Tailoring reaction path in CO₂ hydrogenation to methanol by selective Zr or Ce doping of CoIn catalysts

Abstract

The hydrogenation of CO2 to methanol represents a pivotal route for carbon capture and utilization, yet designing catalysts that concurrently achieve high activity and selectivity remains challenging. This work explored the promotional effects of ZrO2 and CeO2 on CoIn-based catalysts for the CO2 hydrogenation to methanol reaction. While both dopants improve catalytic performance, they exert distinct structural and mechanistic roles. ZrO2 doping primarily enhances CO2 conversion by facilitating the formate pathway with a reduced energy barrier. In contrast, CeO2 incorporation enables high and stable methanol yields even under harsh conditions, due to the dual-pathway mechanism involving formate and CO intermediates. The study establishes that targeted doping is a powerful lever for engineering reaction networks in In2O3 catalysts, providing a clear design principle for advancing CO2 hydrogenation. Graphical abstract: [Figure not available: see fulltext.]