具有丰富活性位点和高电子传导性的非晶MOF用于高效肼氧化

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

催化学报 ›› 2024, Vol. 60: 351-359.DOI: 10.1016/S1872-2067(24)60035-5

具有丰富活性位点和高电子传导性的非晶MOF用于高效肼氧化

丁婕婷^a, 王浩帆^a, 沈葵^a, 韦小明^b, 陈立宇^a^,^*(), 李映伟^a^,^*()

^a华南理工大学化学与化工学院广东省燃料电池技术重点实验室, 广东广州 510640
^b华南理工大学物理与光电学院, 广东广州 510640

收稿日期:2024-01-22 接受日期:2024-03-28 出版日期:2024-05-18 发布日期:2024-05-23
通讯作者: *电子信箱: liyuchen@scut.edu.cn (陈立宇), liyw@scut.edu.cn (李映伟).
基金资助:
国家自然科学基金(21825802);国家自然科学基金(22138003);国家自然科学基金(22108083);国家自然科学基金(22378136);制浆造纸工程国家重点实验室项目(2022C04);制浆造纸工程国家重点实验室项目(2022ZD05);制浆造纸工程国家重点实验室项目(2023PY06);广东省珠江人才计划项目(2021ZT09Z109);广东省珠江人才计划项目(2021QN02C8);广东省自然科学基金(2023B1515040005);广东省自然科学基金(2023A1515010312);广东省自然科学基金(2024A1515011196);广州市科技计划项目(202201010118);广州市科技计划项目(2023A04J0674);清远市科技计划项目(2021YFJH01002);中央高校基本科研业务费项目(2022ZYGXZR017);中央高校基本科研业务费项目(2022ZYGXZR108);中央高校基本科研业务费项目(2022ZYGXZR048)

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

Jieting Ding^a, Hao-Fan Wang^a, Kui Shen^a, Xiaoming Wei^b, Liyu Chen^a^,^*(), Yingwei Li^a^,^*()

^aGuangdong Provincial Key Laboratory of Fuel Cell Technology, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China
^bSchool of Physics and Optoelectronics, South China University of Technology, Guangzhou 510640, Guangdong, China

Received:2024-01-22 Accepted:2024-03-28 Online:2024-05-18 Published:2024-05-23
Contact: *E-mail: liyuchen@scut.edu.cn (L. Chen), liyw@scut.edu.cn (Y. Li).
Supported by:
National Natural Science Foundation of China(21825802);National Natural Science Foundation of China(22138003);National Natural Science Foundation of China(22108083);National Natural Science Foundation of China(22378136);State Key Laboratory of Pulp and Paper Engineering(2022C04);State Key Laboratory of Pulp and Paper Engineering(2022ZD05);State Key Laboratory of Pulp and Paper Engineering(2023PY06);Guangdong Pearl River Talents Program(2021ZT09Z109);Guangdong Pearl River Talents Program(2021QN02C8);Natural Science Foundation of Guangdong Province(2023B1515040005);Natural Science Foundation of Guangdong Province(2023A1515010312);Natural Science Foundation of Guangdong Province(2024A1515011196);Science and Technology Program of Guangzhou(202201010118);Science and Technology Program of Guangzhou(2023A04J0674);Science and Technology Program of Qingyuan City(2021YFJH01002);Fundamental Research Funds for the Central Universities(2022ZYGXZR017);Fundamental Research Funds for the Central Universities(2022ZYGXZR108);Fundamental Research Funds for the Central Universities(2022ZYGXZR048)

摘要/Abstract

摘要：

金属有机框架(MOF)虽然具有完美的结晶性质, 但由于其配位不饱和位点数量不足和电子传导性较低, 这些特性限制了它在电催化领域的应用. 尽管通过去除部分有机配体可以暴露晶体MOF的一些金属位点, 但常用的方法涉及高压、高温、强酸、强碱等苛刻的条件, 很容易造成MOF的多孔结构完全坍塌. 相较于晶态MOF, 非晶态MOF具有短程有序而长程无序的结构特征. 通过快速组装MOF, 有望实现MOF的非晶化, 从而创造大量不饱和位点, 并优化金属位点的电子结构. 因此, 开发高效的非晶态MOF合成策略十分必要.

本文报道了一种诱导非晶态MOF在碳布上快速组装的电合成方法, 制得了具有丰富活性位点和高电子传导性的非晶态MOF(记为aMnFc'/CC). 在电合成过程中, 有机配体在碳布上迅速去质子化, 并与金属离子快速组装, 形成具有大量配位不饱和Mn位点的非晶态aMnFc'. X射线衍射和透射电镜选区电子衍射结果表明, aMnFc'为无定形结构. 电子顺磁共振和X射线吸收近边结构光谱等表明, aMnFc'比cMnFc'含有更多的不饱和Mn金属中心. 随后, 利用三电极体系评估催化剂在肼氧化(HzOR)中的催化活性, 在0.1 mol L⁻¹ PBS + 0.4 mol L⁻¹ N₂H₄电解质中, aMnFc'/CC的起始电位为287 mV (1 mA cm⁻²), 在10 mA cm⁻²下的工作电势为667 mV, 其活性远优于晶态MOF (起始电位为540 mV (1 mA cm⁻²)), 在10 mA cm⁻²下的工作电势为871 mV). aMnFc'/CC在0.1 mol L⁻¹ PBS中的HzOR性能优于大多数已报道的Mn/Fe基催化剂和MOFs催化剂. 四探针法测定cMnFc'和aMnFc'的电导率分别为1.5 × 10⁻⁴和1.8 × 10⁻³ S cm⁻², 表明MOF的非晶化可以提高电导率, 从而增强其电化学性能. 密度泛函理论计算表明, MnFc'-V在费米能级附近的态密度比MnFc'的态密度更强, 说明不饱和Mn中心的存在增强了MOF的导电性. 进一步通过理论计算研究了肼在MnFc'和MnFc'-V表面的逐步脱氢过程, 结果发现, MnFc'和MnFc'-V的决速步都是从*N₂H₃到*N₂H₂的脱氢过程, 其中MnFc'-V的自由能差(0.22 eV)远小于MnFc'的自由能差(0.65 eV). 由此可见, 在aMnFc'中, 不饱和Mn位点使d带中心更接近费米能级, 增强了活性位对N_xH_x中间体的吸附能, 从而提高了HzOR活性.

综上, 本文提出一种电合成方法, 实现了非晶态MOF在碳布上的快速组装, 制备出具有丰富活性位点和高电子传导性的非晶态MOF, 显著提升了其在肼氧化反应中的催化活性. 这一新策略不仅克服了晶态MOF在电催化应用中的局限, 而且为工业电流条件下合成用于HzOR的非晶态MOF提供了参考.

关键词: 非晶化, 缺陷, 电催化, 肼氧化反应, 金属有机框架

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

丁婕婷, 王浩帆, 沈葵, 韦小明, 陈立宇, 李映伟. 具有丰富活性位点和高电子传导性的非晶MOF用于高效肼氧化[J]. 催化学报, 2024, 60: 351-359.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60035-5

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

图/表 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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具有丰富活性位点和高电子传导性的非晶MOF用于高效肼氧化

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

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