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

所提出的研究涉及基于乙酰丙酸的吡咯烷酮的电化学合成，乙酰丙酸是一种基于木质纤维素生物质的有前途的平台化学品。吡咯烷酮是医药产品、溶剂和聚合物的重要中间体。如今，吡咯烷酮的生产通过乙炔作为底物进行以产生α-丁内酯，然后用氨进行气相酰胺化，并且在乙烯基吡咯烷酮作为PVP生产的目标的情况下，再次用乙炔进一步进行Reppe乙烯化。最近的研究证明了乙酰丙酸的化学催化胺化的可行性，而通过这样的途径电化学合成吡咯烷酮，据我们所知，尚未得到证实。通常，与化学催化相比，电化学能够实现更温和的反应条件，并提供将可再生电能整合到化学价值链中的潜力。在所提出的吡咯烷酮合成的情况下，可以避免高氢气压力，并且潜在的水性电解质促进了沿着生物精炼价值链的整合。尽管在科学和工业中具有很高的潜力和不断增长的兴趣，但对电化学转化的基本理解仍然有限。在化学催化生物质价值稳定的情况下，关于平台分子如乙酰丙酸的形成和进一步转化的有针对性的理论和实验研究使得在基本理解方面取得了明显进展，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人对乙酰丙酸的化学催化还原、醇的胺化和生物酸的电化学转化的研究。 因此，我们在这里的目标是一个综合的实验和理论研究乙酰丙酸的电化学胺化。Sautet小组将专注于电催化表面反应的第一性原理模拟，旨在全面了解电催化剂的催化表面反应性的控制因素。Palkovits小组将通过实验研究这种转变，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.