Pyrolysis of ZIF-67/Graphene Composite to Co Nanoparticles Confined in N-Doped Carbon for Efficient Electrocatalytic Oxygen Reduction

doi:10.6023/A22040143

Abstract

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

Cite this article

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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Fig. & Tab. 8

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

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

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

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

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

Table 1. The catalytic performance comparison for different catalysts

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

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

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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