Effect of Water Adsorption on Retention of Structure and Surface Area of Metal–Organic Frameworks

Schoenecker, Paul M.; Carson, Cantwell G.; Jasuja, Himanshu; Flemming, Christine Juliette Jane; Walton, Krista S.

doi:10.1021/ie202325p

Cited by 485 publications

(494 citation statements)

References 48 publications

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“…The structural degradation of the materials was analyzed by N 2 adsorption measurements, and we found that the MOF integrity was lost for UiO67-NH 2 (100) (Figure S10). [16] For Zr(NDC)(NDC-NH 2 ), we chose UiO67-NH 2 (20) as the starting material to introduce transition-metal complexes in the structure, by postsynthesis treatment. This material was characterized by elemental analysis, NMR and FTIR spectroscopy, and thermal analysis, and the results are given in Figures S3, S4, and S9.…”

Section: Resultsmentioning

confidence: 99%

Zirconium Materials from Mixed Dicarboxylate Linkers: Enhancing the Stability for Catalytic Applications

et al. 2014

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We report the synthesis of two series of zirconium‐based metal–organic frameworks from solutions composed of a mixed‐ligand system (naphthalene dicarboxylic acid/4‐amino‐2,6‐naphthalenedicarboxylic acid or [1,1′‐biphenyl]‐4,4′‐dicarboxylic acid (BPDC)/2‐amino‐[1,1′‐biphenyl]‐4,4′‐dicarboxylic acid). Materials synthesized with low loadings of functionalized linkers exhibit higher long‐term chemical stability and similarly high thermal stability relative to those with 100 % amino linkers. These materials and their corresponding rhodium derivatives prove excellent catalysts in one‐pot reactions. Moreover, the recycling experiments demonstrate an interesting prospect for the long‐term reusability of these catalysts.

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Section: Resultsmentioning

confidence: 99%

Zirconium Materials from Mixed Dicarboxylate Linkers: Enhancing the Stability for Catalytic Applications

et al. 2014

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“…N 2 , CO 2 ) deteriorates significantly upon exposure to water vapor. [28][29][30][31][32] Upon hydration, gas sorption measurements show that MOF-74 compounds lose a substantial fraction of their original gas uptake capacity (N 2 , CO 2 ) even at 9% relative humidity and with subsequent thermal regeneration to remove adsorbed water molecules. These results point to an irreversible reaction within MOF-74, but X-ray diffraction measurements and infrared spectroscopy have not been able to detect a notable structural change or chemical transformation following hydration and thermal regeneration.…”

Section: Introductionmentioning

confidence: 99%

Water Reaction Mechanism in Metal Organic Frameworks with Coordinatively Unsaturated Metal Ions: MOF-74

et al. 2014

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Water dissociation represents one of the most important reactions in catalysis, essential to the surface and nano sciences [e.g., Hass et al., Science, 1998, 282, 265-268; Brown et al., Science 2001, 294, 67-69; Bikondoa et al., Nature 2005, 5, 189-192]. However, the dissociation mechanism on most oxide surfaces is not well understood due to the experimental challenges of preparing surface structures and characterizing reaction pathways. To remedy this problem, we propose the metal organic framework MOF-74 as an ideal model system to study water reactions. Its crystalline structure is well characterized; the metal oxide node mimics surfaces with exposed cations; and it degrades in water. Combining in situ IR spectroscopy and first-principles calculations, we explored the MOF-74/water interaction as a function of vapor pressure and temperature. Here, we show that, while adsorption is reversible below the water condensation pressure (~19.7 Torr) at room temperature, a reaction takes place at ~150 ˚C even at low water vapor pressures. This important finding is unambiguously demonstrated by a clear spectroscopic signature for the direct reaction using D 2 O, which is not present using H 2 O due to strong phonon coupling. Specifically, a sharp absorption band appears at 970 cm -1 when D 2 O is introduced at above 150 ˚C, which we attribute to an O-D bending vibration on the phenolate linker. Although H 2 O undergoes a similar dissociation reaction, the corresponding O-H mode is too strongly coupled to MOF vibrations to detect. In contrast, the O-D mode falls in the phonon gap of the MOF and remains localized. First-principles calculations not only positively identify the O-D mode at 970 cm -1 but derive a pathway and kinetic barrier for the reaction and the final configuration: the D (H) atom is transferred to the oxygen of the linker phenolate group, producing the notable O-D absorption band at 970 cm -1 , while the OD (or OH) binds to the open metal sites. This finding explains water dissociation in this case and provides insight into the long-lasting question of MOF-74 degradation. Overall, it adds to the understanding of molecular water interaction with cation-exposed surfaces to enable development of more efficient catalysts for water dissociation.2

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“…[23][24][25][26] Moreover, N-rich MOFs and COPs will yield N-doped porous carbons, which can enhance the properties of porous carbons, for example, N-doped or O-doped carbons may provide faradaic pseudocapacitance, improving specific capacitance of electrode materials. 27,28 MOFs, especially like zeolitic imidazolate frameworks (ZIFs) and MOF-5 have shown unusual potential to develop highly porous carbons as electrode materials in EDLCs.…”

Section: Introductionmentioning

confidence: 99%

Zeolitic imidazolate framework-derived nitrogen-doped porous carbons as high performance supercapacitor electrode materials

Zhong

Zhan

Cao

2015

Carbon

286

113

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Effect of Water Adsorption on Retention of Structure and Surface Area of Metal–Organic Frameworks

Cited by 485 publications

References 48 publications

Zirconium Materials from Mixed Dicarboxylate Linkers: Enhancing the Stability for Catalytic Applications

Zirconium Materials from Mixed Dicarboxylate Linkers: Enhancing the Stability for Catalytic Applications

Water Reaction Mechanism in Metal Organic Frameworks with Coordinatively Unsaturated Metal Ions: MOF-74

Zeolitic imidazolate framework-derived nitrogen-doped porous carbons as high performance supercapacitor electrode materials

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