d-d Orbital coupling induced by crystal-phase engineering assists acetonitrile electroreduction to ethylamine  

作　　者：Honggang Huang Yao Chen Hui Fu Cun Chen Hanjun Li Zhe Zhang Feili Lai Shuxing Bai Nan Zhang Tianxi Liu 

机构地区：[1]Key Laboratory of Synthetic and Biological Colloids,Ministry of Education,School of Chemical and Material Engineering,Jiangnan University,Wuxi 214122,Jiangsu,China [2]Department of Chemistry,KU Leuven,Celestijnenlaan 200F,Leuven 3001,Belgium [3]College of Chemistry and Chemical Engineering,Qingdao University,Qingdao 266071,Shandong,China

出　　处：《Journal of Energy Chemistry》2024年第2期216-225,I0006,共11页能源化学（英文版）

基　　金：financially supported by the National Natural Science Foundation of China(Grant Nos.52161135302,22105087);the Postdoctoral Research Foundation of China(Grant No.2022M721360);the Natural Science Foundation of Jiangsu Province(Grant No.BK20210446)。

摘　　要：The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in electrochemical acetonitrile reduction reaction(ARR)to date.Herein,we successfully realize the structural transformation of Pd Cu metallic aerogels(MAs)from face-centered cubic(FCC)to body-centered cubic(BCC)through annealing treatment.Specifically,the BCC Pd Cu MAs exhibit excellent ARR performance with high ethylamine selectivity of 90.91%,Faradaic efficiency of 88.60%,yield rate of 316.0 mmol h^(-1)g^(-1)_(Pd+Cu)and long-term stability for consecutive electrolysis within 20 h at-0.55 V vs.reversible hydrogen electrode,outperforming than those of FCC Pd Cu MAs.Under the membrane electrode assembly system,BCC Pd Cu MAs also demonstrate excellent ethylamine yield rate of 389.5 mmol h^(-1)g^(-1)_(Pd+Cu).Density functional theory calculation reveals that the d-d orbital coupling in BCC Pd Cu MAs results in an evident correlation effect for the interaction of Pd and Cu sites,which boosts up the Cu sites electronic activities to enhance ARR performance.Our work opens a new route to develop efficient ARR electrocatalysts from the perspective of crystalline structure transformation.

关 键 词：d-d Orbital coupling Crystal-phase engineering Metallic aerogels Acetonitrile electroreduction reaction ETHYLAMINE 

分 类 号：TQ426[化学工程] TQ226.31