Local coordination and electronic interactions of Pd/MXene via dual-atom codoping with superior durability for efficient electrocatalytic ethanol oxidation

Abstract

Catalyst design relies heavily on electronic metal-support interactions, but the metal-support interface with an uncontrollable electronic or coordination environment makes it challenging. Herein, we outline a promising approach for the rational design of catalysts involving heteroatoms as anchors for Pd nanoparticles for ethanol oxidation reaction (EOR) catalysis. The doped B and N atoms from dimethylamine borane (DB) occupy the position of the Ti₃C₂ lattice to anchor the supported Pd nanoparticles. The electrons transfer from the support to B atoms, and then to the metal Pd to form a stable electronic center. A strong electronic interaction can be produced and the d-band center can be shifted down, driving Pd into the dominant metallic state and making Pd nanoparticles deposit uniformly on the support. As-obtained Pd/DB–Ti₃C₂ exhibits superior durability to its counterpart (∼14.6% retention) with 91.1% retention after 2000 cycles, placing it among the top single metal anodic catalysts. Further, in situ Raman and density functional theory computations confirm that Pd/DB–Ti₃C₂ is capable of dehydrogenating ethanol at low reaction energies.