Metal-organic framework (MOF)-derived flower-like Ni-MOF@NiV-layered double hydroxides as peroxidase mimetics for colorimetric detection of hydroquinone

Background: Nanozymes are one of the ideal substitutes for natural enzymes because of their excellent chemical stability and simple preparation methods. However, due to the limited catalytic ability of most reported nanozymes, constructing nanomaterials with low cost and high activity is gradually becoming an exploration focus in the field of nanozymes. Heteroatom doping of metal-organic frameworks is one of potential approaches to design nanozymes with high catalytic performance. Due to their multiple valence states properties, V-doped metal-organic framework (MOF)-derived LDH is expected to be a good enzyme-like catalyst. To our knowledge, the V-doped MOF-derived LDH as nanozyme is not explored before.Results: We report the in-situ synthesis of NiV-layered double hydroxides (LDHs) on nickel-based MOF, i.e. Ni-MOF@NiV-LDHs. The MOF surface is covered by 2D nanosheets. This unique structural design increases the specific surface area of the material, enables more exposure of catalytic active sites to participate in reactions and accelerates the electron transfer rate. The Ni-MOF@NiV-LDHs have high peroxidase-like activity able to catalyze TMB oxidation by H2O2 via the generation of center dot OH and O2 center dot  . Relative to Ni-MOF, the Ni-MOF@NiV-LDHs shows 47-fold peroxidase-like activity rise. It had good affinity to TMB and H2O2, with the Michaelis-Menten constants of 0.12 mM and 0.007 mM, respectively. The hydroquinone (HQ) consumed the reactive oxygen species generated in the TMB + H2O2+Ni-MOF@NiV-LDHs system to inhibit the TMB oxidation. On this basis, a sensitive and rapid assay for determining HQ was developed, with a linear range of 0.50-70 mu M and a LOD of 0.37 mu M.Significance: This work provided some clues for the further development of novel nanozymes with high catalytic performance via a strategy of heteroatom doping. And the constructed colorimetric analysis method was successfully utilized for the determination of HQ in actual waters, which has the potential for practical application in the analysis of environmental pollutants.

Automated summary

This study successfully synthesized NiV-layered double hydroxides with significant peroxidase-like activity for oxidation reactions and developed a method for determining HQ. The findings provided insights for the development of novel nanozymes with high catalytic performance and potential practical application in environmental pollutant analysis.