Significant Promotional Effect of Nb Doping in Bifunctional Pd/WOx Nanocatalysts on One‐Step Benzene Hydroalkylation

Abstract The development of high‐efficiency heterogeneous bifunctional metal‐acid catalysts with an appropriate metal‐acid balance for the production of cyclohexylbenzene (CHB) via the one‐step tandem benzene hydroalkylation still faces a dilemma because of the difficulty in inhibiting the over hydrogenation of benzene substrate and cyclohexene intermediate and controlling target product selectivity. In this study, Nb‐doped WO x supported Pd nanocatalysts were developed. It has been shown that doping Nb into WO x supports altered surface properties and microstructures of catalysts, resulting in the generation of more surface acidic sites and defective W−O v −Nb structures (O v : oxygen vacancies). As‐constructed Pd‐based nanocatalyst with only 0.1 wt % Pd loading and a Nb/(Nb+W) molar ratio of 0.25 exhibited superior catalytic benzene hydroalkylation performance to undoped supported Pd catalyst, with a much higher yield of CHB (35.6 %) at 220 °C. It was authenticated that highly dispersed Pd sites facilitated the dissociation of hydrogen molecules, defective W−O v −Nb structures were conductive to the surface transfer of active hydrogen species, a large number of acidic sites favored benzene/cyclohexene intermediate adsorption, and abundant Brønsted acidic sites promoted the alkylation between cyclohexene intermediate formed and benzene. Accordingly, excellent cooperative catalysis between Pd sites, acidic sites, and oxygen vacancies contributed to improved catalytic performance of Nb‐doped WO x supported Pd catalysts in benzene hydroalkylation. This research presents an alternative for the creation of low‐cost practical bifunctional metal‐acid catalysts for highly efficient benzene hydroalkylation.