NSF-DFG Echem: Strategies to Overcome Contemporary Limitations of Reductive Electrosynthetic Conversions in Aqueous Media

在这个项目中，我们引入了高度破坏性的概念来解决还原有机电合成中析氢和阴极腐蚀的严重缺陷。通过专注于阳离子氢抑制剂和非传统阴极材料，我们将有效地解决阻碍我们的问题，并使这一固有的绿色技术的更广泛实施成为可能。这两个单独的概念都超出了目前有机电合成的前沿。然而，离散的互补方法可以有效地结合在一起，这将在化学、工程和化学工业中产生广泛的影响。我们使用新型阳离子氢抑制剂的目的是选择性地增加析氢反应的过电压，使我们能够进行目前最先进的方法无法实现的反应。我们概念的美妙之处在于，我们可以将这些阳离子氢气抑制剂用作添加剂或将它们(电)接枝到合适的电极材料上。这将赋予高度的灵活性，因为有机阳离子抑制剂也可以为特定的要求量身定做。我们还将重点介绍手性添加剂和磁场。对于前者，我们使用了手性阳离子抑制剂，可以将立体生成信息传递到各种底物上，同时抑制有害的放氢和阴极腐蚀。对于后者，电场和磁场的累积效应将导致阴极更紧密的装饰，这进一步突出了阳离子氢气抑制剂的有益效果。通过使用非传统材料，如Ga/In混合物、锌和铅的三元合金、铋和铋合金作为阴极，可以从不同的角度解决所述的缺点。他们在很多方面都很出色。例如，虽然它们具有高的氢过电位，但它们中的一些具有比还原电化学中经常使用的当代替代品更高的生物兼容性，或者增强了对阴极腐蚀的抵抗力。在所有情况下，它们在有机电合成中的性能尚未完全阐明，这样做可能会为有机电合成开辟新的途径。本文提出的两种概念上的新策略都克服了目前还原电合成在广泛应用中的局限性。即使凭借自己的优点，他们也会在远离当前最先进水平的领域取得进展。在学术界和化学工业中，这两个概念中的任何一个都可以想象到对创新的巨大和立即的推动，通过将这两个不同的战略结合起来，可以预见到进一步放大它们的高影响。

In this project, we introduce highly disruptive concepts to address the severe shortcomings of hydrogen evolution and cathodic corrosion in reductive organic electrosynthesis. By focusing on cationic hydrogen inhibitors and unconventional cathode materials, we will efficiently address both hindering problems and the broader implementation of this inherently green technique is possible. Both individual concepts reside beyond the current forefront in the organic electrosynthesis by themselves. However, the discrete complementary approaches can be fruitfully combined which will have wide ramifications in chemistry, engineering, and chemical industry.Our aim with the novel cationic hydrogen inhibitors is to selectively increase the overvoltage for hydrogen evolution reaction which allows us to perform reactions that are inaccessible by the current state-of-the-art methods. The beauty of our concept lies in the fact that we can use these cationic hydrogen inhibitors either as additives or (electro)graft them to suitable electrode materials. This will grant as high flexibility as also the organic cationic inhibitors can be tailored for specific requirements. We will focus also on chiral additives and magnetic fields. With the former, we employ chiral cationic inhibitors that can transfer sterogenic information to various substrates while suppressing the detrimental hydrogen evolution and cathodic corrosion. With the latter, the cumulative effects of electric and magnetic fields will lead to a tighter decoration of the cathode which further accentuates the beneficial effects of the cationic hydrogen inhibitors. The stated shortcomings can be tackled from a different perspective by using unconventional materials such as Ga/In mixtures, ternary alloys of zinc and lead, bismuth, and bismuth alloys as cathodes. They excel in many aspects. For example, while exhibiting high hydrogen overpotentials, some of them have higher biocompatibilities, or increased resistances towards cathodic corrosion than the contemporary alternatives often used in reductive electrochemistry. In all cases, their performance in organic electrosynthesis has not yet been fully elucidated and it is plausible that doing so will open new avenues for organic electrosynthesis. Both conceptually new strategies presented herein overcome the current limitations in reductive electrosynthesis for a broad range of applications. Even on their own merit, they will advance the field far off from the current state-of-the-art. An enormous and immediate boost in innovation from either of these concepts in both academia and chemical industry is conceivable, and by combining these two distinct strategies, further amplification of their high impact is envisioned.