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

处理二氧化碳最优雅的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。为了使这一过程在能源消耗方面具有效率、经济吸引力和可持续性，考虑具有与二氧化碳相似的氧化状态的材料是有意义的，例如羧酸。此外，为了有效地捕获二氧化碳，考虑烟道气并直接在其旁边处理捕获的二氧化碳是有用的。因此，其他试剂必须运输到二氧化碳捕获点，因此低摩尔质量和可运输性的试剂将是最合适的。理想情况下，该反应的化学计量应有利于使用尽可能多的二氧化碳。因此，我们将考虑在聚酰胺和聚酯等商品化学品中使用的二元酸，特别是对苯二甲酸和己二酸。然而，这些二元酸的合成受制于二氧化碳的惰性--考虑到对苯二甲酸的合成--苯缺乏反应性。此外，在这两种情况下，选择性都必须是正确的：如果向C4试剂中添加两个当量的CO2，它必须区域选择性地产生1，6-二元酸(己二酸)，如果是对苯二甲酸，则两个当量的CO2的加成必须在芳环的对位。该项目将要求对合成化学、催化和光化学有很好的了解，并将在处理两相混合物和加压连续操作装置方面提供化学工程方面的培训。此外，该项目将在一个由六名巴斯夫资助的光化学学生组成的跨学科和整体集群的框架内考虑光氧化还原化学的具体问题。

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.