The direct partial oxidation of CH4 to dimethyl ether (DME) on a Pt/Y2O3 catalyst was studied using a mixture of NO and O-2 as the oxidant. The reaction was carried out in a fixed bed reactor at 0.1 MPa and 275-400 degrees C using 20% CH4, 1% NO, and 1% O-2 in inert gas. No methanol was detected in the effluent and a contact time study demonstrated that DME was a primary product. The DME productivities were comparable to the oxygenate (methanol, formaldehyde) productivities obtained with stronger oxidants such as N2O, H2O2, and O-3. The presence of Pt and the NO + O-2 gas mixture was necessary for DME formation; without NO only CO2 was produced. During the methane partial oxidation reaction NO and NO2 were not reduced to N-2, indicating that they worked as a shuttle to transfer oxygen from O-2 to CH4. In situ Fourier transform infrared showed the formation of a bridged nitrate species on the Pt/Y2O3 catalyst which was associated with the reaction of CH4. A comprehensive study of this bridged nitrate species indicated they were formed on yttria sites close to Pt and were likely responsible for the formation of DME. The characterization of catalysts using X-ray diffraction showed that the Pt was highly dispersed and CO uptake measurements indicated a particle size of similar to 3 nm. Analysis by X-ray absorption fine structure measurements showed the presence of Pt oxide with Pt-O and Pt-Pt bonds. (C) 2020 Elsevier Inc. All rights reserved.