Catalytic transfer hydrogenolysis of lignin derived aromatic ethers over MOF derived porous carbon spheres anchored by Ni species.

The efficient hydrogenolysis of CO ether bonds in lignin is the key for producing bio-oil and high-value chemicals. In this work, we synthesized a series of Ni-MOF-derived porous carbon spheres anchored Ni catalysts (Ni/C-x-T) with different metal/ligand molar ratios and calcination temperatures through solvothermal and carbothermal reduction method, and evaluated their catalytic transfer hydrogenolysis (CTH) performance for lignin model compounds using isopropanol as H-donor. The Ni/C-2-400 catalyst exhibited the excellent CTH performance, affording almost 100 % conversion of 2-phenoxy-1-phenylethanol even at a low reaction temperature of 120 °C. It was worth noting that the further hydrogenation of hydrogenolysis products phenol and ethylbenzene could be controlled by adjusting the reaction conditions, achieving phenol and ethylbenzene as main products at 120 °C, cyclohexanol and ethylbenzene at 140 °C, and cyclohexanol and ethylcyclohexane at 200 °C for 4 h. Based on the characterization results, the high catalytic activity of Ni/C-2-400 was attributed to the good dispersion and small particle size of metal Ni particles. Mechanistic studies showed that the cleavage of CO ether bonds was the main reaction pathway, and high temperature helped accelerate hydrogenolysis and subsequent hydrogenation. Moreover, the Ni/C-2-400 catalyst had good stability and applicability to other model compounds. This work could provide some help for the upgrading of lignin and its derivative.