Scalable fabrication and active site identification of MOF shell-derived nitrogen-doped carbon hollow frameworks for oxygen reduction

doi:10.1016/j.jmst.2020.07.007

Abstract

Abstract:

Nitrogen-doped carbon materials as promising oxygen reduction reaction (ORR) electrocatalysts attract great interest in fuel cells and metal-air batteries because of their relatively high activity, high surface area, high conductivity and low cost. To maximize their catalytic efficiency, rational design of efficient electrocatalysts with rich exposed active sites is highly desired. Besides, due to the complexity of nitrogen species, the identification of active nitrogen sites for ORR remains challenging. Herein, we develop a facile and scalable template method to construct high-concentration nitrogen-doped carbon hollow frameworks (NC), and reveal the effect of different nitrogen species on their ORR activity on basis of experimental analysis and theoretical calculations. The formation mechanism is clearly revealed, including low-pressure vapor superassembly of thin zeolitic imidazolate framework (ZIF-8) shell on ZnO templates, in situ carbonization and template removal. The obtained NC-800 displays better ORR activity compared with other NC-700 and NC-900 samples. Our results indicate that the superior ORR activity of NC-800 is mainly attributed to its content balance of three nitrogen species. The graphitic N and pyrrolic N sites are responsible for lowering the working function, while the pyridinic N and pyrrolic N sites as possible active sites are beneficial for increasing the density of states.

Key words: MOF shell, Nitrogen-doped carbon, Hollow framework, Oxygen reduction, Active nitrogen sites

Jiashen Meng, Ziang Liu, Xiong Liu, Wei Yang, Lianzhou Wang, Yan Li, Yuan-Cheng Cao, Xingcai Zhang, Liqiang Mai. Scalable fabrication and active site identification of MOF shell-derived nitrogen-doped carbon hollow frameworks for oxygen reduction[J]. J. Mater. Sci. Technol., 2021, 66: 186-192.

Figures/Tables 6

Fig. 1. Schematic illustration of the template formation process of nitrogen-doped carbon hollow frameworks, including low-pressure vapor superassembly, in situ carbonization and template removal.

Fig. 2. Characterizations of core-shell ZnO@ZIF-8 nanoparticles. (a) SEM image. (b) TEM image. (c) XRD pattern. (d) FTIR spectra of ZnO, ZIF-8 and ZnO@ZIF-8. (e, f) N2 adsorption-desorption isotherms and pore size distribution of ZnO and ZnO@ZIF-8 nanoparticles. (g-k) SEM image and corresponding EDS elemental maps of Zn, N, C and O.

Fig. 3. Characterizations of nitrogen-doped carbon hollow frameworks. (a, b) SEM images. (c, d) TEM images. (e) HRTEM image. (f) SAED pattern. (g-j) HAADF-STEM image and the corresponding EDS elemental maps for C, N and O.

Fig. 4. Structural characterizations of the obtained NC-700, NC-800 and NC-900 samples. (a) XRD patterns. (b) Raman spectra. (c) The relative contents of C, N and H obtained from elemental analysis. (d) XPS spectra. (e) High-resolution N 1s XPS spectra, which were divided into pyridinic N, pyrrolic N and graphitic N. (f) The corresponding contents.

Fig. 5. ORR electrocatalytic performances of NC-700, NC-800 and NC-900 samples. (a) LSV curves of NC-700, NC-800 and NC-900 samples in O2-saturated 0.1 M KOH at a scan rate of 5 mV·s-l and 1600 rpm. (b) Jk at 0.8 V and E1/2 for NC-700, NC-800 and NC-900 samples, respectively. (c) LSV curves of NC-800 in O2-saturated 0.1 M KOH at a scan rate of 5 mV·s-l and different rotation rates. Inset of (c) is Koutecky-Levich plots and electron transfer number. (d) RRDE voltammograms recorded with NC-800 in O2-saturated 0.1 M KOH at 1600 rpm. (e) Peroxide yields and electron numbers of NC-800 at various potentials based on RRDE data. (f) Chronoamperometric curves of NC-800 and Pt/C in O2-saturated 0.1 M KOH at 1225 rpm and 0.8 V versus RHE.

Fig. 6. (a) Schematic model of a graphene sheet with a hole. (b) Work function summary of pure graphene and various N-doped graphene with different nitrogen species and contents. (c) Calculated total densities of states of pure Gr, graphitic N-Gr (8.06 %), pyridinic N-Gr (8.06 %) and pyrrolic N-Gr (7.81 %) near the Fermi level. (d-g) The corresponding electron density differences in different N-doped graphene structures. Brown and gray balls represent C and N atoms, respectively. Yellow and blue areas represent the increased and decreased electron density, respectively.

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