金属有机骨架（ZIF-8@ZIF-67）衍生的Co/N共掺杂碳基催化剂在氧还原反应（ORR）中的应用研究

ZHANG Ya-ting; LI Si-yi; ZHANG Na-na; LIN Gang; WANG Rui-qi; YANG Meng-nan; LI Ke-ke

doi:10.1016/S1872-5805(22)60609-7

金属有机骨架（ZIF-8@ZIF-67）衍生的Co/N共掺杂碳基催化剂在氧还原反应（ORR）中的应用研究

doi: 10.1016/S1872-5805(22)60609-7

张亚婷^{1, 2, ,},
李思祎^{1, 2},
张娜娜^{1, 2},
林港^{1, 2},
王瑞琪^{1, 2},
杨梦囡^{1, 2},
李可可^{1, 2}

1.
西安科技大学化学与化工学院，陕西西安 710054
2.
自然资源部煤炭资源勘查与综合利用重点实验室，陕西西安 710021

基金项目: 国家自然科学基金项目(No. U1810113, U1703251)；陕西省自然科学基金项目(No. 2019JLP-12)，陕西省创新能力支持计划项目(No. 2019TD-021).

详细信息

通讯作者:
张亚婷，教授. E-mail：isyating@163.com

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出版历程
- 收稿日期: 2021-01-01
- 网络出版日期: 2022-04-22

Co/N-doped carbon catalyst derived from metal-organic framework (ZIF-8@ZIF-67) for efficient oxygen reduction reaction (ORR)

ZHANG Ya-ting^{1, 2
, ,},
LI Si-yi^{1, 2},
ZHANG Na-na^{1, 2},
LIN Gang^{1, 2},
WANG Rui-qi^{1, 2},
YANG Meng-nan^{1, 2},
LI Ke-ke^{1, 2}

1.
College of Chemistry and Chemical Engineering, Xi'an University of Science and Technology, Xi'an 710054, China
2.
Key Laboratory of Coal Resources Exploration and Comprehensive Utilization, Ministry of Natural Resources, Xi'an 710021, China

Funds: This work was supported by the National Natural Science Foundation of China (Nos. U1810113 and U1703251); Natural Science Foundation of Shaanxi(No. 2019JLP-12), Shaanxi Provincial Innovation Capability Support Program (No. 2019TD-021)

More Information

Corresponding author: ZHANG Ya-ting, Ph. D, Professor. E-mail: isyating@163.com

摘要

摘要: 在燃料电池中，碳基氧还原反应 (ORR) 催化剂被认为是昂贵的铂基催化剂的潜在替代品。近年来，由过渡金属和氮原子共掺杂的碳基材料 (M-N-C) 以其低成本和优异的活性而受到研究人员的广泛关注。在此，我们通过精心设计的杨桃状MOF (ZIF-8@ZIF-67) 为前驱体，采用简单的一步热解法制备钴、氮共掺杂多孔碳材料 (命名为Co-N@CNT-C₈₀₀)。Co-N@CNT-C₈₀₀产生了大量碳纳米管 (CNT)，独特的三维结构保证了较高的比表面积和孔隙率，有利于ORR的传质和电子传递。同时，Co-N@CNT-C₈₀₀在碱性介质中表现出优异的半波电位和极限电流密度，分别为0.841 V和5.07 mA·cm⁻²。此外，与商用Pt/C材料相比，Co-N@CNT-C₈₀₀还表现出优异的电化学稳定性和耐甲醇毒性。该策略为制备低成本、高活性的能量转换电催化剂提供了一种有效的方法。
- N掺杂 /
- 碳纳米管 /
- 金属有机骨架 /
- 电催化剂 /
- 氧还原反应
Abstract: Carbon-based oxygen reduction reaction (ORR) catalysts are considered a potential substitution for the expensive platinum-based ORR catalysts in the aspect of energy conversion. Recently, metal and nitrogen codoped carbon materials (M-N-C) formed by transition metals and nitrogen-doped carbon materials have attracted much attention from researchers due to their low cost and excellent activity. Herein, a cobalt- and nitrogen-codoped porous carbon material (Co-N@CNT-C₈₀₀) is prepared via a simple one-step pyrolysis method by well-designed carambola-shaped MOFs (ZIF-8@ZIF-67). The obtained Co-N@CNT-C₈₀₀ consists of many carbon nanotubes (CNTs) with substantial Co doping and N doping. A large surface area (428 m²·g⁻¹) and a favorable three-dimensional structure are also observed. The obtained Co-N@CNT-C₈₀₀ exhibits excellent performance in half-wave potential and limited current density in alkaline media with a value of 0.841 V and 5.07 mA·cm⁻², respectively. In addition, Co-N@CNT-C₈₀₀ also shows excellent electrochemical stability and methanol tolerance compared with commercial Pt/C materials. The proposed strategy inspires a effective way to fabricate low cost and high activity electrocatalysts used for energy conversion.
- N-doped /
- carbon nanotubes /
- Metal-organic frameworks /
- Electrocatalyst /
- Oxygen reduction reaction

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Figure 1. Schematic illustration of the preparation of the Co-N@CNT-C₈₀₀

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Figure 2. (a) ZIF-8 SEM image, (b) ZIF-8@ZIF-67 SEM image, (c) Co-N@CNT-C₈₀₀ high-magnification SEM image, (d, e) TEM images of Co-N@CNT-C₈₀₀, (f) HRTEM image of Co-N@CNT-C₈₀₀, (g) Co-N@CNT-C₈₀₀ SAED patterns, (h) Co-N@CNT-C₈₀₀ elemental mapping image (C, (bule); Co, (red); N,(cyan); ).

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Figure 3. (a) XRD patterns of Co-N@CNT-C₈₀₀, C-ZIF-67₈₀₀, and C-ZIF-8₈₀₀, (b) Raman spectra of Co-N@CNT-C₈₀₀, C-ZIF-67_800, and C-ZIF-8₈₀₀, (c) N₂ sorption isotherms of Co-N@CNT-C₈₀₀, C-ZIF-67_800, and C-ZIF-8₈₀₀, (d) The pore size distribution of the Co-N@CNT-C₈₀₀, C-ZIF-67_800, and C-ZIF-8₈₀₀.

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Figure 4. XPS spectra of Co-N@CNT-C₈₀₀. (a) survey, (b) C 1s, (c) N 1s and (d) Co 2p.

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Figure 5. (a) CVs of Co-N@CNT-C₈₀₀, C-ZIF-8_800, and C-ZIF-67₈₀₀ in 0.1 M O₂/N₂-saturated KOH electrolyte, (b) LSV curves of C-ZIF-8₈₀₀, C-ZIF-67₈₀₀, Co-N@CNT-C₇₀₀, Co-N@CNT-C₈₀₀, Co-N@CNT-C_900, and commercially available Pt/C in O₂-saturated 0.1 M KOH solution, (c) E_1/2 of different samples, (d) Limiting current density for different samples.

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Figure 6. (a) LSV curves of Co-N@CNT-C₈₀₀ in 0.1 M O₂-saturated KOH electrolyte at different rotational speeds (from 400 to 2500 rpm) (scanning rate: 10 mV s⁻¹), (b) Koutecky-Levich profiles of Co-N@CNT-C₈₀₀ catalyst obtained from Fig. 6 (a) at 0.2-0.5V, (c) The number of transferred electrons of Co-N@CNT-C₈₀₀ at 0.2-0.5 V, (d) Tafel profiles of Co-N@CNT-C₈₀₀, C-ZIF-8₈₀₀, C-ZIF-67_800, and commercially available Pt/C.

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Figure 7. (a) RRDE tests (1600 rpm) of Co-N@CNT-C₈₀₀ for ORR in O₂-saturated 0.1 M KOH electrolyte at a scan rate of 10 mV s⁻¹, (b) the number of transferred electrons and yield of H₂O₂ calculated from the RRDE results, (c) Chronoamperometric measurement of Co-N@CNT-C₈₀₀ and the commercial Pt/C by injecting 2 wt % of methanol at 300 s, (d) Chronoamperometric measurement Co-N@CNT-C₈₀₀ and the commercial Pt/C obtained at a fixed potential of 0.60 V in O₂-saturated 0.1 M KOH electrolyte at 1600 rpm.

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