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Sulfoxides are remarkably useful in asymmetric synthesis and drug development. Herein, we propose a new electroenzymatic cascade route to selectively synthesize methyl phenyl sulfoxide rather than methyl phenyl sulfone by the oxidation of thioanisole. Chloroperoxidase (CPO) functionalized with 1-ethyl-3-methylimidazolium bromide (ILEMB) is encapsulated into dendritic N-doped mesoporous carbon nanospheres (NMCNs) modified with polyethyleneimine (NMCNs-PEI) to form a biohybrid (CPO-ILEMB@NMCNs-PEI). The in situ generation of hydrogen peroxide (H2O2) species by the two-electron oxygen reduction reaction (2e−ORR) on NMCNs-PEI initiates the subsequent selective oxidation of thioanisole by CPO-ILEMB. NMCNs-PEI shows not only high electroactivity for the 2e−ORR but also good biocompatibility for CPO-ILEMB immobilization. The mesopores in NMCNs-PEI can provide a protective space for the encapsulated enzyme, ensuring the operational stability of the enzyme and avoiding the escape of H2O2, which result in high catalytic activity. The experimental results suggest that the catalytic efficiency of the electroenzymatic cascade system with the CPO-ILEMB@NMCNs-PEI biohybrid is up to 4.5 times higher than that of the free CPO-ILEMB catalytic system with H2O2 generated by NMCNs-PEI for the oxidation of thioanisole to produce methyl phenyl sulfoxide. [ABSTRACT FROM AUTHOR]

A porous silver nanostructure-supported ionic liquid-modified chloroperoxidase nanohybrid was successfully used in electroenzymatic tandem catalysis to achieve an efficient, mild, and stable approach for the conversion of nitrate into ammonia. [ABSTRACT FROM AUTHOR]

Carbonic anhydrase (CA) is bound to a dendritic porous copper foam (3D-Cu) via electrostatic interaction to form a biohybrid (CA/3D-Cu), which exhibits high selectivity and Faraday efficiency in the electroreduction of carbon dioxide (CO2) to formic acid (selectivity of 98.7%, Faraday efficiency of 82.1%) due to the large specific surface area of the 3D-Cu and the ultra-high CO2 hydration capacity of CA. [ABSTRACT FROM AUTHOR]

Pillared-layer metal–organic frameworks show great promise for gas storage and separation because their pore size as well as functionality usually can be controlled and adjusted synergistically. By combining the common pyridine and carboxylate groups, we design herein a new 3D pillared-layer framework, [Co2(DBPT)(BPY)2(CO3)]n (SNNU-95). Dinuclear [Co2] motifs are connected by DBPT ligands to form a 2D layer, which is further bridged by BPY to obtain the 3D pillar-layered framework of SNNU-95. Remarkably, two un-coordinated pyridine groups of DBPT not only help stabilize the 2D layer through π…π stacking but also point into the 1D channels to create an ultramicroporous environment. Taking advantage of the ultramicroporosity and pyridine Lewis basic sites, SNNU-95 shows not only extra high CO2 over CH4 and C2 hydrocarbons over CH4 selectivity, but also remarkable C2H2/CO2, C2H2/C2H4, and C2H4/CO2 separation under ambient conditions. This synergistic effect resulting from functional groups and pore size provides a promising route to design porous materials for the highest possible gas uptake and separation performance. [ABSTRACT FROM AUTHOR]

Pillared-layer metal-organic frameworks show great promise for gas storage and separation because their pore size as well as functionality usually can be controlled and adjusted synergistically. By combining the common pyridine and carboxylate groups, we design herein a new 3D pillared-layer framework, [Co2(DBPT)(BPY)2(CO3)]n (SNNU-95). Dinuclear [Co2] motifs are connected by DBPT ligands to form a 2D layer, which is further bridged by BPY to obtain the 3D pillar-layered framework of SNNU-95. Remarkably, two un-coordinated pyridine groups of DBPT not only help stabilize the 2D layer through ππ stacking but also point into the 1D channels to create an ultramicroporous environment. Taking advantage of the ultramicroporosity and pyridine Lewis basic sites, SNNU-95 shows not only extra high CO2 over CH4 and C2 hydrocarbons over CH4 selectivity, but also remarkable C2H2/CO2, C2H2/C2H4, and C2H4/CO2 separation under ambient conditions. This synergistic effect resulting from functional groups and pore size provides a promising route to design porous materials for the highest possible gas uptake and separation performance.