Mechanism and Kinetics for Reaction of the Chemical Warfare Agent Simulant, DMMP(g), with Zirconium(IV) MOFs: An Ultrahigh-Vacuum and DFT Study
| Autor: | John R. Morris, Qi Wang, Diego Troya, Weiwei Guo, C. Smith, Anna M. Plonka, J. Kollar, Conor H. Sharp, Anatoly I. Frenkel, Craig L. Hill, Guanyu Wang |
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| Rok vydání: | 2017 |
| Předmět: |
Zirconium
Chemistry Dimethyl methylphosphonate Inorganic chemistry chemistry.chemical_element Infrared spectroscopy 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences 0104 chemical sciences Surfaces Coatings and Films Electronic Optical and Magnetic Materials chemistry.chemical_compound General Energy Adsorption X-ray photoelectron spectroscopy Physisorption Chemisorption Metal-organic framework Physical and Theoretical Chemistry 0210 nano-technology |
| Zdroj: | The Journal of Physical Chemistry C. 121:11261-11272 |
| ISSN: | 1932-7455 1932-7447 |
| DOI: | 10.1021/acs.jpcc.7b00070 |
| Popis: | The mechanism and kinetics of interactions between dimethyl methylphosphonate (DMMP), a key chemical warfare agent (CWA) simulant, and Zr6-based metal organic frameworks (MOFs) have been investigated with in situ infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (PXRD), and DFT calculations. DMMP was found to adsorb molecularly to UiO-66 through the formation of hydrogen bonds between the phosphoryl oxygen and the free hydroxyl groups associated with Zr6 nodes on the surface of crystallites and not within the bulk MOF structure. Unlike UiO-66, the infrared spectra for UiO-67 and MOF-808, recorded during DMMP exposure, suggest that uptake occurs through both physisorption and chemisorption. The XPS spectra of MOF-808 zirconium 3d electrons reveal a charge redistribution following exposure to DMMP. In addition, analysis of the phosphorus 2p electrons following exposure and thermal annealing to 600 K indicates that two types of stable phosphorus-containing species e... |
| Databáze: | OpenAIRE |
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