Controlled formation of porous CuCo2O4 nanorods with enhanced oxidase and catalase catalytic activities using bimetal-organic frameworks as templates

Porous structures with highly dispersed and active catalytic sites are vital to improve the catalytic activity and stability of artificial enzyme-related catalytic reactions. Herein, a novel nanorod-like bimetal-organic framework serving as porous support and supplier of Co2+ and Cu2+ was used to prepare a beneficial porous metal oxide. By optimizing the calcination temperature, the composition of calcined product can be controlled and the nanorods with isolated and highly active CuCo2O4 nanoparticles were obtained. The porous CuCo2O4 nanorods exhibit a pH-dependent catalytic property, that is, they behave as oxidase in acid conditions and catalase in alkaline conditions. The CuCo2O4 nanorods perform dual-enzyme catalytic activity superior to monometallic oxides. What's more, compared with the reported Co3O4 nanoparticles, Co3O4/CuO hollow nanocage hybrids and NiCo2O4 mesoporous spheres, the porous CuCo2O4 nanorods show higher affinity to 3,3',5,5'-tetra-methylbenzidine with a lower Km value. The superior dual-enzyme catalytic activities of CuCo2O4 nanorods benefit from the high catalytic activity of binary metal oxides and structural stability. After incubating in a wide range of pHs, temperatures and ionic strengths, the catalytic activity of CuCo2O4 nanorods can be maintained. The oxidase activity of CuCo2O4 nanorods can be inhibited in the presence of ascorbic acid, which can be applied in effective detection of ascorbic acid. This study opens a new path to prepare stable and highly active porous artificial enzymes.