Monolayer Bi₂W_1–xMo_xO₆ Solid Solutions for Structural Polarity to Boost Photocatalytic Reduction of Nitrobenzene under Visible Light

Abstract

Monolayer nanosheets of Bi2W1–x Mo x O6 solid solutions, possessing an average thickness of 0.98 nm, have been rationally designed and constructed by a facile bottom-up route of a hydrothermal reaction. The tiptop photocatalytic efficiency of Bi2W1–x Mo x O6 monolayer nanosheets can be achieved for effective reduction conversion of nitrobenzene into anilines under visible light, in conspicuous contrast to the homologous pristine Bi2WO6 and Bi2MoO6 components. The optimal Bi2W0.25Mo0.75O6 monolayer nanosheets exhibit a high selectivity and stability for photocatalytic nitrobenzene reduction, affording a high aniline generating rate of 650 μmol g–1.h–1, in excess of the previously reported ordinary photocatalysts. The good photocatalytic property could be due to the lattice distortion in solid solutions for structural polarity by the more electronegative W substitution, leading to the efficient interfacial and interior separation of photogenerated carriers. The structure–activity relationship of Bi2W1–x Mo x O6 demonstrates a novel insight to devise property-controllable photocatalysts at the atomic level with high efficiency for organic photocatalytic reactions.

Photocatalytic Multielectron Reduction of Nitroarenes to Anilines by Utilizing an Electron-Storable Polyoxometalate-Based Metal–Organic Framework

“…However, the nitroarenes with electron-withdrawing groups showed a higher conversion than those with electron-donating substituents because the reduction reaction is enhanced for the lower electron density of −NO 2 with the electron-withdrawing group. With the electron-donating substituent on the nitroaromatic, it is difficult for the nitroaromatic to accept electrons, which results in a slight decrease in conversion …”

“…With the electron-donating substituent on the nitroaromatic, it is difficult for the nitroaromatic to accept electrons, which results in a slight decrease in conversion. 46 2.5. Mechanism Research of Nitrobenzene Reduction.…”

Designing a Polyoxometalate-Incorporated Metal–Organic Framework for Reduction of Nitroarenes to Anilines by Sequential Proton-Coupled Electron Transfers

“…Fuel aniline is a potential intermediate in the industrial synthesis of fine chemicals, dyes, pesticides, and pharmaceuticals. , Generally, the reduction of nitrobenzene (NB) to aniline (AN) is carried out by a hydrogenation reaction catalyzed by Au, Ag, Pt, and Rh composites combining with H 2 and N 2 H 4 reductants in harsh conditions. − With increasing concern about the green and atom economy of organic reactions in the synthesis of fine chemicals, developing sustainable and low-cost alternatives to noble metal composite catalysts has become one of the most significant challenges for chemists. , As a green technology, photocatalytic selective reduction of NB to AN under mild conditions has been developed extensively in recent years. , Generally, the photoreduction of NB is a six-electron, six-proton coupled process. In comparison with the concerted two-electron transfer steps catalyzed by a bulk or nanoparticle electrocatalyst under constant application, a photocatalyst under illumination with a typical photon flux contains a single exciton at any given time and therefore delivers only one electron at a time .…”

“…7,8 As a green technology, photocatalytic selective reduction of NB to AN under mild conditions has been developed extensively in recent years. 9,10 Generally, the photoreduction of NB is a six-electron, six-proton coupled process. In comparison with the concerted two-electron transfer steps catalyzed by a bulk or nanoparticle electrocatalyst under constant application, a photocatalyst under illumination with a typical photon flux contains a single exciton at any given time and therefore delivers only one electron at a time.…”

Simple, controllable and environmentally friendly synthesis of FeCoNiCuZn-based high-entropy alloy (HEA) catalysts, and their surface dynamics during nitrobenzene hydrogenation

“…Amines are important precursors in the plastics, medical, and pigments industries. Intense and extensive research has been devoted to the study of the electrocatalytic hydrogenation of nitro compounds using different methods like thermal catalysis [41][42][43], photocatalysis [44,45], and electrocatalysis [46,47]. Among these, electrocatalysis is the least studied and the one presenting more difficulties, especially regarding the conversion yields, selectivity, stability of the materials and scalability.…”