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Article

Mechanistic Studies of Hydrogen Evolution Reaction on Donor-Acceptor Conjugated Polymer Photocatalysts

1
Department of Engineering and System Science, National Tsing Hua University, Hsinchu 30013, Taiwan
2
Department of Electrical Engineering and Electronics, University of Liverpool, Liverpool L69 3GJ, UK
3
Department of Chemical Engineering, National Tsing Hua University No. 101, Sec. 2, Kuang-Fu Road, Hsinchu 30013, Taiwan
4
Institute of New Drug Development, China Medical University, No.91 Hsueh-Shih Road, Taichung 40402, Taiwan
*
Authors to whom correspondence should be addressed.
Appl. Sci. 2020, 10(20), 7017; https://doi.org/10.3390/app10207017
Received: 29 July 2020 / Revised: 29 September 2020 / Accepted: 30 September 2020 / Published: 9 October 2020
(This article belongs to the Special Issue Nano Hydrogen Production and Storage)
The application of donor-acceptor (D-A) conjugated polymer catalysts for hydrogen evolution reaction (HER) has shown great promise because of the tunability of such catalysts to have desired properties. Herein, we synthesized two polymer catalysts: poly[4,4′-(9-(4-aminophenyl)-9H-carbazole-3,6-diamine-alt-5-oxido-5-phenylbenzo[b]phosphindole-3,7-diyl)dibenzaldehyde] (PCzPO) and poly[N1,N1-bis(4-amino-2-fluorophenyl)-2-fluorobenzene-1,4-diamine-alt-5-oxido-5-phenylbenzo[b]phosphindole-3,7-diyl)dibenzaldehyde] (PNoFPO). The UV-vis absorption spectra showed that the less planar structure and the presence of electronegative fluorine atoms in the donor group of PNoFPO led to a higher optical gap compared to PCzPO, leading to almost five times faster HER rate using PCzPO compared to PNoFPO. However, density functional theory (DFT) calculations show that the frontier orbitals and the highest occupied molecular orbitals – lowest unoccupied molecular orbitals (HOMO-LUMO) gaps of PCzPO and PNoFPO D-A moiety models are very similar, such that, during light absorption, electrons move from donor to acceptor group where proton binding is preferred to happen thereafter. For both PCzPO and PNoFPO D-A moieties, H2 formation through an intramolecular reaction with a barrier of 0.6–0.7 eV, likely occurs at the acceptor group atoms where protons bind through electrostatic interaction. The intermolecular reaction has nearly zero activation energy but is expected to occur only when the repulsion is low between separate polymers chains. Finally, experimental and DFT results reveal the importance of extended configurations of D-A polymers on HER rate. View Full-Text
Keywords: hydrogen evolution reaction; donor-acceptor conjugated polymer; density functional theory; optoelectronic properties; photocatalysis hydrogen evolution reaction; donor-acceptor conjugated polymer; density functional theory; optoelectronic properties; photocatalysis
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MDPI and ACS Style

Reyes, Y.I.A.; Ting, L.-Y.; Tu, X.; Chen, H.-Y.T.; Chou, H.-H.; Coluccini, C. Mechanistic Studies of Hydrogen Evolution Reaction on Donor-Acceptor Conjugated Polymer Photocatalysts. Appl. Sci. 2020, 10, 7017. https://doi.org/10.3390/app10207017

AMA Style

Reyes YIA, Ting L-Y, Tu X, Chen H-YT, Chou H-H, Coluccini C. Mechanistic Studies of Hydrogen Evolution Reaction on Donor-Acceptor Conjugated Polymer Photocatalysts. Applied Sciences. 2020; 10(20):7017. https://doi.org/10.3390/app10207017

Chicago/Turabian Style

Reyes, Yves I.A., Li-Yu Ting, Xin Tu, Hsin-Yi T. Chen, Ho-Hsiu Chou, and Carmine Coluccini. 2020. "Mechanistic Studies of Hydrogen Evolution Reaction on Donor-Acceptor Conjugated Polymer Photocatalysts" Applied Sciences 10, no. 20: 7017. https://doi.org/10.3390/app10207017

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