Electroenzymatic cascade reaction on a biohybrid boosts the chiral epoxidation reaction.

[Display omitted] The chiral epoxidation of styrene and its derivatives is an important transformation that has attracted considerable scientific interest in the chemical industry. Herein, we integrate enzymatic catalysis and electrocatalysis to propose a new route for the chiral epoxidation of styrene and its derivatives. Chloroperoxidase (CPO) functionalized with 1-ethyl-3-methylimidazolium bromide (IL EMB) was loaded onto cobalt nitrogen-doped carbon nanotubes (CoN@CNT) to form a biohybrid (CPO-IL EMB /CoN@CNT). H 2 O 2 species were generated in situ through a two-electron oxygen reduction reaction (2e–ORR) at CoN@CNT to initiate the following enzymatic epoxidation of styrene by CPO. CoN@CNT had high electroactivity for the ORR to produce H 2 O 2 at a more positive potential, prohibiting the conversion of FeIII to FeII in the heme of CPO to maintain enzymatic activity. Meanwhile, CoN@CNT could serve as an ideal carrier for the immobilization of CPO-IL EMB. Hence, the coimmobilization of CPO-IL EMB and CoN@CNT could facilitate the diffusion of intermediate H 2 O 2 , which achieved 17 times higher efficiency than the equivalent amounts of free CPO-IL EMB in bulk solution for styrene epoxidation. Notably, an enhancement (∼45%) of chiral selectivity for the epoxidation of styrene was achieved. [ABSTRACT FROM AUTHOR]