Building MOF Nanocomposites with Oxidized Graphitic Carbon Nitride Nanospheres: The Effect of Framework Geometry on the Structural Heterogeneity

Composite of two MOFs, copper-based Cu-BTC (HKUST-1) and zirconium-based Zr-BDC (UiO-66), with oxidized graphitic carbon nitride nanospheres were synthesized. For comparison, pure MOFs were also obtained. The surface features were analyzed using x-ray diffraction (XRD), sorption of nitrogen, thermal analysis, and scanning electron microscopy (SEM). The incorporation of oxidized g-C(3)N(4) to the Cu-BTC framework caused the formation of a heterogeneous material of a hierarchical pores structure, but a decreased surface area when compared to that of the parent MOF. In the case of UiO-66, functionalized nanospheres were acting as seeds around which the crystals grew. Even though the MOF phases were detected in both materials, the porosity analysis indicated that in the case of Cu-BTC, a collapsed MOF/nonporous and amorphous matter was also present and the MOF phase was more defectous than that in the case of UiO-66. The results suggested different roles of oxidized g-C(3)N(4) during the composite synthesis, depending on the MOF geometry. While spherical units of UiO-66 grew undisturbed around oxidized and spherical g-C(3)N(4), octahedral Cu-BTC units experienced geometrical constraints, leading to more defects, a disturbed growth of the MOF phase, and to the formation of mesopores at the contacts between the spheres and MOF units. The differences in the amounts of CO(2) adsorbed between the MOFs and the composites confirm the proposed role of oxidized g-C(3)N(4) in the composite formation.