.Following such a dual-path OER mechanism,Cu_(0.4)Co_(0.6)S-derived Cu_(0.4)Co_(0.6)OSH not only overcomes the restriction of linear scaling relationship in AEM,but also avoids the structural collapse caused by lattice oxygen migration in LOM,so as to greatly reduce the OER potential and improved stability.
基金support of the research start-up fund of Hubei University of Technology(No.XJ2021007701)Nature Science Foundation of Hubei Province(2021CFB291)。
文摘Prolonging the lifespan of oxygen catalysts in Zn-air batteries was urgently required for the potential commercialization.Herein,two interactional active species were integrated into porous N-doped carbon microspheres(Co-Fe-Ru/PNCS)to act as bifunctional oxygen electrocatalysts.Due to the electron transfer from Ru to Co/Fe element,the high value state of Ru could promote OER performance and reduce the charge voltage of the battery.An extended cycle stability of 200 h was achieved in Co-Fe-Ru/PNCS-based battery.Moreover,the quasi in-situ potentiodynamic sweep of air-electrode in battery cell confirmed it was the incorporation of Ru that avoided the passivation of Co/Fe-based nanoparticles.Accordingly,this novel electrocatalyst may provide a new strategy of designing durable bifunctional oxygen electrocatalyst for Zn-air batteries.
