Journal
ACS APPLIED MATERIALS & INTERFACES
Volume 12, Issue 1, Pages 654-666Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsami.9b17582
Keywords
carbocatalysis; kinetics; metal-free; selective hydrogenation; transfer hydrogenation
Funding
- National Natural Science Foundation of China [U1810111]
- Natural Science Foundation of Guangdong Province, China [2018B030311010]
- Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Zhejiang University [2018BCE002]
- Fundamental Research Funds for the Central Universities [2019QNGG07]
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We reported that phosphorus-doped carbon nanotubes (P-CNTs), showing metal-like properties, can efficiently promote metal-free hydrogenation of nitrobenzene (1a) to aniline (2a) using molecular hydrogen (H-2) as a reducing reagent under very mild conditions with a reaction temperature of only 50 degrees C. The kinetics of 1a hydrogenation over P-CNT reveals that the hydrogenation rate of 1a is a first-order dependence on the H-2 pressure and the P-CNT loading level, and a zero-order dependence on 1a concentration, demonstrating the rate-determining step of H-2 adsorption and activation over P-CNT. The activation energy of P-CNT-catalyzed 1a hydrogenation is 43 +/- 3 kJ mol(-1) with the turnover frequency around 3.60 +/- 0.12 h(-1) at 50 degrees C. In addition to 1a, the general applicability of the P-CNT-promoted metal-free hydrogenation process is further demonstrated by applying various functionalized nitroaromatics with wide industrial interest. The P-CNT shows both excellent yields and selectivities to hydrogenation with respect to reducible, labile, and strong leaving groups on the nitroaromatics molecules. The stability and reusability of the P-CNT demonstrate up to eight-time recycling without evident loss of activity and selectivity. In addition to hydrogenation, metal-free catalytic transfer hydrogenation of 1a is achieved with P-CNT using diverse hydrogen sources, including hydrazine hydrate (N2H4 center dot H2O), carbon monoxide/water (CO/H2O), and formic acid/triethylamine (HCOOH/Et3N).
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