Zhang Yuxuan, Al-Mahayni Hasan, Aguiar Pedro M, Chartrand Daniel, McKee Morgan, Shamekhi Mehdi, Seifitokaldani Ali, Kornienko Nikolay
Department of Chemistry, Université de Montréal, Montréal, QC, Canada.
Department of Chemical Engineering, McGill University, Montréal, QC, Canada.
Nat Commun. 2025 Aug 29;16(1):8106. doi: 10.1038/s41467-025-63450-x.
Co-electrolysis of CO with simple N-species is an appealing route to sustainable fabrication of C-N bond containing products. A prominent challenge in this direction is to promote the C-N coupling step in place of the established CO reduction pathways. This can be particularly difficult when relying on solution-based species (e.g., NH) to intercept intermediates that are continually being reduced on heterogeneous catalyst surfaces. In light of this, we introduce oxy-reductive pulsed electrocatalysis as a tool for C-N bond formation. The reaction routes opened through this method involve both partial reduction and partial oxidation of separate reactants on the same catalyst surface in parallel to co-adsorb their activated intermediates proximal to one another. Using CO and NH as model reactants, the end result is an enhancement of selectivity and formation rates for C-N bond containing products (urea, formamide, acetamide, methylamine) by factors of 3-20 as compared to static electrolysis in otherwise identical conditions. An array of operando measurements is carried out to pinpoint the key factors behind this performance enhancement. Finally, the oxy-reductive coupling strategy is extended to additional carbon and nitrogen reactants and is further applied to C-S coupling.
将一氧化碳与简单含氮物种进行共电解是可持续制备含碳氮键产物的一条有吸引力的途径。在这个方向上一个突出的挑战是促进碳氮偶联步骤，以取代已有的一氧化碳还原途径。当依靠基于溶液的物种（如NH）来拦截在非均相催化剂表面不断被还原的中间体时，这可能会特别困难。有鉴于此，我们引入氧还原脉冲电催化作为形成碳氮键的一种工具。通过这种方法开辟的反应路线包括在同一催化剂表面上对单独的反应物进行部分还原和部分氧化，以便将它们的活化中间体彼此靠近地共吸附。使用一氧化碳和氨作为模型反应物，最终结果是与在其他相同条件下的静态电解相比，含碳氮键产物（尿素、甲酰胺、乙酰胺、甲胺）的选择性和生成速率提高了3至20倍。进行了一系列原位测量，以确定这种性能增强背后的关键因素。最后，氧还原偶联策略扩展到其他碳和氮反应物，并进一步应用于碳硫偶联。
