A facile synthesis of UiO-66, UiO-67 and their derivatives

Katz, Michael J.; Brown, Zachary J.; Colón, Yamil J.; Siu, Paul W.; Scheidt, Karl A.; Snurr, Randall Q.; Hupp, Joseph T.; Farha, Omar K.

doi:10.1039/c3cc46105j

Cited by 1,383 publications

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“…Indeed, N 2 sorption measurements (taken at 77 K up to 1 bar) of all the etched ZIF-8 and ZIF-67 crystals proved that they had consistent sorption capacity (Table 1) as that of the initial crystals (see Figure S10-S20). [9,15] In fact, the newly etched materials exhibited slightly higher porosity-a difference that we attributed to the creation of defects [16] during etching.…”

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Post‐Synthetic Anisotropic Wet‐Chemical Etching of Colloidal Sodalite ZIF Crystals

et al. 2015

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Controlling the shape of metal-organic framework (MOF) crystals is important for understanding their crystallization and useful for myriad applications. However, despite the many advances in shaping of inorganic nanoparticles, post-synthetic shape control of MOFs and, in general, molecular crystals remains embryonic. Herein we report using a simple wet-chemistry process at room temperature to control the anisotropic etching of colloidal ZIF-8 and ZIF-67 crystals. Our work enables uniform reshaping of these porous materials into unprecedented morphologies, including cubic and tetrahedral crystals, and even hollow boxes, via acid-base reaction and subsequent sequestration of leached metal ions. Etching tests on these ZIFs reveal that etching occurs preferentially in the crystallographic directions richer in metal-ligand bonds; that, among these directions, the etching rate tends to be faster on the crystal surfaces of higher dimensionality; and that the etching can be modulated by adjusting the pH of the etchant solution. KeywordsMetal-Organic Frameworks; Zeolitic-Imidazolate Frameworks; anisotropic etching; hollow particles; porosity Chemical etching is an ancient fabrication method that was used by metal and glass craftsmen to obtain sophisticated surface designs. With the advent of controlling the etching orientation at the microscale and nanoscale, anisotropic wet-chemical etching has become highly useful for shaping many materials for diverse applications.[1,2] For example, the anisotropic wet-chemical etching of single-crystal silicon in the presence of a base is essential in microelectronics manufacturing.[1] Anisotropic etching can also be applied to preparation of metal nanocrystals from oxidative species and coordination ligands, for which it enables unprecedented morphologies and complexities, and unique physical properties.[2] Here, we introduce the concept of anisotropic wet-chemical etching for metal-organic frameworks (MOFs)-specifically, for the zeolitic-imidazolate framework (ZIF) subfamily. Figure S1).[9] Recently, several studies have shown that the crystal growth of ZIF-8 starts with formation of cubes exposing six {100} facets, which gradually evolve into truncated rhombic dodecahedra exposing six {100} and twelve {110} facets, and finally, into the thermodynamically more stable rhombic dodecahedra, in which only the twelve {110} facets are exposed ( Figure 1a). [10,11] Figure 1a illustrates the different exposed crystallographic planes for the cubes and for the truncated and non-truncated rhombic dodecahedra. As shown in this figure, each crystal shape has different exposed crystallographic planes, and each crystallographic plane, a distinct chemical composition. In ZIF-8, {100} and {211} planes contain several Zn-2-MIM linkages, whereas the {110} and {111} planes do not contain any of these linkages ( Figure 1b).By exploiting the aforementioned differences, we devised a method for anisotropic wet etching of colloidal crystals of isostructural ZIF-8 and ZIF-67. Our approach combines ...

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Post‐Synthetic Anisotropic Wet‐Chemical Etching of Colloidal Sodalite ZIF Crystals

et al. 2015

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“…[28] Among the most water-stable MOFs are UiO-66(Zr) (UiO = University in Oslo) [21], MIL-53 (Al and Cr) (MIL = Materials Institute Lavoisier) [23], MIL-101 (Cr) [24] and MIL-125(Ti) [25] as well as the ZIF series (ZIF = Zeolithic Imidazolium Frameworks) [27]. Another important water-stable MOF used for photochemical hydrogen production schemes in some examples that will later be discussed in this paper is UiO-67 (Zr) [29]. A main factor determining a MOF's thermodynamic stability in water is the strength of the metal-to-ligand bond, which depends on the basicity (pK a ) of the linker and Lewisacidity of the metal [28].…”

Section: Suitable Mofs As Scaffold For Photocatalytic Hydrogen Producmentioning

confidence: 99%

Photochemical Hydrogen Production with Metal–Organic Frameworks

Pullen

Ott

2016

Top Catal

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Metal-Organic Frameworks (MOFs) have attracted increasing attention for the creation of solid-state platforms for catalysis applications. In this review article, we present strategies to employ MOF-based materials in photochemical hydrogen production. The scope ranges from the incorporation of single functions (catalyst or photosensitizer) to multifunctional MOFs that combine both light-harvesting and catalysis in one scaffold.

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“…Recently, croconic acid showed a Curie temperature above 400 K, 33 but a still higher transition temperature is required for stable usage for a long duration. Here, we report on the phase behavior of thiourea introduced in a stable MOF, 35 It provides the first example of introducing molecular ferroelectric materials inside MOFs and of their thermal and physical properties when confined in the frameworks.Various MOFs such as ZIF-8, 3638 MIL-101(Cr), 39 MIL-53(Al), 40 and UiO-66 were tested in this study because they show stability against gaseous ammonia up to 350°C. 41 As polar guest molecules, thiourea, potassium nitrite, and potassium dihydrogen phosphate were employed.…”

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Introduction of Thiourea into Metal–Organic Frameworks by Immersion Technique and Their Phase Transition Characteristics

Yamada¹,

Kubo

Kimizuka³

2017

Chem. Lett.

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Thiourea was introduced into the micropores of UiO-66 and its derivatives. It provides the first example of doping highly polar molecules into the metalorganic frameworks (MOFs) via a solution process. DSC measurements of the obtained thiourea@ UiO-66 composite showed the disappearance of the phase transition of the guest thiourea in UiO-66 and its family, indicating the formation of hydrogen bonds between the guest and frameworks.Keywords: Metal-organic framework (MOF) | Ferroelectric material | ThioureaConfinement of guest molecules in a well-defined nanospace provides an opportunity to gain insight into how their inherent properties are tuned by the intermolecular interactions with the surrounding environment. Metalorganic frameworks (MOFs) are polymeric coordination compounds that can be prepared from a large variety of bridging organic ligands and metal ions. They show a wide variation of nanosized pore structures in which guest molecules can be introduced, providing a unique platform to control intermolecular forces between the guest molecules and the frameworks. A variety of MOFs have been reported during the last two decades and their unique properties and functions such as gas sorption and storage, 14 and optical, 57 catalytic, 810 and electronic 1114 properties have been actively investigated. Several MOFs show the remarkably high capability to store and separate various gaseous guests such as H 2 , CO 2 , and methane.The property of the introduced guest molecules is affected by the interaction with frameworks, as represented by the recent report on controlled magnetism of dihydrogen molecules by the interaction with hosts.15 MOF frameworks in general are formed by rather weak coordination bonds and the inclusion of polar organic compounds into MOF is still limited by their deteriorating action on the frameworks. Meanwhile, MOF that is chemically stable against water has been recently developed, 16,17 which enabled the investigation of the property of water clusters formed in MOFs and proton conductivity or the phase transition behavior of water clusters. 1824 A typical ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide was also introduced into ZIF-8, which showed maintenance of ionic conductivity below the freezing point of bulk ionic liquid.2527 Polar chemicals such as hydrogen sulfide 28,29 and nitric oxide 3032 have also been introduced into MOFs from the gaseous phase. However, there has been no report on the effect of phase transition of guest molecules between the paraelectric and ferroelectric phases.Here, we report on the phase transition characteristics of ferroelectric materials doped in MOFs. Ferroelectric materials as exemplified by inorganic perovskite materials such as PbZrO 3 and BaTiO 3 have been widely applied to produce actuators, sensors, and memories. Organic ferroelectric materials usually show a low coercive field due to the weak intermolecular interactions, but their low Curie temperature is an issue still at stake. Recently, croconic acid showed a Cur...

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A facile synthesis of UiO-66, UiO-67 and their derivatives

Cited by 1,383 publications

References 39 publications

Post‐Synthetic Anisotropic Wet‐Chemical Etching of Colloidal Sodalite ZIF Crystals

Post‐Synthetic Anisotropic Wet‐Chemical Etching of Colloidal Sodalite ZIF Crystals

Photochemical Hydrogen Production with Metal–Organic Frameworks

Introduction of Thiourea into Metal–Organic Frameworks by Immersion Technique and Their Phase Transition Characteristics

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