Chelating Metal Ions in a Metal-Organic Framework for Constructing a Biomimetic Catalyst Through Post-modification

doi:10.1007/s40242-022-2125-7

高等学校化学研究 ›› 2022, Vol. 38 ›› Issue (6): 1542-1546.doi: 10.1007/s40242-022-2125-7

Chelating Metal Ions in a Metal-Organic Framework for Constructing a Biomimetic Catalyst Through Post-modification

PANG Kuan^1,4, XUE Huan¹, LIU Haixiong¹, SUN Jing², LIU Tianfu^1,3,4

1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China;
2. School of Electronic Information and Electrical Engineering, Shangluo University, Shangluo 726000, P. R. China;
3. Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou 350108, P. R. China;
4. University of Chinese Academy of Sciences, Beijing 100049, P. R. China

收稿日期:2022-04-10 出版日期:2022-12-01 发布日期:2022-12-06
通讯作者: SUN Jing, LIU Tianfu E-mail:202207@slxy.edu.cn;tfliu@fjirsm.ac.cn
基金资助:
This work was supported by the National Key Research and Development Program of China(No.2018YFA0704502), the National Natural Science Foundation of China(No.22033008), and the Foundation of Director of Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China(Nos.2021ZZ103, 2021ZR105).

Chelating Metal Ions in a Metal-Organic Framework for Constructing a Biomimetic Catalyst Through Post-modification

PANG Kuan^1,4, XUE Huan¹, LIU Haixiong¹, SUN Jing², LIU Tianfu^1,3,4

1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China;
2. School of Electronic Information and Electrical Engineering, Shangluo University, Shangluo 726000, P. R. China;
3. Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou 350108, P. R. China;
4. University of Chinese Academy of Sciences, Beijing 100049, P. R. China

Received:2022-04-10 Online:2022-12-01 Published:2022-12-06
Contact: SUN Jing, LIU Tianfu E-mail:202207@slxy.edu.cn;tfliu@fjirsm.ac.cn
Supported by:
This work was supported by the National Key Research and Development Program of China(No.2018YFA0704502), the National Natural Science Foundation of China(No.22033008), and the Foundation of Director of Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China(Nos.2021ZZ103, 2021ZR105).

摘要/Abstract

摘要： Crystal engineering, as a burgeoning technology, has been widely used to construct metalloporphyrins biomimetic catalysts. Herein, a bimetallic metal-organic framework (MOF) was constructed by 4-(4-carboxyphenyl)-1,2,4-triazole ligand, Co²⁺ and Zr⁴⁺ metal ions by solvothermal reaction(named PFC-88). A N,N-chelation site was found between the two adjacent ligands in PFC-88, consequently a porphyrin-like structure was obtained through chelating Fe³⁺ in this site by post-modification, named PFC-88-Fe. The result of a single crystal X-ray technology verified that Fe ions were successfully metalated in the N,N-chelation site of PFC-88, which is assisted by the X-ray absorption near-edge structure(XANES) spectra. An o-phenylenediamine oxidation reaction was applied to assessing the catalytic activity of PFC-88-Fe, in which the absorbance increases of phenazine-2,3-diamine at λ=418 nm were recorded by absorption spectroscopy in kinetic mode, exhibiting the application potential as a biomimetic catalyst.

关键词: Metal-organic framework(MOF), Bimetallic MOF, Crystal structure, Metalation

Abstract: Crystal engineering, as a burgeoning technology, has been widely used to construct metalloporphyrins biomimetic catalysts. Herein, a bimetallic metal-organic framework (MOF) was constructed by 4-(4-carboxyphenyl)-1,2,4-triazole ligand, Co²⁺ and Zr⁴⁺ metal ions by solvothermal reaction(named PFC-88). A N,N-chelation site was found between the two adjacent ligands in PFC-88, consequently a porphyrin-like structure was obtained through chelating Fe³⁺ in this site by post-modification, named PFC-88-Fe. The result of a single crystal X-ray technology verified that Fe ions were successfully metalated in the N,N-chelation site of PFC-88, which is assisted by the X-ray absorption near-edge structure(XANES) spectra. An o-phenylenediamine oxidation reaction was applied to assessing the catalytic activity of PFC-88-Fe, in which the absorbance increases of phenazine-2,3-diamine at λ=418 nm were recorded by absorption spectroscopy in kinetic mode, exhibiting the application potential as a biomimetic catalyst.

Key words: Metal-organic framework(MOF), Bimetallic MOF, Crystal structure, Metalation

PANG Kuan, XUE Huan, LIU Haixiong, SUN Jing, LIU Tianfu. Chelating Metal Ions in a Metal-Organic Framework for Constructing a Biomimetic Catalyst Through Post-modification[J]. 高等学校化学研究, 2022, 38(6): 1542-1546.

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Chelating Metal Ions in a Metal-Organic Framework for Constructing a Biomimetic Catalyst Through Post-modification

Chelating Metal Ions in a Metal-Organic Framework for Constructing a Biomimetic Catalyst Through Post-modification

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