Oxidized g‐C ₃ N ₄ Nanospheres as Catalytically Photoactive Linkers in MOF/g‐C ₃ N ₄ Composite of Hierarchical Pore Structure

Abstract

A unique composite of the copper-based metal-organic framework (Cu-benzene tricarboxylic acid (BTC)) with oxidized graphitic carbon nitride nanospheres is synthesized. For comparison, a hybrid material consisting of g-C N and Cu-BTC is also obtained. Their surface features are analyzed using Fourier transform infrared spectroscopy, X-ray diffraction, sorption of nitrogen, thermal analysis, scanning electron microscopy, photoluminescence, and diffuse reflectance UV-Vis spectroscopy. The results suggest that the formed nanospheres of oxidized g-C N act as linkers between the copper sites, playing a crucial role in the composite building process. Their incorporation to the Cu-BTC framework causes the development of new mesoporosity. Remarkable alterations in the optical properties, as a result of the coordination of oxygen containing functional groups of the oxidized graphitic carbon nitride to the copper atoms of the framework, suggest an increase in photoreactivity. On the other hand, for the hybrid material consisting of Cu-BTC and g-C N , the unaltered pore volume and optical properties support the formation of a physical mixture rather than of a composite. The tests on reactive adsorption and detoxification of G-series organophosphate nerve agent surrogate show the enhanced performance of the composite as catalysts and photocatalyst in visible light.

Carbon Quantum Dot Implanted Graphite Carbon Nitride Nanotubes: Excellent Charge Separation and Enhanced Photocatalytic Hydrogen Evolution

“…[4] At present, various strategies have been developed to promote the photoactivity of pristine g-C 3 N 4 . [5] In addition to the exfoliation of g-C 3 N 4 , [6] g-C 3 N 4 with special geometrical shapes could profit from shorter diffusion pathways and higher specific surface area, [7] elevating the photocatalytic activity from that obtained with conventional bulk counterparts.T hus,agreat deal of effort has been devoted to endowing g-C 3 N 4 with specific nanostructures,such as g-C 3 N 4 nanosheets, [8] hollow nanospheres, [7] and porous frameworks. [9] Recent experimental and theoretical studies have shown the superior photocatalytic activity of g-C 3 N 4 nanotubes under visible light.…”

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

“…For the synthesis process leading to true composites and not to physical mixtures, the interactions of a MOF phase and modifier functional groups are important. Thus, owing to these interactions, the composites of Cu-BTC and oxidized g-C 3 N 4 had hierarchical porosity and exhibited photoactive properties [23].Even though structural or chemical defects were not the focus of the synthesis procedure at the time of the introduction of MOF/other phase composites, the published results showed some distortion in the crystal structure, along with an increase in the porosity and in the population of metal centers [40,48]. Therefore, building the MOF composites with another phase can also be considered as a materials' design strategy for introducing some defects to MOF crystals.…”

“…For the synthesis process leading to true composites and not to physical mixtures, the interactions of a MOF phase and modifier functional groups are important. Thus, owing to these interactions, the composites of Cu-BTC and oxidized g-C 3 N 4 had hierarchical porosity and exhibited photoactive properties [23].…”

Fabrication of WO2.72/UiO‐66 nanocomposites and effects of WO2.72 ratio on photocatalytic performance: judgement of the optimal content and mechanism study

“…Over past years, composites of metal organic frameworks (MOFs) and inorganic nanomaterials have attracted much more attention for photocatalysis not only because of the significant charge separation by inducing charge carrier transfer at the interface of the composites, [1][2][3][4][5] but also due to the porous structure and high specific surface areas of MOFs, which lead to high loading capability and avoiding the agglomeration of inorganic nanomaterials. [6][7][8] To date, such inorganic nanomaterials mainly focus on SnO 2 , 9 PbO, 10 ZnO, 11 g-C 3 N 4 12 and TiO 2 . 13 For instance, Zhao et al used SnO 2 @UiO-66/rGO hybrid to degrade rhodamine B and achieved a 95.5% efficiency within 150 min.…”