Metal–organic frameworks (MOFs) are coordination polymers with high porosity that are constructed from molecular engineering. Constructing MOFs as photocatalysts for the reduction of nitrogen to ammonia is a newly emerging but fast-growing field, owing to MOFs’ large pore volumes, adjustable pore sizes, controllable structures, wide light harvesting ranges, and high densities of exposed catalytic sites. They are also growing in popularity because of the pristine MOFs that can easily be transformed into advanced composites and derivatives, with enhanced catalytic performance. In this review, we firstly summarized and compared the ammonia detection methods and the synthetic methods of MOF-based materials. Then we highlighted the recent achievements in state-of-the-art MOF-based materials for photocatalytic nitrogen fixation. Finally, the summary and perspectives of MOF-based materials for photocatalytic nitrogen fixation were presented. This review aims to provide up-to-date developments in MOF-based materials for nitrogen fixation that are beneficial to researchers who are interested or involved in this field.

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.