Catalytic Oxidative Coupling of Methane: Heterogeneous or Homogeneous Reaction?

Direct valorization of methane via oxidative coupling of methane (OCM) is an encouraging alternative to conventional oil-based processes for the production of light hydrocarbons (ethane and ethylene). Abundant, inexpensive simple oxides such as MgO and La₂O₃ possess the ability to selectively activate methane. However, during OCM, the selective conversion to ethane and the following dehydrogenation to ethylene are threatened by the thermodynamically favored partial and total oxidation reactions to form CO and CO₂, respectively. With the aid of spatially resolved operando analysis of temperature and gas concentration along the catalytic bed, we demonstrate the relevance of highly exothermic reaction paths developed in the gas phase, i.e., the homogeneous reaction, during OCM conditions at the front of the catalytic bed, largely determining the total C₂ yield obtained on those systems. With the new insights provided by the analysis of temperature and concentration gradients along the bed, we redefine the positive effect of promoters (Li, Sr), which enhance the influence of catalyst surfaces. The effect of promoters is recognized in the suppression of the exothermic oxidation paths leading to undesired CO_x, thus limiting the formation of hotspots and driving the reaction toward the desired C₂ products.