In-situ distortion of Bi lattice in Bi28O32(SO4)10 cluster boosted electrocatalytic CO2 reduction to formate

doi:10.1016/S1872-2067(24)60287-1

Abstract

Abstract:

To convert carbon dioxide into high-value-added liquid products such as formate with renewable electricity (CO₂RR) is a promising strategy of CO₂ resource utilization. The key is to find a highly efficient and selective electrocatalyst for CO₂RR. Herein, clustered Bi₂₈O₃₂(SO₄)₁₀ was found to show a high formate Faradaic efficiency (FE_formate) of 96.2% at -1.1 V_RHE and FE_formate above 90% in a wide potential range from -0.9 to -1.3 V_RHE in H-type cell, surpassing the corresponding layered Bi₂O₂SO₄ (85.6% FE_formate at -1.1 V_RHE). The advantageous CO₂RR performance of Bi₂₈O₃₂(SO₄)₁₀ over Bi₂O₂SO₄ was ascribed to a special two-step in-situ reconstruction process, consisting of Bi₂₈O₃₂(SO₄)₁₀ → Bi_-2.1/Bi₂O₂CO₃ → Bi_-2.1/Bi_-0.6 during CO₂RR. It gave metallic Bi_-2.1 with lattice distortion of -2.1% at the first step and metallic Bi_-0.6 with lattice distortion of -0.6% at the second step. In contrast, the usual layered Bi₂O₂SO₄ only formed metallic Bi_-0.6 with weaker lattice strain. The metallic Bi_-2.1 revealed higher efficiency in stabilizing *CO₂ intermediate and reducing the energy barrier of CO₂RR, while suppressing hydrogen evolution reaction and CO formation. This work delivers a high-performance cluster-type Bi₂₈O₃₂(SO₄)₁₀ electrocatalyst for CO₂RR, and elucidates the origin of superior performance of clustered Bi₂₈O₃₂(SO₄)₁₀ electrocatalysts compared with layered Bi₂O₂SO₄.

Key words: Inorganic metal-oxygen clusters, Bi₂₈O₃₂(SO₄)₁₀, Electrocatalytic CO₂ reduction, In-situ reconstruction, Lattice strain

Jinghan Sun, Zhengrong Xu, Deng Liu, Aiguo Kong, Qichun Zhang, Rui Liu. In-situ distortion of Bi lattice in Bi₂₈O₃₂(SO₄)₁₀ cluster boosted electrocatalytic CO₂ reduction to formate[J]. Chinese Journal of Catalysis, 2025, 72: 199-210.

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Figures/Tables 6

Fig. 1. Schematic illustration of the synthesis and reconstruction of layer-type Bi2O2SO4 and cluster-type Bi28O32(SO4)10.

Fig. 2. XRD patterns (a), FT-IR spectra (b) and XPS survey spectra (c), high resolution XPS spectra of Bi 4f (d), S 2p (e), O 1s (f) of Bi2O2SO4 and Bi28O32(SO4)10. SEM and HRTEM images of Bi2O2SO4 (g,h) and Bi28O32(SO4)10 (i,j).

Fig. 3. Electrochemical performances of Bi2O2SO4 and Bi28O32(SO4)10 in H-type cell. (a) LSV curves of Bi2O2SO4 and Bi28O32(SO4)10. FEformate and jformate on Bi2O2SO4 (b) and Bi28O32(SO4)10 (c). (d) Comparison of performances with reported Bi-based electrocatalysts for the CO2RR to formate in H-type cell. (e) Durability test of Bi28O32(SO4)10 at the potential of -1.1 VRHE. Cdl (f), Tafel slopes (g), single oxidative LSV curves (h) in N2-saturated 0.05 mol L-1 NaOH and (i) Nyquist plots of Bi2O2SO4 and Bi28O32(SO4)10.

Fig. 4. In-situ time-resolved XRD patterns (a,b) and Raman spectra (c,d) of Bi2O2SO4 and Bi28O32(SO4)10.

Fig. 5. XRD patterns (a), enlarged XRD diffraction peaks (b) and Bi L3-edge FT-EXAFS spectra (c) of Bi2O2SO4-2h and Bi28O32(SO4)10-2h. SEM, HRTEM images and GPA strain maps of Bi2O2SO4-2h (d-f) and Bi28O32(SO4)10-2h (g-i).

Fig. 6. In-situ ATR-IR spectra of Bi2O2SO4 (a) and Bi28O32(SO4)10 (b). (c) Schematic illustration of CO2RR on the catalyst surface (Bi: purple, C: brown, O: red, H: blue). Gibbs free energy for CO2RR to formate (d), bond length between *CO2 and the surface Bi atom (e), PDOS of p-orbitals of O atom of the absorbed *CO2 intermediate (Fermi level was at 0 eV) (f), Gibbs free energy for H2 formation (g), adsorption energy comparisons of *CO2 and *H (h) over Bi-0.6 and Bi-2.1.

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In-situ distortion of Bi lattice in Bi₂₈O₃₂(SO₄)₁₀ cluster boosted electrocatalytic CO₂ reduction to formate

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