Boosting the selective hydrogenation of biphenyl to cyclohexylbenzene over bimetallic Ni-Ru/SiO2 catalyst via enhancing strong metal-support interaction

Abstract

Tuning the metal-support interaction (MSI) between highly dispersed nanosized metal particles and the support plays a pivotal role in the activity and selectivity of polyaromatics selective hydrogenation. In this work, the supported bimetallic Ni-Ru/SiO2-SEA catalyst was prepared by a strong electrostatic adsorption (SEA) strategy, and applied for the selective hydrogenation of biphenyl (BP) to cyclohexylbenzene (CHB). Compared to the catalysts prepared by the conventional incipient wetness impregnation method and Ni/SiO2-SEA, the significant effects of MSI and hydrogen spillover on Ni-Ru/SiO2-SEA facilitated the highly exposed and uniformly dispersed electron-deficient Niδ+ (0 < δ < 2) species, which could enhance adsorption and activation of the electron-withdrawing phenyl group and H2, thereby promoting the efficient and selective conversion of BP to CHB. At the conditions of 160 ℃ and 2 MPa H2 pressure, BP conversion over Ni-Ru/SiO2-SEA reached nearly 100 % within 3 h, achieving a remarkable selectivity of 97.9 % towards CHB, along with a high turnover frequency of 2756.9 h−1 for the active metallic Ni sites. Importantly, according to the kinetic simulations, the hydrogenation rate constant of Ni-Ru/SiO2-SEA was the highest (2.76 × 10-2 mol·g−1·h−1) among the employed catalysts. Moreover, after six consecutive cycles, no obvious decline in hydrogenation efficiency was observed, confirming the remarkable activity and stability of Ni-Ru/SiO2-SEA. Furthermore, the activation of BP and desorption of CHB pathway on the Niδ+ species were elaborated through temperature-programmed desorption characterization, highlighting the prominent contribution of MSI in enhancing the selective hydrogenation of polyaromatics.