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Functionalization of robust Zr(IV)-based metal-organic framework films via a postsynthetic ligand exchange
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
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2015 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 51, no 1, 66-69 p.Article in journal (Refereed) Published
Abstract [en]

A facile and efficient fabrication approach for homogeneous, crack-free UiO-66 films with exceptionally high crystallinity and tunable thickness on a transparent and conductive glass substrate is reported. Two functionalized species, a catechol ligand and a Fe-2 complex with structural resemblance to the active site of [FeFe] hydrogenase, were introduced into the MOF films via a postsynthetic exchange. Voltammetric studies show the [FeFe] complex in the thinner UiO-66 films (2-5 mu m) can be reduced electrochemically.

Place, publisher, year, edition, pages
2015. Vol. 51, no 1, 66-69 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-241388DOI: 10.1039/c4cc08218dISI: 000345909400008PubMedID: 25364799OAI: oai:DiVA.org:uu-241388DiVA: diva2:783551
Available from: 2015-01-26 Created: 2015-01-12 Last updated: 2017-12-05Bibliographically 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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Supervisors
Available from: 2017-04-28 Created: 2017-03-30 Last updated: 2017-05-05

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Pullen, SonjaWagner, AndreasOtt, Sascha

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