Single-atomic Fe sites modulated by Sn regulator for enhanced electrochemical CO2 reduction

doi:10.1016/S1872-2067(24)60269-X

Abstract

Abstract:

Single-atom Fe catalysts show significant promise in the electrocatalytic reduction of CO₂ (CO₂RR), while their performance remains inferior to that of precious metal catalysts due to the overly strong binding of *CO intermediates. Although the introduction of heteroatoms or transition metal sites can modulate the binding strength of *CO on Fe sites, these regulators often induce competitive hydrogen evolution reaction (HER) with reduced Faraday efficiency (FE). In this work, we employ HER-inert Sn as a regulator to tune the electronic structure of Fe, weakening *CO adsorption and enhancing CO₂RR performance. Diatomic Fe-Sn pairs supported on N-doped carbon (Fe-Sn/NC) were synthesized, achieving FE for CO exceeding 90% over a broad potential range from −0.4 to −0.9 V versus the reversible hydrogen electrode. Fe-Sn/NC shows a high turnover frequency of 1.5 × 10⁴ h⁻¹, much higher than that of Fe/NC. Characterization results and theoretical calculations demonstrate that bonding Sn site to Fe generates electron-rich Fe centers, effectively reducing the adsorption strength of *CO without triggering HER. Additionally, Fe-Sn/NC exhibits exceptional activity in hydrazine oxidation performance (HzOR). The HzOR-assisted CO₂RR system using Fe-Sn/NC as electrodes reduces energy consumption by 38% compared with the conventional CO₂RR coupled oxygen evolution reaction system.

Key words: Atomically dispersed catalyst, Electrochemical CO₂ reduction, Electronic modification, Diatomic pairs, Main-group element

Chenghong Hu, Yue Zhang, Yi Zhang, Qintong Huang, Kui Shen, Liyu Chen, Yingwei Li. Single-atomic Fe sites modulated by Sn regulator for enhanced electrochemical CO₂ reduction[J]. Chinese Journal of Catalysis, 2025, 72: 222-229.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60269-X

https://www.cjcatal.com/EN/Y2025/V72/I5/222

Figures/Tables 5

Fig. 1. (a) Schematic representation of the fabrication of Fe-Sn/NC. (b) SEM image of Fe-Sn/ZIF-8. SEM (c) and TEM (d) images of Fe-Sn/NC. (e) Aberration-corrected HAADF-STEM image of Fe-Sn/NC. (f) Line-scanning intensity profiles obtained from regions 1 and 2 highlighted in (e). (g) HAADF-STEM image and corresponding EDS element mappings of Fe-Sn/NC.

Fig. 2. High-resolution XPS spectra of Fe 2p for Fe/NC and Fe-Sn/NC (a), Sn 3d for Sn/NC and Fe-Sn/NC (b), and N 1s for Fe-Sn/NC (c). XANES spectra (d) and FT- EXAFS spectra (e) of the Fe K-edge for Fe foil, FePc, Fe2O3, FeO, and Fe-Sn/NC. (f) FT-EXAFS fitting of Fe K-edge for Fe-Sn/NC with the proposed structural model inset (Grey: C, blue: N, wine red: Fe, cyan: Sn). XANES spectra (g) and FT-EXAFS spectra (h) of the Sn K-edge for Sn foil, SnO2, and Fe-Sn/NC. (i) FT-EXAFS fitting curves of Sn K-edge for Fe-Sn/NC.

Fig. 3. Electrochemical tests in CO2-saturated 0.1 mol L-1 KHCO3 aqueous solution. LSV curves (a), FECO (b), jCO (c), TOF (d), and Tafel slope (e) of Fe-Sn/NC, Fe/NC, Sn/NC, and NC. (f) Stability test of Fe-Sn/NC at ?0.5 V (vs. RHE).

Fig. 4. (a) Free energy diagrams for CO2RR over various catalyst models. (b) Limiting potential differences for CO2RR and HER on various active moieties. The charge density difference of Fe/NC (c) and Fe-Sn/NC (d) models (yellow and cyan represent electron accumulation and depletion, respectively). Projected DOS for Fe/NC (e) and Fe-Sn/NC (f) with *CO adsorption.

Fig. 5. (a) CV curve of Fe-Sn/NC in 1 mol L-1 KOH with 0.1 mol L-1 N2H4. (b) Schematic diagram of CO2RR//HzOR electrolyzer. (c) Polarization curves for CO2RR//HzOR and CO2RR//OER systems. (d) Chronoamperometry measurement of Fe-Sn/NC as both anode and cathode at ?1.0 V, and the corresponding FEco.

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Single-atomic Fe sites modulated by Sn regulator for enhanced electrochemical CO₂ reduction

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