一维超薄铋系Sillén型化合物表面缺陷的可控构筑及光催化还原CO2机制研究

太阳能驱动的二氧化碳（CO2）还原将清洁可再生的太阳能转化为高附加值的碳氢燃料，被认为是一种有前景的可持续能源转化技术。光吸收，电荷分离和界面CO2催化通常被认为是太阳能CO2还原的三个关键步骤，因此开发设计合理的电子和表面结构光催化剂以优化上述关键过程具有重要意义。本项目基于铋系Sillén相关化合物一维超薄结构的构筑与结构调控，揭示影响其组成、厚度和表面缺陷的主要因素；采用原位红外测试和同位素跟踪以及色谱-质谱联用技术等，从分子水平上阐明一维超薄结构表面缺陷对光催化CO2还原反应过程和关键中间体的形成和转化机制；揭示一维超薄纳米材料微观结构与CO2催化还原活性间的定量构-效关系；利用密度泛函理论计算，结合微观动力学等多尺度方法，在原子尺度上挖掘缺陷型1D超薄结构对CO2光还原反应的反应势垒和速率决定步骤，为进一步提高光转化效率提供理论与数据支持。

Solar-driven reduction of CO2, which converts clean and renewable solar energy into value-added fuels, has been recognized as a promising sustainable energy conversion technology. As photoabsorption, separation of carriers and interfacial CO2 catalysis are generally considered to be the crucial steps during the solar CO2 reduction, it is of great significance to develop approaches to design advanced architectures and engineer the surface structures of catalysts to optimize these critical processes. Herein, one-dimensional ultrathin nanostructures of bismuth-based Sillén-related compounds with oxygen vacancy will be prepared; the main factors which affect its composition, thickness, and surface defects are revealed. The in situ FTIR measurement, isotope tracking, and chromatography-mass spectrometry were used to elucidate the photocatalytic CO2 reduction reaction process and the formation and transformation mechanism of key intermediates from the surface defects of one-dimensional ultrathin structures at the molecular level. The quantitative structure-activity relationship between the microstructure of one-dimensional ultrathin nanomaterials and the photocatalytic CO2 reduction activity will be identified. The in-depth understanding of the reaction barriers and rate-determining steps in CO2 photoreduction at the molecular level through theoretical calculation and in situ characterization techniques is desirable, which can provide theoretical and data support for the further improvement of the conversion efficiency.