Abstract
<h2>Summary</h2> Photocatalysis has offered a promising opportunity for selective transformation of biomass to high-value chemicals or fuels under mild conditions. Whereas titanium oxide has been widely used for photocatalytic pollutant degradation, H<sub>2</sub> evolution, and CO<sub>2</sub> reduction, few studies have been devoted to TiO<sub>2</sub>-based photocatalytic valorization of biomass or biomass-derived platform compounds. Here, we report on surface-controlled photocatalysis of TiO<sub>2</sub> for selective valorization of furfurals and vanillin that are lignocellulose-derived key platform compounds. The reaction can be switched from hydrogenation of aldehyde group to C–C coupling by manipulating exposed facets; furanic and aromatic alcohols or coupling products, which are fine chemicals or jet-fuel precursors, could be produced with high selectivity. Our studies elucidate that the facet-dependent density of oxygen vacancies governs the charge distribution and adsorption strength of surface species and thus controls product selectivity. The present work offers an example of selectivity control by engineering TiO<sub>2</sub> surfaces for valorization of biomass-derived feedstocks.
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