Chemoselective Hydrogenation of Nitro Compounds by MoS₂ via Introduction of Independent Active Hydrogen-Donating Sites

Abstract

The chemoselective hydrogenation of nitro compounds is limited by a trade-off between the activity and selectivity of catalysis. It is found that MoS2-based catalysts can replace noble metals to achieve nearly 100% selectivity toward hydrogenation to aromatic amines. However, the insufficient supply of active hydrogen (Ha) limits the conversion to a low level. To break the trade-off between activity and selectivity, a dual-active site catalyst was designed using exfoliated MoS2 as a support and modifying it with single-atom Pt as independent, active hydrogen-donating sites. Isolated Pt atoms continuously provide Ha to the hydrogenation sites of MoS2. This strategy solves the problem of insufficient Ha supply, which is caused by the competitive adsorption of nitro groups and hydrogen on MoS2, by matching the rate of Ha production and Ha consumption, resulting in a greatly increased reaction rate.

Coupled Co-Doped MoS2 and CoS2 as the Dual-Active Site Catalyst for Chemoselective Hydrogenation

“…Generally, the addition of heterogeneous elements and building a composite system are effective methods of improving performance. 25,26 For example, Fan et al 27 report that modifying exfoliated MoS 2 with single-atom Pt as the independent active hydrogen-donating site shows good catalytic properties and stability. The systematic investigation reveals the synergy between Pt single atoms and S vacancies.…”

“…Despite these progresses, there are few reports on the hydrogenation of substituted nitrobenzene utilizing H 2 and MoS 2 . , This is because MoS 2 -based catalysts generally require harsh operating conditions, namely, high temperature and high hydrogen pressure, to activate H 2 . Generally, the addition of heterogeneous elements and building a composite system are effective methods of improving performance. , For example, Fan et al report that modifying exfoliated MoS 2 with single-atom Pt as the independent active hydrogen-donating site shows good catalytic properties and stability. The systematic investigation reveals the synergy between Pt single atoms and S vacancies.…”

Heterostructure CoS2/MoS2 Nanosheets as a Dual-Active Electrocatalyst for the Oxygen Evolution Reaction

“…Then, the CC@ZIF-67 precursor was put into the solution for ultrasonic treatment for 1 h and moved into a Teflon autoclave. The compound was saved at 200 °C for 24 h, laved, and dried to obtain CC@CoS 2 /MoS 2 . , …”

Atomically dispersed Pt to boost adjacent frustrated Lewis pair for 2,6‐diamino‐3,5‐dinitropyridine hydrogenation

“…Regulation of the local structures of oxygen vacancies to stimulate the frustrated Lewis pair toward enhanced hydrogen activation is thus considered as an effective strategy for improving the catalytic performances of the metal oxide catalysts. Single‐atom catalysts have emerged as promising heterogeneous catalysts due to the unique electronic and geometric structures, which enable to regulate the structures of catalysts at the atomic level 21–23 . Inspired by these, introducing single‐atom promoters onto transition metal oxides is expected to render atomic‐level tailoring for the local environments of the oxygen vacancies in oxide catalysts.…”

“…Single-atom catalysts have emerged as promising heterogeneous catalysts due to the unique electronic and geometric structures, which enable to regulate the structures of catalysts at the atomic level. [21][22][23] Inspired by these, introducing single-atom promoters onto transition metal oxides is expected to render atomic-level tailoring for the local environments of the oxygen vacancies in oxide catalysts.…”