MOF-Derived Defective Co₃O₄ Nanosheets in Carbon Nitride Nanocomposites for CO₂ Photoreduction and H₂ Production

In photocatalysis, especially in CO₂ reduction and H₂ production, the development of multicomponent nanomaterials provides great opportunities to tune many critical parameters toward increased activity. This work reports the development of tunable organic/inorganic heterojunctions comprised of cobalt oxides (Co₃O₄) of varying morphology and modified carbon nitride (CN), targeting on optimizing their response under UV-visible irradiation. MOF structures were used as precursors for the synthesis of Co₃O₄. A facile solvothermal approach allowed the development of ultrathin two-dimensional (2D) Co₃O₄ nanosheets (Co₃O₄-NS). The optimized CN and Co₃O₄ structures were coupled forming heterojunctions, and the content of each part was optimized. Activity was significantly improved in the nanocomposites bearing Co₃O₄-NS compared with the corresponding bulk Co₃O₄/CN composites. Transient absorption spectroscopy revealed a 100-fold increase in charge carrier lifetime on Co₃O₄-NS sites in the composite compared with the bare Co₃O₄-NS. The improved photocatalytic activity in H₂ production and CO₂ reduction is linked with (a) the larger interface imposed from the matching 2D structure of Co₃O₄-NS and the planar surface of CN, (b) improvements in charge carrier lifetime, and (c) the enhanced CO₂ adsorption. The study highlights the importance of MOF structures used as precursors in forming advanced materials and the stepwise functionalization of the individual parts in nanocomposites for the development of materials with superior activity.