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Sustainable Catalysis: Rational Pd Loading on MIL-101Cr-NH2 for More Efficient and Recyclable Suzuki-Miyaura Reactions
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
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2013 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 19, no 51, 17483-17493 p.Article in journal (Refereed) Published
Abstract [en]

Palladium nanoparticles have been immobilized into an amino-functionalized metal-organic framework (MOF), MIL-101Cr-NH2, to form Pd@MIL-101Cr-NH2. Four materials with different loadings of palladium have been prepared (denoted as 4-, 8-, 12-, and 16wt%Pd@MIL-101Cr-NH2). The effects of catalyst loading and the size and distribution of the Pd nanoparticles on the catalytic performance have been studied. The catalysts were characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) spectroscopy, powder X-ray diffraction (PXRD), N-2-sorption isotherms, elemental analysis, and thermogravimetric analysis (TGA). To better characterize the palladium nanoparticles and their distribution in MIL-101Cr-NH2, electron tomography was employed to reconstruct the 3D volume of 8wt%Pd@MIL-101Cr-NH2 particles. The pair distribution functions (PDFs) of the samples were extracted from total scattering experiments using high-energy X-rays (60keV). The catalytic activity of the four MOF materials with different loadings of palladium nanoparticles was studied in the Suzuki-Miyaura cross-coupling reaction. The best catalytic performance was obtained with the MOF that contained 8wt% palladium nanoparticles. The metallic palladium nanoparticles were homogeneously distributed, with an average size of 2.6nm. Excellent yields were obtained for a wide scope of substrates under remarkably mild conditions (water, aerobic conditions, room temperature, catalyst loading as low as 0.15mol%). The material can be recycled at least 10times without alteration of its catalytic properties.

Place, publisher, year, edition, pages
2013. Vol. 19, no 51, 17483-17493 p.
Keyword [en]
cross-coupling, heterogeneous catalysts, metal-organic frameworks, nanoparticles, palladium
National Category
Chemical Sciences
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-99879DOI: 10.1002/chem.201302621ISI: 000327889800030OAI: oai:DiVA.org:su-99879DiVA: diva2:690572
Funder
Knut and Alice Wallenberg FoundationSwedish Research CouncilVINNOVACarl Tryggers foundation
Note

AuthorCount:9;

Available from: 2014-01-24 Created: 2014-01-20 Last updated: 2017-11-09Bibliographically approved
In thesis
1. Catalytic Processes Mediated by Metal−Organic Frameworks: Reactivity and Mechanistic Studies
Open this publication in new window or tab >>Catalytic Processes Mediated by Metal−Organic Frameworks: Reactivity and Mechanistic Studies
2016 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The present thesis describes the development of heterogeneous catalytic methodologies using metal−organic frameworks (MOFs) as porous matrices for supporting transition metal catalysts. A wide spectrum of chemical reactions is covered. Following the introductory section (Chapter 1), the results are divided between one descriptive part (Chapter 2) and four experimental parts (Chapters 3–6).

Chapter 2 provides a detailed account of MOFs and their role in heterogeneous catalysis. Specific synthesis methods and characterization techniques that may be unfamiliar to organic chemists are illustrated based on examples from this work.

Pd-catalyzed heterogeneous C−C coupling and C−H functionalization reactions are studied in Chapter 3, with focus on their practical utility. A vast functional group tolerance is reported, allowing access to substrates of relevance for the pharmaceutical industry. Issues concerning the recyclability of MOF-supported catalysts, leaching and operation under continuous flow are discussed in detail.

The following chapter explores puzzling questions regarding the nature of the catalytically active species and the pathways of deactivation for Pd@MOF catalysts. These questions are addressed through detailed mechanistic investigations which include in situ XRD and XAS data acquisition. For this purpose a custom reaction cell is also described in Chapter 4.

The scope of Pd@MOF-catalyzed reactions is expanded in Chapter 5. A strategy for boosting the thermal and chemical robustness of MOF crystals is presented. Pd@MOF catalysts are coated with a protecting SiO2 layer, which improves their mechanical properties without impeding diffusion. The resulting nanocomposite is better suited to withstand the harsh conditions of aerobic oxidation reactions. In this chapter, the influence of the nanoparticles’ geometry over the catalyst’s selectivity is also investigated.

While Chapters 3–5 dealt with Pd-catalyzed processes, Chapter 6 introduces hybrid materials based on first-row transition metals. Their reactivity is explored towards light-driven water splitting. The heterogenization process leads to stabilized active sites, facilitating the spectroscopic probing of intermediates in the catalytic cycle.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2016. 122 p.
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-132711 (URN)978-91-7649-485-1 (ISBN)
Public defence
2016-10-07, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 5: Submitted. Paper 8: Submitted.

 

Available from: 2016-09-14 Created: 2016-08-19 Last updated: 2017-02-03Bibliographically approved

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