Nano-confinement and hydrophobic ionic-liquid engineering for methanol-selective CO2 electroreduction from dilute streams

doi:10.1016/S1872-2067(26)65253-9

Abstract

Abstract:

The electrocatalytic reduction of dilute carbon dioxide (CO₂) to methanol faces dual challenges of sluggish reaction kinetics and the competing hydrogen evolution reaction (HER). This study presents a nanoconfined ionic liquid catalyst strategy, in which Cu_2‒_xSe nanocrystals are anchored as catalytic engines within mesoporous nitrogen-doped carbon nanofibers (CSNC), followed by impregnation with the ionic liquid [Emim][BF₄] to modulate the reaction microenvironment. The multilevel pore structure of the catalyst enables local enrichment of CO₂ through a nanoconfinement effect, while the homogeneous distribution of the ionic liquid combined with a hydrophobic interface collectively suppresses HER, thereby enhancing methanol selectivity. In an H-type cell with 0.5 mol/L KHCO₃, CSNC/[Emim][BF₄] achieves a peak methanol Faradaic efficiency (FE) of 79.4% at -0.52 V vs. RHE, sustaining > 70% FE over 48 h. In a flow cell with 1 mol/L KOH, FE reaches 78.8% under pure CO₂ and 72.3% under 10% CO₂ (simulating flue gas), 1.67 times higher than CSNC alone, with stable performance over 24 h. In situ spectroscopy and feedstock-switching experiments reveal N-coordination stabilizes *COOH intermediates, favoring methanol via the formate pathway. This strategy advances selective, stable CO₂-to-methanol conversion from dilute streams, promoting sustainable carbon utilization and industrial flue gas valorization.

Key words: Low-concentration CO₂ electroreduction, Ionic liquids, Cu_2-xSe, Nano-confinement, Methanol

Zhen Zhang, Xiangya Zhang, Mai Zhang, Yifei Yang, Yitong Wu, Linlin Zhang, Jianjun Liao, Chunfeng Song. Nano-confinement and hydrophobic ionic-liquid engineering for methanol-selective CO₂ electroreduction from dilute streams[J]. Chinese Journal of Catalysis, 2027, 92: 328-339.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65253-9

https://www.cjcatal.com/EN/Y2027/V92/I1/328

Figures/Tables 6

Fig. 1. (a) Preparation of CSNC/[Emim][BF4] composite catalysts. (b) XRD patterns of the samples. High-resolution XPS spectra of Cu2-xSe, 30-CSNC and CSNC/[Emim][BF4]: Cu 2p (c), Cu LMM (d), Se 3d (e), N 1s (f), and F 1s and B 1s (g).

Fig. 2. SEM images of 20-CSNC (a), 30-CSNC (b), and 40-CSNC (c). TEM images of 20-CSNC (d), 30-CSNC (e), and 40-CSNC (f). (g) HRTEM image of CSNC/[Emim][BF4]. (h) EDX elemental mapping images of CSNC/[Emim][BF4].

Fig. 3. (a) Static contact angle and nitrogen adsorption-desorption isotherms for Cu2‒xSe (b), 30-CSNC (c), and CSNC/[Emim][BF4] (d).

Fig. 4. (a) LSV curves of catalysts in CO2-saturated 0.5 mol/L KHCO3 electrolyte. Cdl of catalysts (b) and Faradaic efficiency (c) of the methanol process using different catalysts. Faradaic efficiency of the CO2RR by Cu2‒xSe (d), 30-CSNC (e), and CSNC/[Emim][BF4] (f). (g) Performance comparison of reported CO2RR-to-methanol electrocatalysts in H-type cells. (h) Stability test of CSNC/[Emim][BF4] at -0.52 V vs. RHE in 0.5 mol/L KHCO3 electrolyte.

Fig. 5. (a) LSV curves of catalysts. (b) Faradaic efficiency of the CO2RR by CSNC/[Emim][BF4]. (c) Methanol Faradaic efficiency of the catalyst under different carbon dioxide concentrations. (d) Methanol Faradaic efficiency of the catalyst under different pH conditions. (e) Stability test of CSNC/[Emim][BF4] at -0.82 V vs. RHE in 10% CO2 concentration.

Fig. 6. (a) Schematic diagram of the pathway for forming methanol through CO2RR. (b) Faradaic efficiency of CSNC/[Emim][BF4] at ‒0.52 V vs. RHE in a 0.5 mol/L KHCO3 electrolyte with different feedstocks: CO2, HCOOH, and CO. (c) In situ Raman and (d) In situ IR spectra of the CSNC/[Emim][BF4] catalyst under various applied potentials. The observed absorption bands correspond to adsorbed intermediates: *CO (2070 cm‒1), *CHO (1750 cm‒1), *H2O (1640 cm‒1), *CH2O (1450 cm‒1), *CH3O (1070 cm‒1) and *COOH (1280, 1390, and 1570 cm‒1). Dashed lines and arrows indicate these characteristic bands. Density functional theory (DFT) calculation. (e) reaction free energy profile of H2O dissociation over 30-CSNC and CSNC/[Emim][BF4] catalysts. (f) Gibbs free energy curves of the reaction pathways for the reduction of CO2 to CH3OH and CH4 by different catalysts.

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Nano-confinement and hydrophobic ionic-liquid engineering for methanol-selective CO₂ electroreduction from dilute streams

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