Mechanistic Studies of Hydrogen Evolution Reaction on Donor-Acceptor Conjugated Polymer Photocatalysts
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-diami...
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MDPI AG
2020-10-01
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| Series: | Applied Sciences |
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| Online Access: | https://www.mdpi.com/2076-3417/10/20/7017 |
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| author | Yves Ira A. Reyes Li-Yu Ting Xin Tu Hsin-Yi Tiffany Chen Ho-Hsiu Chou Carmine Coluccini |
| author_facet | Yves Ira A. Reyes Li-Yu Ting Xin Tu Hsin-Yi Tiffany Chen Ho-Hsiu Chou Carmine Coluccini |
| author_sort | Yves Ira A. Reyes |
| collection | DOAJ |
| description | 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-<i>alt</i>-5-oxido-5-phenylbenzo[b]phosphindole-3,7-diyl)dibenzaldehyde] (PCzPO) and poly[N<sup>1</sup>,N<sup>1</sup>-bis(4-amino-2-fluorophenyl)-2-fluorobenzene-1,4-diamine-<i>alt</i>-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, H<sub>2</sub> 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. |
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| last_indexed | 2024-03-10T15:46:18Z |
| publishDate | 2020-10-01 |
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| spelling | doaj.art-f52992c95c1d44a6b2726a6b7c7cebb52023-11-20T16:27:15ZengMDPI AGApplied Sciences2076-34172020-10-011020701710.3390/app10207017Mechanistic Studies of Hydrogen Evolution Reaction on Donor-Acceptor Conjugated Polymer PhotocatalystsYves Ira A. Reyes0Li-Yu Ting1Xin Tu2Hsin-Yi Tiffany Chen3Ho-Hsiu Chou4Carmine Coluccini5Department of Engineering and System Science, National Tsing Hua University, Hsinchu 30013, TaiwanDepartment of Chemical Engineering, National Tsing Hua University No. 101, Sec. 2, Kuang-Fu Road, Hsinchu 30013, TaiwanDepartment of Electrical Engineering and Electronics, University of Liverpool, Liverpool L69 3GJ, UKDepartment of Engineering and System Science, National Tsing Hua University, Hsinchu 30013, TaiwanDepartment of Chemical Engineering, National Tsing Hua University No. 101, Sec. 2, Kuang-Fu Road, Hsinchu 30013, TaiwanInstitute of New Drug Development, China Medical University, No.91 Hsueh-Shih Road, Taichung 40402, TaiwanThe 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-<i>alt</i>-5-oxido-5-phenylbenzo[b]phosphindole-3,7-diyl)dibenzaldehyde] (PCzPO) and poly[N<sup>1</sup>,N<sup>1</sup>-bis(4-amino-2-fluorophenyl)-2-fluorobenzene-1,4-diamine-<i>alt</i>-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, H<sub>2</sub> 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.https://www.mdpi.com/2076-3417/10/20/7017hydrogen evolution reactiondonor-acceptor conjugated polymerdensity functional theoryoptoelectronic propertiesphotocatalysis |
| spellingShingle | Yves Ira A. Reyes Li-Yu Ting Xin Tu Hsin-Yi Tiffany Chen Ho-Hsiu Chou Carmine Coluccini Mechanistic Studies of Hydrogen Evolution Reaction on Donor-Acceptor Conjugated Polymer Photocatalysts Applied Sciences hydrogen evolution reaction donor-acceptor conjugated polymer density functional theory optoelectronic properties photocatalysis |
| title | Mechanistic Studies of Hydrogen Evolution Reaction on Donor-Acceptor Conjugated Polymer Photocatalysts |
| title_full | Mechanistic Studies of Hydrogen Evolution Reaction on Donor-Acceptor Conjugated Polymer Photocatalysts |
| title_fullStr | Mechanistic Studies of Hydrogen Evolution Reaction on Donor-Acceptor Conjugated Polymer Photocatalysts |
| title_full_unstemmed | Mechanistic Studies of Hydrogen Evolution Reaction on Donor-Acceptor Conjugated Polymer Photocatalysts |
| title_short | Mechanistic Studies of Hydrogen Evolution Reaction on Donor-Acceptor Conjugated Polymer Photocatalysts |
| title_sort | mechanistic studies of hydrogen evolution reaction on donor acceptor conjugated polymer photocatalysts |
| topic | hydrogen evolution reaction donor-acceptor conjugated polymer density functional theory optoelectronic properties photocatalysis |
| url | https://www.mdpi.com/2076-3417/10/20/7017 |
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