PdZn intermetallic compound stabilized on ZnO/nitrogen-decorated carbon hollow spheres for catalytic semihydrogenation of alkynols.

Ye, Chunlin; Chen, Xujian; Li, Shasha; Feng, Binbin; Fu, Yanghe; Zhang, Fumin; Chen, De-Li; Zhu, Weidong

Enhancing the selectivity of noble metal catalysts through electronic modulation is important for academic research and chemical industrial processes. Herein, we report a facile sacrificial template strategy for the synthesis of PdZn intermetallic compound (3–4 nm) highly distributed in ZnO/nitrogen-decorated carbon hollow spheres (PdZn-ZnO/NCHS) to optimize the selectivity of Pd catalysts, which involves carbonization of a core-shell structured polystyrene (PS)@ZIF-8 precursor in an inert atmosphere, impregnation Pd precursor, and subsequent H2 reduction treatment. Due to the unique structural and compositional features, the developed PdZn-ZnO/NCHS delivers an excellent catalytic performance for the semihydrogenation of 2-methyl-3-butyn-2-ol (MBY) to 2-methyl-3-buten-2-ol (MBE) with high activity (> 99%), high selectivity (96%), and good recyclability, outperforming the analog Pd on ZnO (Pd/ZnO) as well as the supported Pd nanoparticles (Pd/C and Pd/NC). Density functional theory (DFT) calculations reveal that the presence of Znδ+ species in PdZn-ZnO/NCHS alters the adsorption modes of reactant and product, leading to a decrease of the adsorption strength and an enhancement of the energy barrier for overhydrogenation, which results in a kinetic favor for the selective transformation of MBY to MBE. In addition, PdZn-ZnO/NCHS was also very effective for the partial hydrogenation of dehydrolinalool to hydrolinalool.

Nano Research, 2022, Vol 15, Issue 4, p3090

1998-0124

Academic Journal

10.1007/s12274-021-3971-1