Interface engineering of a GaN/In2O3 heterostructure for highly efficient electrocatalytic CO2 reduction to formate

doi:10.1016/S1872-2067(23)64455-9

Abstract

Abstract:

Electrocatalytic CO₂ reduction reaction (eCO₂RR) to obtain formate is a promising method to consume CO₂ and alleviate the energy crisis. Indium-based electrocatalysts have demonstrated considerable potential to produce formate. However, their unsatisfactory long-term stability and selectivity restrict their widespread application. In this study, a heterostructure of GaN- and In₂O₃-encapsulated porous carbon nanofibers was constructed via electrospinning and the phase transition of eutectic gallium-indium during calcination. The GaN and In₂O₃ nanoparticle-encapsulated porous carbon nanofibers, when used as electrocatalysts for eCO₂RR, displayed high formate selectivity with a faradaic efficiency of 87% and maximum partial current density of 29.7 mA cm^-2 in a 0.5 mol L^-1 KHCO₃ aqueous solution. The existence of the interface can cause a positive shift in the In 3d binding energy, leading to electronic redistribution. Moreover, the GaN component induced a higher proportion of O-vacancy sites in the In₂O₃ phase, resulting in improved selectivity for CO₂-to-formate. In-situ Raman experiments and density functional theory calculations revealed that the interface between GaN and In₂O₃ could lower the adsorption energy of the key intermediates for formate production, thus providing superior eCO₂RR performance. In addition, the framework of the porous carbon nanofibers exhibited a large electrochemically active surface area, which enabled the full exposure of the active sites. This study highlights the cooperation between GaN and In₂O₃ components and provides new insights into the rational design of catalysts with high CO₂-to-formate conversion efficiencies.

Key words: Electrocatalytic CO₂ reduction reaction, Interface, Formate, Eutectic gallium-indium, In₂O₃

Xuan Li, Xingxing Jiang, Yan Kong, Jianju Sun, Qi Hu, Xiaoyan Chai, Hengpan Yang, Chuanxin He. Interface engineering of a GaN/In₂O₃ heterostructure for highly efficient electrocatalytic CO₂ reduction to formate[J]. Chinese Journal of Catalysis, 2023, 50: 314-323.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64455-9

https://www.cjcatal.com/EN/Y2023/V50/I7/314

Figures/Tables 6

Fig. 1. Schematic illustration of GaN/In2O3@PCNF formation.

Fig. 2. SEM image with low-magnification (a), TEM images with low-magnification (b), and high-magnification (c), and the interface between GaN and In2O3 in GaN/In2O3@PCNF (d). (e) HAADF image and the corresponding elemental mapping (C, N, O, Ga, and In) of GaN/In2O3@PCNF.

Fig. 3. (a) XRD patterns of GaN/In2O3@PCNF (b) XRD patterns of GaIn@PCNF-1, GaIn@PCNF-0.2, GaIn@PCNF-0.1, and GaIn@PCNF-0.05. (c) Raman spectra of PCNF, EGaIn@PCNF, and GaN/In2O3@PCNF. (d) Raman spectroscopies of GaIn@PCNF-1, GaIn@PCNF-0.2, GaIn@PCNF-0.1, and GaIn@PCNF-0.05. (e) O 1s XPS spectra for In2O3@PCNF and GaN/In2O3@PCNF. (f) In 3d XPS spectra for powder In2O3, In2O3@PCNF, and GaN/In2O3@PCNF.

Fig. 4. (a) LSV curves of pure PCNF, In2O3@PCNF, EGaIn@PCNF, and GaN/In2O3@PCNF in CO2-saturated KHCO3 aqueous (0.5 mol L-1). (b) Faradaic efficiency of formate for In2O3@PCNF, EGaIn@PCNF, and GaN/In2O3@PCNF at different applied potentials. (c) Comparison of other reported In-based electrocatalysts toward formate (The corresponding references were shown in Table S4). (d) Partial current density of formate for In2O3@PCNF, EGaIn@PCNF, and GaN/In2O3@PCNF at different potentials. (e) Durability test and FE of formate for GaN/In2O3@PCNF.

Fig. 5. (a) Tafel plots for In2O3@PCNF, EGaIn@PCNF, and GaN/In2O3@PCNF; (b) Double-layer capacitance (Cdl) of PCNF, In2O3@PCNF, EGaIn@PCNF, and GaN/In2O3@PCNF. (c) EIS plots for PCNF, In2O3@PCNF, EGaIn@PCNF, and GaN/In2O3@PCNF. (d) EPR spectra for In2O3@PCNF and GaN/In2O3@PCNF.

Fig. 6. (a) Potential-dependent in-situ Raman spectra of GaN/In2O3@PCNF in CO2-saturated 0.5 mol L-1 KHCO3 solution. (b) Gibbs free energy diagrams for CO2RR toward formate formation. (c) DFT-calculated structural model of In2O3@PCNF and the optimized configurations of CO2 molecule and *OCHO intermediate adsorbed on In2O3@PCNF. (d) DFT-calculated structural model of GaN/In2O3@PCNF and the optimized configuration of CO2 molecule and *OCHO intermediate adsorbed on GaN/In2O3@PCNF. (e) the origin of the superior performance of GaN/In2O3@PCNF toward formate production.

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Interface engineering of a GaN/In₂O₃ heterostructure for highly efficient electrocatalytic CO₂ reduction to formate

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