Molecular Engineering of Conjugated Acetylenic Polymers for Efficient Cocatalyst‐free Photoelectrochemical Water Reduction. Issue 30 (25th June 2019)

• Record Type: Journal Article
• Authors: Sun, Hanjun; Öner, Ibrahim Halil; Wang, Tao; Zhang, Tao; Selyshchev, Oleksandr; Neumann, Christof; Fu, Yubin; Liao, Zhongquan; Xu, Shunqi; Hou, Yang; Turchanin, Andrey; Zahn, Dietrich R. T.; Zschech, Ehrenfried; Weidinger, Inez M.; Zhang, Jian; Feng, Xinliang
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 30(2019)
• Page Start: 10368
• Page End: 10374
• Publication Date: 2019-06-25
• Subjects: cocatalyst-free photocathodes -- conjugated polymers -- Glaser polycondensation -- hydrogen evolution -- molecular engineering; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201904978
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Conjugated polymers featuring tunable band gaps/positions and tailored active centers, are attractive photoelectrode materials for water splitting. However, their exploration falls far behind their inorganic counterparts. Herein, we demonstrate a molecular engineering strategy for the tailoring aromatic units of conjugated acetylenic polymers from benzene‐ to thiophene‐based. The polarized thiophene‐based monomers of conjugated acetylenic polymers can largely extend the light absorption and promote charge separation/transport. The C≡C bonds are activated for catalyzing water reduction. Using on‐surface Glaser polycondensation, as‐fabricated poly(2, 5‐diethynylthieno[3, 2‐b]thiophene) on commercial Cu foam exhibits a record H2 ‐evolution photocurrent density of 370 μA cm −2 at 0.3 V vs. reversible hydrogen electrode among current cocatalyst‐free organic photocathodes (1–100 μA cm −2 ). This approach to modulate the optical, charge transfer, and catalytic properties of conjugated polymers paves a critical way toward high‐activity organic photoelectrodes. Abstract : Photoelectrode materials for water splitting : As‐fabricated poly(2, 5‐diethynylthieno[3, 2‐b]thiophene) on Cu foam exhibits a record H2 ‐evolution photocurrent density of 370 μA cm −2 at 0.3 V vs. reversible hydrogen electrode, in comparison to current cocatalyst‐free organic photocathodes (1–100 μA cm −2 ), during water splitting. This paves a critical way towards the development of high‐activity organic photoelectrodes.