An emerging method for effectively improving the catalytic activity of metal oxide hybrids involves the creation of metal oxide interfaces for facilitating the activation of reagents. Here, we demonstrate that bilayer...An emerging method for effectively improving the catalytic activity of metal oxide hybrids involves the creation of metal oxide interfaces for facilitating the activation of reagents. Here, we demonstrate that bilayer vesicles formed from a hexavanadate cluster functionalized with two alkyl chains are highly efficient catalysts for the oxidation of 3,3＇,5,5＇-tetramethylbenzidine （TMB） with H2O2 at room temperature, a widely used model reaction mimicking the activity of peroxidase in biological catalytic oxidation processes. Driven by hydrophobic interactions, the double-tailed hexavanadate-headed amphiphiles can self-assemble into bilayer vesicles and create hydrophobic domains that segregate the TMB chromogenic substrate. The reaction of TMB with H2O2 takes place at the interface of the hydrophilic and hydrophobic domains, where the reagents also make contact with the catalytic hexavanadate clusters, and it is approximately two times more efficient compared with the reactions carried out with the corresponding unassembled systems. Moreover, the assembled vesicular system possesses affinity for TMB comparable to that of reported noble metal mimic nanomaterials, as well as a higher maximum reaction rate.展开更多
基金We gratefully acknowledge the financially support by the National Natural Science Foundation of China （Nos. 21631007, 21401050, 21471087 and 21271068）, Beijing Natural Science Foundation （No. 2164063）, China Postdoctoral Science Foundation （No. 2014M560948）, the State Key Laboratory of Natural and Biomimetic Drugs （No. K20160202）, the National Natural Science Foundation of Hubei Province （No. 2015CFA131） and Wuhan Applied Basic Research Program （No. 2014010101010020）. T. B. L. acknowledges support from the National Science Foundation （No. CHE1607138） and the University of Akron.
文摘An emerging method for effectively improving the catalytic activity of metal oxide hybrids involves the creation of metal oxide interfaces for facilitating the activation of reagents. Here, we demonstrate that bilayer vesicles formed from a hexavanadate cluster functionalized with two alkyl chains are highly efficient catalysts for the oxidation of 3,3＇,5,5＇-tetramethylbenzidine （TMB） with H2O2 at room temperature, a widely used model reaction mimicking the activity of peroxidase in biological catalytic oxidation processes. Driven by hydrophobic interactions, the double-tailed hexavanadate-headed amphiphiles can self-assemble into bilayer vesicles and create hydrophobic domains that segregate the TMB chromogenic substrate. The reaction of TMB with H2O2 takes place at the interface of the hydrophilic and hydrophobic domains, where the reagents also make contact with the catalytic hexavanadate clusters, and it is approximately two times more efficient compared with the reactions carried out with the corresponding unassembled systems. Moreover, the assembled vesicular system possesses affinity for TMB comparable to that of reported noble metal mimic nanomaterials, as well as a higher maximum reaction rate.
