Qin Jianyu, Zhao Mengyue, Zhang Yanfeng, Shen Jinni, Wang Xuxu
National Demonstration Center for Experimental Chemistry Education, Hebei Key Laboratory of Inorganic Nano-materials, College of Chemistry and Materials Science, Hebei Normal University, Shijiazhuang 050024 China.
National Demonstration Center for Experimental Chemistry Education, Hebei Key Laboratory of Inorganic Nano-materials, College of Chemistry and Materials Science, Hebei Normal University, Shijiazhuang 050024 China.
J Colloid Interface Sci. 2025 May;685:1109-1121. doi: 10.1016/j.jcis.2025.01.233. Epub 2025 Jan 27.
Construction of S-scheme heterojunction for photocatalytic conversion of CO into carbon-neutral fuels under sunlight is of paramount value for the sustainable development of energy. However, few reports are concerned the local structure and electronic structure of semiconductor heterojunction, which are importance of understanding the effect of heterojunction structure on the photocatalytic property. In this work, hierarchical α-FeO/g-CN S-scheme heterojunctions were manufactured via an in situ self-assembly strategy for the efficient reduction of CO. The generation rate of main product CO for optimal α-FeO/g-CN heterojunction is up to 215.8 μmol g h, with selectivity of 93.3 %, which is 17.5 and 6.1 times higher than those of pristine FeO and g-CN, respectively. The local structure and electronic structure for α-FeO/g-CN heterojunction are probed by hard X-Ray Absorption Fine Structure (XAFS) and soft X-Ray Absorption Spectroscopy (XAS), as well as density-functional theory (DFT) calculations. It is found that the Fe(d)-N(p) bond formed in α-FeO/g-CN heterojunction precisely connects the conduction band (CB) of FeO and the valence band (VB) of g-CN, which minimizes the charge transfer distance and facilitates CO photoreduction activity. This work provides important information for understanding the influence of interface local and electronic structure on the performance of photo-catalytic reduction of CO at the atomic level.
构建用于在阳光下将CO光催化转化为碳中和燃料的S型异质结对于能源的可持续发展具有至关重要的价值。然而，很少有报道关注半导体异质结的局部结构和电子结构，而这些结构对于理解异质结结构对光催化性能的影响至关重要。在这项工作中，通过原位自组装策略制备了分级α-FeO/g-CN S型异质结，用于高效还原CO。最佳α-FeO/g-CN异质结的主要产物CO的生成速率高达215.8 μmol g⁻¹ h⁻¹，选择性为93.3%，分别比原始FeO和g-CN高17.5倍和6.1倍。通过硬X射线吸收精细结构（XAFS）、软X射线吸收光谱（XAS）以及密度泛函理论（DFT）计算对α-FeO/g-CN异质结的局部结构和电子结构进行了探测。结果发现，α-FeO/g-CN异质结中形成的Fe(d)-N(p)键精确地连接了FeO的导带（CB）和g-CN的价带（VB），这使得电荷转移距离最小化，并促进了CO光还原活性。这项工作为在原子水平上理解界面局部和电子结构对CO光催化还原性能的影响提供了重要信息。
