Pd/Ni-metal–organic framework-derived porous carbon nanosheets for efficient CO oxidation over a wide pH range

Abstract

Metal nanocrystal ornamented metal–organic frameworks (MOFs) are of particular interest in multidisciplinary applications; however, their electrocatalytic CO oxidation performance over wide pH ranges is not yet reported. Herein, Ni-MOF-derived hierarchical porous carbon nanosheets (Ni-MOF/PC) with abundant Ni–N_x sites decorated with Pd nanocrystals (Pd/Ni-MOF/PC) were synthesized by microwave-irradiation (MW-I) followed by annealing at 900 °C and subsequent etching of Ni-MOF/C prior to Pd deposition. The fabrication mechanism comprises the generation of self-reduced reducing gases from triethylamine during the annealing and selective chemical etching of Ni, thereby facilitating the reduction of Ni-anchored MOF and Pd nanocrystal deposition with the aid of ethylene glycol and MW-I to yield Pd/Ni–N_x enriched MOF/PC. The synthetic strategies endear the Pd/Ni-MOF/PC with unique physicochemical merits: abundant defects, interconnected pores, high electrical conductivity, high surface area, Ni-deficient but more active sites for Pd/Ni–N_x in porous carbon nanosheets, and synergism. These merits endowed the CO oxidation activity and stability on Pd/Ni-MOF/PC substantially than those of Pd/Ni-MOF/C and Pd/C catalysts in wide pH conditions (i.e., KOH, HClO_4, and NaHCO₃). The CO oxidation activity study reveals the utilization of MOF/PC with metal nanocrystals (Pd/Ni) in CO oxidation catalysis.