Record-high catalytic hydrogenated activity in nitroarenes reduction derived from in-situ nascent active metals enabled by constructing bimetallic phosphate

2020 
Abstract Herein, we report an excellent in-situ exsolution triggered hydrogenated catalyst F-Ni/Cu-P-RT started from bimetallic phosphate Ni/Cu-P-RT, affording an ultrafast catalytic hydrogenated rate (20 s even 5 s) in nitrophenol reduction. In the first catalytic cycle, we proved the enhanced catalytic reduction activity of bimetallic Ni/Cu-P-RT within 50 s compared to monometallic counterparts. The kinetics results revealed Ni/Cu-P-RT affords the reaction rate K of 2.85/4.23/6.6 min−1 at 20, 30, and 40 °C with the activation energy 32 kJ/mol. Impressively, the involved reaction induction period is visibly observed and interpreted by reconstruction and evolution of active metal during the reaction, but was eliminated through integrating two metal Cu-Ni by regulation of electronic band energy of phosphate from 4.1–3.5 eV. The nascent Cu and Ni nanoparticles as reaction-preferred active species were in-situ exsolved partially after adding NaBH4, triggering the resulted higher active and stable F-Ni/Cu-P-RT(20 s, 14.1 min−1) in later multiple cycles.
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