Electronic Modulation of Palladium in Metal Phosphide Nanoparticles for Chemoselective Reduction of Halogenated Nitrobenzenes

Tuning the electronic property of a transition metal plays an important role in the selective catalysis. Herein, the control synthesis of (Pd_xNi_y)‐P nanoparticles is reported. The binding energy of Pd3d_5/2 as a function of x/y ratio is well tunable from 335.3 to 335.9 eV. The composition‐induced electronic modulation was correlated with the selective catalysis of (Pd_xNi_y)‐P in the reduction of halogenated nitrobenzenes. The electro‐deficiency of Pd helped to improve the selectivity. The amorphous (Pd₃₈Ni₂₆)P₃₆/C performed an exceptional selectivity in comparison with other related (Pd‐Ni)‐P/C, Pd₃₈Ni₂₆/C, and Pd/C. Various halogenated nitrobenzenes (chlorides, bromides, and iodide) were tolerant and the corresponding halogenated anilines were obtained in high yields. This work provides some clues for the rational design of bimetallic phosphides with covalent interactions to boost the catalysis.