Ghosh Swarbhanu, Ariya Parisa A
Department of Chemistry, McGill University, Montréal, QC Canada.
Department of Atmospheric and Oceanic Sciences, McGill University, Montreal, QC Canada.
Commun Mater. 2024;5(1):196. doi: 10.1038/s43246-024-00639-5. Epub 2024 Sep 19.
Anthropogenic climate change drastically affects our planet, with CO being the most critical gaseous driver. Despite the existing carbon dioxide capture and transformation, there is much need for innovative carbon dioxide hydrogenation catalysts with excellent selectivity. Here, we present a fast, effective, and sustainable route for coupling diverse alcohols, amines and amides with CO via heterogenization of a natural metal-based homogeneous catalyst through decorating on functionalized graphene oxide (GO). Combined synthetic, experimental, and theoretical studies unravel mechanistic routes to convergent 4‑electron reduction of CO under mild conditions. We successfully replace the toxic and expensive ruthenium species with inexpensive, ubiquitously available and recyclable iron. This iron-based functionalized graphene oxide (denoted as Fe@GO-EDA, where EDA represents ethylenediamine) functions as an efficient catalyst for the selective conversion of CO into a formaldehyde oxidation level, thus opening the door for interesting molecular structures using CO as a C1 source. Overall, this work describes an intriguing heterogeneous platform for the selective synthesis of valuable methylene-bridged compounds via 4‑electron reduction of CO.
人为气候变化对我们的星球产生了巨大影响，其中一氧化碳是最关键的气体驱动因素。尽管现已有二氧化碳捕获和转化技术，但仍迫切需要具有优异选择性的创新型二氧化碳加氢催化剂。在此，我们通过在功能化氧化石墨烯（GO）上进行修饰，将一种天然金属基均相催化剂异质化，从而提供了一条快速、有效且可持续的途径，用于将多种醇、胺和酰胺与一氧化碳进行偶联。综合的合成、实验和理论研究揭示了在温和条件下将一氧化碳进行4电子还原的收敛机理途径。我们成功地用廉价、普遍可得且可回收的铁取代了有毒且昂贵的钌物种。这种铁基功能化氧化石墨烯（表示为Fe@GO-EDA，其中EDA代表乙二胺）作为一种高效催化剂，可将一氧化碳选择性转化至甲醛氧化水平，从而为以一氧化碳作为C1源构建有趣的分子结构打开了大门。总体而言，这项工作描述了一个引人入胜的多相平台，用于通过一氧化碳的4电子还原选择性合成有价值的亚甲基桥连化合物。
