MOF-derived Co3O4@Co-Fe oxide double-shelled nanocages as multi-functional specific peroxidase-like nanozyme catalysts for chemo/biosensing and dye degradation

• Published in: Chemical engineering journal (Lausanne, Switzerland : 1996) Switzerland : 1996), 2020-09, Vol.395, p.125130, Article 125130
• Main Authors: Chen, Qiumeng, Zhang, Xiaodan, Li, Siqi, Tan, Jianke, Xu, Chengji, Huang, Yuming
• Format: Article
• Language: English
• Subjects: Double-shelled structure; Dye degradation; Metal organic framework; Nanozymes; Peroxidase-like activity; Peroxymonosulfate activation
• ISSN: 1385-8947; 1873-3212
• DOI: 10.1016/j.cej.2020.125130

[Display omitted] •Co3O4@Co-Fe oxide DSNCs is derived from ZIF-67 and Co-Fe Prussian blue analogue.•Co3O4@Co-Fe oxide shows higher peroxidase-like activity than Co3O4 and Co-Fe oxide.•Co3O4@Co-Fe oxide DSNCs show high PMS activating ability to degrade dye in water.•A sensitive chemo/biosensing assay for H2O2 and AChE with wide linear range.•Recyclability of Co3O4@Co-Fe oxide for AF degradation keeps 92.3% up to 10 cycles. Nanozymes are attractive alternatives to natural enzymes due to their high stability and low cost. However, it is still a great challenge to acquire highly active, specific, and multi-functional nanozyme catalysts for chemo/biosensing and peroxymonosulfate (PMS) activation to degrade toxic dye pollutants. Metal-organic frameworks are attractive templates to construct multi-functional catalysts. Herein, Co3O4@Co-Fe oxide double-shelled nanocages (DSNCs) were prepared via anion-exchange combined with low-temperature pyrolysis by using ZIF-67 as a starting template. They maximized the advantages of a hollow nanostructure, acting as both nanoreactor and substrate channel, to mimic enzymes. This enables high peroxidase-like activity and very weak oxidase-like activity. The Km value of Co3O4@Co-Fe oxide DSNCs for H2O2 was 1.38 and 3.33-fold lower than those of single-shelled Co-Fe oxide and Co3O4 nanozymes, respectively. The high peroxidase-like activity of Co3O4@Co-Fe oxide DSNCs enabled H2O2 linear detection over the range 0.02 to 600 μM, with a detection limit of 20 nM. When coupled with the acetylcholinesterase/acetylthiocholine cascade enzymatic reaction, we proposed an ultra-sensitive colorimetric platform for acetylcholinesterase activity screening in the linear range over 8 × 10−4–1 mU mL−1, with a detection limit of 2 × 10−4 mU mL−1. The Co3O4@Co-Fe oxide DSNCs can active PMS to degrade 99.1% of acid fuchsin within 20 min, along with good reusability over ten-cycle run. The kinetics of 15 mg L−1 acid fuchsin degradation was 0.176 min−1 at 25 °C with 300 mg L−1 PMS and 150 mg L−1 DSNCs. This work details the attractive applications of DSNCs for chemo/biosensing and dye degradation.