The role of atomic orbitals of doped earth-abundant metals on designed copper catalytic surfaces

TL;DR

This study uses computational inverse design to identify optimal doping strategies on copper surfaces with earth-abundant metals, revealing how orbital-specific interactions influence catalytic hydrogenation efficiency.

Contribution

It introduces a novel quantum chemistry method for analyzing orbital-specific binding energies and demonstrates how doping with Fe and Zn improves catalytic surface properties.

Findings

Zn-doped Cu surface has minimal H-binding energy.

Surface Zn 3d-orbitals contribute less to binding energy.

Doping alters electronic structure to enhance catalytic activity.

Abstract

It is a general challenge to design highly active or selective earth-abundant metals for catalytic hydrogenation. Here, we demonstrated an effective computational approach based on inverse molecular design theory to deterministically search for optimal binding sites on Cu (100) surface through the doping of Fe and/or Zn, and a stable Zn-doped Cu (100) surface was found with minimal binding energy to H-atoms. We analyze the electronic structure cause of the optimal binding sites using a new quantum chemistry method called orbital-specific binding energy analysis. Compared to the 3d-orbitals of surface Cu atoms, the 3d-orbitals of surface Zn-atoms show less binding energy contribution and participation, and are much less influenced by the electronic couplings of the media Cu atoms. Our study provides valuable green chemistry insights on designing catalysts using earth-abundant metals, and may lead to the development of novel Cu-based earth-abundant alloys for important catalytic hydrogenation applications such as lignin degradation or CO2 transformation.