Piercy Verity L, Saeed Khezar H, Prentice Andrew W, Neri Gaia, Li Chao, Gardner Adrian M, Bai Yang, Sprick Reiner Sebastian, Sazanovich Igor V, Cooper Andrew I, Rosseinsky Matthew J, Zwijnenburg Martijn A, Cowan Alexander J
Stephenson Institute for Renewable Energy and Department of Chemistry, University of Liverpool, Liverpool L69 7ZF, U.K.
Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, U.K.
J Phys Chem Lett. 2021 Nov 11;12(44):10899-10905. doi: 10.1021/acs.jpclett.1c03073. Epub 2021 Nov 3.
Polymer photocatalysts are a synthetically diverse class of materials that can be used for the production of solar fuels such as H, but the underlying mechanisms by which they operate are poorly understood. Time-resolved vibrational spectroscopy provides a powerful structure-specific probe of photogenerated species. Here we report the use of time-resolved resonance Raman (TR) spectroscopy to study the formation of polaron pairs and electron polarons in one of the most active linear polymer photocatalysts for H production, poly(dibenzo[,]thiophene sulfone), P10. We identify that polaron-pair formation prior to thermalization of the initially generated excited states is an important pathway for the generation of long-lived photoelectrons.
聚合物光催化剂是一类合成多样的材料，可用于生产诸如氢气等太阳能燃料，但人们对其运作的潜在机制了解甚少。时间分辨振动光谱为光生物种提供了一种强大的结构特异性探针。在此，我们报告了使用时间分辨共振拉曼光谱来研究在用于氢气生产的最具活性的线性聚合物光催化剂之一聚（二苯并[，]噻吩砜）（P10）中极化子对和电子极化子的形成。我们确定，在最初产生的激发态热化之前形成极化子对是产生长寿命光电子的重要途径。
