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Updated: May 13, 2026

Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Dual-tuning of morphology and coordination in single-atom catalysts via organic linker engineering for singlet
Hongda Liu1, Weiping Xiong1, Yang Liu2
1College of Environmental Science and Engineering, Hunan University and Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha 410082, China.
Abstract:
In metal-organic framework (MOF)-derived single-atom catalysts (SACs), pyrolyzed organic linkers function as both carbon precursors and coordination shell providers for the metal centers. Therefore, the judicious selection of organic linkers, such as those containing pyridine N (2-methylimidazole) or O (terephthalic acid), can readily "encode" the coordination microenvironment at the final single-atom site. Guided by this linker-encoding principle, we tailor these organic linkers within MOFs to construct two SACs (70-Fe-ZIF-8-900 and 8-Fe-MOF-5-900) with distinct optimal Fe loadings (0.94% and 0.03%, respectively), which achieve precise control over structural morphology and coordination environment. Remarkably, 8-Fe-MOF-5-900 with Fe-C1O3 sites, despite its ultralow Fe loading, exhibits phenol degradation activity 2.69 times higher than that of 70-Fe-ZIF-8-900 in the peroxymonosulfate (PMS) system, underscoring exceptional atomic utilization efficiency. The tailored electronic configuration, featuring an elevated d-band center and increased electron density around iron, enhances PMS activation and induces a singlet oxygen-driven mechanism. Quantitative structure-activity relationship models reveal strong linear correlations (R2 = 0.716-0.855) between the catalytic rate constant and key electronic-structure descriptors in 8-Fe-MOF-5-900/PMS system, demonstrating high predictability for oxidation activity. Overall, this work offers a conceptual framework for designing advanced oxidation processes with controllable redox reactivity, tunable selectivity, and 1O2-dominated catalytic pathways.
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