F-modified Cu/electrolyte interface boosts CO2 electroreduction into C2H4 and C2H5OH products via an alternative CC coupling mechanism

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL Molecular Catalysis Pub Date : 2024-11-05 DOI:10.1016/j.mcat.2024.114662

Lihui Ou

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Abstract

A F⁻-modified Cu(111) electrocatalysts exhibited an ultrahigh Faradaic efficiency and product selectivity towards CO₂ electroreduction into C₂ products. Thus, CO₂ electroreduction mechanisms towards C₂H₄ and C₂H₅OH products at F⁻-modified Cu(111)/H₂O interface based on DFT calculations are studied in this work, by which the influencing mechanism of specifically adsorbed F⁻ on electroreduction activity, product selectivity and a alternative CC coupling mechanism can be revealed. Our present studies indicate that the presence of F⁻ can notably enhance CO₂ electroreduction activity towards key intermediate CO because of significantly changed CO₂ adsorption configuration and weakening effect of F⁻ on COOH adsorption strength. CO dimerization into dimer OCCO through Langmuir-Hinshelwood mechanism is more favorable than CHO formation in the presence of the F⁻. Thus, it can be concluded that CC coupling reaction occurs via CO dimerization. More CO adsorption strength because of modification of F⁻ can explain easier occurrence of CC coupling reaction, thus leading to change of product selectivity. The parallel OCCOH and OCCHO pathways are proposed for CO₂ electroreduction into C₂H₄ and C₂H₅OH products at F⁻-modified Cu(111)/H₂O interface, in which CO dimerization is regarded as the rate-determining step. Ou present studies can unveil CO₂ electroreduction mechanisms and significant role of the specifically adsorbed F⁻ at Cu/electrolyte interface for promoting CO₂ electroreduction activity and improving product selectivity towards C₂ products.

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F 改性铜/电解质界面通过另一种 CC 耦合机制促进 CO2 电还原成 C2H4 和 C2H5OH 产物

一种 F 修饰的 Cu(111) 电催化剂在将 CO2 电还原成 C2 产物方面表现出了超高的法拉第效率和产物选择性。因此，本研究基于 DFT 计算，研究了 F- 改性 Cu(111)/H2O 界面上 CO2 电还原 C2H4 和 C2H5OH 产物的机理，从而揭示了特异性吸附 F- 对电还原活性、产物选择性的影响机理以及另一种 CC 耦合机理。本研究表明，由于 F- 显著改变了 CO2 的吸附构型，并削弱了 F- 对 COOH 的吸附强度，因此 F- 的存在能显著提高 CO2 对关键中间产物 CO 的电还原活性。在 F- 存在的情况下，CO 通过 Langmuir-Hinshelwood 机理二聚为二聚体 OCCO 比 CHO 的形成更有利。因此，可以得出结论，CC 偶联反应是通过 CO 二聚作用发生的。由于 F- 的改性，CO 的吸附力更大，这可以解释为什么 CC 偶联反应更容易发生，从而导致产物选择性的改变。在 F- 修饰的 Cu(111)/H2O 界面上，CO2 电还原成 C2H4 和 C2H5OH 产物的平行 OCCOH 和 OCCHO 途径被提出，其中 CO 二聚化被认为是决定速率的步骤。本研究揭示了 CO2 电还原机制，以及 Cu/电解质界面上特异吸附的 F- 在促进 CO2 电还原活性和提高 C2 产物选择性方面的重要作用。

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来源期刊

Molecular Catalysis Chemical Engineering-Process Chemistry and Technology

CiteScore

6.90

自引率

10.90%

发文量

700

审稿时长

40 days

期刊介绍： Molecular Catalysis publishes full papers that are original, rigorous, and scholarly contributions examining the molecular and atomic aspects of catalytic activation and reaction mechanisms. The fields covered are: Heterogeneous catalysis including immobilized molecular catalysts Homogeneous catalysis including organocatalysis, organometallic catalysis and biocatalysis Photo- and electrochemistry Theoretical aspects of catalysis analyzed by computational methods