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

Giannakoudakis, Dimitrios A.; Bandosz, Teresa J.

doi:10.3390/molecules24244529

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

Dimitrios A. Giannakoudakis

^1,2

and

Teresa J. Bandosz

^1,*

Department of Chemistry and Biochemistry, The City College of New York, New York, NY 10031, USA

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)

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Abstract

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

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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. https://doi.org/10.3390/molecules24244529

AMA Style

Giannakoudakis DA, Bandosz TJ. Building MOF Nanocomposites with Oxidized Graphitic Carbon Nitride Nanospheres: The Effect of Framework Geometry on the Structural Heterogeneity. Molecules. 2019; 24(24):4529. https://doi.org/10.3390/molecules24244529

Chicago/Turabian Style

Giannakoudakis, Dimitrios A., and Teresa J. Bandosz. 2019. "Building MOF Nanocomposites with Oxidized Graphitic Carbon Nitride Nanospheres: The Effect of Framework Geometry on the Structural Heterogeneity" Molecules 24, no. 24: 4529. https://doi.org/10.3390/molecules24244529

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

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