Light Induced Charge Transfer from Transition-metal Doped Aluminium Clusters to Carbon Dioxide

TL;DR

This study investigates how light induces electron transfer between transition-metal doped aluminium clusters and CO2 molecules, revealing different charge transfer behaviors based on the dopant type, which informs the design of aluminium-based photocatalysts.

Contribution

The paper provides a first-principles analysis of light-induced charge transfer in various transition-metal doped aluminium clusters, identifying dopant-dependent charge transfer mechanisms.

Findings

Cu- and Fe-doped clusters show no ground state charge transfer.

Other doped clusters exhibit ground state electron transfer and strong CO2 adsorption.

Light induces electron back-transfer in most systems, affecting catalytic properties.

Abstract

Charge transfer between molecules and catalysts plays a critical role in determining the efficiency and yield of photo-chemical catalytic processes. In this paper, we study light-induced electron transfer between transition metal doped aluminium clusters and CO$_2$ molecules using first-principles time-dependent density-functional theory. Specifically, we carry out calculations for a range of dopants (Zr, Mn, Fe, Ru, Co, Ni and Cu) and find that the resulting systems fall into two categories: Cu- and Fe-doped clusters exhibit no ground state charge transfer, weak CO$_2$ adsorption and light-induced electron transfer into the CO$_2$. In all other systems, we observe ground state electron transfer into the CO$_2$ resulting in strong adsorption and predominantly light-induced electron back-transfer from the CO$_2$ into the cluster. These findings pave the way towards a rational design of atomically precise aluminium photo-catalysts.