A carbon catalyst doped with Co and N derived from the metal-organic framework hybrid (ZIF-8@ZIF-67) for efficient oxygen reduction reaction
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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,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、氮共掺杂多孔炭材料 (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。Abstract: Carbon-based catalysts for the oxygen reduction reaction (ORR) are considered potential substitutes for the expensive platinum-based catalysts. Recently, transition metal and nitrogen co-doped carbon materials (M-N-C) have attracted much attention from researchers due to their low cost and excellent activity. A cobalt- and nitrogen-co-doped porous carbon material (Co-N@CNT-C800) was prepared by the simple one-step pyrolysis of a star fruit-like MOF hybrid (ZIF-8@ZIF-67) at 800 °C. It consisted of CNTs with substantial Co and N co-doping and had a large surface area (428 m2·g−1). It had an excellent half-wave potential and good current density in alkaline media in the ORR with values of 0.841 V and 5.07 mA·cm−2, respectively. Compared with commercial Pt/C materials it also had excellent electrochemical stability and methanol tolerance. This research provides an effective way to fabricate low cost, high activity electrocatalysts for use in energy conversion.
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Key words:
- N-doped /
- Carbon nanotubes /
- Metal-organic frameworks /
- Electrocatalyst /
- Oxygen reduction reaction
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Figure 2. (a) SEM image of ZIF-8. (b) SEM image of ZIF-8@ZIF-67. (c) High-magnification SEM image of Co-N@CNT-C800. (d, e) TEM images of Co-N@CNT-C800. (f) HRTEM image of Co-N@CNT-C800. (g) SAED patterns of Co-N@CNT-C800. (h) Elemental mapping image of C (bule), Co (red) and N (cyan) in Co-N@CNT-C800
Figure 5. (a) CVs of Co-N@CNT-C800, C-ZIF-8800, and C-ZIF-67800 in 0.1 mol L−1 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-C900 and commercially available Pt/C in O2-saturated 0.1 mol L−1 KOH solution. (c) E1/2 values of different samples. (d) Limiting current densities for different samples
Figure 6. (a) LSV curves of Co-N@CNT-C800 in 0.1 mol L−1 O2-saturated KOH electrolyte at different rotational speeds (from 400 to 2500 r min−1) (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-67800 and commercially available Pt/C
Figure 7. (a) RRDE tests (1600 r min−1) of Co-N@CNT-C800 for ORR in O2-saturated 0.1 mol L−1 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 of Co-N@CNT-C800 and the commercial Pt/C obtained at a fixed potential of 0.60 V in O2-saturated 0.1 mol L−1 KOH electrolyte at 1600 r min−1
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Supporting Information-20220012.pdf