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Research Papers

Characterization of a Laser-Based Heating System Coupled With In Operando Raman Spectroscopy for Studying Solar Thermochemical Redox Cycles

[+] Author and Article Information
Kangjae Lee

Department of Mechanical and
Aerospace Engineering,
University of Florida,
Gainesville, FL 32611-6250

Jonathan R. Scheffe

Department of Mechanical and
Aerospace Engineering,
University of Florida,
Gainesville, FL 32611-6250
e-mail: jscheffe@ufl.edu

1Corresponding author.

Contributed by the Solar Energy Division of ASME for publication in the JOURNAL OF SOLAR ENERGY ENGINEERING: INCLUDING WIND ENERGY AND BUILDING ENERGY CONSERVATION. Manuscript received September 11, 2018; final manuscript received November 22, 2018; published online January 8, 2019. Guest Editors: Tatsuya Kodama, Christian Sattler, Nathan Siegel, Ellen Stechel

J. Sol. Energy Eng 141(2), 021013 (Jan 08, 2019) (7 pages) Paper No: SOL-18-1428; doi: 10.1115/1.4042229 History: Received September 11, 2018; Revised November 22, 2018

A 200 W CO2 laser-based heating system coupled with in operando Raman spectroscopy has been developed. The system delivers highly concentrated radiation capable of driving thermochemical reactions and simulates heat fluxes expected by 3D solar concentrating systems. 10 mol% Gd-doped and pure ceria pellets were prepared and used to characterize the system because of their well-established thermodynamic and kinetic properties, as well as their strong Raman peak due to F2 g symmetrical mode at 460 cm−1. Reduction in an H2 atmosphere has been carried out to investigate the behavior of the full width at half maximum (FWHM) of the F2 g Raman peak resulting from changes in temperature and oxidation state. For both samples, an increase in temperature during heating in air (i.e., fully oxidized) resulted in a peak shift toward low wavenumber and an increase of FWHM. The FWHM versus temperature curves were then measured for controlled reduction extents ranging between sample averaged nonstoichiometries of δ = 0–0.209 as a function of temperature. At a fixed temperature, Gd-doped ceria exhibited an increase in FWHM with increasing reduction extent until δ = 0.056. At greater reduction extents, the FWHM decreased with increasing reduction extents. We attribute this to changes in the lattice parameter caused by the eventual formation of intermediate cubic Ce2O3 at the radiated surface. This study demonstrates the promise of utilizing Raman spectroscopy to probe thermochemical reactions in operando. Going forward, we expect that this will be an especially promising tool for characterizing emerging thermochemical materials with complex phase equilibria, especially for nonequilibrium processes.

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Figures

Grahic Jump Location
Fig. 1

Left: A schematic of a laser-based heating system coupled with in operando Raman spectroscopy. Center: sectional view rendering of a pellet within a sample holder. The reacting pelletized sample is placed within the porous Al2O3 sample holder (6-way CF cube chamber), and irradiated with a CO2 heating laser from the front, and impinged with a 532 nm Raman laser from the back. A bored hole through the side provides access for thermocouple measurements. Right: photograph of a Gd-doped ceria pellet contained within the sample holder.

Grahic Jump Location
Fig. 2

Normalized Raman spectra of fully oxidized ceria and Gd-doped ceria at 28 °C in 100% Ar atmosphere

Grahic Jump Location
Fig. 3

(a) Raman spectra of fully oxidized undoped ceria during heating from 28 °C to 595 °C and (b) FWHM and Raman peak shift of fully oxidized undoped ceria versus temperature

Grahic Jump Location
Fig. 4

(a) Raman spectra of fully oxidized Gd-doped ceria during heating from 28 °C to 400 °C and (b) FWHM and Raman peak shift of fully oxidized Gd-doped ceria versus temperature

Grahic Jump Location
Fig. 5

Normalized Raman spectra of fully oxidized and reduced Gd-doped ceria (δ = 0.209)

Grahic Jump Location
Fig. 6

(a) FWHM versus temperature curves of Gd-doped ceria with various reduction extents (from δ = 0 to δ = 0.209) during cooling and (b) FWHM versus reduction extent of Gd-doped ceria with various temperatures (from T = 33 °C to T = 40 °C) during cooling. Lines are drawn for visual purposes only.

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