Improving sustainability of cellulose nanofibrils production: FTIR spectroscopy for online control of the synthesis of recyclable magnetic TEMPO catalyst

Abstract

2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and its derivatives are well-established catalysts for various oxidation processes, despite its hazardous nature, causing harm to aquatic ecosystems. Thus, the reuse of TEMPO with a sustained high activity has gained significant importance for its industrial application, which has led to the development of supported TEMPO catalyst. In this context, the efficiency of the support process acquires high relevance. Therefore, this research is aimed at the improvement of the TEMPO supported on silica magnetically modified with Fe3O4 through the application of an online Fourier transform infrared spectroscopy (FTIR) probe to monitor its synthesis. FTIR effectively controlled the synthesis of supported TEMPO, by tracking online the concentration of 3-aminopropyltriethoxysilane (APTES) and tetraethyl orthosilicate (TEOS). Additionally, the presence of Fe3O4 particles in the core of the catalyst allowed its convenient recovery and subsequent reuse. Furthermore, the supported TEMPO catalyst was successfully applied in the oxidation of cellulose to produce nano/microfibrils. The carboxyl groups of the initial untreated cellulose increase from 0.05 mmol/g to 0.68 mmol/g with the supported TEMPO catalyst in presence of sodium hypochlorite and sodium bromide at 50 °C