ZIF-67/石墨烯复合物衍生的氮掺杂碳限域Co纳米颗粒用于高效电催化氧还原

doi:10.6023/A22040143

摘要/Abstract

燃料电池阴极氧还原(ORR)催化剂目前主要以商业Pt/C为主, 其高成本和稀缺性极大地限制了燃料电池的广泛应用. 为了替代Pt/C催化剂, 廉价高效的非贵金属催化剂目前受到了广泛的研究和关注. 利用氧化石墨烯(GO)为诱导模板, 借助表面丰富的含氧官能团, 实现了Co基金属有机框架材料(MOF) (ZIF-67)在GO表面的原位生长, 构筑了ZIF-67/GO层状复合材料. 热解过程中, 石墨烯的存在有效抑制了Co纳米颗粒的团聚, 并且很好地维持了原始的层状结构. 最终获得的Co@N-C/rGO复合催化剂材料实现了活性位的高度分散, 并且具有丰富的孔结构和优异的导电性能. 在电化学性能测试中Co@N-C/rGO表现出优异的ORR性能, 其起始电位为0.96 V, 半波电位0.83 V, 远优于ZIF-67直接热解得到的Co@N-C材料, 且性能与商业Pt/C催化剂相当. 此外, Co@N-C/rGO复合催化剂还表现出良好的催化稳定性和甲醇耐受性, 显示出该材料作为燃料电池氧还原催化剂的重要潜力.

关键词: 金属有机框架材料, 氮掺杂碳, 石墨烯, 电催化, 氧还原反应

Commercial Pt/C, with the ideal 4e^- transfer process for oxygen reduction reaction (ORR), is regarded as the optimal cathode catalyst of fuel cells at present. However, as a noble metal element, the high cost and scarcity of Pt seriously restrict the wide application of fuel cells. On account of this, cheap and high-performance non-noble metal catalysts receive extensive research attentions at present. In this work, by using graphene oxide (GO) as the template, we can realize the in-situ growth of Co-based metal organic framework (MOF) (ZIF-67) on the GO surface by means of the abundant oxygen-containing functional groups on GO, forming the ZIF-67/GO layered composite. During the pyrolysis at 700 ℃ in N₂ atmosphere, the graphene can effectively inhibit the agglomeration of Co nanoparticles with the well retained layered morphology, which can be confirmed by scanning electron microscope (SEM) and transmission electron microscopy (TEM). The X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and nitrogen isothermal adsorption tests were used to analyze the components and microstructure of obtained materials. Moreover, the catalytic performances of different material towards ORR have been also measured by cyclic voltammetry (CV) and linear sweep voltammetry (LSV) analysis in alkaline electrolyte with rotating disk electrode (RDE) at different speeds. Thanks to the high dispersion of active sites, abundant pore structures and excellent conductivity of the obtained Co@N-C/rGO composite, it shows excellent ORR performances with an initial potential of 0.96 V and a half-wave potential of 0.83 V, far superior to that of the Co@N-C catalyst obtained by direct pyrolysis of ZIF-67, and even comparable to that of commercial Pt/C catalyst. In addition, the Co@N-C/rGO composite also exhibits good catalytic stability under constant potential for 20000 s and shows favorable methanol tolerance which is better than Pt/C, demonstrating its great potential as an oxygen reduction catalyst for fuel cell applications.

Key words: metal-organic framework, nitrogen-doped carbon, graphene, electrocatalysis, oxygen reduction reaction

引用此文

闫绍兵, 焦龙, 何传新, 江海龙. ZIF-67/石墨烯复合物衍生的氮掺杂碳限域Co纳米颗粒用于高效电催化氧还原[J]. 化学学报, 2022, 80(8): 1084-1090.

Shaobing Yan, Long Jiao, Chuanxin He, Hailong Jiang. Pyrolysis of ZIF-67/Graphene Composite to Co Nanoparticles Confined in N-Doped Carbon for Efficient Electrocatalytic Oxygen Reduction[J]. Acta Chimica Sinica, 2022, 80(8): 1084-1090.

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图/表 8

图1. (a) ZIF-67和ZIF-67/GO的XRD图谱, (b) Co@N-C和 Co@N-C/rGO的XRD图谱

Figure 1. XRD patterns of (a) ZIF-67 and ZIF-67/GO, (b) Co@N-C and Co@N-C/rGO

图2. ZIF-67的(a) SEM图像与(b) TEM图像, Co@N-C的(c) SEM图像与(d) TEM图像

Figure 2. SEM (a) and TEM (b) images of ZIF-67, SEM (c) and TEM (d) images of Co@N-C

图3. (a) ZIF-67/GO的SEM图像, Co@N-C/rGO的(b) SEM图像和 (c) TEM图像. (d) Co@N-C/rGO的HRTEM图像(插图: Co@N-C/rGO的选区电子衍射(SAED)图片), (e) Co@N-C/rGO的元素分布图片

Figure 3. (a) SEM image of ZIF-67/GO, (b) SEM and (c) TEM images of Co@N-C/rGO, (d) HRTEM image (inset: the SAED image of Co@N-C/rGO), (e) elemental mapping images of Co@N-C/rGO

图4. (a) Co@N-C/rGO的高分辨Co 2p XPS谱图, (b) Co@N-C/rGO的高分辨N 1s XPS谱图

Figure 4. High-resolution spectra of Co 2p for (a) Co@N-C/rGO, high-resolution spectra of N 1s for (b) Co@N-C/rGO

图5. (a)催化剂在N2和O2条件下的CV曲线, (b)催化剂的LSV性能曲线

Figure 5. (a) The CV curves under N2 and O2 atmosphere, (b) the LSV curves of different catalysts (a) The CV curves under N2 and O2 atmosphere, (b) the LSV curves of different catalysts

催化剂	起始电位 (vs. RHE)/V	半波电位 (vs. RHE)/V	电子转移数	J_k/ (mA•cm^–2)
Co@N-C	0.94	0.79	3.11	8.84
Co@N-C/rGO	0.96	0.83	3.72	14.09
Pt/C	0.94	0.81	3.85	14.01

表1. 不同催化剂的催化性能参数对比

Table 1. The catalytic performance comparison for different catalysts

图6. (a) Co@N-C/rGO催化剂在O2饱和的0.1 mol/L KOH溶液中不同转速下的LSV曲线, (b) Co@N-C/rGO催化ORR的转移电子数

Figure 6. (a) The LSV curves for Co@N-C/rGO in O2 saturated 0.1 mol/L KOH under different rotation speeds, (b) the electron transfer number calculation for Co@N-C/rGO (a) The LSV curves for Co@N-C/rGO in O2 saturated 0.1 mol/L KOH under different rotation speeds, (b) the electron transfer number calculation for Co@N-C/rGO

图7. (a) Co@N-C/rGO和Pt/C催化剂的恒电位稳定性测试, (b)甲醇耐受性测试

Figure 7. (a) Stability tests at constant potential, (b) methanol tolerance tests for Co@N-C/rGO and Pt/C

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