Modulating the microenvironment structure of single Zn atom: ZnN4P/C active site for boosted oxygen reduction reaction

doi:10.1016/S1872-2067(22)64089-0

Abstract

Abstract:

The electronic structure of catalytic active sites can be influenced by modulating the coordination bonding of the central single metal atom, but it is difficult to achieve. Herein, we reported the single Zn-atom incorporated dual doped P, N carbon framework (Zn-N₄P/C) for ORR via engineering the surrounding coordination environment of active centers. The Zn-N₄P/C catalyst exhibited comparable ORR activity (E_1/2 = 0.86 V) and significantly better ORR stability than that of Pt/C catalyst. It also shows respectable performance in terms of maximum peak power density (249.6 mW cm^-2), specific capacitance (779 mAh g^-1), and charge-discharge cycling stability for 150 hours in Zn-air battery. The high catalytic activity is attributed to the uniform active sites, tunable electronic/geometric configuration, optimized intrinsic activity, and faster mass transfer during ORR-pathway. Further, theoretical results exposed that the Zn-N₄P configuration is more electrochemically active as compared to Zn-N₄ structure for the oxygen reduction reaction.

Key words: N-, P-doping, Oxygen reduction reaction, Zn-air battery, Single-atom catalyst, Microenvironment modulation

Syed Shoaib Ahmad Shah, Tayyaba Najam, Jiao Yang, Muhammad Sufyan Javed, Lishan Peng, Zidong Wei. Modulating the microenvironment structure of single Zn atom: ZnN₄P/C active site for boosted oxygen reduction reaction[J]. Chinese Journal of Catalysis, 2022, 43(8): 2193-2201.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64089-0

https://www.cjcatal.com/EN/Y2022/V43/I8/2193

Figures/Tables 6

Scheme 1. Schematic illustration for the fabrication of ZnN4P/C catalyst.

Fig. 1. (a,b) TEM and HR-TEM images of ZnN4P/C. (c) Aberration corrected HAADF-STEM image of ZnN4P/C. (d) HAADF-TEM image and (e) Corresponding element mapping images for ZnN4P/C.

Fig. 2. (a) N2 adsorption-desorption isotherms of ZnN4P/C and ZnN4/C (insert: pore-size distribution). (b) High-resolution XPS spectra of Zn 2p for ZnN4P/C and ZnN4/C. (c) Zn K-edge XANES spectra of ZnN4P/C, ZnO, ZnPc and Zn-foil. (d) Fourier transforms of k3-weighted Zn K-edge EXAFS of ZnN4P/C, ZnO, ZnPc and Zn-foil. (e) Corresponding EXAFS fitting in k and R space foil (inset: suggested structural model of ZnN4P/C). (f) Wavelet transforms for the k3-weighted Zn K-edge EXAFS signals of Zn-foil, ZnO, ZnPc, and ZnN4P/C.

Fig. 3. (a) RRDE curves and corresponding peroxide (%). (b) Tafel plots. (c) Comparative study of half-wave potential calculated from ORR-LSV curves and kinetic current density (Jk). (d) The electron transferred number calculated from RRDE test and corresponding peroxide yield. (e) Comparative study of long-term stability test carried out for 8000 CV-cycles.

Fig. 4. Comparative study of Zn-air battery performance. (a) The peak power density and corresponding discharge voltage curves. (b) Galvanostatic discharge voltage curves at various current densities. (c) Charge-discharge cycling performance at 10 mA cm-2 of current density. (d) Specific capacitance curves calculated at a current density of 20 mA/cm2.

Fig. 5. (a,b) Calculated charge density difference of ZnN4/C and ZnN4P/C (blue and yellow regions represent electron depletion and electron accumulation, respectively). (c) Partial density of states (PDOS) for Zn atoms of ZnN4/C, and ZnN4P/C (inset: structural models of ZnN4/C and ZnN4P/C). (d) Gibbs-free energy diagram of ZnN4/C, and ZnN4P/C calculated at U = 0 V. (e) Gibbs-free energy for the elementary reaction of ORR on ZnN4/C and ZnN4P/C models.

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Modulating the microenvironment structure of single Zn atom: ZnN₄P/C active site for boosted oxygen reduction reaction

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