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

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 À 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.

The tail of imidazole regulated the assembly of two robust sandwich-type polyoxotungstate-based open frameworks with efficient visible-white-light-driven catalytic oxidation of sulfides

“…Visible-light-driven organic conversion is one of the prospective strategies to directly effectuate chemical bond functionalization under ambient conditions. 1–3 The promising strategy could synchronously ameliorate widespread concerns over energy crisis and environmental issues, pursuing sustainable and high-quality development of chemical industries. 4 Among these photocatalytic organic transformations, the selective aerobic oxidation of sulfides is one of the paramount methods to produce high value-added sulfoxides.…”

Selective Oxidation of Methane to Oxygenates using Oxygen via Tandem Catalysis

“…The introduction of photo-electron over sensitizer containing thiophene can convert triplet oxygen ( 3 O 2 ) to singlet oxygen ( 1 O 2 ), and 1 O 2 is easier to be converted to H 2 O 2 to enhance methane oxidation. [56] Another topic is that piezoelectric materials can be induced by an asymmetric distribution of surface charge under ultrasonic vibration, which can be applied for activating H 2 O and O 2 to reaction oxygen species. [57] In addition, gamma irradiation (γ-rays) can penetrate the stainlesssteel autoclave and generate a very high concentration of OH species in a fraction of microsecond.…”

1,3,5-Triazine and dithienothiophene-based conjugated polymers for highly effective photocatalytic hydrogen evolution

“…In recent years, the nitrogen-rich Tz core has often been incorporated into conjugated polymers used as photocatalysts for water splitting. [40][41][42][43][44] Li and co-workers reported dibenzo[b,d]thiophene sulfone-and triazine-based CMPs which demonstrated an HER rate of 16.3 mmol h −1 g −1 under UV-Vis irradiation. 45 Our group has previously reported pyrene-and triazine-based CMPs which demonstrated an out-standing HER rate of 10.3 mmol h −1 g −1 under simulated sunlight.…”