Revealing the Role of d Orbitals of Transition-Metal-Doped Titanium Oxide on High-Efficient Oxygen Reduction  

作　　者：Fei Lu Weiwei Xie Ding Yi Yan Wang Fengchu Zhang Yong Xu Bo Zhou Shoujie Liu Xi Wang Jiannian Yao 

机构地区：[1]Department of Physics,School of Science,Beijing Jiaotong University,Beijing 100044 [2]Key Laboratory of Photochemistry,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190 [3]Institute of Physical Chemistry,Karlsruhe Institute of Technology,Karlsruhe 76131 [4]Chemistry and Chemical Engineering Guangdong Laboratory,Shantou 515031

出　　处：《CCS Chemistry》2021年第11期180-188,共9页中国化学会会刊（英文）

基　　金：supported by the Fundamental Research Funds for the Central Universities(grant nos.2018JBZ107 and 2019RC035);supported financially by the National Natural Science Foundation of China(grant nos.91961125 and 21905019);the Key Program for International S&T Cooperation Projects of China from the Ministry of Science and Technology of China(grant no.2018YFE0124600);the Chemistry and Chemical Engineering Guangdong Laboratory(nos.1932001,1932004,1911020,and 1911023).

摘　　要：Precise catalysis is critical for the high-quality catalysis industry.However,it remains challenging to fundamentally understand precise catalysis at the atomic orbital level.Herein,we propose a new strategy to unravel the role of specific d orbitals in catalysis.The oxygen reduction reaction(ORR)catalyzed by atomically dispersed Pt/Co-doped Ti_(1−x)O_(2) nanosheets(Pt_(1)/Co_(1)-Ti_(1−x)O_(2))is used as a model catalysis.The z-axis d orbitals of Pt/Co-Ti realms dominate the O2 adsorption,thus triggering ORR.In light of orbital-resolved analysis,Pt_(1)/Co_(1)-Ti_(1−x)O_(2) is experimentally fabricated,and the excellent ORR catalytic performance is further demonstrated.Further analysis reveals that the superior ORR performance of Pt_(1)-Ti_(1−x)O_(2) to Co_(1)-Ti_(1−x)O_(2) is ascribed to stronger activation of Ti by Pt than Co via the d-d hybridization.Overall,this work provides a useful tool to understand the underlying catalytic mechanisms at the atomic orbital level and opens new opportunities for precise catalyst design.

关 键 词：transition-metal-doped titanium oxide oxygen reduction reaction orbital-resolved analysis d-d hybridization theory-driven catalyst design 

分 类 号：O64[理学—物理化学]