Polyoxometalate-Based Chiral MOF Featuring Superior Enantioselective Electrocatalytic Oxidation Performance

The critical role of chirality in biological and chemical systems has driven the demand for advanced nanocatalytic platforms capable of achieving efficient chiral selective recognition and conversion. The present study details the design of chiral polyoxometalate metal-organic frameworks (POMOFs) based on polyoxometalates, which mimic enzyme-catalyzed multiphase catalysis by combining the redox activity of Keggin-type polyoxometalates with the stereoselectivity of chiral MOFs. This design strategy precludes the aggregation of catalytic sites through uniformly dispersed POM clusters. The resulting NENU-5 chiral composite displays excellent electrochemical enantiomeric recognition of tryptophan enantiomers (<i>I</i>_D/<i>I</i>_L = 2.11), attributed to its high density of metal active sites, high electron transfer efficiency, and superior electrocatalytic performance. Experiments revealed that the optimal conditions for recognition (pH = 6.0, 5 mM concentration, 30 s incubation) achieved detection limits of 0.28 μM (l-Trp) and 0.70 μM (d-Trp). This study provides novel insights into the design of suitable chiral nanocatalysts for asymmetric chiral selective recognition and catalysis and further expands their application prospects in electrochemical chiral recognition.