(Invited) In-Situ Optical Diagnostics of Plasma Electrochemical Reactors

Abstract

Many methods for synthesizing nanomaterials are complex and can require high temperature, acids, bases, or reducing agents. The plasma electrochemical reactor (PEC), composed of an atmospheric-pressure low-temperature plasma in contact with an aqueous electrode, may provide unique physico-chemical conditions that sidestep these disadvantages because non-equilibrium electrochemistry and nucleation are initiated in solution without additional heating or strong/toxic reagents. Indeed, PECs have successfully synthesized graphene quantum dots (GQD) [1,2].The precise mechanism of GQD growth is likely to be complex, involving non-equilibrium plasma chemistry and interactions near the plasma-liquid interface. Up to now, investigations of the liquid-phase chemistry have relied principally on ex situ measurements with little or no spatially-resolved information. In addition, conventional experimental techniques can suffer from a lack of selectivity and/or degradation of dyes, chemical probes, or spin traps introduced into the liquid.To extend the scope of diagnostics, we employ an in situ approach using multiple diagnostic techniques to study a wide range of physical and chemical properties at the plasma-water interface. The centrepiece of this platform is in situ spontaneous Raman microspectroscopy, which is advantageous because of its non-intrusiveness, selectivity, versatility, and straightforward calibration. Shaping the laser beam into a light sheet enables probing of the interfacial region with micron-scale spatial resolution. To observe the effect of the plasma on the solvent, we tracked the Raman spectrum of water. Analysis of the –OH stretch band reveals that the plasma weakens the hydrogen bonding network of water. This effect becomes especially pronounced near the interface, at a depth of a few tens of microns. Likewise, at a similar depth, the concentrations of aqueous H2O2 and NO3 - both exceed those of the bulk liquid [3]. Similar interfacial layers have been modeled in past studies for radical species such as OH but not for long-lived species such as NO3 -.Concerning GQDs, we tracked their production via in situ photoluminescence (PL) and UV-VIS absorption spectroscopies. Both the PL and absorption intensities reached a maximum not at the interface but rather at a depth of a few millimeters. This observation corroborates with liquid flow field measurements by particle image velocimetry, which revealed a low-velocity zone at this depth. Under certain conditions, we could observe the consumption of the carbon precursor over the course of plasma treatment using in situ Raman spectroscopy. Finally, we characterized plasma properties near the interface, such as the electron number density, using optical emission spectroscopy. Together, these results provide the fullest description to date of the reaction environment during GQD synthesis. Acknowledgments Financial support: ANR grants ANR-15-CE06-0007-01 and ANR-11-LABX-0017-01, PHC Orchid 40938YL, CNRS-IEA “GRAFMET”, Fédération Plas@Par, EUR PLASMAScience, Poitou-Charentes region (CPER program) References [1] Orrière, T., Kurniawan, D., Chang, Y. C., Pai, D. Z., & Chiang, W. H. (2020). Nanotechnology 31 (485001).[2] Yang, J. S., Pai, D. Z., & Chiang, W. H. (2019). Carbon 153, 315-319.[3] Pai, D. Z. (2021) J. Phys. D. : Appl. Phys. 54, 355201