Role of catalytic nitrile decomposition in tricopper complex mediated direct partial oxidation of methane to methanol

Synthetic homogeneous system known to date performing methane to methanol conversion using O2 as terminal oxidant is unique and based on copper complex with piperazine-based ligand (Cu3L in Fig. 1) in a medium of acetonitrile. Prior work have shown that in order to achieve catalytic turnover, hydrogen peroxide is needed to regenerate the active site. We show in this paper that reaction solvent based on organic nitrile decompose concurrently with methane activation and that in the absence of either acetonitrile, Cu complex or hydrogen peroxide, the catalytic turnover does not happen. We show in this manuscript that the direct methane oxidation to methanol might have been mediated by catalytic Radziszewski oxidation between acetonitrile and H2O2. Additionally we have discovered that in the absence of methane, peroxide mediated acetonitrile decomposition also makes methanol via a background reaction which was hitherto unknown.

Selective Methanol Formation via CO-Assisted Direct Partial Oxidation of Methane over Copper Containing CHA-type Zeolites Prepared by One-pot Synthesis

Catalytic CO-assisted direct conversion of methane into methanol was demonstrated over Cu-CHA zeolites. Methanol was selectively produced as a solo oxygenate product. The results suggested the necessity of low copper...

Isotopic 18O/16O substitution study on the direct partial oxidation of CH4 to dimethyl ether over a Pt/Y2O3 catalyst using NO/O2 as an oxidant

Dimethyl ether (DME) is produced by partial oxidation of CH4 with NO/O2 on Pt/Y2O3. Isotopic oxygen (18O2) is used to confirm molecular O2 as the ultimate oxidant and a kinetic isotope effect for 18O/16O is observed.