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 unrave...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.展开更多
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)+1 种基金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).
文摘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.
