Mild Deoxygenation of Sulfoxides over Plasmonic Molybdenum Oxide Hybrid with Dramatic Activity Enhancement under Visible Light

Abstract

Harvesting solar light to boost commercially important organic synthesis still remains a challenge. Coupling of conventional noble metal catalysts with plasmonic oxide materials which exhibit intense plasmon absorption in the visible light region is a promising option for efficient solar energy utilization in catalysis. Herein, we for the first time demonstrate that plasmonic hydrogen molybdenum bronze coupled with Pt nanoparticles (Pt/H MoO) shows a high catalytic performance in the deoxygenation of sulfoxides with 1 atm of H at room temperature, with dramatic activity enhancement under visible light irradiation relative to dark conditions. The plasmonic molybdenum oxide hybrids with strong plasmon resonance peaks pinning at around 556 nm are obtained via a facile H-spillover process. Pt/H MoO hybrid provides excellent selectivity for the deoxygenation of various sulfoxides as well as pyridine N-oxides, in which drastically improved catalytic efficiencies are obtained under the irradiation of visible light. Comprehensive analyses reveal that oxygen vacancies massively introduced via a H-spillover process are the main active sites, and the reversible redox property of Mo atoms and strong plasmonic absorption play key roles in this reaction. The catalytic system works under extremely mild conditions and can boost the reaction by the assistance of visible light, offering an ultimately greener protocol to produce sulfides from sulfoxides. Our findings may open up a new strategy for designing plasmon-based catalytic systems that can harness visible light efficiently.

Defect Engineering of MoS2 and Its Impacts on Electrocatalytic and Photocatalytic Behavior in Hydrogen Evolution Reactions

“…Synthesis of Ru/(1T/2H‐)MoS 2− x . Ru/(1T/2H‐)MoS 2− x was synthesized by the hydrogen reduction reaction according to a reported procedure . Generally, the 1T/2H‐MoS 2 was mixed with solution (ethanol:water=1:2) according to the mass ratio of MoS 2 :Ru=100:1.…”

“…Synthesis of Ru/(1T/2H-)MoS 2À Àx .R u/(1T/2H-)MoS 2Àx was synthesized by the hydrogen reduction reaction according to ar eported procedure. [53,54] Generally,t he 1T/2H-MoS 2 was mixed with solution (ethanol:water = 1:2) according to the mass ratio of MoS 2 :Ru = 100:1. The solution was stirred for 2hours and under an ultrasonic treatment for 1h our,t hen dried in vacuum at room temperature.…”

Facile Fabrication of Amorphous Molybdenum Oxide as a Sensitive and Stable SERS Substrate under Redox Treatment

“…Noble metals are commonly used to achieve selective photocatalytic reaction by combination with metal oxides . By benefitting from the fingerprint spectrum, in situ SERS monitoring of reaction processes is expected to help achieve precise photocatalyst design.…”

Defect engineering: A versatile tool for tuning the activation of key molecules in photocatalytic reactions

“…12 e). Furthermore, the robust adsorption and activation of organic molecules at defect sites can also induce bond cleavage, achieving various photocatalytic organic reactions under mild conditions [148][149][150] . For instance, nonstoichiometric W 18 O 49 with abundant OVs was employed as a catalyst towards photocatalytic dehydration of isopropyl alcohol (IPA) to propylene [148] .…”