Production of mono-phenols through hydrodeoxygenation is one of the most promising routes for value-added lignin valorization. However, the adsorption characteristic of key intermediates and hydrodeoxygenation mechanism of key linkages in lignin have received inadequate attentions. In this paper, experiments combined with density functional theory calculations were done to explore the adsorption and catalytic HDO mechanism of lignin dimers. It was found that NiFe(1 1 1)-Mo₂C(0 0 1) had a better ability on linkages activation, and showed stronger adsorption on CO containing intermediates, which was favor for further hydrodeoxygenation. Moreover, the calculation results certificated the cleavage of β-O-4 was prior to the hydrodeoxygenation of CO, and the hydrodeoxygenation of β-O-4 included a H· addition to O atom before the C-O cleavage. Finally, the elementary reactions energy barriers were efficiently reduced by NiFe(1 1 1)-Mo₂C(0 0 1) catalyst during the hydrodeoxygenation reactions, which elucidated the superior performance of NiFe catalyst. This work provides a theoretical basis on efficient lignin utilization.

通过加氢脱氧生产单酚是木质素增值最有前途的途径之一。然而，木质素中关键中间体的吸附特性和关键键的加氢脱氧机制尚未受到足够的重视。本文通过实验结合密度泛函理论计算来探讨木质素二聚体的吸附和催化HDO机理。结果发现NiFe(1 1 1)-Mo ₂ C(0 0 1)具有更好的键活化能力，并且对C表现出更强的吸附能力。 含O中间体，有利于进一步加氢脱氧。此外，计算结果证明β-O-4的裂解先于C的加氢脱氧。 O，β-O-4的加氢脱氧包括在CO裂解之前H ·加成到O原子上。最后，NiFe(1 1 1)-Mo ₂ C(0 0 1)催化剂在加氢脱氧反应过程中有效降低了基元反应能垒，说明了NiFe催化剂的优越性能。该工作为木质素的高效利用提供了理论基础。