Asymmetric Copper-Sulphur Sites Promote C–C Coupling for Selective CO2 Electroreduction to C2 Products,Advanced Energy Materials

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Asymmetric Copper-Sulphur Sites Promote C–C Coupling for Selective CO2 Electroreduction to C2 Products
Advanced Energy Materials ( IF 24.4 ) Pub Date : 2024-01-21 , DOI: 10.1002/aenm.202304224
Liang Liang ₁ , Li Yang _{2,

3} , Thomas Heine _{2,

3} , Aleks Arinchtein ₁ , Xingli Wang ₁ , Jessica Hübner ₁ , Johannes Schmidt ₄ , Arne Thomas ₄ , Peter Strasser ₁

Affiliation

Sustainable multicarbon e-chemicals are of particular interest due to their potential future, high market values, and demand. In the direct electrocatalytic formation of multicarbon e-chemicals from CO₂, the elementary C–C coupling by CO dimerization is considered the rate-limiting step. Here, a generalized surface structural design principle of asymmetric metal pair sites is proposed, explored, and experimentally tested in order to promote CO dimerization on surfaces. First a computational model of N-doped Cu₂S layers featuring adjacent, electronically asymmetric Cu^δ1+-Cu^δ2+ (0 < δ₁⁺ < δ₂⁺ < 1) metal atomic pairs evidenced by their non-uniform charge distribution is considered. The electronic asymmetry resulted in distinct CO adsorption energies and the associated self-adjusting structures, which lowered C–C coupling energy barriers significantly. The computational hypotheses are experimentally tested using X-ray photoelectron spectroscopy of Cu-N moieties within N-doped Cu₂S layers. In-situ Fourier-transform infrared spectroscopy confirms linear *CO and *CO-CO adsorption configuration by the peaks of ≈2080 and 1920 cm⁻¹, respectively. After N-doping, the catalytically C₂ faradaic efficiency can significantly be elevated to 14.72% due to the promotion of C–C coupling.

中文翻译：

不对称铜硫位点促进 C-C 耦合，选择性 CO2 电还原为 C2 产品

可持续多碳电子化学品因其潜在的未来、高市场价值和需求而受到特别关注。在从 CO ₂直接电催化形成多碳电子化学品的过程中，CO 二聚的基本 C-C 偶联被认为是限速步骤。在这里，提出、探索和实验测试了不对称金属对位点的广义表面结构设计原理，以促进表面上的CO二聚化。首先考虑 N 掺杂 Cu ₂ S 层的计算模型，该模型具有相邻的、电子不对称的 Cu ^δ1+ -Cu ^δ2+ (0 < δ ₁⁺ < δ ₂⁺ < 1) 金属原子对，这由它们的非均匀电荷分布证明。电子不对称性导致不同的CO吸附能和相关的自调节结构，从而显着降低了C-C耦合能垒。使用N掺杂Cu ₂ S层内的Cu-N部分的X射线光电子能谱对计算假设进行了实验测试。原位傅里叶变换红外光谱分别通过约2080和1920 cm ^-1的峰确认了线性*CO和*CO-CO吸附构型。 N掺杂后，由于C-C耦合的促进，催化C ₂法拉第效率可显着提高至14.72%。

更新日期：2024-01-21

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