| Autor: |
Fernando NK; Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, U.K., Cairns AB; Department of Materials, Royal School of Mines, Imperial College London, Exhibition Road, London SW7 2AZ, U.K., Murray CA; Diamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, U.K., Thompson AL; Chemical Crystallography, Chemistry Research Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K., Dickerson JL; MRC Laboratory of Molecular Biology, Cambridge Biomedical Campus, Francis Crick Avenue, Cambridge CB2 0QH, U.K., Garman EF; Department of Biochemistry, University of Oxford, South Parks Road, Oxford OX1 3QU, U.K., Ahmed N; Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, U.K., Ratcliff LE; Department of Materials, Royal School of Mines, Imperial College London, Exhibition Road, London SW7 2AZ, U.K., Regoutz A; Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, U.K. |
| Abstrakt: |
X-ray characterization techniques are invaluable for probing material characteristics and properties, and have been instrumental in discoveries across materials research. However, there is a current lack of understanding of how X-ray-induced effects manifest in small molecular crystals. This is of particular concern as new X-ray sources with ever-increasing brilliance are developed. In this paper, systematic studies of X-ray-matter interactions are reported on two industrially important catalysts, [Ir(COD)Cl] 2 and [Rh(COD)Cl] 2 , exposed to radiation in X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) experiments. From these complementary techniques, changes to structure, chemical environments, and electronic structure are observed as a function of X-ray exposure, allowing comparisons of stability to be made between the two catalysts. Radiation dose is estimated using recent developments to the RADDOSE-3D software for small molecules and applied to powder XRD and XPS experiments. Further insights into the electronic structure of the catalysts and changes occurring as a result of the irradiation are drawn from density functional theory (DFT). The techniques combined here offer much needed insight into the X-ray-induced effects in transition-metal catalysts and, consequently, their intrinsic stabilities. There is enormous potential to extend the application of these methods to other small molecular systems of scientific or industrial relevance. |
