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Structural and electronic effects of X-ray irradiation on prototypical [M(COD)Cl]2 catalysts

DOI: 10.1021/acs.jpca.1c05759 DOI Help

Authors: Nathalie K. Fernando (University College London) , Andrew B. Cairns (Imperial College London) , Claire A. Murray (Diamond Light Source) , Amber L. Thompson (University of Oxford) , Joshua L. Dickerson (MRC Laboratory of Molecular Biology) , Elspeth F. Garman (University of Oxford) , Nayera Ahmed (University College London) , Laura E. Ratcliff (Imperial College London) , Anna Regoutz (Imperial College London)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: The Journal Of Physical Chemistry A

State: Published (Approved)
Published: August 2021
Diamond Proposal Number(s): 19420 , 22705

Abstract: 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.

Journal Keywords: X-rays; Catalysts; Diffraction; Transition metals; Irradiation

Subject Areas: Chemistry, Technique Development

Instruments: I11-High Resolution Powder Diffraction , I19-Small Molecule Single Crystal Diffraction

Added On: 23/08/2021 15:17

Discipline Tags:

Physical Chemistry Technique Development - Chemistry Catalysis Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD) X-ray Powder Diffraction