The design of efficient chiral catalysts is of crucial importance since it allows generating enantiomerically pure compounds. Tremendous efforts have been made over the past decades regarding the development of materials with enantioselective properties for various potential applications ranging from sensing to catalysis and separation. Recently, chiral features have been generated in mesoporous metals. Although these monometallic matrices show interesting enantioselectivity, they suffer from rather low stability, constituting an important roadblock for applications. Here, a straightforward strategy to circumvent this limitation by using nanostructured platinum-iridium alloys is presented. These materials can be successfully encoded with chiral information by co-electrodeposition from Pt and Ir salts in the simultaneous presence of a chiral compound and a lyotropic liquid crystal as asymmetric template and mesoporogen, respectively. The alloys enable a remarkable discrimination between chiral compounds and greatly improved enantioselectivity when used for asymmetric electrosynthesis (>95 %ee), combined with high electrochemical stability.
The development of surfaces with chiral features is a fascinating challenge for modern material science, especially when they are used for chiral separation technologies. In this contribution, the design of hierarchically structured chiral macroporous ZIF-8 electrodes is presented. They are elaborated by an electrochemical depositiondissolution technique, based on the electrodeposition of metal through a colloidal crystal template, followed by controlled electrooxidation. This generates locally metal cations, which can interact with a chiral ligand present in solution to form Metal-Organic Frameworks (MOFs). The macroporous structure facilitates the access of the chiral recognition sites, located in the mesoporous MOF and thus helps to overcome mass transport limitations. The efficiency of the designed functional materials for chiral adsorption and separation can be fine-tuned by applying an adjustable electric potential to the electrode surfaces. This hierarchical chiral ZIF-8 structure was deposited at the walls of a microfluidic device and used as a stationary phase for enantioselective separation. The potential-controlled interaction between the stationary phase and the chiral analytes allows baseline separation of two enantiomers. This opens up interesting perspectives for using hierarchically structured chiral MOF as an efficient material for the selective adsorption and separation of chiral compounds.
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