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Catalyst accessibility to chemical reductants in metal–organic frameworks
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
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2017 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 53, no 22, 3257-3260 p.Article in journal (Refereed) Published
Abstract [en]

A molecular H2-evolving catalyst, [Fe2(cbdt)(CO)6] ([FeFe], cbdt = 3-carboxybenzene-1,2-dithiolate), has been attached covalently to an amino-functionalized MIL-101(Cr) through an amide bond. Chemical reduction experiments reveal that the MOF channels can be clogged by ion pairs that are formed between the oxidized reductant and the reduced catalyst. This effect is lessened in MIL-101-NH-[FeFe] with lower [FeFe] loadings. On longer timescales, it is shown that large proportions of the [FeFe] catalysts within the MOF engage in photochemical hydrogen production and the amount of produced hydrogen is proportional to the catalyst loading.

Place, publisher, year, edition, pages
2017. Vol. 53, no 22, 3257-3260 p.
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:uu:diva-318972DOI: 10.1039/c7cc00022gISI: 000398998500023PubMedID: 28261731OAI: oai:DiVA.org:uu-318972DiVA: diva2:1085639
Available from: 2017-03-29 Created: 2017-03-29 Last updated: 2017-05-02Bibliographically approved
In thesis
1. Mimicking the Outer Coordination Sphere in [FeFe]-Hydrogenase Active Site Models: From Extended Ligand Design to Metal-Organic Frameworks
Open this publication in new window or tab >>Mimicking the Outer Coordination Sphere in [FeFe]-Hydrogenase Active Site Models: From Extended Ligand Design to Metal-Organic Frameworks
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Biomimetic catalysis is an important research field, as a better understanding of nature´s powerful toolbox for the conversion of molecules can lead to technological progress. [FeFe]-hydrogenases are very efficient catalysts for hydrogen production. These enzymes play a crucial role in the metabolism of green algae and certain cyanobacteria. Their active site consists of a diiron complex that is embedded in an interactive protein matrix.

In this thesis, two pathways for mimicking the outer coordination sphere effects resulting from the protein matrix are explored.

The first is the construction of model complexes containing phosphine ligands that are coordinated to the iron center as well as covalently linked to the bridging ligand of the complex. The effect of such linkers is an increased energy barrier for the rotation of the Fe(CO2)(PL3)-subunit, which potentially could stabilize a terminal hydride that is an important intermediate in the proton reduction cycle.

The second pathway follows the incorporation of [FeFe]-hydrogenase active site model complexes into metal-organic frameworks (MOFs). Resulting MOF-catalysts exhibit increased photocatalytic activity compared to homogenous references due to a stabilizing effect on catalytic intermediates by the surrounding framework. Catalyst accessibility within the MOF and the influence of the framework on chemical reactivity are examined in the work presented. Furthermore, an initial step towards application of MOF-catalysts in a device was made by interfacing them with electrodes.

The work of this thesis highlights strategies for the improvement of biomimetic model catalysts and the knowledge gained can be transferred to other systems mimicking the function of enzymes. 

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2017. 115 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1498
Keyword
[FeFe]-hydrogenases, outer coordination sphere, model complexes, biomimetic catalysis, artificial photosynthesis, metal-organic frameworks
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-318975 (URN)978-91-554-9878-8 (ISBN)
Public defence
2017-05-19, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
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Available from: 2017-04-28 Created: 2017-03-30 Last updated: 2017-05-05

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