In Situ Encapsulation of Graphene Quantum Dots in Highly Stable Porphyrin Metal-Organic Frameworks for Efficient Photocatalytic CO2 Reduction.

Photocatalytic CO2 reduction to valuable hydrocarbon solar fuel is of great significance but still challenging. Strong CO2 enrichment ability and easily adjustable structures make metal-organic frameworks (MOFs) potential photocatalysts for CO2 conversion. Even though pure MOFs have the potential for photoreduction of CO2, the efficiency is still quite low due to rapid photogenerated electron-hole recombination and other drawbacks. In this work, graphene quantum dots (GQDs) were in situ encapsulated into highly stable MOFs via a solvothermal method for this challenging task. The GQDs@PCN-222 with encapsulated GQDs showed similar Powder X-ray Diffraction (PXRD) patterns to PCN-222, indicating the retained structure. The porous structure was also retained with a Brunauer-Emmett-Teller (BET) surface area of 2066 m2/g. After incorporation of GQDs, the shape of GQDs@PCN-222 particles remained, as revealed by the scanning electron microscope (SEM). As most of the GQDs were covered by thick PCN-222, it was hard to observe those GQDs using a transmission electron microscope (TEM) and a high-resolution transmission electron microscope (HRTEM) directly, the treatment of digested GQDs@PCN-222 particles by immersion in a 1 mM aqueous KOH solution can make the incorporated GQDs visible in TEM and HRTEM. The linker, deep purple porphyrins, make MOFs a highly visible light harvester up to 800 nm. The introduction of GQDs inside PCN-222 can effectively promote the spatial separation of the photogenerated electron-hole pairs during the photocatalytic process, which was proved by the transient photocurrent plot and photoluminescence emission spectra. Compared with pure PCN-222, the obtained GQDs@PCN-222 displayed dramatically enhanced CO production derived from CO2 photoreduction with 147.8 μmol/g/h in a 10 h period under visible light irradiation with triethanolamine (TEOA) as a sacrificial agent. This study demonstrated that the combination of GQDs and high light absorption MOFs provides a new platform for photocatalytic CO2 reduction.