A bifunctional catalyst, composed of a hydrogenation active metal and an oxophilic promoter for CAr–O bond weakening, is effective in the deoxygenation of lignin derivatives due to a contact synergy. A systematic comparison of the physicochemical properties of Ni-based catalysts promoted by metal oxides (i.e., FeO x , MoO x , and WO x ) with different extents of oxophilicity was conducted, and their catalytic behaviors were evaluated in the conversion of p-cresol. Ni promoted by WO x displays the highest oxophilicity among all promoters and is intrinsically more active than NiMo and NiFe in direct deoxygenation (DDO); this characteristic is possibly related to its great hydride mobility. However, in a H2-pressured system, Ni promoted by MoO x , which has moderate oxophilicity compared with the employed promoters, generated more DDO product (toluene) than NiFe and NiW. This study discovered that this discrepancy, between the result of the chemical test under normal pressure and the result of the reaction test in an authentic pressurized system concerning the relation between toluene yield and a promoter’s oxophilicity, is related to different hydrogenation rates of toluene. Toluene derived from DDO of p-cresol can be subsequently hydrogenated and thus be turned into methylcyclohexane more rapidly by the NiW catalyst than by NiMo and NiFe catalysts. Hence, both the oxophilicity of a promoter and the inertness of hydrogenation of toluene should be considered in designing a bimetallic catalyst in the conversion of lignin derivatives.

Hydrogenation of adipic acid (AA) is a potential way to prepare 1,6‐hexanediol (HDOL). Herein, silica‐supported copper catalysts derived from copper phyllosilicates were synthesized, characterized, and tested in the hydrogenation of AA to HDOL. In a full conversion of AA, a high yield of HDOL (approximately 90 %) was obtained through the use of each Cu‐based catalyst. The turnover frequency calculated according to the consumption rate of AA was discovered to be dependent on the Cu+/(Cu0+Cu+) ratio and the reduction condition. Moreover, recycling tests showed that a catalyst derived from a copper phyllosilicate had better stability compared with Cu/SiO2 made through impregnation due to a stronger interaction between Cu and silica. The kinetic analyses based on the global rate expression and Langmuir−Hinshelwood−Hougen−Watson (LHHW) formalism of AA conversion were conducted. The possible competitive adsorption between AA and its derivatives, including hydroxycaproic acid and ϵ‐caprolactone, was thereby revealed.