Symmetry-breaking of Dibenzo[b,d]thiophene Sulfone Enhancing Polaron Generation for Boosted Photocatalytic Hydrogen Evolution

Wei-Cheng Lin; Yi-Hsiang Wu; Yu-En Sun; Mohamed M Elsenety; Wan-Chi Lin; Jui-Chen Yen; Hung-Kai Hsu; Bo-Han Chen; Hung-Yi Huang; Chia-An Chang; Tse-Fu Huang; Ying-Rang Zhuang; Yuan-Ting Tseng; Kun-Han Lin; Shang-Da Yang; Chi-Hua Yu; Ho-Hsiu Chou

doi:10.1002/anie.202407702

Symmetry-breaking of Dibenzo[b,d]thiophene Sulfone Enhancing Polaron Generation for Boosted Photocatalytic Hydrogen Evolution

Angew Chem Int Ed Engl. 2024 May 16:e202407702. doi: 10.1002/anie.202407702. Online ahead of print.

Authors

Wei-Cheng Lin¹, Yi-Hsiang Wu², Yu-En Sun², Mohamed M Elsenety³, Wan-Chi Lin⁴, Jui-Chen Yen⁵, Hung-Kai Hsu⁵, Bo-Han Chen⁵, Hung-Yi Huang⁶, Chia-An Chang⁷, Tse-Fu Huang⁶, Ying-Rang Zhuang⁶, Yuan-Ting Tseng⁶, Kun-Han Lin⁶, Shang-Da Yang⁵, Chi-Hua Yu⁸, Ho-Hsiu Chou⁹

Affiliations

¹ National Tsing Hua University Department of Chemical Engineering, Department of Chemical Engineering, 101, Section 2, Kuang-Fu Road, Hsinchu 300044, Taiwan R.O.C., Hsinchu, 30013, Hsinchu, TAIWAN.
² National Tsing Hua University Department of Chemical Engineering, Department of Chemical Engineering, 101, Section 2, Kuang-Fu Road, Hsinchu 300044, Taiwan R.O.C., 30013, Hsinchu, TAIWAN.
³ National Tsing-Hua University Department of Chemical Engineering, Department of Chemical Engineering, 101, Section 2, Kuang-Fu Road, Hsinchu 300044, Taiwan R.O.C., Hsinchu, TAIWAN.
⁴ National Cheng Kung University, Academy of Innovative Semiconductor and Sustainable Manufacturing, TAIWAN.
⁵ National Tsing Hua University, Institute of Photonics Technologies & Department of Electrical Engineering, TAIWAN.
⁶ National Tsing Hua University Department of Chemical Engineering, Department of Chemical Engineering, TAIWAN.
⁷ National Tsing Hua University, Department of Chemical Engineering, TAIWAN.
⁸ National Cheng Kung University, Department of Engineering Science, TAIWAN.
⁹ National Tsing Hua University, Department of Chemical Engineering, NO. 101, Sec 2, Kuang-Fu Road, 300044, Hsinchu, TAIWAN.

PMID: 38751355
DOI: 10.1002/anie.202407702

Abstract

The current bottleneck in the development of efficient photocatalysts for hydrogen evolution is the limited availability of high-performance acceptor units. Over the past nine years, dibenzo[b,d]thiophene sulfone (DBS) has been the preferred choice for the acceptor unit. Despite extensive exploration of alternative structures as potential replacements for DBS, a superior substitute remains elusive. In this study, a symmetry-breaking strategy was employed on DBS to develop a novel acceptor unit, BBTT-1SO. The asymmetric structure of BBTT-1SO proved beneficial for increasing multiple moment and polarizability. BBTT-1SO-containing polymers showed higher efficiencies for hydrogen evolution than their DBS-containing counterparts by up to 166%. PBBTT-1SO exhibited an excellent hydrogen evolution rate (HER) of 222.03 mmol g-1 h-1 and an apparent quantum yield of 27.5% at 500 nm. Transient spectroscopic studies indicated that the BBTT-1SO-based polymers facilitated electron polaron formation, which explains their superior HERs. PBBTT-1SO also showed 14% higher HER in natural seawater splitting than that in deionized water splitting. Molecular dynamics simulations highlighted the enhanced water-PBBTT-1SO polymer interactions in salt-containing solutions. This study presents a pioneering example of a substitute acceptor unit for DBS in the construction of high-performance photocatalysts for hydrogen evolution.

Keywords: Symmetry-breaking * Benzo[b]benzo[4,5]thieno[2,3-d]thiophene 5,5-dioxide * Polarizability * Polaron population * Photocatalytic hydrogen evolution.