Insights into Reduction of CO_(2) to CO Catalyzed by Pyramidal-4Ni Clusters Supported on Doped CeO_(2)  

金属掺杂CeO_(2)(111)负载锥体4Ni团簇催化CO_(2)还原为CO的见解

作　　者：Ruimin Qin Shenyu Shen Boyang Li Tingyi Zhu Tiantian Wu Shujiang Ding Yaqiong Su 秦瑞敏;申坤玉;李博阳;朱婷宜;武甜甜;丁书江;苏亚琼(西安交通大学化学学院,教育部储能材料与设备工程研究中心,国家储能技术产教融合创新平台(中心),西安710049)

机构地区：[1]School of Chemistry,Engineering Research Center of Energy Storage Materials and Devices of Ministry of Education,National Innovation Plaform(Center)for Industry-Education Integration of Energy Storage Technology,Xi'an Jiaotong University,Xi'an 710049,China

出　　处：《Chinese Journal of Chemical Physics》2024年第5期591-598,I0028-I0037,I0099,共19页化学物理学报（英文）

基　　金：This work is financially supported by the National Natural Science Foundation of China(No.22403073 and No.22103059);the Natural Science Program on Basic Research Project of Shaanxi Province(2023-JC-QN-0155);the Fundamental Research Funds for the Central Universities(xzy012024052);Yaqiong Su also acknowledges the"Young Talent Support Plan"of Xi`an Jiaotong University.Supercomputing facilities were provided by Hefei Advanced Computing Center and Computing Center in Xi'an.

摘　　要：Converting CO_(2) into valuable chemicals has become a widely used research method for CO_(2) conversion.In this work,the catalytic performance of pyramidal-4Ni catalysts supported on rare earth metal-doped CeO_(2)toward CO_(2) reductionreaction(CO_(2)RR)was investigated by using density-functional theorycalculations.For rare earth metal-doped CeO_(2),2Ce is substituted by 2 trivalent cations and at the same time one oxygen vacancy is created to make charge compensation.We investigated the oxygen vacancy nearest(Vo,N)and next-nearest(Vo,NN)to 4Ni,and found releasing CO and CO_(2) dissociation are the rate-determining steps,respectively,via the path of Vo,N and Vo,NN.Among the studied dopants(Ga,Sb,Lu,Gd,Pr,La,Bi),Gd is identified as the best dopant for catalyzing the reduction of CO_(2) at 823 K,with the turn-over frequency(TOF)of 104 times as large as that over 4Ni supported on pure CeO_(2).This exploration provides theoretical support and guidance for the research and application of rare earth metaldoped CeO_(2)-loaded Ni catalysts in the field of CO_(2) reduction.将CO_(2)转化为有价值的化学物质已成为一种广泛应用的CO_(2)转化研究方法本文采用密度泛函理论计算方法研究了稀土金属掺杂CeO_(2)负载锥体4Ni催化剂对CO_(2)还原反应的催化性能.对于稀土金属掺杂的氧化铈,2个Ce被2个三价阳离子取代,同时产生一个氧空位来进行电荷补偿.研究了离4Ni最近(VoN)和次邻近(VoNN)的氧空位,发现释放CO和CO_(2)解离分别是路径VoN和VoNN的决速步.在所研究的掺杂剂(Ga,Sb,Lu,Gd,Pr,La,Bi)中,Gd被认为是催化CO_(2)还原的最佳掺杂剂,其在823K下的翻转频率是纯CeO_(2)负载4Ni的104倍.这一探索为稀土金属掺杂氧化铈负载镍催化剂在二氧化碳还原领域的研究和应用提供了理论支持和指导。

关 键 词：Carbon dioxide reduction CeO_(2)(111) Oxygen VACANCY Density functional theory 

分 类 号：O64[理学—物理化学]