Selective electrocatalytic reduction of CO2 to formate via carbon-shell-encapsulated In2O3 nanoparticles/graphene nanohybrids

doi:10.1016/j.jmst.2022.01.006

Abstract

Abstract:

Constructing nanohybrids with a synergistic effect using multi-components and specific micro/nanostructures can significantly enhance their electrocatalytic activity. In this work, we fabricated an In₂O₃⊃NC@GO nanohybrid, in which In₂O₃ nanoparticles (NPs) were encapsulated by an N-doped carbon (NC) shell and supported on graphene. The multi-components in In₂O₃⊃NC@GO synergistically optimize the structural and electronic properties of the material. The particle size and dispersion of In₂O₃ NPs were optimized owing to the separation effect of the amorphous NC shell and graphene support. This separation effect exposes more number of active sites for the electrochemical reaction. Abundant oxygen vacancies exist in In₂O₃, leading to a stronger ability for the adsorption and activation of CO₂. The NC shell inhibits the direct contact between the electrolyte and In₂O₃, which significantly suppresses competitive H₂ evolution. The charge transfer during the electrocatalysis process is also effectively enhanced due to the carbon components. The synergistic effect of multi-components in the In₂O₃⊃NC@GO sample results in a significantly improved CO₂ reduction reaction performance with a high HCOO^- Faradic efficiency (FE) of 91.2% and a current density of 40.38 mA cm^-2 at -0.8 V obtained using a flow cell. The present work demonstrates that rationally designing nanohybrids with multifunctional components is an effective strategy for optimizing the structural and electrocatalytic properties of materials for energy conversion.

Key words: In₂O₃, CO₂ reduction electrocatalyst, Oxygen vacancies, N-doped carbon, Nanohybrids

Yidu Wang, Jingnan Ding, Jun Zhao, Jiajun Wang, Xiaopeng Han, Yida Deng, Wenbin Hu. Selective electrocatalytic reduction of CO₂ to formate via carbon-shell-encapsulated In₂O₃ nanoparticles/graphene nanohybrids[J]. J. Mater. Sci. Technol., 2022, 121: 220-226.

Figures/Tables 4

Fig. 1. (a) Schematic illustration for the preparation of In2O3?NC@GO. (b) XRD patterns of different samples. (c) Scanning electron microscopy (SEM) and (d) transmission electron microscopy (TEM) images (inset: the histogram of particle size distribution) of In2O3?NC@GO. HRTEM images of (e) In2O3?NC@GO and (f) In2O3@GO. (g) Elemental mapping images of C, N, In, and O elements in In2O3?NC@GO.

Fig. 2. (a) O 1 s XPS spectra of In2O3?NC@GO and In2O3@GO. (b) In 3d XPS spectra of In2O3?NC@GO and In2O3@GO. (c) High-resolution N 1 s XPS spectra of In2O3?NC@GO. (d) High-resolution C 1 s XPS spectra of In2O3?NC@GO. (e) Electron spin resonance spectra of In2O3?NC@GO and In2O3@GO. (f) Raman spectrum in 200-800 cm-1 of In2O3?NC@GO.

Fig. 3. (a) Polarization curves of In2O3?NC@GO, In2O3@GO, and NC@GO in CO2-saturated KHCO3 solutions. (b) FE values for HCOO-, and (c) FE values for H2 of In2O3?NC@GO, In2O3@GO, and NC@GO in a CO2-saturated 0.5 M KHCO3 electrolyte. (d) Geometrical HCOO- partial current densities. (e) Schematic illustration of the flow cell used in this work. (f) HCOO- Faradaic efficiency in the flow cell. (g) HCOO- current density of In2O3?NC@GO in different cells. (h) Comparison of JHCOO- at -0.8 V vs RHE of various In-based CO2RR catalysts. (i) 10 h electrolysis of In2O3?NC@GO at -0.6 V.

Fig. 4. (a) Cd1 of tested catalysts. (b) ECSA-normalized HCOO- partial current density of tested catalysts. (c) Tafel slopes of In2O3?NC@GO, In2O3@GO, and NC@GO. (d) CO2-TPD profiles of the In2O3?NC@GO and In2O3@GO. (e) Nyquist plots of tested catalysts. (f) Scheme of the CO2 processes in In2O3?NC@GO.

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Selective electrocatalytic reduction of CO₂ to formate via carbon-shell-encapsulated In₂O₃ nanoparticles/graphene nanohybrids

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