▎ 摘　　要

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 m(2)/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 & mu;mol/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.