A versatile liquid-jet/sessile droplet system for operando studies of reactions in liquid dispersions and solutions by X-ray absorption spectroscopy

• Published in: Reaction chemistry & engineering 2019-04, Vol.4 (4), p.679-687
• Main Authors: Chang, S.-Y., Kathyola, T. A., Willneff, E. A., Willis, Colin John, Wilson, P., Dowding, P. J., Cibin, G., Kroner, A. B., Shotton, E. J., Schroeder, S. L. M.
• Format: Article
• Language: English
• Subjects: Absorption spectroscopy; Ambient temperature; Boring tools; Calcium carbonate; Chemical reactors; Dispersions; Droplets; Fluorescence; Gas-liquid reactions; Monitoring; Nozzles; Organic chemistry; Particulates; Portable equipment; Pressure drop; Slaked lime; Spectrum analysis; Vapor phases; X ray absorption; X-ray spectroscopy
• ISSN: 2058-9883; 2058-9883
• DOI: 10.1039/C8RE00207J

Herein, we designed a versatile cell for operando X-ray absorption spectroscopy (XAS) monitoring of chemical and physical transformations in liquid solutions and dispersions by fluorescence-yield detection. The cell operates under atmospheric pressure, and the composition of the gas phase can be varied, allowing monitoring of gas–liquid reactions. Samples can be examined as a flowing liquid-jet or as a sessile droplet. Both liquid-jet and droplet operations of the cell were demonstrated at the Ca K-edge through time-resolved studies of CaCO 3 formation from CO 2 and solid Ca(OH) 2 in an aqueous suspension. The liquid-jet reaction was performed at 28 °C, and the droplet reaction was performed at ambient temperature, but both configurations had the scope to be modified for operations at higher temperatures. The liquid-jet volumes were recycled, permitting the use of the cell in a continuous sampling loop for process studies in larger reactor vessels. The jet supply tube was interchangeable, permitting adjustment of the jet size through the tubing bore size. Larger bore sizes minimized the pressure drop at the nozzle and thereby the risk of blockage of the liquid supply by the suspended particulates or growth of solid deposits. Sessile droplet operation enabled studies with minimal sample volumes and mechanical disturbances under controlled environmental conditions. The cell is portable and modular and is based on readily available standard vacuum equipment parts. Furthermore, the operation under a He atmosphere allows measurements above 4 keV, covering part of the tender X-ray range, and it is also applicable to the hard X-ray range.