Hefei National Laboratory for Physical Sciences at the MicroscaleCAS Key Laboratory of Soft Matter ChemistryDepartment of Polymer Science and EngineeringUniversity of Science and Technology of China Hefei 230026 P.R. China

Hefei National Laboratory of Physical Sciences at the MicroscaleCAS Center for Excellence in NanoscienceDepartment of Materials Science and EngineeringCAS Key Laboratory of Materials for Energy ConversionSynergetic Innovation of Quantum Information & Quantum TechnologyUniversity of Science and Technology of China Hefei 230026 P.R. China

National Synchrotron Radiation LaboratoryUniversity of Science and Technology of China Hefei 230029 P. R. China

Understanding the water dissociation pathways on polymer photocatalysts is critically important for developing new conjugated polymers toward solar fuel generation by virtue of their diverse bond‐forming reactions. Until now, the detailed reaction pathways on the surface active sites of polymer photocatalysts still remain unknown. Herein, we employed in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to unravel the water dissociation pathways on two‐dimensional 1,3‐diyne‐linked conjugated polymers synthesized via oxidative coupling of 1,3,5‐tris‐(4‐ethynylphenyl)‐benzene and 1,3,5‐triethynylbenzene. In addition, we also used quasi in situ X‐ray photoelectron spectroscopy (XPS) and near edge X‐ray absorption fine structure (NEXAFS) to further validate the results obtained from DRIFTS. In this way, several crucial intermediates formed during photocatalytic water splitting were identified and can be correlated to the computational results. It is shown that the water dissociation pathways are different for different polymers, exemplifying the significance of structural control in developing polymer photocatalysts. This study not only provides significant insights into the microscopic processes of the water splitting reaction catalyzed by metal‐free polymer photocatalysts but also offers essential principles for future development of metal‐free polymer photocatalysts toward solar‐to‐chemical energy conversion. 中文翻译： 理解聚合物光催化剂上的水离解途径对于开发新型共轭聚合物，因为它们的键形成反应多种多样，对太阳能燃料的生产至关重要。到目前为止，聚合物光催化剂在表面活性位上的详细反应途径仍然是未知的。本文中，我们采用了原位漫反射红外傅里叶变换光谱（DRIFTS）来揭示通过1,3,5-tris-（4-乙炔基苯基）-苯和1,3,5-三乙炔基苯。此外，我们还使用准原位X射线光电子能谱（XPS）和近边缘X射线吸收精细结构（NEXAFS）进一步验证了从DRIFTS获得的结果。这样，确定了在光催化水分解过程中形成的几种关键中间体，这些中间体可以与计算结果相关联。结果表明，对于不同的聚合物，水的离解途径是不同的，这说明了在开发聚合物光催化剂中结构控制的重要性。这项研究不仅为无金属聚合物光催化剂催化的水分解反应的微观过程提供了重要的见识，而且为无金属聚合物光催化剂未来向太阳能到化学能转化的发展提供了基本原理。举例说明了结构控制在开发聚合物光催化剂中的重要性。这项研究不仅为无金属聚合物光催化剂催化的水分解反应的微观过程提供了重要的见识，而且为无金属聚合物光催化剂未来向太阳能到化学能转化的发展提供了基本原理。举例说明了结构控制在开发聚合物光催化剂中的重要性。这项研究不仅为无金属聚合物光催化剂催化的水分解反应的微观过程提供了重要的见识，而且为无金属聚合物光催化剂未来向太阳能到化学能转化的发展提供了基本原理。