Immobilization of chitosan-templated MnO2 nanoparticles onto filter paper by redox method as a retrievable Fenton-like dip catalyst

By exploiting the hydrophilicity of cellulose filter paper (FP) and the excellent chelating property of chitosan (CH) for Mn2+, we have designed an efficient and retrievable dip catalyst MnO2/CH-FP for Fenton-like degradation of methylene blue (MB) over a wide pH range from 2.8 to 11.2. The MnO2 nanoparticles were uniformly immobilized in the CH-FP matrix by in-situ redox precipitation method where Mn(NO3)2 was treated with KMnO4 at mild conditions. A series of MnO2/CH-FP hybrids with different MnO2 loading were fabricated via varying concentration of Mn(NO3)2 solution, and their structure-function relationships were discussed based on detailed characterization. The optimal catalyst 1.0MnO2/CH-FP could cooperate with multiple low-concentration dosages of H2O2 to efficiently degrade 95.6% MB in 90 min (50 mg L−1 MB, 1 g L−1 catalyst, 30 mg L−1 H2O2, pH 7). It is also shown that 1.0MnO2/CH-FP could still keep 83.3% degradation efficiency of MB after six cycles. Moreover, the activity of this composite greatly surpassed that of bare MnO2 for nearly 50%, owing to its larger surface area and more accessible active sites. This method for preparing MnO2/CH-FP could effectively avoid the agglomeration of MnO2 nanoparticles and make the reaction turn on/off almost instantaneously by mere insertion/removal. [Display omitted] •Nano-MnO2 was in-situ anchored on the biopolymer by redox precipitation method.•It was an efficient and highly retrievable dip catalyst for Fenton-like degradation.•The hybrid has lager surface area and more accessible active sites than bare MnO2.•The relationship between MnO2 loading and degradation efficiency was discussed.•Multiple low-concentration doses of H2O2 could achieve better decolorization.