Efficient deep hydrodeoxygenation (HDO) of lignin-derived phenolics is hindered by the accumulation of saturated oxygenates. This work combines catalytic experiments and DFT calculations to elucidate how the support regulates reaction pathways and product selectivity during m-cresol HDO, particularly the further deoxygenation of methylcyclohexanol to methylcyclohexane.  
Mesoporous TiO₂ (m-TiO₂) was synthesized by using an evaporation-induced self-assembly route and used as a support for Ni. Ni/m-TiO₂ and Ni/C were evaluated under pressurized H₂ in a batch reactor. The effects of reaction temperature, time and pressure were examined. When the designated time has elapsed, the reactor was cooled to room temperature. The reactants and products were analyzed by Shimadzu GC-2014. All the DFT calculations were performed using periodic plane-wave density functional theory methods implemented in the Vienna Ab-initio Simulation Package (VASP). 
The conversion of m-cresol over Ni/C was 100% at 260 °C. The dominant product was methylcyclohexanol, whereas the selectivity of methylcyclohexane was below 8%. By contrast, Ni/m-TiO₂ achieved 100% conversion and 100% methylcyclohexane selectivity under the same conditions. The time-resolved experiments indicated that methylcyclohexane was formed through the sequential hydrogenation of m-cresol to methylcyclohexanol, followed by the deoxygenation of the methylcyclohexanol. The role of the support was investigated using various characterizations and DFT calculations. In five consecutive cycles, complete conversion was retained, and methylcyclohexane selectivity remained above 90% in the fifth cycle. 
These results showed that the dominant reaction path over Ni/m-TiO₂ was m-cresol→methylcyclohexanol→methylcyclohexane. TiO₂ was not merely an inert support but played a critical role in promoting the deoxygenation of methylcyclohexanol. This support effect was attributed to cooperative Ni-TiO₂ interfacial sites that facilitated the activation and cleavage of the C-O bond.