Sulfone‐Decorated Conjugated Organic Polymers Activate Oxygen for Photocatalytic Methane Conversion. Issue 28 (5th May 2022)

• Record Type: Journal Article
• Authors: An, Bo; Zhang, Qin‐hua; Zheng, Bo‐shi; Li, Miao; Xi, Yan‐yan; Jin, Xin; Xue, Sheng; Li, Zhong‐tao; Wu, Ming‐bo; Wu, Wen‐ting
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 28(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-05-05
• Subjects: Conjugated Organic Polymer -- Methane Conversion -- Oxygen Activation -- Photocatalysis -- Sulfone Group; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202204661
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Oxidizing CH4 into liquid products with O2 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 O2 →H2 O2 →⋅OH to oxidize CH4 into CH3 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 H2 O2 were 81.21 % and 4.83 mmol gcat −1 respectively, and CH4 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 CH4, and the ⋅S could supply electrons for 1 O2 to generate H2 O2 and then for decomposing the H2 O2 into ⋅OH timely to oxidize CH4 . This research provided a novel organic catalysis approach for oxygen activation and utilization. Abstract : In a process of methane conversion photocatalyzed by the sulfone‐decorated conjugated organic polymer, S‐CTTP, light irradiation first induced the homolytic dissociation of S=O bonds in sulfone groups on the catalyst surface to generate free radicals. The radicals drive efficient conversion of 1 O2 to H2 O2 and then ⋅OH, for selective oxidation of adsorbed CH4 into CH3 OH and HCOOH.