NH2-Modified UiO-66: Structural Characteristics and Functional Properties

Тимофеев, К. Л.; Kulinich, Sergei A.; Kharlamova, Tamara

doi:10.3390/molecules28093916

Cited by 14 publications

(5 citation statements)

References 48 publications

(72 reference statements)

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“…This confirms the successful synthesis of UiO-66 and its derivatives in the experimental procedure. Notably, both functionalized and pristine UiO-66 demonstrate identical topology, in accordance with existing literature findings. − However, upon careful scrutiny, it becomes apparent that the distinct peak profiles of UiO-66-(SH) 2 and UiO-66-(COOH) 2 exhibit a slightly broader nature when compared to those of other functionalized UiO-66 crystals. This observation implies that lower crystallinity may serve as a contributing factor.…”

Section: Resultssupporting

confidence: 89%

Evaluating the Role of Functional Groups in the Selective Capture of Ag(I) onto UiO-66-Type Metal–Organic Frameworks

Wang,

Ding

et al. 2024

Langmuir

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UiO-66-type metal−organic frameworks have been considered as promising adsorbents for capturing Ag(I) from wastewater. However, uncertainties persist regarding the specific absorptivity of individual functional groups to the UiO-66 framework structure. In this study, UiO-66-type metal−organic frameworks (UiO-66-X), featuring diverse functional groups (X = −(OH) 2 , −(COOH) 2 , −NO 2 , −NH 2 , −SO 3 H, −(SH) 2 ), were synthesized in situ for Ag(I) capture. The findings revealed that functionalization significantly enhanced the adsorption capacity of Ag(I). Notably, quantitative analysis showed that 1 mol of −SH functional group onto the UiO-66 framework structure can adsorb 0.73 mol of Ag(I) ions, surpassing those of −COOH, −OH, −NH 2 , −SO 3 H, and −NO 2 by 2.4-, 3.5-, 3.8-, 9.1-, and 24.3-fold, respectively. This represents the first assessment of the adsorption capacity of functionalized UiO-66 for Ag(I) based on each effective functional group, addressing limitations in traditional unit mass calculations. Further, the adsorption mechanism of UiO-66-X for selectively capturing Ag(I) was elucidated through experimental and theoretical analyses. Additionally, selectivity and practical applications confirm that UiO-66-(SH) 2 exhibits strong anti-interference ability, whether in natural water bodies with complex compositions or in industrial wastewater under harsh conditions. We anticipate that this study will enhance our understanding of structure−performance dependencies of multivariate MOFs for designing novel adsorbents for Ag(I) capture.

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Section: Resultssupporting

confidence: 89%

Evaluating the Role of Functional Groups in the Selective Capture of Ag(I) onto UiO-66-Type Metal–Organic Frameworks

Wang,

Ding

et al. 2024

Langmuir

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“…As expected, the thermogravimetric analysis profiles of the two materials are like those previously reported and confirm the thermal stability of MOF-808 up to about 500 °C and up to 400 °C for UiO-66-NH2 (Figure 5d) [45,46]. The FT-IR and FT-Raman spectra obtained for both the Zr-based MOF-based materials reveal the main vibrational band characteristics as expected from the two MOF structures (Figure 5a,b; spectra shown in the 1900-400 cm −1 wavenumber region) [42,43]. Briefly, the medium and strong intensity bands to vibrational modes of the carboxylate groups can be assigned from 1600 to 1390 cm −1 ; a vibrational band around 1450 cm −1 ascribed to aromatic (C-C) bonds of the organic ligands; as well as a group of vibrational bands associated with Zr-(µ 3 -O) framework bonds in the range of 800-600 cm −1 , and a band (FT-IR) around 450 cm −1 assigned to Zr-(OC) bonds.…”

Section: Preparation and Characterization Of The Catalystssupporting

confidence: 87%

Porous Coordination Polymer MOF-808 as an Effective Catalyst to Enhance Sustainable Chemical Processes

Ferreira,

Santos-Vieira,

Gomes

et al. 2024

Polymers

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The improvement of sustainable chemical processes plays a pivotal role in safe environmental and societal development, for example, by reducing the use of hazardous substances, preventing chemical waste, and improving the efficiency of chemical reactions to obtain added-value compounds. In this context, the porous coordination polymer MOF-808 (MOF, metal–organic framework) was prepared by a straightforward method in water, at room temperature, and was unequivocally characterized by powder X-ray diffraction, vibrational spectroscopy, thermogravimetric analysis, and scanning electron microscopy. MOF-808 material was applied for the first time as catalysts in ring-opening aminolysis reactions of epoxides. It demonstrated high activity and selectivity for reactions of styrene oxide and cyclohexene oxide with aniline, using a very low amount of an eco-sustainable solvent (0.5 mL of EtOH), at 70 °C. Moreover, MOF-808 demonstrated high stability in the catalytic reaction conditions applied, and a notable reuse capacity of up to 20 consecutive reaction cycles, without significant variation in its catalytic performance. In fact, this Zr-based porous coordination polymer prepared by environment-friendly conditions proved to be a novel efficient heterogeneous catalyst, promoting the ring-opening reaction of epoxides under more sustainable conditions, and using a very low amount of catalyst.

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“…With the addition of acetic acid, the defective UiO-66-NH 2 displayed a significant uptake of N 2 gas at low pressures, confirming the presence of micropores. Additionally, the defective material showed slight adsorption–desorption hysteresis in the range of 0.8 < P / P 0 < 1.0, further indicating the existence of additional mesopores in the adsorbent . The pore size distribution graph showed an increase in the number of mesopores (2–50 nm), indicating the possible presence of additional mesoporous structures in the defective material (Figure d,e).…”

Section: Resultsmentioning

confidence: 93%

“…Additionally, the defective material showed slight adsorption− desorption hysteresis in the range of 0.8 < P/P 0 < 1.0, further indicating the existence of additional mesopores in the adsorbent. 47 The pore size distribution graph showed an increase in the number of mesopores (2−50 nm), indicating the possible presence of additional mesoporous structures in the defective material (Figure 3d,e). Table S3 reveals that the BET surface area of the defective material was greater than that of the nondefective material, encompassing surface area, pore volume, and average mesopore diameter, with a range of 715 to 1154 m 2 •g −1 .…”

Section: Resultsmentioning

confidence: 97%

Highly Defective Zirconium-Based Metal–Organic Frameworks for the Efficient Adsorption and Detection of Sugar Phosphates in the Biological Sample

Feng,

Hu,

Wang

et al. 2024

ACS Appl. Mater. Interfaces

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Enrichment and quantification of sugar phosphates (SPx) in biological samples were of great significance in biological medicine. In this work, a series of zirconium-based metal−organic frameworks (MOFs) with different degrees of defects, namely, HP-UiO-66-NH 2 -X, were synthesized using acetic acid as a modulator and were utilized as high-capacity adsorbents for the adsorption of SPx in biological samples. The results indicated that the addition of acetic acid altered the morphology of HP-UiO-66-NH 2 -X, with corresponding changes in pore size (3.99−9.28 nm) and specific surface area (894.44−1142.50 m 2 •g −1 ). HP-UiO-66-NH 2 -10 showed the outstanding performance by achieving complete adsorption of all four SPx using only 80 μg of the adsorbent. The excellent adsorption efficiency of HP-UiO-66-NH 2 -10 was also obtained with a wide pH range and short adsorption time (10 min). Adsorption experiments demonstrated that the adsorption process involved chemical adsorption and multilayer adsorption. By utilizing X-ray photoelectron spectroscopy and density functional theory to explain the adsorption mechanism, it was found that various interactions (including coordination, hydrogen bonding, and electrostatic interactions) collectively contributed to the exceptional adsorption capability of HP-UiO-66-NH 2 -10. Those results indicated that the defect strategy not only increased the specific surface area and pore size, providing additional adsorption sites, but also reduced the adsorption energy between HP-UiO-66-NH 2 -10 and SPx. Moreover, HP-UiO-66-NH 2 -10 showed a low limit of detection (0.001−0.01 ng•mL −1 ), high precision (<13.77%), and accuracy (80.10−111.83%) in serum, liver, and cells, good stability, high selectivity (SPx/glucose, 1:100 molar ratio), and high adsorption capacity (292 mg•g −1 for SPx). The practical detection of SPx from human serum was also verified, prefiguring the great potentials of defective zirconium-based MOFs for the enrichment and detection of SPx in the biological medicine.

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NH2-Modified UiO-66: Structural Characteristics and Functional Properties

Cited by 14 publications

References 48 publications

Evaluating the Role of Functional Groups in the Selective Capture of Ag(I) onto UiO-66-Type Metal–Organic Frameworks

Evaluating the Role of Functional Groups in the Selective Capture of Ag(I) onto UiO-66-Type Metal–Organic Frameworks

Porous Coordination Polymer MOF-808 as an Effective Catalyst to Enhance Sustainable Chemical Processes

Highly Defective Zirconium-Based Metal–Organic Frameworks for the Efficient Adsorption and Detection of Sugar Phosphates in the Biological Sample

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