Designing efficient and long-lasting non-metal electrocatalysts is an urgent task for addressing the issue of kinetic hysteresis in electrochemical oxidation reactions.The bimetallic hydroxides,catalyzing the oxygen e...Designing efficient and long-lasting non-metal electrocatalysts is an urgent task for addressing the issue of kinetic hysteresis in electrochemical oxidation reactions.The bimetallic hydroxides,catalyzing the oxygen evolution reaction(OER),have significant research potential because hydroxide reconstruction to generate an active phase is a remarkable advantage.Herein,the complete reconstruction of ultrathin CoNi(OH)_(2) nanosheets was achieved by embedding Ag nanoparticles into the hydroxide to induce a spontaneous redox reaction(SRR),forming heterojunction Ag@CoNi(OH)_(2) for bifunctional hydrolysis.Theoretical calculations and in situ Raman and ex situ characterizations revealed that the inductive effect of the Ag cation redistributed the charge to promote phase transformation to highly activate Ag-modified hydroxides.The Co-Ni dual sites in Co/NiOOH serve as novel active sites for optimizing the intermediates,thereby weakening the barrier formed by OOH^*.Ag@CoNi(OH)_(2) required a potential of 1.55 V to drive water splitting at a current density of 10 mA cm^(-2),with nearly 98.6% Faraday efficiency.Through ion induction and triggering of electron regulation in the OER via the synergistic action of the heterogeneous interface and surface reconstruction,this strategic design can overcome the limited capacity of bimetallic hydroxides and bridge the gap between the basic theory and industrialization of water decomposition.展开更多
Efficient synthesis of transition metal hydroxides on conductive substrate is essential for enhancing their merits in industrialization of energy storage field.However,most of the synthetic routes at present mainly re...Efficient synthesis of transition metal hydroxides on conductive substrate is essential for enhancing their merits in industrialization of energy storage field.However,most of the synthetic routes at present mainly rely on traditional bottom-up method,which involves tedious steps,time-consuming treatments,or additional alkaline media,and is unfavorable for high-efficiency production.Herein,we present a facile,ultrafast and general avenue to synthesize transition metal hydroxides on carbon substrate within 13 s by Joule-heating method.With high reaction kinetics caused by the instantaneous high temperature,seven kinds of transition metal-layered hydroxides(TM-LDHs)are formed on carbon cloth.Therein,the fastest synthesis rate reaches~0.46 cm^(2)s^(-1).Density functional theory calculations further demonstrate the nucleation energy barriers and potential mechanism for the formation of metal-based hydroxides on carbon substrates.This efficient approach avoids the use of extra agents,multiple steps,and long production time and endows the LDHs@carbon cloth with outstanding flexibility and machinability,showing practical advantages in both common and micro-zinc ion-based energy storage devices.To prove its utility,as a cathode in rechargeable aqueous alkaline Zn(micro-)battery,the NiCo LDH@carbon cloth exhibits a high energy density,superior to most transition metal LDH materials reported so far.展开更多
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
To prevent and mitigate environmental degradation,high-performance and cost-effective electrochemical flexible energy storage systems need to be urgently developed.This demand has led to an increase in research on ele...To prevent and mitigate environmental degradation,high-performance and cost-effective electrochemical flexible energy storage systems need to be urgently developed.This demand has led to an increase in research on electrode materials for high-capacity flexible supercapacitors and secondary batteries,which have greatly aided the development of contemporary digital communications and electric vehicles.The use of layered double hydroxides(LDHs)as electrode materials has shown productive results over the last decade,owing to their easy production,versatile composition,low cost,and excellent physicochemical features.This review highlights the distinctive 2D sheet-like structures and electrochemical characteristics of LDH materials,as well as current developments in their fabrication strategies for expanding the application scope of LDHs as electrode materials for flexible supercapacitors and alkali metal(Li,Na,K)ion batteries.展开更多
Layered double hydroxides(LDHs) have attracted considerable attention as a cost effective alternative to the precious iridium-and ruthenium-based electrocatalysts for an oxygen evolution reaction(OER),a bottleneck of ...Layered double hydroxides(LDHs) have attracted considerable attention as a cost effective alternative to the precious iridium-and ruthenium-based electrocatalysts for an oxygen evolution reaction(OER),a bottleneck of water electrolysis for sustainable hydrogen production.Despite their excellent OER performance,the structural and electronic properties of LDHs,particularly during the OER process,remain to be poorly understood.In this study,a series of LDH catalysts is investigated through in situ X-ray absorption fine structure analyses and density functional theory(DFT) calculations.Our experimental results reveal that the LDH catalyst with equal amounts of Ni and Fe(NF-LDH) exhibits the highest OER activity and catalytic life span when compared with its counterparts having equal amounts of Ni and Co(NC-LDH)and Ni only(Ni-LDH).The NF-LDH shows a markedly enhanced OER kinetics compared to the NC-LDH and the Ni-LDH,as proven by the lower overpotentials of 180,240,and 310 mV,respectively,and the Tafel slopes of 35.1,43.4,and 62.7 mV dec^(-1),respectively.The DFT calculations demonstrate that the lowest overpotential of the NF-LDH is associated with the active sites located at the edge planes of NF-LDH in contrast to those located at the basal planes of Ni-LDH and NC-LDH.The current study pinpoints the active sites on various LDHs and presents strategies for optimizing the OER performance of the LDH catalysts.展开更多
This study presents a facile and rapid method for synthesizing novel Layered Double Hydroxide(LDH)nanoflakes,exploring their application as a photocatalyst,and investigating the influence of condensed phosphates'g...This study presents a facile and rapid method for synthesizing novel Layered Double Hydroxide(LDH)nanoflakes,exploring their application as a photocatalyst,and investigating the influence of condensed phosphates'geometric linearity on their photocatalytic properties.Herein,the Mg O film,obtained by plasma electrolysis of AZ31 Mg alloys,was modified by growing an LDH film,which was further functionalized using cyclic sodium hexametaphosphate(CP)and linear sodium tripolyphosphate(LP).CP acted as an enhancer for flake spacing within the LDH structure,while LP changed flake dispersion and orientation.Consequently,CP@LDH demonstrated exceptional efficiency in heterogeneous photocatalysis,effectively degrading organic dyes like Methylene blue(MB),Congo red(CR),and Methyl orange(MO).The unique cyclic structure of CP likely enhances surface reactions and improves the catalyst's interaction with dye molecules.Furthermore,the condensed phosphate structure contributes to a higher surface area and reactivity in CP@LDH,leading to its superior photocatalytic performance compared to LP@LDH.Specifically,LP@LDH demonstrated notable degradation efficiencies of 93.02%,92.89%,and 88.81%for MB,MO,and CR respectively,over a 40 min duration.The highest degradation efficiencies were observed in the case of the CP@LDH sample,reporting 99.99%for MB,98.88%for CR,and 99.70%for MO.This underscores the potential of CP@LDH as a highly effective photocatalyst for organic dye degradation,offering promising prospects for environmental remediation and water detoxification applications.展开更多
An exfoliated layered double hydroxides/poly（methyl methacrylate） （LDHs/PMMA） nanocomposite was prepared by in situ solution polymerization of methyl methacrylate （MMA） in the presence of 4-vinylbenzenesulfonate...An exfoliated layered double hydroxides/poly（methyl methacrylate） （LDHs/PMMA） nanocomposite was prepared by in situ solution polymerization of methyl methacrylate （MMA） in the presence of 4-vinylbenzenesulfonate intercalated LDHs（MgAl-VBS LDHs）. MgAl-VBS LDHs was prepared by the ion exchange method, and the structure and composition of the MgAl-VBS LDHs were determined by X-ray diffraction （XRD）, infrared spectroscopy and elemental analysis. XRD and transmission electron microscopy （TEM） were employed to examine the structure of LDHs/PMMA nanocomposite. It was indicated that the LDHs layers were well exfoliated and dispersed in the PMMA matrix. The grafting of PMMA onto LDHs was confirmed by the extraction result and the weight fraction of grafted PMMA increased as the weight fraction of LDHs in the nanocomposites increased.展开更多
基金supported by the Inner Mongolia R&D Program Plan(2021ZD0042,2021EEDSCXSFQZD006)the National Natural Science Foundation of China(21902123)the Natural Science Basic Research Program of Shaanxi(2023-JC-ZD-22)。
文摘Designing efficient and long-lasting non-metal electrocatalysts is an urgent task for addressing the issue of kinetic hysteresis in electrochemical oxidation reactions.The bimetallic hydroxides,catalyzing the oxygen evolution reaction(OER),have significant research potential because hydroxide reconstruction to generate an active phase is a remarkable advantage.Herein,the complete reconstruction of ultrathin CoNi(OH)_(2) nanosheets was achieved by embedding Ag nanoparticles into the hydroxide to induce a spontaneous redox reaction(SRR),forming heterojunction Ag@CoNi(OH)_(2) for bifunctional hydrolysis.Theoretical calculations and in situ Raman and ex situ characterizations revealed that the inductive effect of the Ag cation redistributed the charge to promote phase transformation to highly activate Ag-modified hydroxides.The Co-Ni dual sites in Co/NiOOH serve as novel active sites for optimizing the intermediates,thereby weakening the barrier formed by OOH^*.Ag@CoNi(OH)_(2) required a potential of 1.55 V to drive water splitting at a current density of 10 mA cm^(-2),with nearly 98.6% Faraday efficiency.Through ion induction and triggering of electron regulation in the OER via the synergistic action of the heterogeneous interface and surface reconstruction,this strategic design can overcome the limited capacity of bimetallic hydroxides and bridge the gap between the basic theory and industrialization of water decomposition.
基金the NSFC(22075019)National Key R&D Program of China(2017YFB1104300)。
文摘Efficient synthesis of transition metal hydroxides on conductive substrate is essential for enhancing their merits in industrialization of energy storage field.However,most of the synthetic routes at present mainly rely on traditional bottom-up method,which involves tedious steps,time-consuming treatments,or additional alkaline media,and is unfavorable for high-efficiency production.Herein,we present a facile,ultrafast and general avenue to synthesize transition metal hydroxides on carbon substrate within 13 s by Joule-heating method.With high reaction kinetics caused by the instantaneous high temperature,seven kinds of transition metal-layered hydroxides(TM-LDHs)are formed on carbon cloth.Therein,the fastest synthesis rate reaches~0.46 cm^(2)s^(-1).Density functional theory calculations further demonstrate the nucleation energy barriers and potential mechanism for the formation of metal-based hydroxides on carbon substrates.This efficient approach avoids the use of extra agents,multiple steps,and long production time and endows the LDHs@carbon cloth with outstanding flexibility and machinability,showing practical advantages in both common and micro-zinc ion-based energy storage devices.To prove its utility,as a cathode in rechargeable aqueous alkaline Zn(micro-)battery,the NiCo LDH@carbon cloth exhibits a high energy density,superior to most transition metal LDH materials reported so far.
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the National Natural Science Foundation of China(NSFC Grant No.62174152).
文摘To prevent and mitigate environmental degradation,high-performance and cost-effective electrochemical flexible energy storage systems need to be urgently developed.This demand has led to an increase in research on electrode materials for high-capacity flexible supercapacitors and secondary batteries,which have greatly aided the development of contemporary digital communications and electric vehicles.The use of layered double hydroxides(LDHs)as electrode materials has shown productive results over the last decade,owing to their easy production,versatile composition,low cost,and excellent physicochemical features.This review highlights the distinctive 2D sheet-like structures and electrochemical characteristics of LDH materials,as well as current developments in their fabrication strategies for expanding the application scope of LDHs as electrode materials for flexible supercapacitors and alkali metal(Li,Na,K)ion batteries.
基金supported by the National Research Foundation of Korea (NRF-2022R1C1C1004171)supported by the National Science Foundation (Grant number ACI1548562)。
文摘Layered double hydroxides(LDHs) have attracted considerable attention as a cost effective alternative to the precious iridium-and ruthenium-based electrocatalysts for an oxygen evolution reaction(OER),a bottleneck of water electrolysis for sustainable hydrogen production.Despite their excellent OER performance,the structural and electronic properties of LDHs,particularly during the OER process,remain to be poorly understood.In this study,a series of LDH catalysts is investigated through in situ X-ray absorption fine structure analyses and density functional theory(DFT) calculations.Our experimental results reveal that the LDH catalyst with equal amounts of Ni and Fe(NF-LDH) exhibits the highest OER activity and catalytic life span when compared with its counterparts having equal amounts of Ni and Co(NC-LDH)and Ni only(Ni-LDH).The NF-LDH shows a markedly enhanced OER kinetics compared to the NC-LDH and the Ni-LDH,as proven by the lower overpotentials of 180,240,and 310 mV,respectively,and the Tafel slopes of 35.1,43.4,and 62.7 mV dec^(-1),respectively.The DFT calculations demonstrate that the lowest overpotential of the NF-LDH is associated with the active sites located at the edge planes of NF-LDH in contrast to those located at the basal planes of Ni-LDH and NC-LDH.The current study pinpoints the active sites on various LDHs and presents strategies for optimizing the OER performance of the LDH catalysts.
基金the National Research Foundation of Korea(NRF)funded by the Korean Government(MSIT)(No.2022R1A2C1006743)。
文摘This study presents a facile and rapid method for synthesizing novel Layered Double Hydroxide(LDH)nanoflakes,exploring their application as a photocatalyst,and investigating the influence of condensed phosphates'geometric linearity on their photocatalytic properties.Herein,the Mg O film,obtained by plasma electrolysis of AZ31 Mg alloys,was modified by growing an LDH film,which was further functionalized using cyclic sodium hexametaphosphate(CP)and linear sodium tripolyphosphate(LP).CP acted as an enhancer for flake spacing within the LDH structure,while LP changed flake dispersion and orientation.Consequently,CP@LDH demonstrated exceptional efficiency in heterogeneous photocatalysis,effectively degrading organic dyes like Methylene blue(MB),Congo red(CR),and Methyl orange(MO).The unique cyclic structure of CP likely enhances surface reactions and improves the catalyst's interaction with dye molecules.Furthermore,the condensed phosphate structure contributes to a higher surface area and reactivity in CP@LDH,leading to its superior photocatalytic performance compared to LP@LDH.Specifically,LP@LDH demonstrated notable degradation efficiencies of 93.02%,92.89%,and 88.81%for MB,MO,and CR respectively,over a 40 min duration.The highest degradation efficiencies were observed in the case of the CP@LDH sample,reporting 99.99%for MB,98.88%for CR,and 99.70%for MO.This underscores the potential of CP@LDH as a highly effective photocatalyst for organic dye degradation,offering promising prospects for environmental remediation and water detoxification applications.
基金This work was supported by the Zhejiang Grant Science and Technology Program(No.2005C11039).
文摘An exfoliated layered double hydroxides/poly（methyl methacrylate） （LDHs/PMMA） nanocomposite was prepared by in situ solution polymerization of methyl methacrylate （MMA） in the presence of 4-vinylbenzenesulfonate intercalated LDHs（MgAl-VBS LDHs）. MgAl-VBS LDHs was prepared by the ion exchange method, and the structure and composition of the MgAl-VBS LDHs were determined by X-ray diffraction （XRD）, infrared spectroscopy and elemental analysis. XRD and transmission electron microscopy （TEM） were employed to examine the structure of LDHs/PMMA nanocomposite. It was indicated that the LDHs layers were well exfoliated and dispersed in the PMMA matrix. The grafting of PMMA onto LDHs was confirmed by the extraction result and the weight fraction of grafted PMMA increased as the weight fraction of LDHs in the nanocomposites increased.
