In Situ Growth of Mn-Co₃O₄ on Mesoporous ZSM-5 Zeolite for Boosting Lean Methane Catalytic Oxidation

The low-temperature oxidation of methane gas in coal mine exhaust gas is important for reducing the greenhouse effect and protecting the environment. Unfortunately, the carbon–hydrogen bonds in methane molecules are highly stable, requiring higher reaction temperatures to achieve effective catalytic oxidation. However, metal oxide-based catalysts face the problem of easy sintering and the deactivation of active components at high temperatures, which is an important challenge that catalysts need to overcome in practical applications. In this work, a series of Mn-Co₃O₄ active components were grown in situ on ZSM-5 zeolite with mesoporous pore structures treated with an alkaline solution via a hydrothermal synthesis method. Due to the presence of polyethylene glycol as a structure-directing agent, manganese can be uniformly doped into the Co₃O₄ lattice. The large specific surface area of ZSM-5 zeolite allows the active component Mn-Co₃O₄ to be uniformly dispersed, effectively preventing the sintering and growth of active component particles during the catalytic reaction process. It is worth mentioning that the Mn-Co₃O₄/meso-ZSM-5-6.67 catalyst has a methane conversion rate of up to 90% at a space velocity of 36,000 mL·g⁻¹·h⁻¹ and a reaction temperature of 363 °C. This is mainly due to the mesoporous ZSM-5 carrier with a high specific surface area, which is conducive to the adsorption and mass transfer of reaction molecules. The active component has an abundance of oxygen vacancies, which is conducive to the activation of reaction molecules and enhances its catalytic activity, which is even higher than that of noble metal-based catalysts. The new ideas for the preparation of metal oxide-based low-temperature methane oxidation catalysts proposed in this work are expected to provide new solutions for low-temperature methane oxidation reactions and promote technological progress in related fields.