Layered double hydroxides(LDHs)are promising electrocatalysts for the oxygen evolution reaction(OER),yet their practical application remains limited by poor electrical conductivity and sluggish reaction kinetics.In th...Layered double hydroxides(LDHs)are promising electrocatalysts for the oxygen evolution reaction(OER),yet their practical application remains limited by poor electrical conductivity and sluggish reaction kinetics.In this work,we synthesize three high-entropy LDHs(HELDHs)featuring a hierarchical architecture of microspheres assembled from ultrathin nanosheets,via a simple hydrothermal method using a combination of low-cost,catalytically active transition metals(Fe,Co,Ni,Mn,Zn,Cu,and Cr).Among them,the FeCoNiMnZn HELDH exhibits outstanding OER performance,requiring an overpotential of only 306 mV to reach a current density of 100 mA cm^(-2).Notably,during 200 h of continuous operation,the device exhibits a stable and,in some cases,increasing current output.This exceptional activity is attributed to the formation of abundant cation vacancies,induced by Zn leaching,which enhance the intrinsic catalytic properties by optimizing the adsorption energies of key OER intermediates.Density functional theory calculations further validate that these vacancies modulate the electronic structure and lower reaction barriers,underscoring the effectiveness of cation-vacancy engineering in high-entropy systems for efficient and durable water oxidation catalysis.The optimized catalyst was further evaluated as the air cathode in a zinc-air battery,demonstrating practical electrochemical performance.展开更多
The deactivation behavior by crystallite growth of nickel nanoparticles on various supports（carbon nanofibers, zirconia, Si C, α-Al2O3 and γ-Al2O3） was investigated in the aqueous phase reforming of ethylene glyco...The deactivation behavior by crystallite growth of nickel nanoparticles on various supports（carbon nanofibers, zirconia, Si C, α-Al2O3 and γ-Al2O3） was investigated in the aqueous phase reforming of ethylene glycol. Supported Ni catalysts of ~10 wt% were prepared by impregnation of carbon nanofibers（CNF）,Zr O2, SiC, γ-Al2O3 and α-Al2O3. The extent of the Ni nanoparticle growth on various support materials follows the order CNF ~ ZrO2〉 SiC 〉 γ-Al2O3〉〉 α-Al2O3 which sequence, however, was determined by the initial Ni particle size. Based on the observed nickel leaching and the specific growth characteristics; the particle size distribution and the effect of loading on the growth rate, Ostwald ripening is suggested to be the main mechanism contributing to nickel particle growth. Remarkably, initially smaller Ni particles（~12 nm） supported on α-Al2O3 were found to outgrow Ni particles with initially larger size（~20 nm）. It is put forward that the higher susceptibility with respect to oxidation of the smaller Ni nanoparticles and differences in initial particle size distribution are responsible for this behavior.展开更多
基金supported by the National Natural Science Foundation of China(NSFC)(22302151,52502312)Natural Science Foundation of Hubei Province(2024AFB755,2024AFB267)+1 种基金Key Project of Hubei Provincial Department of Education Scientific Research Plan(F2023007)Wuhan Institute of Technology Graduate Education Innovation Fund(CX2024285)。
文摘Layered double hydroxides(LDHs)are promising electrocatalysts for the oxygen evolution reaction(OER),yet their practical application remains limited by poor electrical conductivity and sluggish reaction kinetics.In this work,we synthesize three high-entropy LDHs(HELDHs)featuring a hierarchical architecture of microspheres assembled from ultrathin nanosheets,via a simple hydrothermal method using a combination of low-cost,catalytically active transition metals(Fe,Co,Ni,Mn,Zn,Cu,and Cr).Among them,the FeCoNiMnZn HELDH exhibits outstanding OER performance,requiring an overpotential of only 306 mV to reach a current density of 100 mA cm^(-2).Notably,during 200 h of continuous operation,the device exhibits a stable and,in some cases,increasing current output.This exceptional activity is attributed to the formation of abundant cation vacancies,induced by Zn leaching,which enhance the intrinsic catalytic properties by optimizing the adsorption energies of key OER intermediates.Density functional theory calculations further validate that these vacancies modulate the electronic structure and lower reaction barriers,underscoring the effectiveness of cation-vacancy engineering in high-entropy systems for efficient and durable water oxidation catalysis.The optimized catalyst was further evaluated as the air cathode in a zinc-air battery,demonstrating practical electrochemical performance.
基金the support of the Smart Mix Program of The Netherlands Ministry of Economic Affairs, Agriculture and Innovation and The Netherlands Ministry of Education, Culture and Science (Grant no. 053.70.011)
文摘The deactivation behavior by crystallite growth of nickel nanoparticles on various supports（carbon nanofibers, zirconia, Si C, α-Al2O3 and γ-Al2O3） was investigated in the aqueous phase reforming of ethylene glycol. Supported Ni catalysts of ~10 wt% were prepared by impregnation of carbon nanofibers（CNF）,Zr O2, SiC, γ-Al2O3 and α-Al2O3. The extent of the Ni nanoparticle growth on various support materials follows the order CNF ~ ZrO2〉 SiC 〉 γ-Al2O3〉〉 α-Al2O3 which sequence, however, was determined by the initial Ni particle size. Based on the observed nickel leaching and the specific growth characteristics; the particle size distribution and the effect of loading on the growth rate, Ostwald ripening is suggested to be the main mechanism contributing to nickel particle growth. Remarkably, initially smaller Ni particles（~12 nm） supported on α-Al2O3 were found to outgrow Ni particles with initially larger size（~20 nm）. It is put forward that the higher susceptibility with respect to oxidation of the smaller Ni nanoparticles and differences in initial particle size distribution are responsible for this behavior.
