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
Center for Advancing Electronics Dresden (cfaed) and Department of Chemistry and Food Chemistry, Dresden University of Technology, Mommsenstrasse 4, 01062, Dresden, Germany.
Chair of Electrochemistry, Dresden University of Technology, 01062, Dresden, Germany.
Angew Chem Int Ed Engl. 2019 Jul 22;58(30):10368-10374. doi: 10.1002/anie.201904978. Epub 2019 Jun 25.
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 H -evolution photocurrent density of 370 μA cm at 0.3 V vs. reversible hydrogen electrode among current cocatalyst-free organic photocathodes (1-100 μA cm ). This approach to modulate the optical, charge transfer, and catalytic properties of conjugated polymers paves a critical way toward high-activity organic photoelectrodes.
具有可调带隙/位置和定制活性中心的共轭聚合物是用于水分解的有吸引力的光电极材料。然而，它们的研究进展远远落后于无机同类材料。在此，我们展示了一种分子工程策略，用于将共轭炔聚合物的芳香单元从基于苯的调整为基于噻吩的。共轭炔聚合物的极化噻吩基单体可以大大扩展光吸收并促进电荷分离/传输。C≡C键被激活用于催化水还原。使用表面Glaser缩聚反应，在商用泡沫铜上制备的聚（2,5-二乙炔基噻吩并[3,2-b]噻吩）在0.3 V相对于可逆氢电极时，在当前无共催化剂的有机光阴极（1 - 100 μA cm）中表现出创纪录的370 μA cm的析氢光电流密度。这种调节共轭聚合物光学、电荷转移和催化性能的方法为制备高活性有机光电极铺平了关键道路。
