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Open AccessFeature PaperArticle

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

1
Department of Chemistry and Biochemistry, The City College of New York, New York, NY 10031, USA
2
Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
*
Author to whom correspondence should be addressed.
Academic Editors: Victoria Samanidou, Eleni Deliyanni and Rafael Lucena
Molecules 2019, 24(24), 4529; https://doi.org/10.3390/molecules24244529
Received: 3 November 2019 / Revised: 23 November 2019 / Accepted: 10 December 2019 / Published: 11 December 2019
(This article belongs to the Special Issue Metal Organic Frameworks: Synthesis and Application)
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-C3N4 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-C3N4 during the composite synthesis, depending on the MOF geometry. While spherical units of UiO-66 grew undisturbed around oxidized and spherical g-C3N4, 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 CO2 adsorbed between the MOFs and the composites confirm the proposed role of oxidized g-C3N4 in the composite formation. View Full-Text
Keywords: metal organic framework composites; oxidized graphitic carbon nitride nanoparticles; porosity; structural heterogeneity metal organic framework composites; oxidized graphitic carbon nitride nanoparticles; porosity; structural heterogeneity
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MDPI and ACS Style

Giannakoudakis, D.A.; Bandosz, T.J. Building MOF Nanocomposites with Oxidized Graphitic Carbon Nitride Nanospheres: The Effect of Framework Geometry on the Structural Heterogeneity. Molecules 2019, 24, 4529.

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