A highly stable dimethyl-functionalized Ce(<scp>iv</scp>)-based UiO-66 metal–organic framework material for gas sorption and redox catalysis

Dalapati, Rana; Sakthivel, B.; Dhakshinamoorthy, Amarajothi; Buragohain, Amlan; Bhunia, Asamanjoy; Janiak, Christoph; Biswas, Shyam

doi:10.1039/c6ce01704e

Cited by 88 publications

(47 citation statements)

References 89 publications

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“…Additionally, by introducing hydrophobic groups into the framework, the stability of Ce 4+ ‐MOFs toward water and acid can be enhanced. Indeed, the resulting MOF, Ce‐UiO‐66‐(CH 3 ) 2 , is reported to be stable in 1 m HCl aqueous solution …”

Section: Stable Metal–organic Frameworkmentioning

confidence: 99%

Stable Metal–Organic Frameworks: Design, Synthesis, and Applications

et al. 2018

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Metal-organic frameworks (MOFs) are an emerging class of porous materials with potential applications in gas storage, separations, catalysis, and chemical sensing. Despite numerous advantages, applications of many MOFs are ultimately limited by their stability under harsh conditions. Herein, the recent advances in the field of stable MOFs, covering the fundamental mechanisms of MOF stability, design, and synthesis of stable MOF architectures, and their latest applications are reviewed. First, key factors that affect MOF stability under certain chemical environments are introduced to guide the design of robust structures. This is followed by a short review of synthetic strategies of stable MOFs including modulated synthesis and postsynthetic modifications. Based on the fundamentals of MOF stability, stable MOFs are classified into two categories: high-valency metal-carboxylate frameworks and low-valency metal-azolate frameworks. Along this line, some representative stable MOFs are introduced, their structures are described, and their properties are briefly discussed. The expanded applications of stable MOFs in Lewis/Brønsted acid catalysis, redox catalysis, photocatalysis, electrocatalysis, gas storage, and sensing are highlighted. Overall, this review is expected to guide the design of stable MOFs by providing insights into existing structures, which could lead to the discovery and development of more advanced functional materials.

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Section: Stable Metal–organic Frameworkmentioning

confidence: 99%

Stable Metal–Organic Frameworks: Design, Synthesis, and Applications

et al. 2018

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“…Other examples in the literature reporting the use of UiO-66 type materials as catalysts for the oxidation of benzyl alcohol, [42] thiophenol, [43] cyclohexene [44] and Ti IV supported as part of the node in UiO-66 for the oxidation of cyclohexene using hydrogen peroxide [45] have also been reported.…”

Section: Nodes As Redox Sitesmentioning

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 the same reasons the UiO-66, -67 and -68 family has already been subjected to several functionalization procedures, involving both the Zr 6 O 4 (OH) 4 inorganic cornerstone and the organic linkers, as well as intentionally toned defect insertion. [35][36][37][38] As far as the inorganic cornerstone functionalization is concerned, Zr atoms have been partially or totally substituted with Hf 39,40 or Ce [41][42][43][44] atoms. Substitution with cerium allows alteration of the Ce(IV) 4 Ce(III) redox chemistry, providing some reactivity to the cornerstone.…”

Section: Introductionmentioning

confidence: 99%

Tuning Pt and Cu sites population inside functionalized UiO-67 MOF by controlling activation conditions

et al. 2017

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The exceptional thermal and chemical stability of the UiO-66, -67 and -68 classes of isostructural MOFs [J. Am. Chem. Soc., 2008, 130, 13850] makes them ideal materials for functionalization purposes aimed at introducing active centres for potential application in heterogeneous catalysis. We previously demonstrated that a small fraction (up to 10%) of the linkers in the UiO-67 MOF can be replaced by bipyridine-dicarboxylate (bpydc) moieties exhibiting metal-chelating ability and enabling the grafting of Pt(ii) and Pt(iv) ions in the MOF framework [Chem. Mater., 2015, 27, 1042] upon interaction with PtCl or PtCl precursors. Herein we extend this functionalization approach in two directions. First, we show that by controlling the activation of the UiO-67-Pt we can move from a material hosting isolated Pt(ii) sites anchored to the MOF framework with Pt(ii) exhibiting two coordination vacancies (potentially interesting for C-H bond activation) to the formation of very small Pt nanoparticles hosted inside the MOF cavities (potentially interesting for hydrogenation reactions). The second direction consists of the extension of the approach to the insertion of Cu(ii), obtained via interaction with CuCl, and exhibiting interesting redox properties. All materials have been characterized by in situ X-ray absorption spectroscopy at the Pt L- and Cu K-edges.

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A highly stable dimethyl-functionalized Ce(iv)-based UiO-66 metal–organic framework material for gas sorption and redox catalysis

Cited by 88 publications

References 89 publications

Stable Metal–Organic Frameworks: Design, Synthesis, and Applications

Stable Metal–Organic Frameworks: Design, Synthesis, and Applications

Engineering UiO‐66 Metal Organic Framework for Heterogeneous Catalysis

Tuning Pt and Cu sites population inside functionalized UiO-67 MOF by controlling activation conditions

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