Sustainable CO2 utilization as a reagent for commodity chemicals (funded by BASF)

处理二氧化碳的最佳方法是将其用于生产有价值的化学品。我们使用的大多数化学品都是碳基的。为了使这种方法有效、经济上有吸引力并且在能量消耗方面可持续，考虑具有与CO2类似氧化态的材料（例如羧酸）是有意义的。此外，为了有效地捕集CO2，考虑烟道气并直接在其旁边处理捕集的CO2是有用的。因此，其他试剂必须运输到CO2捕集点，因此低摩尔质量和良好运输性的试剂将是最合适的。理想地，反应的化学计量将有利于使用尽可能多的CO2。因此，我们将考虑用于商品化学品如聚酰胺和聚酯的二酸，特别是对对苯二甲酸和己二酸。然而，这些二酸的合成受到CO2的惰性和-考虑到对苯二甲酸的合成-苯缺乏反应性的影响。此外，在这两种情况下，选择性需要是正确的：如果将两当量的CO2加入到C4试剂中，则必须区域选择性地产生1，6-二羧酸（己二酸），在对对苯二甲酸的情况下，两当量的CO2的加入必须在芳环的帕拉。该项目将需要对合成化学，催化和光化学有很好的理解，并将提供化学工程方面的培训，以处理两相混合物和加压连续操作装置。此外，该项目将考虑光氧化还原化学的具体情况，在一个由六名BASF资助的光化学学生组成的跨学科和整体集群的框架内。

The most elegant way of disposing of CO2 is to utilize it for the production of valuable chemicals. Most of the chemicals we use are carbon-based. In order to make such a process efficient, economically attractive, and sustainable with respect to energy consumption, it makes sense to consider materials that have a similar oxidation state as CO2, e.g. carboxylic acids. Moreover, in order to capture CO2 efficiently, it is useful to consider flue gas and process the captured CO2 directly next to it. Consequently, the other reagents must be transported to the point of CO2 capture and therefore reagents of low molar mass and fair transportability would be best suited. Ideally the stoichiometry of the reaction would be in favour of using as much CO2 as possible. We will therefore consider di-acids that are used in commodity chemicals such as polyamides and polyesters, in particular p-terephthalic acid and adipic acid. The synthesis of these diacids, however, suffers from the inertness of CO2 and - considering the synthesis of terephthalic acid - the lack of reactivity of benzene. Moreover, in both cases the selectivity needs to be correct: if adding two equivalents of CO2 to a C4 reagent it must yield regioselectively the 1,6-dicarboxylic acid (adipic acid), in case of p-terephthalic acid the addition of two equivalents of CO2 must be in the para position of the aromatic ring. This project will require a good understanding of synthetic chemistry, catalysis and photochemistry and will provide training in chemical engineering with respect to handling bi-phasic mixtures and pressurized continuously operated setups. Moreover, the project will consider the specifics of photo-redox-chemistry in the framework of an interdisciplinary and holistic cluster of six BASF-funded students on photochemistry.