Mn_xWO₄ Nanostructure-Based Catalysts for Single-Step Oxidation of Cyclohexane and Methane to Oxygenates

Activation of the C–H bond in cyclohexane (CYH) and methane is a crucial step to obtain desirable oxygenated products using nanostructured catalyst and is a great challenge and an efficient route to mitigate the inauspicious effects of climate change. The active sites were identified using XRD, HR-TEM, SEM, N 2 sorption analysis, TPR, Raman, XPS, TGA, in situ DRIFT, XAS, etc. In optimal reaction conditions, 46% of CYH was converted into adipic acid (AA) on Mn x WO 4 nanostructures within 6 h. The recyclability test confirmed the catalyst heterogeneity, which revealed no appreciable loss of catalytic activity even after three consecutive reactions. In situ DRIFT study reveals that CYH is oxidized to cyclohexanone and cyclohexanol (KA oil) and is further oxidized to AA via carboxylate intermediates. DFT studies disclosed that MnOx species are responsible for the C–H activation of CYH, and the Mn 2+/ Mn 3+ redox centers play a vital role in the absorption of KA oil to form AA. Herein, we demonstrated the significant role of the “MnOx” species and that adequate Lewis and Bronsted acidic sites, redox centers of (Mn 2+ /Mn 3+ ), and lattice oxygen are accountable for the CYH conversion toward the AA. Additionally, we have reported the oxidation of methane to methanol (146 μmole per gram of catalyst) in the presence of water at 75 °C without over-oxidation products.