Citation: Yu-Xuan CHEN, Yu GONG, Wen-Da ZHANG, Xiao-Dong YAN, Zhi-Guo GU. An Iron(Ⅱ) Metal-Organic Layer: Synthesis, Structure and Ultrafast Biomimetic Catalytic Performance[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(3): 519-527. doi: 10.11862/CJIC.2022.060 shu

An Iron(Ⅱ) Metal-Organic Layer: Synthesis, Structure and Ultrafast Biomimetic Catalytic Performance

School of Chemistry and Material Engineering, Jiangnan University, Wuxi, Jiangsu 214122, China

Corresponding author: Zhi-Guo GU, zhiguogu@jiangnan.edu.cn
Received Date: 14 November 2021
Revised Date: 13 January 2022

Figures(6)

A new two-dimensional metal-organic framework (Fe-MOF) was self-assembled by ferrous tetrafluoroborate hexahydrate, potassium tetracyanoplatinate trihydrate, and 4-picoline-N-oxide in water and ethanol. Singlecrystal X-ray crystallography reveals that Fe-MOF crystallized in the monoclinic space group P2₁/c. [Pt(CN)₄]^2- is bridged by four Fe atoms through the cyano group, while Fe atom is connected with four N atoms from [Pt(CN)₄]^2-, forming Fe-MOF with (4, 4)-grid structure. Fe-MOF is stacked by a two-dimensional layer in an AB mode along the caxis by virtue of van der Waals forces, and the layer distance is 0.6 nm. The Fe(Ⅱ) centers have two [FeN₄O₂] octahedral coordination environments: one of them is connected axially with two water molecules, while the other is connected axially with a water molecule and a 4-picoline-N-oxide. Metal-organic layer (Fe-MOL) was prepared by ultrasonically exfoliating Fe-MOF. Fe-MOL maintained the two-dimensional crystalline structure as evidenced by infrared spectroscopy (FT-IR) and X-ray powder diffraction (PXRD). Scanning electron microscope (SEM) and transmission electron microscope (TEM) characterizations showed that Fe-MOL had a nanolayered structure. Fe-MOL was proved to be an ultra-thin layered structure of about 5 nm by atomic force microscopy (AFM). Fe-MOL exhibited ultrafast catalytic speed and ultrahigh catalytic efficiency in the catalytic oxidation reaction of 2, 2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) due to the coordination environment of the Fe(Ⅱ) center possessing a similar natural heme structure. The color of the solution changed from colorless to dark green in just 16 s, and the apparent second-order rate constant (k_cat/K_m; k_cat is catalytic constant, K_m is Michaelis constant) was as high as 4.70×10⁶ mmol^-1·L·s^-1. Fe-MOL exhibited good cycle stability and it still had 90% catalytic activity after five catalytic cycles. The excellent catalytic efficiency of Fe-MOL exceeded most of the reported MOF biomimetic catalysts.
- 2D metal-organic framework,
- ultrasonic exfoliation,
- metal-organic layer,
- biomimetic catalysis,
- catalysis rate
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