Upgrading biomass-derived phenolic compounds provides a valuable approach for the production of higher-value-added fuels and chemicals. However, most established catalytic systems display low hydrodeoxygenation (HDO) activities even under harsh reaction conditions. Here, we found that Pd supported on –NH₂-modified hierarchically porous carbon (Pd/HPC–NH₂) with formic acid (FA) as hydrogen source exhibits unprecedented performance for the selective HDO of benzylic ketones from crude lignin-derived oxygenates. Designed experiments and theoretical calculations reveal that the H⁺/H⁻ species generated from FA decomposition accelerates nucleophilic attack on carbonyl carbon in benzylic ketones and the formate species formed via the esterification of intermediate alcohol with FA expedites the cleavage of C–O bonds, achieving a TOF of 152.5 h⁻¹ at 30°C for vanillin upgrading, 15 times higher than that in traditional HDO processes (∼10 h⁻¹, 100°C–300°C). This work provides an intriguing green route to produce transportation fuels or valuable chemicals from only biomass under mild conditions.

升级生物质衍生的酚类化合物为生产高附加值的燃料和化学品提供了一种有价值的方法。然而，大多数成熟的催化系统即使在苛刻的反应条件下也表现出低加氢脱氧 (HDO) 活性。在这里，我们发现以甲酸 (FA) 为氢源的–NH ₂修饰的分级多孔碳 (Pd/HPC–NH ₂ ) 上负载的 Pd 对来自粗木质素衍生的含氧化合物的苄基酮的选择性 HDO 表现出前所未有的性能。设计的实验和理论计算表明 H ⁺ /H ^-FA 分解产生的物种加速了对苄基酮中羰基碳的亲核攻击，通过中间醇与 FA 的酯化形成的甲酸盐物种加速了 C-O 键的断裂，在 30°C 下实现了香兰素152.5 h ^-1的 TOF升级，比传统 HDO 工艺（~10 h ^-1，100°C–300°C）高 15 倍。这项工作提供了一条有趣的绿色途径，可以在温和的条件下仅从生物质中生产运输燃料或有价值的化学品。