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

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.