Abstract
Photo-oxidation of methane (CH(4)) using hydrogen peroxide (H(2)O(2)) synthesized in situ from air and water under sunlight offers an attractive route for producing green methanol while storing intermittent solar energy. However, in commonly used aqueous-phase systems, photocatalysis efficiency is severely limited due to the ultralow availability of CH(4) gas and H(2)O(2) intermediate at the flooded interface. Here, we report an atomically modified metal-organic framework (MOF) membrane nanoreactor that promotes direct CH(4) photo-oxidation to methanol at the gas-solid interface in a reticular open framework. We show that the domino synergy between colocalized single-atom palladium and iron on MOF nodes enables efficient generation and in situ utilization of H(2)O(2) in the absence of liquid water, thus circumventing H(2)O(2) dilution. Meanwhile, the "breathable" MOF membrane, optimized by solar-driven interfacial water management, provides high-flux channels to facilitate efficient gas diffusion and rapid methanol desorption and transfer. As a result, we demonstrate over 210 hours of continuous photosynthesis of 0.25 M methanol with unity selectivity, achieving an exceptional methanol productivity of 14.4 millimoles per gram of catalyst per hour.