Mechanism of Ni-catalyzed selective C[sbnd]O cleavage of lignin model compound benzyl phenyl ether under mild conditions

Abstract

Selective cleavage of CO bonds in benzyl phenyl ether (BPE) as a typical lignin α-O-4 ether to produce aromatics is a challenging and attractive topic. Herein, the earth-abundant first-row transition metals, such as Co, Ni and Cu were supported on activated carbon (Co/AC, Ni/AC and Cu/AC) to identify their ability for cleaving CO bond of BPE. Among these catalysts, Ni/AC exhibit highest activity for cleavage of CO bond. The reaction with BPE was carried out at pretty mild condition of 140 °C and 2 MPa H2, which is highly selective afforded toluene and phenol as the major products with the optimum yields of 88.5 and 86.5%, respectively. Based on the test, the reaction pathways were proposed. A abundant of dissociated H· atoms on Ni(0) sites forms surface active NiH species; Ni(0) activates and facilitates cleavage of the CO bond in BPE to form benzyl (C6H5C·) and phenoxy radicals (C6H5O·); H· atoms spill from active species NiH recombined together with C6H5C· and C6H5O· forming the products of toluene and phenol, respectively.