Institute of Applied Physics and Materials Engineering, University of Macau, Macao SAR, China.
State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, 350002, China.
Chemphyschem. 2023 Jun 1;24(11):e202200937. doi: 10.1002/cphc.202200937. Epub 2023 Mar 24.
Carbon neutrality has drawn increasing attention for realizing the carbon cyclization and reducing the greenhouse effect. Although the C1 products, such as CO, can be achieved with a high Faraday efficiency, the targeted production of C2 fuels as well as the mechanism have not been systematically investigated. In this work, we carry out a first-principles study to screen dual-atom catalysts (DACs) for producing C2 fuels through the electrocatalytic carbon monoxide reduction reaction (e-CORR). We find that methanol, ethanol and ethylene can be produced on both DAC-Co and DAC-Cu, while acetate can be achieved on DAC-Cu only. Importantly, methanol and ethylene are preferred on DAC-Co, while acetate and ethylene on DAC-Cu. Furthermore, we show that the explicit solvent can enhance the adsorption and influence the protonation steps, which subsequently affects the protonation and dimerization behavior as well as the performance and selectivity of e-CORR on DACs. We further demonstrate that the C-C coupling is easy to be formed and stabilized if the Integrated Crystal Orbital Hamilton Population (ICOHP) is low because of the low energy barrier. Our findings provide not only guidance on the design of novel catalysts for e-CORR, but an insightful understanding on the reduction mechanism.
碳中和受到越来越多的关注，以实现碳循环和减少温室效应。虽然 C1 产物（如 CO）可以获得很高的法拉第效率，但尚未系统地研究 C2 燃料的靶向生产以及相关机制。在这项工作中，我们通过电催化一氧化碳还原反应（e-CORR），进行了一项第一性原理研究，以筛选用于生产 C2 燃料的双原子催化剂（DAC）。我们发现甲醇、乙醇和乙烯可以在 DAC-Co 和 DAC-Cu 上生成，而只有在 DAC-Cu 上才能生成乙酸盐。重要的是，甲醇和乙烯在 DAC-Co 上优先生成，而乙酸盐和乙烯在 DAC-Cu 上优先生成。此外，我们表明，显含溶剂可以增强吸附作用，并影响质子化步骤，从而影响质子化和二聚化行为，以及 DAC 上 e-CORR 的性能和选择性。我们进一步证明，如果集成晶体轨道哈密顿人口（ICOHP）较低，C-C 偶联很容易形成和稳定，因为能量势垒较低。我们的发现不仅为 e-CORR 新型催化剂的设计提供了指导，而且对还原机制有了深入的理解。
