31473-75-3Relevant articles and documents
Bandgap engineering of novel peryleno[1,12-bcd]thiophene sulfone-based conjugated co-polymers for significantly enhanced hydrogen evolution without co-catalyst
Gong, Xueqing,Hua, Jianli,Wang, Zhiqiang,Yang, Zhicheng,Ye, Haonan,Zhang, Shicong
, p. 20062 - 20071 (2020)
Low-cost conjugated polymers as efficient photocatalytic semiconductors for hydrogen evolution have attracted worldwide attention in recent years. However, the narrow visible-light absorption spectrum, fast electron-hole recombination and expensive co-catalysts have limited their large-scale practical application in water splitting. In this work, we first developed the new peryleno[1,12-bcd]thiophene sulfone unit with extended π-conjugation, then prepared a series of sulfone-based hybrid conjugated co-polymers (PS-1-PS-8) by statistically adjusting the molar ratio of the monomer. The experimental results and DFT calculations indicated that with the gradual increase in the peryleno[1,12-bcd]thiophene sulfone contents in the polymer backbone, the optical bandgaps of co-polymers could be fine-tuned from 2.72 eV to 1.58 eV, and showed a red-shift in the visible-light region for improving the light-capturing capability. Besides, the internal charge separation capability along the co-polymers (PS-1-PS-8) was promoted. However, the driving force for proton reduction and the dispersibility of these co-polymers in aqueous solution were gradually decreased. When the molar ratio of dibenzo[b,d]thiophene sulfone to peryleno[1,12-bcd]thiophene sulfone was 19 : 1, the polymerPS-5achieved the highest hydrogen evolution rate (HER), so far, of 7.5 mmol h?1g?1without co-catalyst under visible light, with an apparent quantum yield (AQY) of 15.3% at 420 nm. The HER performance was almost 3 times higher than that of the typical dibenzo[b,d]thiophene sulfone-based conjugated polymerP7. This work provides a strategy for maximizing the HERs of organic semiconductors by balancing the bandgap, charge recombination, driving force and wettability.
Photodeoxygenation of phenanthro[4,5-bcd]thiophene S-oxide, triphenyleno[1,12-bcd]thiophene S-oxide and perylo[1,12-bcd]thiophene S-oxide
Chintala, Satyanarayana M.,Petroff II, John T.,Barnes, Andrew,McCulla, Ryan D.
, p. 503 - 515 (2019/05/29)
Sulfoxides, upon irradiation with ultraviolet (UV) light undergo α-cleavage, hydrogen abstraction, photodeoxygenation, bimolecular photoreduction, and stereo-mutation. The UV irradiation of dibenzothiophene S-oxide (DBTO) yields dibenzothiophene (DBT) as a major product along with ground-state atomic oxygen [O(3P)]. This is a common method for generating O(3P) in solution. The low quantum yield of photodeoxygenation and the requirement of UVA light are drawbacks of using this method. The sulfoxides benzo[b]naphtho-[1,2,d]thiophene S-oxide, benzo[b]naphtho [2,1,d]thiophene S-oxide, benzo[b] phenanthro[9,10-d]thiophene S-oxide, dinaphtho- [2,1-b:1’,2’-d]thiophene S-oxide, and dinaphtho[1,2-b:2’,1’-d]thiophene S-oxide have shown to deoxygenate up to three times faster than DBTO upon UVA irradiation; however, the photodeoxygenation of these sulfoxides does not appear to be limited to the production of O(3P). In this work, phenanthro[4,5-bcd]thiophene S-oxide, triphenyleno[1,12-bcd]thiophene-S-oxide, and perylo[1,12-bcd]thiophene-S-oxide were synthesized and their photodeoxygenation was studied. Phenanthro[4,5-bcd]thiophene-S-oxide, triphenyleno[1,12-bcd]thiophene-S-oxide, and perylo[1,12-bcd]thiophene-S-oxide deoxygenated upon UVA irradiation. However, the common intermediate experiments did not conclusively identify the photodeoxygenation mechanism of these sulfoxides.
Application of flash vacuum pyrolysis to the synthesis of sulfur- containing heteroaromatic systems
Imamura, Koichi,Hirayama, Daigo,Yoshimura, Hitoshi,Takimiya, Kazuo,Yoshio, Aso,Otsubo, Tetsuo
, p. 2789 - 2792 (2007/10/03)
The FVP method of ethynyl and chlorovinyl materials is applied to the ready formation of sulfur-containing fused heteroaromatic systems. The pyrolysis of the chlorovinyl materials is assumed to involve a mechanism different from that of the ethynyl materials.
