N-doped bamboo-like carbon nanotube-encapsulated CuNi alloy to enrich nitrate and boost electrochemical ammonia synthesis  

作　　者：Guohao Jia Yuanqing Sun Peilin Liu Jiaqing Luo Peng Zhang Yuechang Wei Weiyu Song Zhenxing Li Zhen Zhao Jian Liu 

机构地区：[1]State Key Laboratory of Heavy Oil Processing,China University of Petroleum,Beijing 102249,China [2]College of Science,Beijing Key Laboratory of Oil and Gas Optical Detection Technology,and Basic Research Center for Energy Interdisciplinary,China University of Petroleum,Beijing 102249,China [3]State Key Laboratory of Heavy Oil Processing at Karamay,China University of Petroleum Beijing at Karamay,Karamay 834000,China [4]Petrochemical Research Institute,PetroChina Company Limited,Beijing 102206,China [5]Institute of Catalysis for Energy and Environment,College of Chemistry and Chemical Engineering,Shenyang Normal University,Shenyang 110034,China

出　　处：《Nano Research》2025年第4期78-89,共12页纳米研究(英文版)

基　　金：the financial support from the National Natural Science Foundation of China(Nos.22035009 and 22122113).

摘　　要：Ammonia plays an irreplaceable role in agricultural production and also is an important chemical raw material and energy carrier.Developing a catalyst for the electrochemical NO_(3)-reduction reaction(NO_(3)RR)to synthesize ammonia is crucial for energy,food security and pollution control.Herein,by adjusting the Cu/Ni ratio,we report a simple impregnation and calcination method to synthesize a N-doped bamboo-like carbon nanotube(CNT)-encapsulated CuNi alloy catalyst(Cu_(7)Ni_(3)-CNT).Cu_(7)Ni_(3)-CNT reveals an excellent ammonia synthesis performance,which has the highest Faraday efficiency(FE,99.18%)at -0.8 V vs.reversible hydrogen electrode(RHE),along with an ammonia production rate of 20.90 mg·cm^(-2)·h^(-1).In addition,the highest ammonia production rate of Cu_(7)Ni_(3)-CNT can reach 23.21 mg·cm^(-2)·h^(-1),with a high FE(90.80%)at -1.0 V vs.RHE.At the same time,the electrocatalyst displays exceptional stability,which can operate steadily for 400 h at 300 mA·cm^(-2).The high catalytic activity and excellent stability derive from catalyst structure and the synergistic effect between Cu_(7)Ni_(3) alloy and encapsulating bamboo-like CNT.The incorporation of Ni enhances the intrinsic activity of Cu for NO_(3)RR.CNT endows the catalyst with a larger specific surface area,more exposed active sites to further improve the apparent activity,and higher stability.The internal cavity of CNT also contributes to the enrichment of nitrate.Furthermore,in-situ Raman spectroscopy and density functional theory(DFT)calculations reveal that Cu in the alloy can effectively adjust the adsorption energy of *NO_(3) by Ni element and increase the activity of *H as the reduction driving force,thereby improving the intrinsic activity of NO_(3)RR.

关 键 词：carbon nanotube CuNi alloy NO_(3)-reduction reaction ammonia synthesis nitrate enriching 

分 类 号：O643.36[理学—物理化学]