Unraveling the role of Co3O4 facet for photothermal catalytic oxidation of methanol via operando spectroscopy and theoretical investigation

摘要

Tubular, pie- and bread-shaped forms of Co3O4 with exposed {110}, {112} and {111} facets were prepared and compared in their photothermal catalytic performance and reaction pathways during the oxidation of methanol. Among them, the Co3O4 with exposed {1 1 0} facet exhibited the best photothermal catalytic performance (95% methanol conversion, 93% CO2 yield) under solar irradiation, while also maintaining good stability and moisture resistance. Reaction mechanism studies showed that the {1 1 0} facets had a strong adsorption capacity for formaldehyde, which facilitated its conversion to formate. The transformation of formaldehyde to formate species was the key step. The key step on the {1 1 0} facet was conversion of formaldehyde to a mono-dentate formate species, while conversion on the {1 1 2} and {1 1 1} facets was mainly to bi-dentate formate species. This study demonstrated that the design of preferential exposed crystal facet can regulate the pathway of photothermal catalytic reaction and realize efficient solar energy utilization.

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