双金属导电金属有机框架材料Ni/Co-CAT的制备及其氧还原催化性能研究

doi:10.6023/A21120617

化学学报 ›› 2022, Vol. 80 ›› Issue (6): 748-755.DOI: 10.6023/A21120617 上一篇下一篇

研究论文

双金属导电金属有机框架材料Ni/Co-CAT的制备及其氧还原催化性能研究

耿元昊^a^,^b^,^c, 林小秋^a^,^b^,^c, 孙亚昕^a^,^b^,^c, 李惠雨^a^,^b^,^c, 秦悦^a^,^b^,^c, 李从举^a^,^b^,^c^,^*()

a 北京科技大学能源与环境工程学院北京 100083
b 北京科技大学北京市工业典型污染物资源化处理重点实验室北京 100083
c 北京市高校节能与环保工程研究中心北京 100083

投稿日期:2021-12-31 发布日期:2022-07-07
通讯作者: 李从举
基金资助:
国家自然科学基金(52170019); 国家自然科学基金(51973015); 中央高校基本科研业务费专项资金(06500100); 中央高校基本科研业务费专项资金(FRF-TP-19-046AIZ)

Preparation of Bimetallic Conductive Metal-organic Framework Material Ni/Co-CAT for Electrocatalytic Oxygen Reduction

Yuanhao Geng^a^,^b^,^c, Xiaoqiu Lin^a^,^b^,^c, Yaxin Sun^a^,^b^,^c, Huiyu Li^a^,^b^,^c, Yue Qin^a^,^b^,^c, Congju Li^a^,^b^,^c()

a School of Energy and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China
b Beijing Key Laboratory of Resource-oriented Treatment of Industrial Pollutants, Beijing 100083, China
c Energy Conservation and Environmental Protection Engineering Research Center in Universities of Beijing, Beijing 100083, China

Received:2021-12-31 Published:2022-07-07
Contact: Congju Li
Supported by:
National Natural Science Foundation of China(52170019); National Natural Science Foundation of China(51973015); Fundamental Research Funds for the Central Universities(06500100); Fundamental Research Funds for the Central Universities(FRF-TP-19-046AIZ)

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1. Supporting Information-A21120617.pdf(133KB)

摘要/Abstract

以2,3,6,7,10,11 -六羟基三亚苯(2,3,6,7,10,11-Hexahydroxytriphenylene, HHTP)为有机配体, Ni、Co为金属中心, 通过水热法制备了对应的儿茶酚酯盐(Ni-catecholate、Ni-Co-catecholate, 以下简称Ni-CAT和Ni-Co-CAT). 对其进行表征后, 选用单室反应器装置搭建微生物燃料电池(Microbial fuel cell, MFC). 将Ni-CAT和Ni-Co-CAT与炭黑以3∶1的质量比混合后应用于MFC阴极催化氧还原反应(Oxygen reduction reaction, ORR). 结果表明, Ni-Co-CAT催化的MFC反应器性能最好, 其MFC反应器的最大输出电压和功率密度分别为310 mV和190 mW/cm², 与商业Pt/C的性能相当. Ni-Co-CAT催化MFC的极限电流密度为2.84 mA/cm², 优于Ni-CAT的2.18 mA/cm², 表明在Ni-CAT结构中引入Co后, MFC产电效能得到了提升. 主要原因是, Ni-Co-CAT与炭黑充分混合后, 具有了更高的孔隙率和比表面积, 其结构上的金属位点M-O₆(M=Ni或Co)提供了更多的催化活性, 使Ni-Co-CAT具有最优的电化学催化性能.

关键词: 微生物燃料电池, 新型导电金属有机框架, 空气阴极, 产电效能, 氧还原反应

Ni-catecholate and Ni-Co-catecholate (hereafter referred to as Ni-CAT and Ni-Co-CAT) were prepared by hydrothermal method using 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) as the organic ligand and Ni and Co as the metal centers, respectively. After characterization, a microbial fuel cell (MFC) was constructed in a single chamber reactor device. Single chamber air cathode microbial fuel cell reactors offer the advantages of both small reactor size and no aeration. Ni-CAT and Ni-Co-CAT were mixed with carbon black in a 3∶1 mass ratio and applied to the cathode of MFC to catalyze the oxygen reduction reaction (ORR). The experiments included the preparation of M-CAT (M=Co or Ni), the preparation of air cathode and the assembly and operation of MFC. When preparing the catalytic layer of the air cathode, the conductive MOF and carbon black were mixed in a 3∶1 mass ratio to improve the catalytic effect. Furthermore, the air cathode was mixed with dispersant (isopropanol) and polytetrafluoroethylene (PTFE) to make it waterproof and breathable. The results showed that the MFC reactor catalyzed by Ni-Co-CAT had the best performance. This is due to the fact that bimetallic MOFs have stronger oxygen reduction activity compared to their monometallic counterparts. The MFC reactor catalyzed by Ni-Co-CAT had a maximum output voltage and power density of 310 mV and 190 mW/cm², respectively, which were comparable to the performance of commercial Pt/C. The limiting current density of the MFC reactor catalyzed by Ni-Co-CAT was 2.84 mA/cm², which was better than that of Ni-CAT (2.18 mA/cm²), indicating that the MFC power production efficiency was enhanced by the introduction of Co in the Ni-CAT structure. The main reason is that Ni-Co-CAT has a higher porosity and specific surface area when fully mixed with carbon black, and the metal sites M-O₆ (M=Ni or Co) on its structure provide more catalytic activity, which gives Ni-Co-CAT an optimal electrochemical catalytic performance.

Key words: microbial fuel cell, new conductive metal organic frameworks, air cathode, power generation efficiency, oxygen reaction reduction

引用此文

耿元昊, 林小秋, 孙亚昕, 李惠雨, 秦悦, 李从举. 双金属导电金属有机框架材料Ni/Co-CAT的制备及其氧还原催化性能研究[J]. 化学学报, 2022, 80(6): 748-755.

Yuanhao Geng, Xiaoqiu Lin, Yaxin Sun, Huiyu Li, Yue Qin, Congju Li. Preparation of Bimetallic Conductive Metal-organic Framework Material Ni/Co-CAT for Electrocatalytic Oxygen Reduction[J]. Acta Chimica Sinica, 2022, 80(6): 748-755.

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图/表 6

图1. (a) Ni-CAT的高倍SEM图, 放大倍数为92000倍; (b) Ni-Co-CAT的高倍SEM图, 放大倍数为90000倍; (c)沿着c轴的Ni-CAT的结构示意图[22]; (d)用于ORR的Ni-Co-CAT的结构示意图[29]; (e) Ni-Co-CAT的EDS图谱及元素质量分数

Figure 1. (a) High power SEM of Ni-CAT with a magnification of 92000 times; (b) high power SEM of Ni-Co-CAT with a magnification of 90000 time; (c) structural schematic of Ni-CAT along the c axis[22]; (d) schematic representation for the construction of Ni-Co-CATs for ORR[29]; (e) EDS pattern and elemental mass fraction of Ni-Co-CAT

图2. (a) Ni-CAT和Ni-Co-CAT的XRD图谱; (b) Ni-CAT的C 1s XPS图谱; (c) Ni-CAT的Ni 2p XPS图谱; (d) Ni-Co-CAT的C 1s XPS图谱; (e) Ni-Co-CAT的Ni 2p XPS图谱; (f) Ni-Co-CAT的Co 2p XPS图谱

Figure 2. (a) XRD patterns of Ni-CAT and Ni-Co-CAT; (b) C 1s and (c) Ni 2p XPS spectra of Ni-CAT; (d) C 1s, (e) Ni 2p and (f) Co 2p XPS spectra of Ni-Co-CAT

图3. Ni-CAT和Ni-Co-CAT的(a) N2吸附-脱附曲线和(b)孔径分布

Figure 3. N2 adsorption-desorption isotherms (a) and pore size distribution curves (b) of Ni-CAT and Ni-Co-CAT

图4. (a) Ni-CAT、Ni-Co-CAT、炭黑和Pt/C的CV曲线; (b) Ni-CAT、Ni-Co-CAT、炭黑和Pt/C的LSV曲线; (c) Ni-CAT、Ni-Co-CAT、炭黑和Pt/C的EIS曲线; (d) Ni-CAT、Ni-Co-CAT、炭黑和Pt/C的塔菲尔曲线

Figure 4. (a) CV curves of Ni-CAT, Ni-Co-CAT, carbon black and Pt/C; (b) LSV curves of Ni-CAT, Ni-Co-CAT, carbon black and Pt/C; (c) EIS curves of Ni-CAT, Ni-Co-CAT, carbon black and Pt/C; (d) Tafel curves of Ni-CAT, Ni-Co-CAT, carbon black and Pt/C

图5. (a)驯化后饰有Ni-CAT、Ni-Co-CAT、炭黑和Pt/C四种催化剂反应器的功率密度曲线; (b)驯化后饰有Ni-CAT、Ni-Co-CAT、炭黑和Pt/C四种催化剂反应器的极化曲线; (c) Ni-CAT的输出电压曲线; (d) Ni-Co-CAT的输出电压曲线; (e)炭黑的输出电压曲线; (f) Pt/C的输出电压曲线

Figure 5. (a) The power density curves of the reactor decorated with Ni-CAT, Ni-Co-CAT, carbon black and Pt/C catalysts after domestication; (b) the polarization curves of the reactor decorated with Ni-CAT, Ni-Co-CAT, carbon black and Pt/C catalysts after domestication; (c) output voltage curve of Ni-CAT; (d) output voltage curve of Ni-Co-CAT; (e) output voltage curve of carbon black; (f) output voltage curve of Pt/C

图6. Ni-Co-CAT、Ni-CAT、炭黑和Pt/C四种催化剂的COD去除率

Figure 6. COD removal rates of Ni-Co-CAT, Ni-CAT, carbon black and Pt/C catalysts

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双金属导电金属有机框架材料Ni/Co-CAT的制备及其氧还原催化性能研究

Preparation of Bimetallic Conductive Metal-organic Framework Material Ni/Co-CAT for Electrocatalytic Oxygen Reduction

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