Metal organic framework-ionic liquid hybrid catalysts for the selective electrochemical reduction of CO2 to CH4

doi:10.1016/S1872-2067(21)63970-0

Abstract

Abstract:

The electrochemical reduction of CO₂ towards hydrocarbons is a promising technology that can utilize CO₂ and prevent its atmospheric accumulation while simultaneously storing renewable energy. However, current CO₂ electrolyzers remain impractical on a large scale due to the low current densities and faradaic efficiencies (FE) on various electrocatalysts. In this study, hybrid HKUST-1 metal-organic framework‒fluorinated imidazolium-based room temperature ionic liquid (RTIL) electrocatalysts are designed to selectively reduce CO₂ to CH₄. An impressive FE of 65.5% towards CH₄ at -1.13 V is achieved for the HKUST-1/[BMIM][PF₆] hybrid, with a stable FE greater than 50% maintained for at least 9 h in an H-cell. The observed improvements are attributed to the increased local CO₂ concentration and the improved CO₂-to-CH₄ thermodynamics in the presence of the RTIL molecules adsorbed on the HKUST-1-derived Cu clusters. These findings offer a novel approach of immobilizing RTIL co-catalysts within porous frameworks for CO₂ electroreduction applications.

Key words: CO₂ electroreduction, Methane, Room temperature ionic liquid, Metal organic framework, Catalyst design, DFT calculation

Ernest Pahuyo Delmo, Yian Wang, Jing Wang, Shangqian Zhu, Tiehuai Li, Xueping Qin, Yibo Tian, Qinglan Zhao, Juhee Jang, Yinuo Wang, Meng Gu, Lili Zhang, Minhua Shao. Metal organic framework-ionic liquid hybrid catalysts for the selective electrochemical reduction of CO₂ to CH₄[J]. Chinese Journal of Catalysis, 2022, 43(7): 1687-1696.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63970-0

https://www.cjcatal.com/EN/Y2022/V43/I7/1687

Figures/Tables 4

Fig. 1. (a) FTIR spectra of the HKUST-1/[BMIM][PF6] hybrids. The peaks labelled with arrows are signals from the [BMIM][PF6] RTIL [35]. The peaks marked with asterisks (*) are signals from the HKUST-1 MOF [33,34]. The IR spectra of the pure HKUST-1 MOF and the pure [BMIM][PF6] RTIL are shown for reference. Cu 2p3/2 (b), N 1s (c), C 1s (d), and F 1s (e) XPS spectra of the HKUST-1/[BMIM][PF6] hybrid. The green, black, and gray (dashed) curves represent the peak sum, raw intensity, and background of the spectra, respectively.

Fig. 2. HAADF-STEM images (a) and EDS elemental mapping (b-e) of the HKUST-1/[BMIM][PF6] catalyst. The fluorine and nitrogen peaks in the EDS spectra were very weak (as observed in Fig. S9(b)) due to their low atomic mass; hence, they were not included in the mapping images. (f) HAADF-STEM images of the HKUST-1/[BMIM][PF6] after 1 h electrolysis at -1.7 V vs. RHE (not iR-corrected).

Fig. 3. Faradaic efficiency (a) and geometric partial current density towards CH4 (b) of the pristine HKUST-1 sample and the HKUST-1/RTIL hybrids; Faradaic efficiency (c) and geometric partial current density towards H2 (d) of the pristine HKUST-1 sample and the HKUST-1/RTIL hybrids. Time-varying current density (e) and faradaic efficiency data (f) of the HKUST-1/[BMIM][PF6] hybrid for 10 h at -1.21 V vs. RHE (iR-corrected using the initial ohmic resistance of the system).

Fig. 4. (a) The lowest energy configuration of the Cu (110) surface with one molecule each of adsorbed [BMIM][PF6] and H2O (left image). The lowest energy configuration of the interface in the presence of the adsorbed *COOH intermediate (right image). (b) Projected density of states of the d-orbital of Cu with and without the adsorbed RTIL molecule; Free energy diagram for hydrogen evolution (c) and CO2-to-CH4 reduction (d) with and without the adsorbed RTIL molecule.

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Metal organic framework-ionic liquid hybrid catalysts for the selective electrochemical reduction of CO₂ to CH₄

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