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A zirconium metal–organic framework with UiO-66 topology was synthesized using a 1,4-naphthalenedicarboxylic acid (NDC) linker (UiO-66-NDC). From synchrotron powder X-ray diffraction (PXRD), we found that the naphthalene rings of the NDC linker are out of (a,c)-plane equilibrium by 30°, similar to the situation found by single crystal XRD for the benzene rings in UiO-67 (Cryst. Growth Des.2014145370). Different fractions of the benzene-carboxylic (BC) acid modulator versus NDC were used to tune structural properties of the final product. The modulator increases both the crystal size and the surface area of the product, but reduces its thermal stability owing to insertion of defects: missing linkers and missing Zr6(OH)4O4 clusters. This study proves that the defect density (fraction of BC incorporation) can be tuned in UiO-66-NDC materials up to almost 50%. At that stage, the crystal is characterized also by a high density of missing Zr6(OH)4O4 inorganic cornerstones. Notwithstanding such structural defectivity, even the most defective material is stable after thermal activation at 200 °C (able to fully remove the solvent) and in water conditions, opening possibilities for application in the fields of catalysis and molecule sorption.

Water (or tetragonal-ZrO2 NPs) in the synthesis batch of Zr-BDC MOFs reacts with ZrCl4 forming the SBU of the UiO-66 phase.

We describe the synthesis and corresponding full characterization of the set of UiO-66 metal−organic frameworks (MOFs) with 1,4-benzenedicarboxylate (C 6 H 4 (COOH) 2 , hereafter H 2 BDC) and 1,4-naphthalenedicarboxylate (C 10 H 6 (COOH) 2 , hereafter H 2 NDC) mixed linkers with NDC contents of 0, 25, 50, and 100%. Their structural (powder X-ray diffraction, PXRD), adsorptive (N 2 , H 2 , and CO 2 ), vibrational (IR/Raman), and thermal stability (thermogravimetric analysis, TGA) properties quantitatively correlate with the NDC content in the material. The UiO-66 phase topology is conserved at all relative fractions of BDC/NDC. The comparison between the synchrotron radiation PXRD and 77 K N 2 -adsorption isotherms obtained on the 50:50 BDC/NDC sample and on a mechanical mixture of the pure BDC and NDC samples univocally proves that in the mixed linkers of the MOFs the BDC and NDC linkers are shared in each MOF crystal, discarding the hypothesis of two independent phases, where each crystal contains only BDC or NDC linkers. The careful tuning of the NDC content opens a way for controlled alteration of the sorption properties of the resulting material as testified by the H 2 -adsorption experiments, showing that the relative ranking of the materials in H 2 adsorption is different in different equilibrium-pressure ranges: at low pressures, 100NDC is the most efficient sample, while with increasing pressure, its relative performance progressively declines; at high pressures, the ranking follows the BDC content, reflecting the larger internal pore volume available in the MOFs with a higher fraction of smaller linkers. The H 2 -adsorption isotherms normalized by the sample Brunauer−Emmett−Teller specific surface area show, in the whole pressure range, that the surface-area-specific H 2adsorption capabilities in UiO-66 MOFs increase progressively with increasing NDC content. Density functional theory calculations, using the hybrid B3LYP exchange correlation functional and quadruple-ζ with four polarization functions (QZ4P) basis set, show that the interaction of H 2 with the H 2 NDC linker results in an adsorption energy larger by about 15% with respect to that calculated for adsorption on the H 2 BDC linker.

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