Thiophene-Based Conjugated Acetylenic Polymers with Dual Active Sites for Efficient Co-Catalyst-Free Photoelectrochemical Water Reduction in Alkaline Medium

Borrelli M, Querebillo CJ, Pastoetter DL, Wang T, Milani A, Casari C, Hoang Khoa Ly , He F, Hou Y, Neumann C, Turchanin A, Sun H, Weidinger IM, Feng X (2021)

Publication Type: Journal article

Publication year: 2021

Journal

Angewandte Chemie International Edition Wiley

Book Volume: 60

Pages Range: 18876-18881

Journal Issue: 34

DOI: 10.1002/anie.202104469

Abstract

Although being attractive materials for photoelectrochemical hydrogen evolution reaction (PEC HER) under neutral or acidic conditions, conjugated polymers still show poor PEC HER performance in alkaline medium due to the lack of water dissociation sites. Herein, we demonstrate that tailoring the polymer skeleton from poly(diethynylthieno[3,2-b]thiophene) (pDET) to poly(2,6-diethynylbenzo[1,2-b:4,5-b′]dithiophene (pBDT) and poly(diethynyldithieno[3,2-b:2′,3′-d]thiophene) (pDTT) in conjugated acetylenic polymers (CAPs) introduces highly efficient active sites for water dissociation. As a result, pDTT and pBDT, grown on Cu substrate, demonstrate benchmark photocurrent densities of 170 μA cm−2 and 120 μA cm−2 (at 0.3 V vs. RHE; pH 13), which are 4.2 and 3 times higher than that of pDET, respectively. Moreover, by combining DFT calculations and electrochemical operando resonance Raman spectroscopy, we propose that the electron-enriched Cβ of the outer thiophene rings of pDTT are the water dissociation active sites, while the −C≡C− bonds function as the active sites for hydrogen evolution.

Involved external institutions

Technische Universität Dresden DE Germany (DE) Westlake Institute of Advanced Study WIAS CN China (CN) Politecnico di Milano IT Italy (IT) Zhejiang University CN China (CN) Friedrich-Schiller-Universität Jena DE Germany (DE)

How to cite

APA:

Borrelli, M., Querebillo, C.J., Pastoetter, D.L., Wang, T., Milani, A., Casari, C.,... Feng, X. (2021). Thiophene-Based Conjugated Acetylenic Polymers with Dual Active Sites for Efficient Co-Catalyst-Free Photoelectrochemical Water Reduction in Alkaline Medium. Angewandte Chemie International Edition, 60(34), 18876-18881. https://doi.org/10.1002/anie.202104469

MLA:

Borrelli, Mino, et al. "Thiophene-Based Conjugated Acetylenic Polymers with Dual Active Sites for Efficient Co-Catalyst-Free Photoelectrochemical Water Reduction in Alkaline Medium." Angewandte Chemie International Edition 60.34 (2021): 18876-18881.

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