TY - JOUR
T1 - Molecular Engineering of Robust Starburst-Based Organic Photosensitizers for Highly Efficient Photocatalytic Hydrogen Generation from Water
AU - Kwok, Yan Yi
AU - Ho, Po Yu
AU - Wei, Ying
AU - Zheng, Zhong
AU - Yiu, Sze Chun
AU - Ho, Cheuk Lam
AU - Huang, Shuping
N1 - Funding Information:
C.-L.H. thanks the Hong Kong Research Grants Council (PolyU 123021/17P), the Science, Technology, and Innovation Committee of Shenzhen Municipality (JCYJ20180306173720000), Environment and Conservation Fund (ECF 79/2020) from the Government of HKSAR, and the Hong Kong Polytechnic University (ZVVU and ZVXU) for their financial support.
Publisher Copyright:
© 2022 American Chemical Society.
PY - 2022/6/28
Y1 - 2022/6/28
N2 - Six donor-donor-π-acceptor (D-D-π-A) triphenylamine-based starburst organic dyes with different electron-donating moieties and thiophene-based π-linkers were synthesized and characterized. Their photophysical and electrochemical properties, together with their photocatalytic hydrogen evolution performance as photosensitizers (PSs), were investigated. Distinctive and prolonged hydrogen evolution performances of these PSs under visible-light irradiation from water in their platinized TiO2 composites were demonstrated: a turnover number (TON) of up to 24900 (252 h) with 1560 μmol (37.6 mL) hydrogen produced, an initial turnover frequency (TOFi) of 1130 h-1, initial activity (Activityi) of 705 mmol g-1 h-1, and initial apparent quantum yield (AQYi) of 12.1%. To the best of our knowledge, according to the TOF and TON values, the designed PS system is one of the most efficient and robust photocatalytic H2 generation systems adopting a TiO2-anchoring molecular PS in the literature. The results showed that the starburst triarylamine donor moiety with phenothiazine functionality and the alkyl chain on the thiophene π-linker could boost the performance and longevity of the photocatalytic system, providing a powerful strategy for the development of starburst-based highly efficient and robust D-D-π-A organic photosensitizers in the future.
AB - Six donor-donor-π-acceptor (D-D-π-A) triphenylamine-based starburst organic dyes with different electron-donating moieties and thiophene-based π-linkers were synthesized and characterized. Their photophysical and electrochemical properties, together with their photocatalytic hydrogen evolution performance as photosensitizers (PSs), were investigated. Distinctive and prolonged hydrogen evolution performances of these PSs under visible-light irradiation from water in their platinized TiO2 composites were demonstrated: a turnover number (TON) of up to 24900 (252 h) with 1560 μmol (37.6 mL) hydrogen produced, an initial turnover frequency (TOFi) of 1130 h-1, initial activity (Activityi) of 705 mmol g-1 h-1, and initial apparent quantum yield (AQYi) of 12.1%. To the best of our knowledge, according to the TOF and TON values, the designed PS system is one of the most efficient and robust photocatalytic H2 generation systems adopting a TiO2-anchoring molecular PS in the literature. The results showed that the starburst triarylamine donor moiety with phenothiazine functionality and the alkyl chain on the thiophene π-linker could boost the performance and longevity of the photocatalytic system, providing a powerful strategy for the development of starburst-based highly efficient and robust D-D-π-A organic photosensitizers in the future.
UR - http://www.scopus.com/inward/record.url?scp=85133500139&partnerID=8YFLogxK
U2 - 10.1021/acs.chemmater.2c00556
DO - 10.1021/acs.chemmater.2c00556
M3 - Journal article
AN - SCOPUS:85133500139
SN - 0897-4756
VL - 34
SP - 5522
EP - 5534
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 12
ER -