Role of hydroxyl groups in Zn‐containing nanosized MFI zeolite for the photocatalytic oxidation of methane

Effective conversion of methane to a mixture of more valuable hydrocarbons and hydrogen under mild conditions is a great scientific and practical challenge. Here, we synthesized Zn‐containing nanosized MFI zeolite for direct oxidation of methane in the presence of H2O and air. The presence of the surface hydroxyl groups on nanosized MFI‐type zeolite and their significant reduction in the Zn‐containing nanosized MFI zeolite were confirmed with Infrared Fourier Transform (FTIR) spectroscopy. Incorporation of zinc atoms into the framework of nanosized MFI zeolite is revealed by Nuclear Magnetic Resonance, X‐ray Diffraction a UV‐Vis Spectroscopy. Unexpectedly, pure silica MFI zeolite exhibited the highest photocatalytic performance. Our finds demonstrated that large number of isolated silanol groups and silanol nests increase the formation of •OH, and enhance the productivity of oxygenate compounds and C2H6, while the Zn incorporated into the zeolite framework or attached to the silanol nests of the nanosized zeolites are less efficient. A mechanism of photocatalytic methane oxidation is proposed. These findings provide insights into developing active nanosized zeolite photocatalysts with extended amount of surface hydroxyl groups that can play a key role in photocatalytic methane conversion.