Direct electrosynthesis of methylamine from carbon dioxide and nitrate
Direct electrosynthesis of methylamine from carbon dioxide and nitrate
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DOI：
10.1038/s41893-021-00705-7
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发表时间：
2021-04-05
影响因子：
27.6
通讯作者：
Wang, Hailiang
中科院分区：
文献类型：
--
作者：
Wu, Yueshen;Jiang, Zhan;Wang, Hailiang
二氧化碳的电化学还原是一项有吸引力的技术，它以化学形式存储可再生电力，并有可能改变当今碳燃料的使用方式。虽然在烷烃、烯烃和醇的电合成方面已经取得了成功，但获得烷基胺等有机氮分子的途径在很大程度上仍然超出了目前的电催化的范围。本文首次报道了碳纳米管负载的四氨基酞菁钴分子催化剂在水相介质中催化二氧化碳和硝酸盐生成甲胺的首次电化学反应。整个反应涉及14个电子和15个质子的转移以形成每个甲胺分子，是一个由催化剂表面附近的两个活性中间体耦合而成的八步催化级联过程。关键的C-N键形成步骤被发现是硝酸盐还原产生的羟胺溢出以及随后与二氧化碳还原产生的甲醛的缩合。这项研究提供了一个从无机碳和氮废料中可持续合成烷基胺的成功范例，这可能有助于在碳中性的未来缓解温室气体排放。二氧化碳的电还原为获得增值燃料和化学品提供了一条可持续的途径。在这里，作者展示了一个级联反应，从二氧化碳和硝酸盐中产生甲胺。随着对多步骤催化过程的详细了解，目前的发现进一步推动了这项技术的边界。
The electrochemical reduction of carbon dioxide is an appealing technology that stores renewable electricity in the chemical form and has the potential to transform the way carbon fuels are utilized today. While there have been successes in the electrosynthesis of alkanes, alkenes and alcohols, access to organonitrogen molecules such as alkylamines remains largely beyond the reach of current electrocatalysis. Here we report the first electrochemical reaction that converts carbon dioxide and nitrate to methylamine in aqueous media under ambient conditions catalysed by a cobalt beta-tetraaminophthalocyanine molecular catalyst supported on carbon nanotubes. The overall reaction, involving the transfer of 14 electrons and 15 protons to form each methylamine molecule, is an eight-step catalytic cascade process enabled by the coupling of two reactive intermediates near the catalyst surface. The key C-N bond-forming step is found to be the spillover of hydroxylamine from nitrate reduction and its subsequent condensation with formaldehyde from carbon dioxide reduction. This study provides a successful example of sustainable alkylamine synthesis from inorganic carbon and nitrogen wastes, which could contribute to greenhouse gas mitigation for a carbon-neutral future.The electroreduction of CO2 provides a sustainable pathway to value-added fuels and chemicals. Here the authors show a cascade reaction that yields methylamine from CO2 and nitrate. With detailed insight into the multistep catalytic process, the current findings further push the boundaries of this technology.