Black phosphorus hybridizing produces electron-deficient active sites on palladium nanoparticles for catalysis

• The as-synthesized Pd P/FL-BP exhibits ultrahigh catalytic activity for the hydrogenation of 4-NP. • Experiments and theory calculations demonstrate the electron-deficient structure of Pd NPs in Pd P/FL-BP. • DFT calculations indicate the electron-deficient Pd NPs are the catalytic active sites. The electronic structure of supported metal catalysts efficiently affects molecule adsorption energy and reaction energy barriers, which are crucial to the activity of a catalyst. By preparing nanohybrids palladium nanoparticle supported on few-layer black phosphorus (Pd P/FL-BP) as a catalyst, the electron-deficient structure of palladium nanoparticles induced by black phosphorus modification is demonstrated. The as-synthesized Pd P/FL-BP exhibits much enhanced catalytic activity for the hydrogenation of 4-nitrophenol to 4-aminophenol, even higher than the best performances reported to date. Density functional theory calculations indicate that the high activity correlates with the electron-deficient Pd atoms, which help to reduce the adsorption energy of reactants and promote desorption of products from the electron-deficient active sites.