Gholizadeh Reza, Pavlin Matic, Likozar Blaž, Huš Matej
Department of Catalysis and Chemical Reaction Engineering, National Institute of Chemistry, Hajdrihova 19, SI-1000, Ljubljana, Slovenia.
Department of Environmental Sciences, Jožef Stefan Institute, SI-1000, Ljubljana, Slovenia.
Chempluschem. 2025 Feb;90(2):e202400346. doi: 10.1002/cplu.202400346. Epub 2024 Dec 3.
Electrochemical reduction reaction of CO (eCORR) to produce valuable chemicals offers an attractive strategy to solve energy and environmental problems simultaneously. We have mapped out entire reaction pathways of eCORR to CO on Cu(100), including all intermediates and transition states using first-principles simulations. To accurately account for the solvent effect, the reaction was investigated with and without explicit water molecules, highlighting the limitations of the often (mis)used vacuum reaction pathway simplification. The results show that the reduction reaction was initiated under neutral pH conditions at an applied potential of -0.11 V (RHE, reversible hydrogen electrode) and all elementary reactions were thermodynamically favorable, while an applied potential of -1.24 V is required to ensure that all reactions exhibit spontaneous behavior. Detailed analysis revealed that solvation significantly influences the stability of the adsorbates and intermediates. Its inclusion notably alters the calculated reaction kinetics and energetic parameters by lowering the barrier energies and Gibbs free energies of all reactions. CO production proceeded mainly via the COOH* pathway (CO →trans-COOH*→cis-COOH*→CO*+OH*→CO*→CO). The use of water as a more sustainable and cost-effective solvent is compared to other options such as organic solvents, ionic liquids and mixed solvent systems, which are less sustainable and more expensive.
通过电化学还原反应（eCORR）将CO转化为有价值的化学品，为同时解决能源和环境问题提供了一种有吸引力的策略。我们利用第一性原理模拟，绘制了在Cu(100)上eCORR生成CO的完整反应路径，包括所有中间体和过渡态。为了准确考虑溶剂效应，研究了有无明确水分子存在时的反应，突出了经常（错误）使用的真空反应路径简化方法的局限性。结果表明，还原反应在中性pH条件下，于-0.11 V（RHE，可逆氢电极）的外加电势下开始，所有基元反应在热力学上都是有利的，而需要-1.24 V的外加电势才能确保所有反应都表现出自发行为。详细分析表明，溶剂化显著影响吸附质和中间体的稳定性。考虑溶剂化后，通过降低所有反应的能垒和吉布斯自由能，显著改变了计算得到的反应动力学和能量参数。CO的生成主要通过COOH途径（CO→反式-COOH→顺式-COOH*→CO*+OH*→CO*→CO）进行。将水作为一种更具可持续性和成本效益的溶剂，与其他选择（如有机溶剂、离子液体和混合溶剂体系）进行了比较，后者的可持续性较差且成本更高。
