NSF-DFG Echem: Electrochemical pyrrolidone synthesis: an integrated experimental and theoretical investigation of the electrochemical amination of levulinic acid (ElectroPyr)

本研究涉及基于乙酰丙酸的吡咯烷酮类化合物的电化学合成，乙酰丙酸是一种基于木质纤维生物质的有前景的平台化学品。吡咯烷酮类化合物是医药、溶剂和聚合物的重要中间体。如今，生产吡咯烷酮的方法是以乙炔为底物，生成-丁内酯，然后与氨气相酰胺化，如果是以乙烯基吡咯烷酮为生产目标，则再次与乙炔进行Reppe乙烯化反应。最近的研究证明了乙酰丙酸化学催化胺化的可行性，而据我们所知，通过这种途径电化学法合成吡咯烷酮还没有被证明。总体而言，与化学催化相比，电化学使反应条件更温和，并提供了将可再生电能整合到化学价值链中的潜力。在建议的吡咯烷酮合成的情况下，可以避免高氢压，潜在的水溶液有助于沿着生物精炼价值链进行整合。尽管有很高的潜力和对科学和工业日益增长的兴趣，但对电化学转化的基本了解仍然有限。在生物质化学催化作价的情况下，有针对性的理论和实验研究，如乙酰丙酸等平台分子的形成和进一步转化，使基础理解有了显著的进步，并为设计可行的生物精炼概念奠定了坚实的基础。先前工作的例子包括申请者关于乙酰丙酸的化学催化还原、醇的胺化和生物原酸的电化学转化的研究。因此，本论文旨在对乙酰丙酸的电化学胺化反应进行综合的实验和理论研究。SAUTET小组将专注于电催化表面反应的第一性原理模拟，旨在全面了解机理，并深入了解控制电催化剂表面催化反应的因素。帕尔科维茨小组将对这种转变进行实验研究，重点是电催化剂和工艺参数的影响。

The proposed research relates to the electrochemical synthesis of pyrrolidones based on levulinic acid, a promising platform chemical available based on lignocellulosic biomass. Pyrrolidones are important intermediates for pharmaceutical products, solvents and polymers. Today, pyrrolidone production proceeds via acetylene as substrate to yield -butyrolactone followed by gas-phase amidation with ammonia and, in case of vinyl-pyrrolidone as target for PVP production, further Reppe vinylation again with acetylene. Recent studies demonstrate feasibility of a chemo-catalytic amination of levulinic acid, while an electrochemical pyrrolidone synthesis via such a pathway has, to the best of our knowledge, not been demonstrated yet. In general electrochemistry enables milder reaction conditions compared to chemocatalysis and provides the potential to integrate renewable electrical energy into chemical value chains. In case of the proposed pyrrolidone synthesis, high hydrogen pressure can be avoided and potentially aqueous electrolytes facilitate an integration along the biorefinery value chain. Despite the high potential and rising interest in science and industry, the fundamental understanding of electrochemical transformations remains limited. In case of the chemocatalytic biomass valorization, targeted theoretical and experimental investigations regarding the formation and further transformation of platform molecules such as levulinic acid enabled distinct advance in the fundamental understanding and served as strong base for the design of feasible biorefinery concepts. Examples on prior work include studies by the applicants on the chemocatalytic reduction of levulic acid, the amination of alcohols, and the electrochemical conversion of biogenic acids . Accordingly, we herein aim for an integrated experimental and theoretical investigation of the electrochemical amination of levulinic acid. The Sautet group will focus on first-principles simulations of the electrocatalytic surface reaction aiming for a comprehensive mechanistic understanding together with insight into factors controlling catalytic surface reactivity of the electrocatalyst. The Palkovits group will experimentally investigate the transformation with emphasis on the influence of electrocatalyst and process parameters.