Steric effects of CO2 binding to transition metal-benzene complexes: a first-principles study

TL;DR

This study uses DFT calculations to analyze how steric hindrance affects CO2 adsorption on transition metal-benzene complexes, revealing limitations of the 18-electron rule and proposing a new steric hindrance model.

Contribution

It introduces the use of the Tolman cone angle occupation function to accurately predict CO2 adsorption limits considering steric effects.

Findings

Maximum of three CO2 molecules adsorbed on Sc or Ti complexes.

18-electron rule fails to predict CO2 adsorption due to steric hindrance.

Tolman cone angle effectively models steric hindrance in CO2 adsorption.

Abstract

Using density functional theory (DFT) calculations, we investigated the adsorption of CO2 molecules on 3d transition metal (TM)-benzene complexes. Our calculations show that the maximum number of CO2 molecules adsorbable on Sc or Ti atoms is three, but the 18-electron rule predicts it should be four. The 18-electron rule is generally successful in predicting the maximum H2 adsorption number for TM atoms including Sc or Ti atoms. We found that the 18-electron rule fails to correctly predict CO2 binding on Sc- or Ti-benzene complexes because CO2 binding, in contrast to H2 binding, requires additional consideration for steric hindrance due to the large bond length of CO2. We calculated the occupation function for CO2 using the Tolman cone angle, which shows that three CO2 molecules fully occupy the available space around Sc- and Ti-benzene complexes. This estimation is the same maximum CO2 adsorption number predicted by DFT calculations. Therefore, we propose that the occupation function for CO2 using the Tolman cone angle is an efficient model for evaluating steric hindrance of CO2 adsorption on a surface.