Enhanced Photocatalytic Nitrogen Fixation over Nano-UiO-66(Zr) via Natural Chlorophyll Sensitization
Yangyang Sun, Tianyu Huang, Wanchang Feng, Guangxun Zhang, Houqiang Ji, Ying Zhu, Huijie Zhou, Fei Dou, Yichun Su, Zheng Liu, Meifang Yang, Huan Pang
Abstract
Metal–organic frameworks (MOFs) are potential semiconductor materials, but they still face limitations, such as insufficient photoresponse, high recombination rates, and inadequate N 2 adsorption/activation capabilities. Herein, a UiO-66-based system is designed via a natural chlorophyll sensitization strategy. Density functional theory calculations confirm the coordination interactions between chlorophyll and UiO-66. The chlorophyll-sensitized UiO-66 (Chlor@UiO-66) exhibits an improved NH 3 production rate of 73.1 μmol g –1 h –1, compared to UiO-66 (6.3 μmol g –1 h –1 ). This enhancement is attributed to the dye properties of chlorophyll and the electron-donating effect of the structure, which broadens the visible light absorption range and facilitates charge carrier separation and transfer, as well as N 2 adsorption/activation. In situ FT-IR characterization combined with theoretical calculations demonstrates that the reduction of N 2 at the Chlor@UiO-66 surface follows the alternating hydrogenation pathway. This research provides new insights for the design and synthesis of novel natural chlorophyll-sensitized nanomaterials for the photocatalysis of small molecules.