Serra-Maia Rui, Varley Joel B, Weitzner Stephen E, Yu Henry, Shi Rongpei, Biener Jurgen, Akhade Sneha A, Stach Eric A
Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, PA 19104, USA.
Materials Sciences Division, Lawrence Livermore National Laboratory, Livermore, CA 94550, USA.
iScience. 2025 Jan 20;28(3):111851. doi: 10.1016/j.isci.2025.111851. eCollection 2025 Mar 21.
Copper-based nanoparticles are key electrocatalysts for CO electrochemical reduction (CO ER) to liquid fuels and other value-added products. However, the copper catalyst can undergo rapid electrochemical corrosion, leading to a loss of catalyst material, fluctuations in the reaction conditions and increasing operational costs. We establish a mechanistic understanding of this detrimental process using electrochemical electron microscopy and density functional theory (DFT). We find that copper corrosion can occur in the presence of CO in electroless conditions and before the onset potentials required for CO ER. The effects are isolated from pH changes resulting from dissolved CO. Particles of corroded copper have oxidized surfaces, in contrast to copper surfaces exposed to CO-free electrolytes. DFT calculations identify multiple routes by which CO can behave as a dissolution agent for copper and copper-oxide surfaces and suggest that formate-intermediates are a key driver of corrosion. This study highlights microenvironment-based factors that affect copper performance and degradation, facilitating strategies to inhibit and reverse copper degradation during CO ER.
铜基纳米颗粒是将一氧化碳电化学还原（CO ER）为液体燃料和其他增值产品的关键电催化剂。然而，铜催化剂会迅速发生电化学腐蚀，导致催化剂材料损失、反应条件波动并增加运营成本。我们使用电化学电子显微镜和密度泛函理论（DFT）对这一有害过程建立了机理理解。我们发现，在无电镀条件下且在CO ER所需的起始电位之前，CO存在时铜就会发生腐蚀。这些影响与溶解的CO导致的pH变化无关。与暴露于无CO电解质的铜表面相比，腐蚀后的铜颗粒具有氧化表面。DFT计算确定了CO作为铜和氧化铜表面溶解剂的多种途径，并表明甲酸盐中间体是腐蚀的关键驱动因素。这项研究突出了影响铜性能和降解的基于微环境的因素，有助于制定在CO ER过程中抑制和逆转铜降解的策略。
