配体-缺陷协同催化剂局部增强CO2浓度实现高效低浓度CO2电化学还原

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

摘要/Abstract

摘要：

利用可再生能源驱动二氧化碳还原反应(CO₂RR)以合成高价值化学品, 被认为是实现“碳闭环”的关键技术路径, 对于应对全球能源和环境危机具有重要战略意义. 相较于气态产物, 将CO₂还原为甲酸等液相产物, 在常温常压下稳定性更高、储存和运输更便利, 应用价值突出. 为实现这一目标, 各种催化剂已被研究和应用于CO₂RR. 其中, 铋基材料因其对*OCHO中间体具有适中的吸附能而对*H吸附能较弱, 被公认为生产甲酸最有前途的催化剂之一. 然而, 在实际应用中, 由于CO₂传质限制, 其在低浓度条件下的转化仍面临关键挑战.

本文利用原位电化学还原制备了一种2-氨基对苯二甲酸修饰的铋配位化合物(Re-BiBDC-NH₂), 用于低浓度CO₂的电化学还原. 具体而言, 原位还原后保留的氨基官能团诱导产生丰富的不饱和配位位点, 增强了CO₂吸附能力, 即使在低浓度CO₂供给下也能实现局域浓度富集. 更重要的是, 原位电化学重构后残留的表面氨基配体与铋缺陷位点可协同产生动态受阻路易斯酸碱对, 这有助于在低CO₂浓度下强化CO₂吸附. 在H型电解池中, Re-BiBDC-NH₂催化剂在−0.7至−1.4 V(相对于可逆氢电极)的宽电位窗口内保持> 80%的甲酸盐法拉第效率(FE_formate), 并在−1.0 V时观察到FE_formate最佳性能为96.94%. 该催化剂进一步表现出对不同CO₂浓度(15%-100%)和温度(10-50 °C)的耐受性, FE_formate均能保持在75%以上. 在电流密度为300 mA cm^-2的流动池中, Re-BiBDC-NH₂催化剂在不同pH环境(pH = 1.7, 7和14)下FE_formate均能实现> 95%. 值得注意的是, 在酸性电解质(pH = 1.7)中, 因可避免碳酸盐产生, 其单程碳效率达到71.60%. 这种配体-缺陷协同作用动态调控了反应界面, 克服了传统催化剂在pH、温度和CO₂浓度方面的局限性. 原位光谱分析和密度泛函理论计算表明, 由氨基和缺陷形成的动态受阻路易斯酸碱对能够富集CO₂并稳定反应中间体*OCHO, 从而降低反应能垒, 同步提升催化活性与选择性.

综上, 本研究为低浓度CO₂RR提供了一种具有配体-缺陷协同效应的催化剂, 为连接催化剂基础研究与实际CO₂转化应用提供了新的见解.

关键词: 二氧化碳电化学还原, 铋基催化剂, 甲酸, 受阻路易斯酸碱对, 宽pH值窗口

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

刘均炎, 邵涛, 彭珣, 刘升卫. 配体-缺陷协同催化剂局部增强CO₂浓度实现高效低浓度CO₂电化学还原[J]. 催化学报, 2026, 86: 265-276.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65031-0

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

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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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配体-缺陷协同催化剂局部增强CO₂浓度实现高效低浓度CO₂电化学还原

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

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