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.
A hybrid film composed of chiral encoded mesoporous platinum and polypyrrole shows differential wireless actuation as a function of the chiral nature of an enantiomer present in solution.
Concepts leading to single enantiomers of chiral molecules are of crucial importance for many applications, including pharmacology and biotechnology. Recently, mesoporous metal phases encoded with chiral information have been developed. Fine‐tuning of the enantioaffinity of such structures by imposing an electric potential is proposed, which can influence the electrostatic interactions between the chiral metal and the target enantiomer. This allows the binding affinity between the chiral metal and the target enantiomer to be increased, and thus, the discrimination between two enantiomers to be improved. The concept is illustrated by generating chiral encoded metals in a microfluidic channel by reduction of a platinum salt in the presence of a liquid crystal and l‐tryptophan as a chiral model template. After removal of the template molecules, the modified microchannel retains a pronounced chiral character. The chiral recognition efficiency of the microchannel can be fine‐tuned by applying a suitable potential to the metal phase. This enables the separation of both components of a racemate flowing through the channel. The approach constitutes a promising and complementary strategy in the frame of chiral discrimination technologies.
The enantioselective synthesis of chiral compounds is of crucial importance for a wide range of potential applications, especially in cosmetic and pharmaceutical industries. Recently, chiral imprinted mesoporous platinum films, produced by the electrodeposition of the metal, in the simultaneous presence of a lyotropic liquid crystalline phase of non-ionic surfactants as mesoporogens and chiral templates, have been applied as electrocatalysts and selective stationary phases for the asymmetric synthesis and separation of chiral compounds, respectively. However, platinum is an expensive metal and therefore it is mandatory to explore the possibility to apply this concept also to other metals. In this contribution, we propose mesoporous chiral imprinted nickel as an alternative cheap and earth-abundant metal. The designed surface layers not only demonstrate electrochemical discrimination between two enantiomers, but most importantly, also allow stereospecific electroreduction of a prochiral compound, with very significant enantioselectivity of up to 80% ee. These results open up very promising perspectives for the development of low cost non-noble metal matrices for the synthesis of chiral compounds.
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.
The sustainable conversion of biomass-derived compounds into high added-value products is a very important contemporary scientific challenge. In this context, we report here the simultaneous electro-oxidation/-reduction of a biomass-derived compound...
The development of heterogeneous catalysts for asymmetric synthesis is one of the most challenging topics in chemistry, as it allows obtaining enantiomerically pure compounds. Recently, metal layers incorporating molecular chiral cavities, obtained by electroreduction of a metal source in the simultaneous presence of a non‐ionic surfactant and asymmetric molecules, have been proposed for a wide range of applications, including enantioselective electroanalysis and electrosynthesis, as well as chiral separation. In contrast to this previous work, solely based on electrochemical phenomena, herein we designed and employed nanostructured chiral encoded Pt−Ir alloys, supported on high surface area nickel foams, as heterogeneous catalysts for the asymmetric hydrogenation of aromatic ketones. Fine‐tuning the experimental conditions allows achieving very high enantioselectivity (>80%), combined with improved catalyst stability.
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