An efficient 3D ordered mesoporous Cu sphere array electrocatalyst for carbon dioxide electrochemical reduction

doi:10.1016/j.jmst.2019.08.059

Abstract

Abstract:

The electrochemical reduction of CO₂ is a promising solution for sustainable energy research and carbon emissions. However, this solution has been challenged by the lack of active and selective catalysts. Here, we report a two-step synthesis of 3D ordered mesoporous Cu sphere arrays, which is fabricated by a dual template method using a poly methyl methacrylate (PMMA) inverse opal and the nonionic surfactant Brij 58 to template the mesostructure within the regular voids of a colloidal crystal. Therefore, the well-ordered 3D interconnected bi-continuous mesopores structure has advantages of abundant exposed catalytically active sites, efficient mass transport, and high electrical conductivity, which result in excellent electrocatalytic CO₂RR performance. The prepared 3D ordered mesoporous Cu sphere array (3D-OMCuSA) exhibits a low onset potential of -0.4 V at a 1 mA cm^-2 electrode current density, a low Tafel slope of 109.6 mV per decade and a long-term durability in 0.1 M potassium bicarbonate. These distinct features of 3D-OMCuSA render it a promising method for the further development of advanced electrocatalytic materials for CO₂ reduction.

Key words: 3D ordered mesoporous Cu sphere array electrocatalyst, Copper nanoparticles, Dual-template method, CO₂ electrochemical reduction reaction

Jun-Tao Luo, Guo-Long Zang, Chuang Hu. An efficient 3D ordered mesoporous Cu sphere array electrocatalyst for carbon dioxide electrochemical reduction[J]. J. Mater. Sci. Technol., 2020, 55: 95-106.

Figures/Tables 10

Fig. 1. Schematic of the preparation of the 3D-OMCuSA.

Fig. 2. SEM images of (a) SiO2 opal Inset: at a higher magnification. and (b) SiO2 opal-MMA. (c) PMMA inverse opal. (d-e) SEM image of 3DOMCuSA. (f-h) Higher magnification TEM image of one of the mesoporous Cu spheres.

Fig. 3. SEM images of (a-d) 3DOMCuSA and (e-f) copper nanoparticles.

Fig. 4. (a) Cu catalyst XRD spectra; (b) Cu catalyst XPS spectra; (c) Cu 2p and (d) O 1s XPS spectra of 3D-OMCuSA before and after the experiment.

Table 1 XPS surface composition percentages (at%) of 3D-OMCuSA before and after the experiments.

	Cu	O	B	C
Before the experiment	23.83	43.01	6.89	26.26
After the experiment	36.83	29.63	5.96	27.57

Fig. 5. Nitrogen adsorption/desorption isotherm and pore size distribution curve for 3D-OMCuSA.

Fig. 6. (a) Cu catalyst ECSA figure and (b) Tafel plot of the Cu catalyst in CO2-saturated KHCO3 electrolyte. (c) LSV plot of the Cu catalyst in the CO2-saturated KHCO3 electrolyte. and (d) I-t plot of the Cu catalyst in a CO2-saturated KHCO3 electrolyte.

Fig. 7. Activity of various electrodes in water. Comparison of the performance of different electrodes on the basis of the partial current density with CO at variable potentials [6,14,15,40].

Fig. 8. Comparison of the electrocatalytic activities of 3DOMCuSA and Cu nanoparticles. (a) Faradaic efficiencies for CO and HCOOH vs potential and (b) Faradaic efficiencies for C2H4 and C2H5OH vs potential and (c) current density for CO and HCOOH vs potential and (d) current density for C2H4 and C2H5OH vs potential.

Fig. 9. Schematic graph of the formation process of nanocrystal clusters of 3D-OMCuSA.

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