Abstract
The recent discovery that metal-free polyterthiophene (PTTh) prepared by iodine-vapor-assisted polymerization (IVP) can catalyze the hydrogen evolution reaction (HER) when illuminated, and this light-enhanced electrolysis expresses a non-Nernstian relation with pH, provides the foundation for further improvement of the photovoltage of the reaction by engineering the band structure of the light-absorbing polymer. Deviating from an all-thiophene backbone, using poly(1,4-di(2-thienyl))benzene (PDTB) lowers the highest occupied molecular orbital level by ≈0.3 eV compared with polythiophene, and PDTB simultaneously maintains the photoelectrocatalytic properties without an all-thiophene backbone, resulting in very high conversion rate of 600 mmol(H2) h−1 g−1 at 0 V versus the reversible hydrogen electrode (RHE) at pH 11. PDTB shows the same non-Nernstian behavior as PTTh with increasing onset potential (versus RHE) at higher pH, and the open circuit potential on PDTB under visible light reaches 1.4 V versus RHE at pH 12. The PDTB photocathode thus produces a photovoltage above the theoretical potential for the complete water-splitting (1.229 V) and is indeed able to produce hydrogen in a one-photon-per-electron light-driven water splitting setup with MnOx as the anode at a rate of 6.4 mmol h−1 gPDTB −1.
| Original language | English |
|---|---|
| Article number | 1803286 |
| Journal | Advanced Energy Materials |
| DOIs | |
| Publication status | Accepted/In press - 2018 Jan 1 |
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Keywords
- high pH
- hydrogen evolution
- photocathodes
- poly(1,4-di(2-thienyl))benzene
- water splitting
ASJC Scopus subject areas
- Renewable Energy, Sustainability and the Environment
- Materials Science(all)
Cite this
Poly(1,4-di(2-thienyl))benzene Facilitating Complete Light-Driven Water Splitting under Visible Light at High pH. / Oka, Kouki; Noguchi, Kanako; Suga, Takeo; Nishide, Hiroyuki; Winther Jensen, Bjorn.
In: Advanced Energy Materials, 01.01.2018.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Poly(1,4-di(2-thienyl))benzene Facilitating Complete Light-Driven Water Splitting under Visible Light at High pH
AU - Oka, Kouki
AU - Noguchi, Kanako
AU - Suga, Takeo
AU - Nishide, Hiroyuki
AU - Winther Jensen, Bjorn
PY - 2018/1/1
Y1 - 2018/1/1
N2 - The recent discovery that metal-free polyterthiophene (PTTh) prepared by iodine-vapor-assisted polymerization (IVP) can catalyze the hydrogen evolution reaction (HER) when illuminated, and this light-enhanced electrolysis expresses a non-Nernstian relation with pH, provides the foundation for further improvement of the photovoltage of the reaction by engineering the band structure of the light-absorbing polymer. Deviating from an all-thiophene backbone, using poly(1,4-di(2-thienyl))benzene (PDTB) lowers the highest occupied molecular orbital level by ≈0.3 eV compared with polythiophene, and PDTB simultaneously maintains the photoelectrocatalytic properties without an all-thiophene backbone, resulting in very high conversion rate of 600 mmol(H2) h−1 g−1 at 0 V versus the reversible hydrogen electrode (RHE) at pH 11. PDTB shows the same non-Nernstian behavior as PTTh with increasing onset potential (versus RHE) at higher pH, and the open circuit potential on PDTB under visible light reaches 1.4 V versus RHE at pH 12. The PDTB photocathode thus produces a photovoltage above the theoretical potential for the complete water-splitting (1.229 V) and is indeed able to produce hydrogen in a one-photon-per-electron light-driven water splitting setup with MnOx as the anode at a rate of 6.4 mmol h−1 gPDTB −1.
AB - The recent discovery that metal-free polyterthiophene (PTTh) prepared by iodine-vapor-assisted polymerization (IVP) can catalyze the hydrogen evolution reaction (HER) when illuminated, and this light-enhanced electrolysis expresses a non-Nernstian relation with pH, provides the foundation for further improvement of the photovoltage of the reaction by engineering the band structure of the light-absorbing polymer. Deviating from an all-thiophene backbone, using poly(1,4-di(2-thienyl))benzene (PDTB) lowers the highest occupied molecular orbital level by ≈0.3 eV compared with polythiophene, and PDTB simultaneously maintains the photoelectrocatalytic properties without an all-thiophene backbone, resulting in very high conversion rate of 600 mmol(H2) h−1 g−1 at 0 V versus the reversible hydrogen electrode (RHE) at pH 11. PDTB shows the same non-Nernstian behavior as PTTh with increasing onset potential (versus RHE) at higher pH, and the open circuit potential on PDTB under visible light reaches 1.4 V versus RHE at pH 12. The PDTB photocathode thus produces a photovoltage above the theoretical potential for the complete water-splitting (1.229 V) and is indeed able to produce hydrogen in a one-photon-per-electron light-driven water splitting setup with MnOx as the anode at a rate of 6.4 mmol h−1 gPDTB −1.
KW - high pH
KW - hydrogen evolution
KW - photocathodes
KW - poly(1,4-di(2-thienyl))benzene
KW - water splitting
UR - http://www.scopus.com/inward/record.url?scp=85059304157&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85059304157&partnerID=8YFLogxK
U2 - 10.1002/aenm.201803286
DO - 10.1002/aenm.201803286
M3 - Article
AN - SCOPUS:85059304157
JO - Advanced Energy Materials
JF - Advanced Energy Materials
SN - 1614-6832
M1 - 1803286
ER -