School of Chemistry and Chemical Engineering, Yancheng Institute of Technology, Yancheng 224051, China.
College of Chemistry and Materials Science, Jiangsu Key Laboratory of Bio-Functional Materials, Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials, Key Laboratory of Applied Photochemistry, Nanjing Normal University, Nanjing 210023, China.
Nanoscale. 2023 Feb 16;15(7):3542-3549. doi: 10.1039/d2nr06264j.
Metal-organic framework (MOF)-based heterostructures have aroused widespread interest owing to their extensive compositional tunability and interesting catalytic properties. However, the precise edge-oriented growth of transition metal compounds at the edges of 2D MOFs to construct edge mode heterostructures remains a great challenge due to their inherent thermodynamic instability. Here, edge-oriented growth of NiP at the edges of a 2D Ni-MOF was achieved for the first time by precisely tuning the phosphorus source content and phosphating temperature. Owing to the formation of the edge mode Ni-MOF/NiP heterostructure, the as-prepared heterostructure showed upregulated d-band center, more robust 4-nitrophenol (4-NP) adsorption capacity, lowered energy barrier of the rate-determining step (RDS), and higher specific surface area, resulting in the best performance of the hydrogenation reduction of 4-NP to 4-aminophenol (4-AP) in the presence of non-precious metal catalysts.
基于金属有机骨架（MOF）的杂化材料由于其广泛的组成可调性和有趣的催化性能而引起了广泛的关注。然而，由于过渡金属化合物的固有热力学不稳定性，要在二维 MOF 的边缘精确地定向生长过渡金属化合物以构建边缘模式杂化材料仍然是一个巨大的挑战。在这里，首次通过精确调控磷源含量和磷化温度，实现了 NiP 在二维 Ni-MOF 边缘的定向生长。由于形成了边缘模式的 Ni-MOF/NiP 杂化结构，所制备的杂化结构表现出上调的 d 带中心、更强的 4-硝基苯酚（4-NP）吸附能力、更低的速率决定步骤（RDS）能量势垒和更高的比表面积，从而在非贵金属催化剂存在下，对 4-NP 加氢还原为 4-氨基酚（4-AP）表现出最佳性能。
