Defect-Domianted Intrinsic Activity of Carbon Governs Pd Nanoparticles for Boosted Formic Acid Dehydrogenation

The defect-rich characteristic nanoarchitectures carbon is in favor of changing polarity and electron distribution of carbon matrix, thus providing the possibility for achieving efficient ions adsorption. Herein, the B,N,F-tridoped carbon material with more defective sites was successfully prepared by directly one-step calcining a powder mixture of ethylenediaminetetraacetic acid tetrasodium salt and ammonium tetrafluoroborate. The co-existence of electron-donating atoms and electron-accepting atoms caused asymmetrical spin and charge density, resulting in Pd NPs well dispersed on the carbon matrix by a typical impregnation-reduction process. The B,N,F-tridoped carbon material not only efficiently controls the formation and growth of Pd nanoparticles, but also governs the intrinsic activity of the Pd/BNF-C catalyst, and endows significantly enhanced catalytic performance for hydrogen evolution from formic acid with a TOF value of 3828 h -1 at 313 K. Besides, the Pd/BNF-C catalyst showed lower activation barrier (36.4 kJ/mol) and excellent reusability than that of without B,F-doped catalyst. These efficiencies might be caused by strong interaction between Pd NPs and B,N,F-heteroatoms and the electron transfer from carbon material to Pd NPs, with the benefit of the significant coupling effect of B,N,F-tridoping down to the atomic scale, abundant surface active defects, in-plane nanopore defects and more adjacent metal active sites