Chalcogen heteroatoms doped nickel-nitrogen-carbon single-atom catalysts with asymmetric coordination for efficient electrochemical CO2 reduction

doi:10.1016/S1872-2067(24)60103-8

Abstract

Abstract:

The electronic configuration of central metal atoms in single-atom catalysts (SACs) is pivotal in electrochemical CO₂ reduction reaction (eCO₂RR). Herein, chalcogen heteroatoms (e.g., S, Se, and Te) were incorporated into the symmetric nickel-nitrogen-carbon (Ni-N₄-C) configuration to obtain Ni-X-N₃-C (X: S, Se, and Te) SACs with asymmetric coordination presented for central Ni atoms. Among these obtained Ni-X-N₃-C (X: S, Se, and Te) SACs, Ni-Se-N₃-C exhibited superior eCO₂RR activity, with CO selectivity reaching ~98% at -0.70 V versus reversible hydrogen electrode (RHE). The Zn-CO₂ battery integrated with Ni-Se-N₃-C as cathode and Zn foil as anode achieved a peak power density of 1.82 mW cm^-2 and maintained remarkable rechargeable stability over 20 h. In-situ spectral investigations and theoretical calculations demonstrated that the chalcogen heteroatoms doped into the Ni-N₄-C configuration would break coordination symmetry and trigger charge redistribution, and then regulate the intermediate behaviors and thermodynamic reaction pathways for eCO₂RR. Especially, for Ni-Se-N₃-C, the introduced Se atoms could significantly raise the d-band center of central Ni atoms and thus remarkably lower the energy barrier for the rate-determining step of *COOH formation, contributing to the promising eCO₂RR performance for high selectivity CO production by competing with hydrogen evolution reaction.

Key words: Electrochemical CO₂ reduction reaction, Chalcogen heteroatoms, Single-atom catalysts, Asymmetric coordination, CO production

Jialin Wang, Kaini Zhang, Ta Thi Thuy Nga, Yiqing Wang, Yuchuan Shi, Daixing Wei, Chung-Li Dong, Shaohua Shen. Chalcogen heteroatoms doped nickel-nitrogen-carbon single-atom catalysts with asymmetric coordination for efficient electrochemical CO₂ reduction[J]. Chinese Journal of Catalysis, 2024, 64: 54-65.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60103-8

https://www.cjcatal.com/EN/Y2024/V64/I9/54

Figures/Tables 5

Fig. 1. Synthesis and morphology characterizations of Ni-N4-C and Ni-X-N3-C (X: S, Se, and Te) SACs. (a) Synthesis procedure of Ni-N4-C and Ni-X-N3-C (X: S, Se, and Te). TEM images of Ni-N4-C (b), Ni-S-N3-C (c), Ni-Se-N3-C (d), and Ni-Te-N3-C (e). HAADF-STEM images of Ni-N4-C (f), Ni-S-N3-C (g), Ni-Se-N3-C (h), and Ni-Te-N3-C (i), with transition-metal single atoms marked by red circles.

Fig. 2. Structural characterizations of Ni-N4-C and Ni-X-N3-C (X: S, Se, and Te) SACs. (a) High-resolution XPS Ni 2p spectra of Ni-N4-C, Ni-S-N3-C, Ni-Se-N3-C, and Ni-Te-N3-C. Ni K-edge XANES spectra (inset shows the fitted pre-edge region) (b), and Fourier-transformed k3-weighted EXAFS spectra of Ni-S-N3-C, Ni-Se-N3-C, Ni-Te-N3-C, and corresponding references (c). (d) Wavelet transformed EXAFS spectra of Ni foil, NiO, and Ni-Se-N3-C. FT-EXAFS fitting curves and (inset) corresponding structure model of Ni-S-N3-C (e), Ni-Se-N3-C (f), and Ni-Te-N3-C (g).

Fig. 3. eCO2RR performances and in-situ spectral characterizations of Ni-N4-C and Ni-X-N3-C (X: S, Se, and Te) SACs. CO Faradaic efficiencies (FEs) (a) and CO partial current densities (b) for Ni-N4-C, Ni-S-N3-C, Ni-Se-N3-C, and Ni-Te-N3-C at different applied potentials. (c) TOFs for CO production over Ni-N4-C, Ni-S-N3-C, Ni-Se-N3-C, and Ni-Te-N3-C. In-situ Raman spectra of Ni-S-N3-C (d), Ni-Se-N3-C (e), and Ni-Te-N3-C (f) in the range of 1350-1900 cm-1. (g) Reaction pathways for electrochemical CO2-to-CO reduction at Ni-X-N3-C (X: S, Se, and Te).

Fig. 4. Theoretical investigations. (a) Bader charge analysis of Ni-S, Ni-Se, and Ni-Te moieties. (b) Calculated projected density of states (PDOS) of Ni-N4-C, Ni-S-N3-C, Ni-Se-N3-C, and Ni-Te-N3-C for *COOH adsorption. Reaction pathways and free energy diagrams of eCO2RR (c) and HER (d) over Ni-N4-C, Ni-S-N3-C, Ni-Se-N3-C, and Ni-Te-N3-C at 0 V vs. RHE. (e) Calculated limiting potential differences between eCO2RR and HER at Ni-N4-C, Ni-S-N3-C, Ni-Se-N3-C, and Ni-Te-N3-C.

Fig. 5. Electrochemical performance of Ni-Se-N3-C SAC based Zn-CO2 battery. (a) Schematic illustration of the Ni-Se-N3-C SAC based Zn-CO2 battery. Charging and discharging curves (b) and power density curve (c) of Ni-Se-N3-C SAC based Zn-CO2 battery. (d) LEDs powered by the Ni-Se-N3-C SAC based Zn-CO2 battery. (e) Galvanostatic discharge-charge curves of Ni-Se-N3-C SAC based Zn-CO2 battery at 2 mA cm-2.

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Chalcogen heteroatoms doped nickel-nitrogen-carbon single-atom catalysts with asymmetric coordination for efficient electrochemical CO₂ reduction

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