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Sulfone‐Decorated Conjugated Organic Polymers Activate Oxygen for Photocatalytic Methane Conversion

Bo An, Qinhua Zhang, Bo‐shi Zheng, Miao Li, Yanyan Xi, Xin Jin, Sheng Xue, Zhong‐tao Li, Ming‐bo Wu, Wenting Wu

2022Angewandte Chemie International Edition75 citationsDOI

Abstract

Abstract Oxidizing CH 4 into liquid products with O 2 under mild conditions still mainly relies on metal catalysis. We prepared a series of sulfone‐modified conjugated organic polymers and found that the catalyst with proper S VI content (0.10) could drive O 2 →H 2 O 2 →⋅OH to oxidize CH 4 into CH 3 OH and HCOOH directly and efficiently at room temperature under light irradiation. Experimental results showed that after 4 h reaction, decomposition rate and residual amounts of H 2 O 2 were 81.21 % and 4.83 mmol g cat −1 respectively, and CH 4 conversion rate was 22.81 %. Mechanism studies revealed that illumination could induce the homolytic dissociation of S=O bonds on catalyst to produce oxygen and sulfur radicals, where the ⋅O could adsorb and activate CH 4 , and the ⋅S could supply electrons for 1 O 2 to generate H 2 O 2 and then for decomposing the H 2 O 2 into ⋅OH timely to oxidize CH 4 . This research provided a novel organic catalysis approach for oxygen activation and utilization.

Topics & Concepts

CatalysisPhotocatalysisChemistryPhotochemistryOxidizing agentHomolysisOxygenPolymerSulfoneRadicalDecompositionDissociation (chemistry)Conjugated systemAdsorptionMethaneInorganic chemistryOrganic chemistryCovalent Organic Framework ApplicationsAdvanced Photocatalysis TechniquesCatalytic Processes in Materials Science