Differences between the isostructural IRMOF-1 and MOCP-L porous adsorbents

Calleja, Guillermo; Botas, Juan A.; Orcajo, M. Gisela; Sánchez‐Sánchez, Manuel

doi:10.1007/s10934-009-9268-5

Cited by 30 publications

(31 citation statements)

References 18 publications

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“…The remaining potential catalytic centers in MOF-5 will be Zn-OH groups and coordinatively unsaturated Zn 2+ sites, which may come from partial hydrolysis of the framework or from the inclusion of ZnO particles during the synthesis of the MOF. As we have already mentioned above, the amount of ZnO (or Zn(OH)2) impurities present in the MOF sample will depend on the synthesis procedure [14,15]. Thus, when MOF-5 samples are prepared with the fast precipitation method with triethylamine reported by Huang et al [3], the ZnO content of the resulting MOF-5 is not negligible.…”

Section: Catalytic Activity Of Mof-5mentioning

confidence: 96%

“…We have also considered that the MOF sample contained ZnO nanoparticles of about 15-20 nm in diameter, as suggested by Calleja et al [15]. Due to the larger particle size of the commercial ZnO sample, this has a surface-to-volume ratio which is about 6 times lower than in the ZnO nanoparticles in MOF-5, as calculated by simple geometric considerations and assuming spherical particles in both cases.…”

Section: Catalytic Activity Of Mof-5mentioning

confidence: 99%

“…There are experimental evidences indicating that, depending on the preparation procedure, MOF-5 may contain variable amounts of ZnO impurities either as segregated crystallites or nanoparticles entrapped inside the pore cavities [14,15]. The remaining potential catalytic centers in MOF-5 will be Zn-OH groups and coordinatively unsaturated Zn 2+ sites, which may come from partial hydrolysis of the framework or from the inclusion of ZnO particles during the synthesis of the MOF.…”

Section: Catalytic Activity Of Mof-5mentioning

confidence: 99%

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An unexpected bifunctional acid base catalysis in IRMOF-3 for Knoevenagel condensation reactions

Xamena

Cirujano

Corma

2012

Microporous and Mesoporous Materials

154

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In this work we have reexamined the catalytic properties of zinc aminoterephthalate IRMOF-3 for the Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate. The active sites for this reaction were previously proposed to consist in the amino groups of the aminoterephthalate linkers [1]. We have now found that the reaction can also be catalyzed by MOF-5, which has the same crystalline structure than IRMOF-3, but in which the aminoterephthalate ligand is replaced by terephthalate, thus lacking the amino groups that are present in IRMOF-3. It has been found that the catalytic activity of MOF-5 is related with the presence of defects and/or occluded metal oxides. Different preparation routes of MOF-5 have been followed that result in different concentration of defects and different reactivity. These defects sites can also be present in IRMOF-3 and contribute to the catalytic activity. Therefore, depending on the preparation conditions and on the concentration of defects, in the case of IRMOF-3 we can pass from a simple, monofunctional base to a (unintentional) bifunctional catalyst.

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Section: Catalytic Activity Of Mof-5mentioning

confidence: 96%

Section: Catalytic Activity Of Mof-5mentioning

confidence: 99%

Section: Catalytic Activity Of Mof-5mentioning

confidence: 99%

See 1 more Smart Citation

An unexpected bifunctional acid base catalysis in IRMOF-3 for Knoevenagel condensation reactions

Xamena

Cirujano

Corma

2012

Microporous and Mesoporous Materials

154

View full text Add to dashboard Cite

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“…This is primarily because the purity of the MOF-5 framework is highly dependent on the synthesis route, where reduced surface areas are often reported arising from either framework interpenetration or the incorporation of organic and/or zinc species within the pore system. [99,100] The latter issue is particularly significant since these species have the potential to manifest semiconductor-like behaviours in photoluminescence spectra which could then be attributed (rightly or wrongly) to energy or charge transfer processes in the framework itself.…”

Section: Oxide-based Qd@mof Compositesmentioning

confidence: 99%

Synthesis and applications of metal-organic framework–quantum dot (QD@MOF) composites

Aguilera‐Sigalat

Bradshaw

2016

Coordination Chemistry Reviews

320

119

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Please cite this article as: J. Aguilera-Sigalat, D. Bradshaw, Synthesis and applications of metal-organic frameworkndashquantum dot (QD@MOF) composites, Coordination Chemistry Reviews (2015), http://dx.doi.org/10. 1016/j.ccr.2015.08.004 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.Page 1 of 56 A c c e p t e d M a n u s c r i p t Highlights:1. General strategies for the synthesis of QD@MOF composites 2. Consideration of the semiconductor behaviour of MOFs 3. Applications of QD@MOF composites, including photocatalysis, light-harvesting, sensing, imaging and gas storage. Future outlook for QD@MOF compositesPage 2 of 56 A c c e p t e d M a n u s c r i p t Synthesis and applications of metal-organic framework -quantum dot (QD@MOF) compositesJordi Aguilera-Sigalat* and Darren Bradshaw* School of Chemistry, University of Southampton, Southampton, U.K. AbstractThe combination of the high surface areas, microporosity and tuneable compositions of metalorganic frameworks (MOFs) with the desirable photo-physical behaviour of semiconductor nanoparticles or quantum dots (QDs), allows the preparation of composite materials with enhanced properties for applications in photocatalysis, energy, gas-storage and sensing. These QD@MOF composites are an emergent class of materials and in this review we discuss current strategies for their synthesis, consider the semiconductor behaviour of MOFs themselves and present the applications of the various materials reported this far grouped by the nature of the QD component.Article contents

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“…We then tested Co(nim) 2 for Knoevenagel reaction with an initial conversion of over 90% obtained for both solvent free and solvent condition that took 20 and 30 min, respectively, and there was no observed loss of intrinsic catalytic activity after reusability test as shown in Figure 13. Consequently, the slight lower conversion obtained with Co(nim) 2 could be attributed to the base weakening influence of the nitro group on the imidazolate linker, however, Co(im) 2 0.5 DMA is more basic with a corresponding higher conversion and shorter reaction time activate the carbonyl substrates of the Knoevenagel condensation acting as catalyst or co-catalyst for the reaction (Gascon et al, 2009;Llabrés et al, 2012); markedly, the extra frameworks of CoO (impurities entrapped inside the pore cavities as either nanoparticles or segregated crystallites) also contribute to the catalytic activities of CO-ZIFs (Llabrés et al, 2012;Hafizovic et al, 2007;Calleja et al, 2010;Neogi et al, 2009).…”

Section: Knoevenagel Condensationmentioning

confidence: 99%

Utilization of Co-Zeolite imidazolate frameworks (Co-ZIF) as catalyst for organic transformations

Olamoyesan¹,

Wang²,

Zhang³

et al. 2014

J. Chem. Eng. Mater. Sci.

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An excellent conversions of benzaldehyde was obtained under solvent and solvent free conditions by utilizing Co(im) 2 0.5 DMA as catalyst for the synthesis of benzylidene malononitrile. The catalytic prospect of this crystalline porous framework was extended to oxidation reactions involving ethylene glycol (EG) and ethylbenzene (EB). Unexpectedly, EG was totally oxidized to oxalic acid; which demonstrates the catalyst non-selectivity towards glycolic acid. For EB oxidation under a solvent less condition in the presence of oxygen as oxidant (0.8 Mpa), and a 42% conversion was achieved with 78.4% selectivity for acetophenone at 120°C for a period of 2 h.

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Differences between the isostructural IRMOF-1 and MOCP-L porous adsorbents

Cited by 30 publications

References 18 publications

An unexpected bifunctional acid base catalysis in IRMOF-3 for Knoevenagel condensation reactions

An unexpected bifunctional acid base catalysis in IRMOF-3 for Knoevenagel condensation reactions

Synthesis and applications of metal-organic framework–quantum dot (QD@MOF) composites

Utilization of Co-Zeolite imidazolate frameworks (Co-ZIF) as catalyst for organic transformations

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