Amorphization of MOFs with rich active sites and high electronic conductivity for hydrazine oxidation

doi:10.1016/S1872-2067(24)60035-5

Abstract

Abstract:

The applications of metal-organic frameworks (MOFs) in electrocatalysis are limited by the perfect crystalline nature with insufficient coordinatively unsaturated sites and low electronic conductivity. Here, we report an electrosynthesis method to induce rapid assembly of amorphous MOFs on carbon cloth (denoted as aMnFc'/CC), achieving the amorphization of MOFs with rich active sites and high electronic conductivity. The long-range disordered structure of aMnFc'/CC forms a large number of oxygen vacancies to modify the coordination and electronic structures of Mn sites. In the electrocatalytic hydrazine oxidation reaction (HzOR), the aMnFc'/CC electrocatalyst exhibits superior activity to its crystalline MOF counterparts. Density functional theory calculations reveal that the unsaturated Mn centers present in aMnFc'/CC facilitate efficient electron transfer while simultaneously lowering the free energy of the rate-determining step in the HzOR process.

Key words: Amorphization, Defect, Electrocatalysis, Hydrazine oxidation reaction, Metal-organic framework

Jieting Ding, Hao-Fan Wang, Kui Shen, Xiaoming Wei, Liyu Chen, Yingwei Li. Amorphization of MOFs with rich active sites and high electronic conductivity for hydrazine oxidation[J]. Chinese Journal of Catalysis, 2024, 60: 351-359.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60035-5

https://www.cjcatal.com/EN/Y2024/V60/I5/351

Figures/Tables 4

Fig. 1. Synthesis and microstructure of cMnFc'/CC and aMnFc'/CC. (a) Schematic synthesis process of cMnFc'/CC and aMnFc'/CC. SEM (b1,c1), TEM (b2,c2), HRTEM (b3,c3) images and SAED patterns (insets), HAADF-STEM (b4) and the corresponding EDS elemental mapping images (c4) of cMnFc'/CC (b) and aMnFc'/CC (c).

Fig. 2. Characterizations of cMnFc' and aMnFc'. (a) XRD patterns of cMnFc', aMnFc', cMnFc'/CC, and aMnFc'/CC. (b) FT-IR spectra of cMnFc', aMnFc', and Fc'. The high-resolution Mn 2p XPS spectra (c), Mn K-edge XANES spectra (d), Mn K-edge k3χ(k) oscillation curves (e), Fourier-transform EXAFS spectra (f), and the WT contour plots (g-j) of cMnFc' and aMnFc'.

Fig. 3. Electrochemical performance of electrodes for the HzOR. (a) LSV curves of cMnFc'/CC and aMnFc'/CC without iR compensation. (b) Onset potential and overpotentials at 10 mA cm?2. (c) Comparison of the onset potentials for aMnFc'/CC with the reported MOF catalysts. (d) Tafel plots of aMnFc'/CC and cMnFc'/CC in 0.1 mol L?1 PBS/0.4 mol L?1 N2H4. (e) EIS of samples recorded at a constant potential of 0.8 V (vs. RHE). (f) LSV polarization curves of aMnFc'/CC and cMnFc'/CC normalized by ECSA. (g) In-situ Raman spectra of aMnFc'/CC in HzOR. (h) The i-t test of aMnFc'/CC at 0.8 V (vs. RHE). (i) LSV curves of different aMFc' materials.

Fig. 4. DFT calculations of N2H4 oxidation performance. The DOS calculated for MnFc' (a) and MnFc'-V (b). (c) The electron density difference plots of corresponding MnFc' and MnFc'-V. (d) Free energy profile for the HzOR process on MnFc', and MnFc'-V. Optimized geometric configurations of various reaction intermediates along the reaction path of hydrazine oxidation on MnFc'-V (inset). (e) The local structures and charge difference maps of the MnFc', and MnFc'-V for *N2H3 adsorption at the RDS step for HzOR. The yellow and blue isosurfaces donate electron gain and loss, respectively.

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