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The fluorine element is used in domains as diverse as medicine, energy, microelectronics and everyday plastic objects. Rare in the natural state, a tremendous number of elegant syntheses of fluorinated organic compounds has been developed by using catalysts to improve both activity and selectivity. Catalyzed fluorination by HF in the gas phase is largely operated at industrial scale, essentially for non-functionalized aliphatic fluorinated compounds prepared from chlorinated precursors by Cl/F exchange. In contrast, this strategy is neither applicable to functionalized aliphatic fluorinated compounds due to the sensitivity of most organic functions towards HF, nor for fluoroaromatics which are essentially produced by 2 liquid phase reactions (Balz-Schiemann and HALEX). However, these reactions, poorly selective, generate large volumes of non-recoverable effluents. Therefore, new selective fluorination methods are needed, ideally more efficient, selective and environmentally sustainable. Such an alternative approach, already successfully used for non-functionalized aliphatic fluorinated molecules, is the one-step fluorination of chlorinated aromatic molecules via a gas phase process based Cl/F exchange under anhydrous HF involving catalysts. Additionally, no solvent is required and HCl is the only by-product which is recoverable. Recently, nanofluorides were used as efficient catalysts for the fluorination of 2-chloropyridine. While the selectivity of this reaction is optimal, the activity, related to the weak strength of Lewis acidity of active sites, could be enhanced by increasing the catalyst surface area. Indeed, under harsh conditions (HF gas at 350°C), the nanofluoride catalysts undergo a sintering process leading to a drastic loss of the initially promising surface areas. This stumbling block forces us to explore innovative directions in order to develop such materials, fulfilling the 3 key requirements of a catalyst: activity related to its specific area, selectivity and stability under extreme operating conditions. The innovation of the OPIFCat project is to prepare inorganic fluorinated metallic materials as efficient, selective and stable catalysts under the harsh fluorination conditions of chlorinated reagents under HF gas. In this context, we will explore new architectures and innovative production methods focused on ordered porous inorganic fluorides (OPIFs) supposed to resist such conditions and whose design methodology will be soon patented by the team of IMMM. The chemical composition of the OPIF catalysts will be guided by computer modelling of reaction site chemistry. We will target new Cl/F exchange reactions involving nucleophilic aliphatic and aromatic substitution with five molecules which are involved in domains of energy, agrochemistry and medicine. This project aims to understand the catalyst structure-activity relationship and to establish a “catalyst library” with various strength of Lewis acidity which will help chemists to rapidly select the most appropriate catalyst for the Cl/F exchange as a function of the reactant characteristics (aliphatic/aromatic, activated or not, bearing one or several heteroatoms,…). This OPIFCat project relies on a transdisciplinary consortium with complementary skills, and involves a large industrial group proactive in the sustainable energy transition. It is composed of highly qualified scientists with expertise in the elaboration of fluorinated and polymer materials (IMMM) as well as heterogeneous catalysis (IC2MP), and is completed by an expert of modelling interaction of nanomaterials with reactive species (IMN). Solvay will ensure the scale-up of the OPIF materials and their catalytic properties will be validated in a continuous tubular reactor.
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