Hydrodeoxygenation (HDO) is a promising process for biomass upgrading. A challenge is designing and developing related efficient catalysts. Here, we developed a defects enhancement engineering to synthesize carbon-based supported Pd catalysts (0.5%Pd/CNS) for vanillin HDO under mild condition. It is found that the degree of carbon defects was negative correlation with the cross-linked degree of resorcinol–formaldehyde (RF) resin sphere (carbon precursor), which can be modulated by amount of ammonium fluoride (NH₄F) (0, 0.01, 0.03, and 0.05 g). The RF resin sphere (RF-0.03) with the lowest cross-linked degree was obtained by addition of 0.03 g NH₄F, and then 0.5%Pd/CNS-0.03 possessed rich carbon defects obtained by carbonization of RF-0.03. The catalyst possessing the most degree of carbon defects (1.96 of A_D1/A_G from Raman data, D1 ∼ defective carbon, G ∼ graphitic carbon) exhibited the highest activity among as-prepared catalysts: 100% of vanillin conversion and 100% of yield to creosol in vanillin HDO over 0.5%Pd/CNS-0.03 (0.03 g of NH₄F) at 60 °C, 0.1 MPa H₂, and 1 h. The excellent performance can be attributed to the rich carbon defects on surface of catalysts, which can play an important role on growth of active metal and activation of reactants. This work improves green catalysis of HDO with a strategy of defect engineering to surface microenvironment modulation.

加氢脱氧（HDO）是一种很有前景的生物质升级过程。一个挑战是设计和开发相关的高效催化剂。在这里，我们开发了一种缺陷增强工程，以在温和条件下合成用于香兰素 HDO 的碳基负载 Pd 催化剂 (0.5% Pd/CNS)。发现碳缺陷程度与间苯二酚-甲醛（RF）树脂球（碳前驱体）的交联度呈负相关，可通过氟化铵（NH ₄ F）的量进行调节（0, 0.01 、0.03 和 0.05 克）。加入0.03 g NH ₄得到交联度最低的RF树脂球(RF-0.03)F, 然后是 0.5% Pd/CNS-0.03 具有通过 RF-0.03 碳化获得的丰富碳缺陷。具有最大程度碳缺陷的催化剂（拉曼数据的 A _D1 / _{AG G}为1.96 ，D1 ∼ 缺陷碳，G ∼ 石墨碳）在所制备的催化剂中表现出最高的活性：100% 的香兰素转化率和 100% 的在 0.5% Pd/CNS-0.03（0.03 g NH ₄ F）条件下，在 60 °C、0.1 MPa H ₂和 1 h条件下，在香草醛 HDO 中生成甲酚。其优异的性能归功于催化剂表面丰富的碳缺陷，它对活性金属的生长和反应物的活化起着重要作用。这项工作通过缺陷工程策略改善了HDO的绿色催化，以调节表面微环境。