Role of Catalyst Support and Regioselectivity of Molecular Adsorption on a Metal Oxide Surface: NO Reduction on Cu/{\gamma}-alumina

TL;DR

This study uses computational models to investigate how catalyst support and regioselectivity influence NO reduction on Cu/{b3}-alumina, revealing the support's role in electron transfer and energy dissipation during the reaction.

Contribution

It introduces a novel computational approach employing vibronic coupling density to analyze regioselectivity and support effects in NO reduction on Cu/{b3}-alumina.

Findings

Cu atoms are anchored on Lewis-basic O atoms in tetrahedral sites.

The b3-alumina support raises the frontier orbital of Cu, facilitating electron back-donation.

NO reduction occurs even in oxidative atmospheres due to strong Cu-NO bonds.

Abstract

The role of catalyst support and regioselectivity of molecular adsorption on a metal oxide surface is investigated for the NO reduction on a Cu/{\gamma}-alumina heterogeneous catalyst. For the solid surface, computational models of the {\gamma}-alumina surface are constructed based on the Step-by-Step Hydrogen Termination (SSHT) approach. Dangling bonds, which appear by cutting the crystal structure of a model, are terminated stepwise with H atoms until the model has an appropriate energy gap. The obtained SSHT models exhibit the realistic infrared (IR) and ultraviolet-visible (UV/Vis) spectra. Vibronic coupling density (VCD), as a reactivity index, is employed to elucidate the regioselectivity of the Cu adsorption on the {\gamma}-alumina and that of the NO adsorption on the Cu/{\gamma}-alumina in place of the frontier orbital theory that could not provide clear results. We discovered that the highly dispersed Cu atoms are loaded on Lewis-basic O atoms, which is known as anchoring effect, located in the tetrahedral sites of the {\gamma}-alumina surface. The role of the {\gamma}-alumina support is to raise the frontier orbital of the Cu catalyst, which in turn gives rise to the electron back-donation from the Cu/{\gamma}-alumina to NO. In addition, the penetration of the VCD distribution of the Cu/{\gamma}-alumina into the {\gamma}-alumina support indicates that the excessive reaction energies dissipate into the support after the NO adsorption and reduction. In other words, the support plays the role of a heat bath. The NO reduction on the Cu/{\gamma}-alumina proceeds even in an oxidative atmosphere because the Cu-NO bond is strongly bounded compared to the Cu-O2 bond.