H. Reinsch

Towards metal–organic framework based field effect chemical sensors: UiO-66-NH2 for nerve agent detection

L. Stassen, B. Bueken, H. Reinsch, J.F.M. Oudenhoven, D. Wouters, J. Hajek, V. Van Speybroeck, N. Stock, P.M. Vereecken, R. Van Schajik, D. De Vos, R. Ameloot
Chemical Science
7, 5827-5832
2016
A1

Abstract 

We present a highly sensitive gas detection approach for the infamous ‘nerve agent’ group of alkyl phosphonate compounds. Signal transduction is achieved by monitoring the work function shift of metal–organic framework UiO-66-NH2 coated electrodes upon exposure to ppb-level concentrations of a target simulant. Using the Kelvin probe technique, we demonstrate the potential of electrically insulating MOFs for integration in field effect devices such as ChemFETs: a three orders of magnitude improvement over previous work function-based detection of nerve agent simulants. Moreover, the signal is fully reversible both in dry and humid conditions, down to low ppb concentrations. Comprehensive investigation of the interactions that lead towards this high sensitivity points towards a series of confined interactions between the analyte and the pore interior of UiO-66-NH2.

Open Access version available at UGent repository

A Flexible Photoactive Titanium Metal-Organic Framework Based on a [Ti-3(IV)(mu(3)-O)(O)(2)(COO)(6)] Cluster

B. Bueken, F. Vermoortele, D.E.P. Vanpoucke, H. Reinsch, C. Tsou, P. Valvekens, T. De Baerdemaeker, R. Ameloot, C. Kirschhock, V. Van Speybroeck, J. Mayer, D. De Vos
Angewandte Chemie int. Ed.
127, 14118 –14123
2015
A1

Abstract 

The synthesis of titanium-carboxylate metal-organic frameworks (MOFs) is hampered by the high reactivity of the commonly employed alkoxide precursors. Herein, we present an innovative approach to titanium-based MOFs by the use of titanocene dichloride to synthesize COK-69, the first breathing Ti MOF, which is built up from trans-1,4-cyclo-hexanedicarboxylate linkers and an unprecedented [Ti-3(IV)(mu(3)-O)(O)(2)(COO)(6)] cluster. The photoactive properties of COK-69 were investigated in depth by proton-coupled electron-transfer experiments, which revealed that up to one Ti-IV center per cluster can be photoreduced to Ti-III while preserving the structural integrity of the framework. The electronic structure of COK-69 was determined by molecular modeling, and a band gap of 3.77 eV was found.

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