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Reaction on a Rink: Kondo-Enhanced Heterogeneous Single-Atom Catalysis

preprint
submitted on 26.02.2021, 05:57 and posted on 26.02.2021, 13:54 by Xiangyang Li, Hong Gong, Qingfeng Zhuang, Bing Wang, Xiao Zheng, Jinlong Yang

Boosting the efficiency of heterogeneous single-atom catalysts (SACs) by adjusting the microenvironment of the active atom has recently attracted enormous attention. However, attempts to tune the spin-spin interaction between the SAC and its microenvironment have remained rather scarce. Some interesting questions can be raised, among which a fundamental one is: can the surrounding environment influence the local spin state of an SAC, and if so, can such influence be utilized to enhance the catalytic activity?

In this work, we explore such a possibility by investigating the thermochemical effect of Kondo screening of a local atomic spin by free electrons in the metal support. Inspired by the exothermicity of the spin-screening interaction, a novel approach to heterogeneous catalysis -- reaction on a rink (ROAR) -- is proposed. In contrast to the conventional notion of thermal catalytic reaction, lowering the temperature of metal support is predicted to result in a reduced reaction barrier. As a proof of concept, CO oxidation catalyzed by the Co@CoPc/Au(111) composite is scrutinized. By combining the density functional theory and a hierarchical equations of motion approach, it predicts that the existing s-d hybridization between the magnetic d orbital of Co adatom and the substrate metallic states in the transition state will lower the free energy barrier and accelerate the reaction rate. Furthermore, if the strength of s-d hybridization is enlarged, a more appreciable speedup will be achieved.

This work highlights the potential usefulness of the spin degrees of freedom to heterogeneous single-atom catalysis, and our proposed ROAR approach could open up a new horizon for exploiting the role of atomic spin in chemical reactions.


Funding

National Key Research and Development Program of China (Grant No. 2016YFA0200600)

Theoretical Study on the Accurate Regulation of Local Quantum States on Surface Molecular Systems

National Natural Science Foundation of China

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Dynamic chemical frontier research

National Natural Science Foundation of China

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Strategic Priority Research Program of Chinese Academy of Sciences (Grant No. XDB36000000)

Anhui Initiative in Quantum Information Technologies (Grant No. AHY090000)

History

Email Address of Submitting Author

xyangli@mail.ustc.edu.cn

Institution

University of Science and Technology of China

Country

China

ORCID For Submitting Author

0000-0002-0142-8522

Declaration of Conflict of Interest

The authors declare no competing interests.

Version Notes

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