The development of precious-metal-free catalysts to promote the sustainable production of fuels and chemicals from biomass remains an important and challenging target. Here, we report the efficient hydrogenolysis of biomass-derived 5-hydroxymethylfurfural to 2,5-dimethylfuran over a unique core-shell structured catalyst, Co@CoO that affords the highest productivity among all catalysts, including noble-metal-based catalysts, reported to date. Surprisingly, we find that the catalytically active sites reside on the shell of CoO with oxygen vacancies rather than the metallic Co. The combination of various spectroscopic experiments and computational modelling reveals that the CoO shell incorporating oxygen vacancies not only drives the heterolytic cleavage, but also the homolytic cleavage of H₂ to yield more active H^δ− species, resulting in the exceptional catalytic activity. Co@CoO also exhibits excellent activity toward the direct hydrodeoxygenation of lignin model compounds. This study unlocks, for the first time, the potential of simple metal-oxide-based catalysts for the hydrodeoxygenation of renewable biomass to chemical feedstocks.

开发无贵金属催化剂以促进生物质燃料和化学品的可持续生产仍然是一个重要且具有挑战性的目标。在这里，我们报道了在独特的核壳结构催化剂 Co@CoO 上将生物质衍生的 5-羟甲基糠醛高效氢解为 2,5-二甲基呋喃，该催化剂在所有催化剂（包括贵金属基催化剂）中提供最高的生产率，据报道迄今为止。令人惊讶的是，我们发现催化活性位点位于具有氧空位的 CoO 壳上，而不是金属 Co。各种光谱实验和计算模型的结合表明，包含氧空位的 CoO 壳不仅驱动了异解裂解，而且还H ₂的均裂产生更多活性的 H ^δ-物种，从而产生出色的催化活性。Co@CoO 对木质素模型化合物的直接加氢脱氧也表现出优异的活性。这项研究首次揭示了简单的金属氧化物催化剂在可再生生物质加氢脱氧为化学原料方面的潜力。