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, H₂ evolution, and CO₂ reduction, few studies have been devoted to TiO₂-based photocatalytic valorization of biomass or biomass-derived platform compounds. Here, we report on surface-controlled photocatalysis of TiO₂ 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 TiO₂ surfaces for valorization of biomass-derived feedstocks.

光催化为在温和条件下将生物质选择性转化为高价值化学品或燃料提供了广阔的机遇。尽管二氧化钛已广泛用于光催化污染物的降解，H _2的释放和CO _2的还原，但是很少有研究致力于基于TiO ₂的生物质或生物质衍生的平台化合物的光催化增值。在这里，我们报道了TiO _2的表面控制光催化作用用于糠醛和香草醛的选择性增值，糠醛和香草醛是木质纤维素衍生的关键平台化合物。通过处理暴露的小平面，可以将反应从醛基的加氢切换为C-C偶联。可以高选择性地生产呋喃和芳族醇或偶联产物，它们是精细化学品或喷气燃料的前体。我们的研究阐明了氧空位的刻面依赖性密度控制着表面物种的电荷分布和吸附强度，从而控制了产品的选择性。本工作提供了一个通过对TiO ₂表面进行工程化来控制生物质衍生原料的选择性控制的例子。