New insights on how metal clusters in MIL-68-NH2 influence the photocatalytic nitrogen fixation

IF 5.8 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Journal of Alloys and Compounds Pub Date : 2025-03-31 DOI:10.1016/j.jallcom.2025.180123

Qiufan Sun, Yuxiang Zhu, Yan Wang, Zhengtao Jia, Xiang Zhong, Jianfeng Yao

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Abstract

Three isostructural MIL-68(M)-NH₂ frameworks (M = In, Fe, or Al) featuring different metal centers were synthesized to investigate their photocatalytic activities for nitrogen fixation. The influence of the metaloxo clusters on the crystalline structures, morphologies, and optical characteristics was examined. MIL-68(In)-NH₂ (MNI) with one-dimensional microrod structures has a larger surface area than bulk MIL-68(Fe)-NH₂ (MNF) and spherical MIL-68(Al)-NH₂ (MNA), and achieves an ammonia generation rate (140.34 μmol g_cat⁻¹ h⁻¹) ca. 3.4 and 1.6 times higher than those of MNF (37.25 μmol g_cat⁻¹ h⁻¹) and MNA (87.5 μmol g_cat⁻¹ h⁻¹), respectively. The superior performance can be attributed to its high crystallinity, strong coordination between the In−oxo clusters and ligands, and microrod morphology, which enhance electron transfer, improve mass transport, and extend visible light absorption. Moreover, MNI shows greater stability in ethanol aqueous solution than other sacrificial reagents, such as methanol, potassium sulfite, and triethanolamine. While slight surface corrosion of the microrods occurs in methanol and potassium sulfite solutions, complete collapse is observed in triethanolamine.

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MIL-68-NH2中金属簇如何影响光催化固氮的新见解

合成了三个具有不同金属中心的MIL-68(M)-NH2框架（M = In, Fe, Al），研究了它们的光催化固氮活性。研究了金属氧团簇对晶体结构、形貌和光学特性的影响。具有单维微棒结构的MIL-68(In)-NH2 （MNI）比块状MIL-68(Fe)-NH2 （MNF）和球形MIL-68(Al)-NH2 （MNA）表面积更大，氨生成速率为140.34 μmol gcat-1 h-1，分别是MNF （37.25 μmol gcat-1 h-1）和MNA （87.5 μmol gcat-1 h-1）的3.4倍和1.6倍。优异的性能可归因于其高结晶度，In -氧簇与配体之间的强配位以及微棒形态，从而增强了电子转移，改善了质量传递，并延长了可见光吸收。此外，MNI在乙醇水溶液中表现出比其他牺牲试剂（如甲醇、亚硫酸钾和三乙醇胺）更大的稳定性。微棒在甲醇和亚硫酸钾溶液中发生轻微的表面腐蚀，而在三乙醇胺中观察到完全崩溃。

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来源期刊

Journal of Alloys and Compounds 工程技术-材料科学：综合

CiteScore

11.10

自引率

14.50%

发文量

5146

审稿时长

67 days

期刊介绍： The Journal of Alloys and Compounds is intended to serve as an international medium for the publication of work on solid materials comprising compounds as well as alloys. Its great strength lies in the diversity of discipline which it encompasses, drawing together results from materials science, solid-state chemistry and physics.