Cu3P辅助诱导Ni2P电荷定向转移和表面重构以获得高效析氧活性OA北大核心CSTPCD
Cu3P-Induced Charge-Oriented Transfer and Surface Reconstruction of Ni2P to Achieve Efficient Oxygen Evolution Activity
与助催化剂形成异质结,通过调整活性位点的电子结构和电荷输运来提高Ni2P的电催化活性是一种可行的方法.本文成功构建了一种高效的Cu3P/Ni2P异质结催化剂,其中Cu3P本身仅作为助催化剂,通过调节Ni2P的电子转移和表面重构来提高电催化活性.结果表明,在10 mA·cm-2的电流密度下,Cu3P/Ni2P具有优异的析氧反应(OER)活性,过电位为213 mV.结合实验结果和理论计算可知,Cu3P助催化剂可以有效调整Ni中心的电子结构,实现电荷重分布,降低反应能垒,从而显著提高OER催化活性.此外,Cu3P助催化剂诱导的丰富的晶界和晶格畸变促进了表面重构,形成Ni5O(OH)9,为OER提供了有效的活性位点.本工作通过引入助催化剂构建了一种新型异质结电催化剂,为优化过渡金属磷化物的电催化性能提供了一条有效途径.
Owing to the increasingly serious environmental problems,there is an urgent need for clean energy with a high energy density and low carbon emissions.As such,electrocatalytic water decomposition has attracted significant interest as an efficient hydrogen production method.The electrolysis of water has two important half-reactions:the hydrogen evolution reaction(HER)and the oxygen evolution reaction(OER).Among these two reactions,OER is considered to be the crucial and rate-determining step due to its slower kinetic process and higher overpotential compared to HER.Although noble metal oxides such as IrO2 and RuO2 have excellent OER properties under alkaline conditions,their high cost and scarcity limit their commercial application.Therefore,it is of significant interest to develop alternative OER electrodes with excellent catalytic activity,extremely low overpotential,high durability,and low cost.Ni2P has attracted interest as an electrocatalyst and has improved activity after combination with a cocatalyst.The improved activity is due to heterojunction formation changing the electronic structure and charge transport at the active site.To this end,a novel highly efficient Cu3P/Ni2P heterojunction catalyst has been successfully constructed,in which Cu3P functions solely as a cocatalyst to enhance the electrocatalytic activity by regulating the electron transfer and surface reconstruction of Ni2P.Consequently,Cu3P/Ni2P exhibits superior OER activity and has an ultra-low overpotential of 213 mV at a current density of 10 mA·cm-2 and a small Tafel slope of 62 mV·dec-1 in 1 mol·L-1 KOH.Additionally,this peculiar self-supporting electrode possesses excellent electrochemical stability and long-term durability at a current density of 10 mA·cm-2 in an alkaline medium.Through a combination of experimental results and theoretical calculations,it has been shown that the Cu3P cocatalyst effectively tailors the electronic structure of the Ni center.This results in charge redistribution and a lower reaction energy barrier,thereby significantly improving the OER catalytic activity.In addition,the abundant grain boundaries and lattice distortions induced by the Cu3P cocatalyst promote surface reconstruction to form Ni5O(OH)9,providing an efficient active site for OER.This work constructed a novel heterojunction electrocatalyst by introducing a cocatalyst,offering an avenue for the optimization of the electrocatalytic performance of transition metal phosphide.
邢雅娟;薛辉;孙静;郭念坤;宋天山;孙佳雯;郝翊茹;王勤
内蒙古大学化学化工学院,呼和浩特 010021
化学
磷化物异质结助催化剂表面重构析氧反应
PhosphideHeterojunctionCocatalystSurface reconstructionOxygen evolution reaction
《物理化学学报》 2024 (003)
31-32 / 2
The project was supported by the National Natural Science Foundation of China(22269015)and Natural Science Foundation of Inner Mongolia Autonomous Region of China(2021ZD11).国家自然科学基金(22269015)和内蒙古自治区自然科学基金(2021ZD11)资助项目
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