Missing Linkers: An Alternative Pathway to UiO-66 Electronic Structure Engineering

Vos, Arthur De; Hendrickx, Kevin; Voort, Pascal Van Der; Speybroeck, Véronique Van; Lejaeghere, Kurt

doi:10.1021/acs.chemmater.6b05444

Cited by 203 publications

(188 citation statements)

References 95 publications

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“…This experimental observation could be interpreted considering that the population of BDC linkers that undergo faster decarboxylation are those located at structural defects. The use of MOFs containing defective structures has been reported as an effective method to enhance the photocatalytic activity of these materials . These defects could act as recombination centers, inhibiting further photodecarboxylation.…”

Section: Resultsmentioning

confidence: 99%

Long‐Term Photostability in Terephthalate Metal–Organic Frameworks

et al. 2019

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Prolonged (weeks) UV/Vis irradiation under Ar of , UiO66 Zr-NO 2 ,M IL101 Fe,M IL125 Ti-NH 2 , MIL101 Cr and MIL101 Cr(Pt) shows that these MOFs undergo photodecarboxylation of benzenedicarboxylate (BDC) linker in as ignificant percentage depending on the structure and composition of the material. Routine characterization techniques such as XRD,U V/Vis spectroscopya nd TGA fail to detect changes in the material, although porosity and surface area change upon irradiation of powders.I n contrast to BCD-containing MOFs,zeolitic imidazolate ZIF-8 does not evolve CO 2 or any other gas upon irradiation.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under https://doi.

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Section: Resultsmentioning

confidence: 99%

Long‐Term Photostability in Terephthalate Metal–Organic Frameworks

et al. 2019

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“…[15][16][17] One of the examples of these modulators used in the generation of defects in the structure is trifluoroacetic acid under synthesis conditions typically employing HCl. [15][16][17] One of the examples of these modulators used in the generation of defects in the structure is trifluoroacetic acid under synthesis conditions typically employing HCl.…”

Section: Synthesis Of Uio-66mentioning

confidence: 99%

Engineering UiO‐66 Metal Organic Framework for Heterogeneous Catalysis

et al. 2019

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frameworks (MOFs) are currently attracting considerable attention as heterogeneous catalysts at moderate temperatures, mainly for liquid-phase reactions. Since structural stability is one of the major concerns for the use of MOFs in catalysis, particularly considering that frequently some of the reported MOF materials are very unstable, the interest in this area has been focused on those MOFs exhibiting the highest structural robustness, UiO-66 being among the most widely used. Two introductory sections deal with the synthesis, structure and main properties of UiO-66, including its remarkable thermal (up to 350°C) and chemical (aqueous solution in a wide pH range) stability. The main body of the review summarizes those examples of using UiO-66 in catalysis grouped according to the nature of the active sites, starting with the use of UiO-66 as Lewis acids. In this section, emphasis has been made in the recent strategies to create structural defects in a controlled way that generate Lewis acidity. Other sections cover examples illustrating substituted terephthalate as active sites and the evidence that there is a synergy between acid and basic sites in close proximity that make some of these UiO-66 with substituents at the linker to act as dual acid-base catalysts. Other sections are focused on the use of UiO-66 as hosts of metal nanoparticles, metal oxides and other host, remarking the influence that the nature of UiO-66 and the possible presence of substituents in the framework play on the activity of the incorporated guest. The last section summarizes the current state of the art in the use of UiO-66 in catalysis and provides our views on future developments regarding the application of UiO-66 in industrial processes.

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“…For UiO-66(Ce) samples obtained in this work, the weight loss in the 260-600 • C range was lower, indicating the presence of structural defects due to missing linker molecules. It was reported [33,47] that removing some BDC linkers from UiO-66 yields a stable framework. According to our calculations (done based on Katz et al [48]), one inorganic Ce 6 O 4 (OH) 4 cluster coordinated average from 9.8 to 11.1 BDC ligands (Table 3).…”

Section: Structure Defects and Thermal Stability Of Uio-66(ce)mentioning

confidence: 99%

The Impact of Synthesis Method on the Properties and CO2 Sorption Capacity of UiO-66(Ce)

et al. 2019

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A series of cerium-based UiO-66 was obtained via hydrothermal and sonochemical methods, using the same quantities of reagents (cerium ammonium nitrate (CAN), terephthalic acid (H2BDC)) and solvents) in each synthesis. The impact of synthesis method and metal to linker ratio on the structural and textural properties of obtained UiO-66(Ce), as well as their composition in terms of Ce4+/Ce3+ ratio, structure defects resulting from missing linker, and CO2 adsorption capacity was discussed. By using typical characterization techniques and methods, such as XRD, N2 and CO2 sorption, TGA, XPS, and SEM, it was shown that the agitation of reacting mixture during synthesis (caused by stirring or ultrasounds) allows to obtain structures that have more developed surfaces and fewer linker defects than when MOF was obtained in static conditions. The specific surface area was found to be of minor importance in the context of CO2 adsorption than the contribution of Ce3+ ions that were associated with the concentration of linker defects.

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Missing Linkers: An Alternative Pathway to UiO-66 Electronic Structure Engineering

Cited by 203 publications

References 95 publications

Long‐Term Photostability in Terephthalate Metal–Organic Frameworks

Long‐Term Photostability in Terephthalate Metal–Organic Frameworks

Engineering UiO‐66 Metal Organic Framework for Heterogeneous Catalysis

The Impact of Synthesis Method on the Properties and CO2 Sorption Capacity of UiO-66(Ce)

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