Modeling plasma-induced surface charge effects on CO2 activation by single atom catalysts supported on reducible and irreducible metal oxides

Abstract

The accumulation of negative surface charge on catalytic surfaces in the presence of low-temperature plasma (LTP) could influence catalytic performance. However, it is difficult to disentangle the role of surface charging and other LTP catalytic effects in experiment. Herein, we use density functional theory (DFT) modeling to understand the effect of plasma-induced surface charging on CO2 activation by atomically dispersed single atom (SA) catalysts on both reducible and irreducible metal oxide supports. We model CO2 adsorption strength and CO2 dissociation barriers for Co1, Ni1, Cu1, Rh1, Pd1, and Ag1 SAs on both reducible and irreducible supports, namely, CeO2(100), TiO2(101), and γ-Al2O3(110), to elucidate trends. We find that accumulated surface charge on the SA increases the CO2 adsorption strength and decreases the CO2 dissociation barrier for all studied SA/support combinations. For both charged and uncharged (neutral) systems, SAs on the reducible CeO2(100) support generally adsorb CO2 more weakly compared to when on irreducible supports like γ-Al2O3(110). SAs on γ-Al2O3(110) typically have larger barriers for CO2 dissociation for both charged and uncharged systems compared to TiO2(101) and CeO2(100). The magnitude of surface charging effects on CO2 binding energies and dissociation barriers depends sensitively on both the SA and the support. In some cases, the CO2 activation trends qualitatively change between neutral and charged systems for a fixed SA across different supports. This DFT modeling study demonstrates that surface charging should be considered in strong electric fields because it can have a large effect on molecule adsorption and bond-breaking on catalytic surfaces.