Thermochemical Properties of the Lattice Oxygen in W,Mn-Containing Mixed Oxide Catalysts for the Oxidative Coupling of Methane

Mixed NaWMn/SiO₂ oxide, samples containing individual components (Na, W, Mn) and their double combinations (Na–W, Na–Mn, W–Mn) supported on silica were studied by temperature programmed reduction (TPR) and desorption (TPD), and heat flow calorimetry during their reoxidation with molecular oxygen in pulse mode. The NaWMn/SiO₂ mixed oxide was shown to contain two different types of reactive lattice oxygen. The weakly-bonded oxygen can be reversibly released from the oxide in a flow of inert gas in the temperature range of 575‒900°C, while the strongly-bonded oxygen can be removed during the reduction of the sample with hydrogen at 700–900°C. The measured thermal effect of oxygen consumption for these two oxygen forms are 185 and 350 kJ/mol, respectively. The amount of oxygen removed at reduction (~443 μmol/g) considerably exceeded the amount desorbed in an inert gas flow (~56 μmol/g). The obtained results suggest that the reversible oxygen desorption is due to the redox process in which manganese ions are involved, while during the temperature programmed reduction, mainly oxygen bonded with tungsten is removed.