Ligand-defect synergistic catalyst for localized CO2 concentration enhancement in electrochemical reduction of low concentration CO2

doi:10.1016/S1872-2067(26)65031-0

Abstract

Abstract:

Electrochemical CO₂ reduction reaction (CO₂RR) is a potential strategy for mitigating severe greenhouse effect. Despite its potential, CO₂RR encounters critical challenges to convert low CO₂ concentrations in practical scenarios, due to the CO₂ mass transfer limitations. Herein, we prepared a reduced 2-aminoterephthalic acid modified bismuth coordination compound (Re-BiBDC-NH₂) for CO₂RR in low CO₂ concentrations. Retained amino groups after in situ reduction induce abundant unsaturated coordination sites, enhancing CO₂ adsorption and enabling localized concentration enhancement even under low CO₂ supply concentrations. As such, the optimized Re-BiBDC-NH₂ achieves a Faradaic efficiency for formate (FE_formate) of > 80% at a wide potential range of 700 mV, FE_formate of >75% across 15%-100% CO₂ concentrations. Furthermore, in a flow cell at a current density of 300 mA cm^-² and across a wide pH range (pH = 1.7, 7, and 14), the Re-BiBDC-NH₂ catalyst achieved FE_formate > 95%, with a single-pass carbon efficiency (SPCE) reaching 71.6% in acidic electrolyte (pH = 1.7). In situ spectroscopies and Density functional theory calculations reveal that dynamically frustrated Lewis pairs formed by amino groups and defects concentrate CO₂, and stabilize *OCHO intermediates to reduce energy barriers, thereby not only enhancing the CO₂RR performance but also allowing reaction to operate under low CO₂ concentrations. This work presents a promising ligand-defect synergistic catalyst for low-concentration CO₂RR, offering insights for bridging catalyst research and practical CO₂ conversion.

Key words: CO₂ electrochemical reduction, Bi-based catalysts, Formate, Frustrated Lewis pairs, Wide pH window

Junyan Liu, Tao Shao, Xun Peng, Shengwei Liu. Ligand-defect synergistic catalyst for localized CO₂ concentration enhancement in electrochemical reduction of low concentration CO₂[J]. Chinese Journal of Catalysis, 2026, 86: 265-276.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65031-0

https://www.cjcatal.com/EN/Y2026/V86/I7/265

Figures/Tables 6

Fig. 1. (a) Schematic illustration of the preparation procedure of Re-BiBDC and Re-BiBDC-NH2. SEM image of BiBDC (b), Re-BiBDC (c), BiBDC-NH2 (d) and Re-BiBDC-NH2 (e). TEM (f), HRTEM (g), localized enlarged view of HRTEM (h) and SAED (i) images of Re-BiBDC-NH2. (j) EDS elemental mapping for Bi, O, N and C elements on Re-BiBDC-NH2.

Fig. 2. (a) XRD patterns of the prepared samples. (b) ATR-FTIR spectra of H2BDC, H2BDC-NH2, BiBDC, Bi BDC-NH2, Re-BiBDC, Re-BiBDC-NH2 and Bi2O2CO3. High-resolution Bi 4f (b) and O 1s (d) XPS spectra for BiBDC, BiBDC-NH2, Re-BiBDC, and Re-BiBDC-NH2. Bi L3-edge XANES spectra (e) with the corresponding R-space FT-EXAFS spectra (f), and WT-EXAFS spectra (g) of Bi2O2CO3 and Re-BiBDC-NH2, comparing with Bi reference.

Fig. 3. (a) LSV curves of Re-BiBDC and Re-BiBDC-NH2 in CO2 or Ar-saturated 0.5 mol L?1 KHCO3. (b) Comparison of FEs for formate over Re-BiBDC and Re-BiBDC-NH2. (c) Potential-dependent FEs for detected H2, CO, and HCOO? products with current density over Re-BiBDC-NH2. (d) Tafel plots of formate comparison of Re-BiBDC and Re-BiBDC-NH2. (e) Double-layer capacitances (Cdl) of Re-BiBDC and Re-BiBDC-NH2 (scatter: experiment, line: fit). (f) ECSA-normalized formate partial current density of Re-BiBDC and Re-BiBDC-NH2. (g) Single oxidative LSV scans in Ar-saturated 0.1 mol L?1 KOH for Re-BiBDC and Re-BiBDC-NH2. (h) Stability test of Re-BiBDC-NH2 cathode at ?0.9 V vs. RHE.

Fig. 4. (a) Schematic diagram of the flow cell, GDE: gas diffusion electrode. (b) LSV curves of Re-BiBDC-NH2 with different electrolytes in flow cell. (c) FEformate in flow cell with different electrolytes in flow cell. (d) FEformate of Re-BiBDC-NH2 at 300 mA cm?2 in an electrolyte with pH 1.7 at different CO2 flow rates in flow cell. (e) SPCE of Re-BiBDC-NH2 at different CO2 flow rates. (f) Stability test of Re-BiBDC-NH2 cathode at 300 mA cm?2 in flow cell. (g) LSV curves of Re-BiBDC-NH2 with different CO2 concentrations in H-cell. (h) FEformate of Re-BiBDC and Re-BiBDC-NH2 at ?0.9 V vs. RHE with different CO2 concentrations in H-cell. (i) FEformate of Re-BiBDC and Re-BiBDC-NH2 at ?0.9 V vs. RHE with different temperatures in H-cell.

Fig. 5. (a) In-situ Raman spectra of Re-BiBDC-NH2 during electrochemical CO2RR with elevating applied potentials in 0.5 mol L-1 KHCO3 solution. In-situ ATR-FTIR spectra of Re-BiBDC (b) and Re-BiBDC-NH2 (c) during electrochemical CO2RR with elevating applied potentials in 0.5 mol L-1 KHCO3 solution. (d) Schematic diagram of the electrochemical CO2RR to formate process over the Re-BiBDC-NH2 catalyst.

Fig. 6. (a) Bader charges of Def-BiBDC. (b) Bader charges of Def-BiBDC-NH2. (c) Gibbs free energy diagram for *H on Bi, Def-Bi, Def-BiBDC, and def-BiBDC-NH2 models. (d) Adsorption energy for the CO2 adsorption in the OHP layer. (e) PDOS of the O p in *OCHO intermediate and Bi p in the Bi, Def-Bi, Def-BiBDC, and Def-BiBDC-NH2 models. (f) Gibbs free energy diagrams for CO2 to HCOOH on different positions 1, 2, and 3. (g) Gibbs free energy diagram for CO2 to HCOOH on Bi, Def-Bi, Def-BiBDC, and Def-BiBDC-NH2 models. (h) Geometric configures of the *CO2 and *OCHO intermediates on different models.

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Ligand-defect synergistic catalyst for localized CO₂ concentration enhancement in electrochemical reduction of low concentration CO₂

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