Single‐Atom Zn Interface Engineering for Efficient Noble‐Metal‐Free Photocatalytic Non‐Oxidative Coupling of Methane

ABSTRACT ZnO‐based photocatalysts have attracted extensive attention for methane (CH 4 ) conversion because their intrinsic internal electric field can effectively polarize and activate CH 4 . However, the mismatch between charge‐carrier dynamics and surface reaction kinetics limits the utilization of photogenerated reactive species, making noble‐metal modification necessary to achieve efficient methane conversion. In this study, we report a noble‐metal‐free single‐atom photocatalyst in which isolated Zn atoms are anchored onto anatase TiO 2 via µ‐oxo bridges (Zn─O─TiO 2 ) for photocatalytic non‐oxidative coupling of methane (NOCM). This structure not only promotes efficient charge separation and suppresses carrier recombination, enabling the formation of long‐lived Zn + and O − reaction centers, but also provides active sites to accelerate surface reaction kinetics. Consequently, the catalyst achieves an ethane rate of 44.75 µmol·g −1 ·h −1 in a batch reactor, and 1.09 mmol·g −1 ·h −1 in a flow reactor. The apparent quantum efficiency reaches 8.81% at 350 nm. Mechanistic studies reveal that photogenerated holes at O − centers activate CH 4 to CH 3 radicals, while electrons at Zn + sites drive H 2 evolution, synergistically enabling efficient NOCM. This work establishes single‐atom interface engineering as an effective strategy for simultaneously promoting charge separation and enhancing surface catalytic reaction, providing a general strategy for designing noble‐metal‐free photocatalysts for small‐molecule activation.