Blueprint for a modern sustainable phosphorus chemistry

目前可用原生磷资源的枯竭令人极为担忧，这就是欧盟将磷矿石和元素磷列入关键原材料清单的原因。到目前为止，从磷矿石到基础化学品的价值链并不符合“绿色化学”的指导原则。此外，通过合适的大规模再循环工艺来回收有价值的磷化合物的磷回收问题在未来将变得更加尖锐。由于这些原因，迫切需要在重要元素磷的价值链中开发新的和创新的化学方法。在我们现代可持续磷化学的蓝图中，我们研究了系统的、原子和能源效率高的方法来去除磷酸和回收磷酸盐资源（来自污水污泥的鸟粪石，来自阴极材料的LiFePO 4）。我们的方法的优点是避免了将磷酸盐转化为白色磷（将P（V）还原为P（0））和再氧化/氯化为目前最重要的磷中间体PCl 3、OPCl 3和P4 O 10（将P（0）氧化为P（III）或P（V））的非常耗能的转化。我们的目标是将磷酸盐（PO 43-）或其他P（V）试剂直接转化为P1结构单元，从而实现各种有价值的P（V）化合物的“氧化还原中性”合成，从而提供直接获得各种平台化学品的途径。此外，从这些P（V）化合物开始，我们将开发电化学还原过程以制备P（III）化合物（例如膦）。用合适的酸酐（例如，Tf 2 O）在碱（例如，LN）将提供P1结构单元，包括（LN）2 PO 2 [OTf]类型的结构单元，其可以“氧化还原中性”转化为磷（V）平台化学品。这种方法的一个具有挑战性的扩展是从高度成问题的耗尽化合物UF 6开始合成各种PF 6盐，这对电池电解质非常重要。通过这一探索性项目，我们将联合收割机可持续磷化学的新方法与处置贫化六氟化铀的替代合成路线相结合，从而为现代化学最紧迫的问题之一-不可再生和/或关键资源的可持续管理以及危险废物的风险缓解-作出全面贡献。

The current depletion of available primary phosphorus resources is extremely worrying, which is why the EU has included phosphate rock and elemental phosphorus in the list of critical raw materials. So far, the value chain from phosphate ores to basic chemicals does not correspond to the guiding principle of "green chemistry". In addition, the problem of phosphorus recovery through suitable large-scale recycling processes to recover valuable phosphorus compounds will become drastically more acute in the future. For these reasons, the development of new and innovative chemical methods in the value chain of the important element phosphorus is urgently needed. In our blueprint for a modern sustainable phosphorus chemistry, we investigate systematic as well as atom and energy efficient ways to deoxygenate phosphoric acid and recycled phosphate resources (struvite from sewage sludge, LiFePO4 from cathode material). The advantage of our approach is the avoidance of the very energy-intensive conversion of phosphate to white phosphorus (reduction of P(V) to P(0)) and reoxidation/chlorination to the currently most important phosphorus intermediates PCl3, OPCl3 and P4O10 (oxidation of P(0) to P(III) or P(V)). Our goal here is the direct conversion of phosphates (PO43-) or other P(V) reagents to P1 building blocks, allowing "redox neutral" synthesis of a variety of valuable P(V) compounds, thus providing direct access to a wide range of platform chemicals. Furthermore, starting from these P(V) compounds, we will develop electrochemical reduction processes to P(III) compounds (e.g. phosphanes). The conversion of phosphate resources with suitable anhydrides (e.g., Tf2O) in the presence of a base (e.g., LN) will provide P1 building blocks, including those of the type (LN)2PO2[OTf], which can be converted "redox neutrally" to phosphorus (V) platform chemicals. A challenging extension of this approach is the synthesis of various PF6 salts, very important for battery electrolytes, starting from the highly problematic depleted compound UF6. With this exploratory project, we will combine new approaches in sustainable phosphorus chemistry with alternative synthetic routes for the disposal of depleted uranium hexafluoride (UF6), thus contributing overall to one of the most pressing problems of modern chemistry - the sustainable management of non-renewable and/or critical resources and risk mitigation of hazardous waste.