Catalysis

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

Authors

  • Xiangyang Li University of Science and Technology of China ,
  • Hong Gong University of Science and Technology of China ,
  • Qingfeng Zhuang University of Science and Technology of China ,
  • Bing Wang University of Science and Technology of China ,
  • Xiao Zheng University of Science and Technology of China ,
  • Jinlong Yang University of Science and Technology of China

Abstract

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 [email protected]/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.

Version notes

Modification of the layout format of the manuscript, modification of Figure 2 in the manuscript, further analysis of the nature of ROAR, and Influence of RKKY exchange interaction between different Co adatoms on the reaction energy barrier.

Content

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Supplementary material

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Reaction on a rink SI
Details of computational methodology, influence of the RKKY interaction on energy barrier, co-adsorption of gas molecule on [email protected]/Au(111), analysis on the s-d hybridization strength, analysis on the PDOS of central Co ion of CoPc, magnetic properties of Co adatom and fitting parameters for the free energy change, and reduction of free energy barrier by considering vibrational entropy correction.