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[Display omitted] • Ti 3 C 2 /Pd was designed for efficient catalytic transfer hydrogenation of nitrobenzene. • Experimental and DFT theoretical studies unravel unique catalytic mechanism. • Electron transfer at Ti 3 C 2 /Pd interfaces changes Pd electron configure (4 d 10 → 4 d 10-x). • Electron-deficient Pd boosts formic acid dissociation for atomic H* production. • Ti 3 C 2 /Pd chemisorbs active H* and inhibits undesirable H 2 evolution. Catalytic transfer hydrogenation (CTH) with formic acid attracts much interest in catalysis, but the sluggish H* production and undesirable H 2 evolution reaction (HER) limit its practical applications. Herein we anchored Pd nanoparticles (NPs) on layered Ti 3 C 2 MXene for efficient and selective CTH of nitrobenzene in the presence of formic acid. Some electrons in Pd NPs transferred to Ti 3 C 2 MXene upon formation of Ti 3 C 2 /Pd nanohybrids, as confirmed by XPS and DFT simulations. The electron transfer changed Pd valance electron configuration from 4 d 10 to 4 d 10-x. Such electron-deficient Pd NPs tuned reaction pathway and promoted formic acid dissociation, both of which favored the production of active H* atoms, i.e., the exact reductant for CTH. Compared with Pd NPs, Ti 3 C 2 /Pd showed stronger adsorption of H* and therefore inhibited the occurrence of HER (2H*→H 2). Owing to favorable H* production and HER inhibition, Ti 3 C 2 /Pd (15 wt% Pd) showed enhanced nitrobenzene CTH performance with turnover frequency of 351.7 h−1 and 99% aniline selectivity, outperforming most of current catalysts. Our work might inspire designing more advanced CTH catalysts by tuning their valance electron configurations with 2D MXene materials. [ABSTRACT FROM AUTHOR]