Abstract

Metal–organic frameworks (MOFs) have recently been identified as versatile sacrificing templates to construct functional nanomaterials for heterogeneous catalysis. Herein, we report a thermal transformation strategy to directly fabricate metal Pd nanoclusters inlaid within a ZrO2@nitrogen‐doped porous carbon (Pd/ZrO2@CN) composite using Pd@NH2‐UiO‐66(Zr) as a precursor that was pre‐synthesized by a one‐pot hydrothermal method. The developed Pd/ZrO2@CN as a robust catalyst delivered remarkable stability and activity to the catalytic hydrogenation of 2,3,5‐trimethylbenzoquinone (TMBQ) to 2,3,5‐trimethylhydroquinone (TMHQ), a key reaction involved in vitamin E production. The hydrogenation was carried out at 110 °C with 1.0 MPa H2, and it resulted in 98% TMHQ yield as the sole product over five consecutive cycles, outperforming the analogue Pd/ZrO2@C without nitrogen doping templated from Pd@UiO‐66(Zr). The excellent catalytic properties of Pd/ZrO2@CN likely originated from the highly stable ultrafine Pd nanoclusters inlaid within ZrO2@CN matrix on account of the strong interaction between N and Pd, as well as on the Lewis acidity of ZrO2, which was beneficial to the hydrogenation.

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