Interaction dust-plasma in Titan's ionosphere: feedbacks on the gas phase composition

Titan's organic aerosols are formed in the ionosphere, a layer ionized by solar VUV photons and energetic particles from the magnetosphere of Saturn, forming a natural N2-CH4-H2 plasma. Previous works showed some chemical evolution processes: VUV photons slightly alter the aerosols nitrile bands, hydrogen atoms tend to hydrogenate their surface and carbon-containing species participate to the growth of the aerosols. This work investigates the effect of the other plasma species, namely the N2-H2 derived ions, radicals and excited states. Industrial plasmas often use N2-H2 discharges to form ammonia-based fertilizers, for metal nitriding, and to erode organic surfaces. Consequently, these are likely to affect Titan's organic aerosols. We therefore developed the THETIS experiment to study the interactions between analogues of Titan's aerosols (tholins) and the erosive N2-H2 plasma species found in Titan's ionosphere. Following a first paper on the evolution of the solid phase by Scanning Electron Microscopy and IR transmission spectroscopy (Chatain et al., Icarus, 2020), this paper focuses on evolution of the gas phase composition, by neutral and ion mass spectrometry. Newly formed HCN, NH3-CN and C2N2 are extracted from the tholins as well as some other carbon-containing species and their derived ions. On the other hand, the production of ammonia strongly decreases, probably because the H, NH and N radicals are rather used for the production of HCN at the surface of tholins. Heterogeneous processes are suggested: chemical processes induced by radicals at the surface would modify and weaken the tholin structure, while ion sputtering would desorb small molecules and highly unsaturated ions. The effect of plasma erosion on aerosols in Titan's ionosphere could therefore lead to the formation of CN bonds in the aerosol structure and the production of HCN or R-CN species in the gas phase.Comment: This paper has been accepted in Icarus (February 2023). The current version in arXiv is the submitted versio

Time-resolved nanosecond imaging of the propagation of a corona-like plasma discharge in water at positive applied voltage polarity

International audienceThe present paper is an experimental study of a pulsed filamentary plasma discharge inside liquid water in pin to plane electrode configuration. Time resolved electrical and imaging diagnostics have been performed. The initiation and the propagation of the discharge have been studied for several experimental parameters. The propagation is continuous and is followed by reilluminations at low water conductivity. The measured propagation velocity of the plasma discharge is 30km/s for the secondary positive mode. This velocity was found to be surprisingly constant whatever the experimental parameters and especially as a function of the water conductivity

Characterization of a DC glow discharge in N2-H2 with electrical measurements and neutral and ion mass spectrometry

The addition of small amounts of H2 were investigated in a DC glow discharge in N2, at low pressure (~1 mbar) and low power (0.05 to 0.2 W.cm-3). We quantified the electric field, the electron density, the ammonia production and the formation of positive ions for amounts of H2 varying between 0 and 5%, pressure values between 0.5 and 4 mbar, and currents between 10 and 40 mA. The addition of less than 1% H2 has a strong effect on the N2 plasma discharges. Hydrogen quenches the (higher) vibrational levels of N2 and some of its highly energetic metastable states. This leads to the increase of the discharge electric field and consequently of the average electron energy. As a result, higher quantities of radical and excited species are suspected to be produced. The addition of hydrogen also leads to the formation of new species. In particular, ammonia and hydrogen-bearing ions have been observed: N2H+ and NH4+ being the major ones, and also H3+, NH+, NH2+, NH3+, N3H+ and N3H3+. The comparison to a radiofrequency capacitively coupled plasma (RF CCP) discharge in similar experimental conditions shows that both discharges led to similar observations. The study of N2-H2 discharges in the laboratory in the adequate ionization conditions then gives some insights on which plasma species made of nitrogen and hydrogen could be present in the ionosphere of Titan. Here, we identified some protonated ions, which are reactive species that could participate to the erosion of organic aerosols on Titan.Comment: Paper accepted in Plasma Sources Science and Technology in March 2023. The current version on arXiv is the submitted versio

N2-H2 capacitively coupled radio-frequency discharges at low pressure: II. Modeling results: The relevance of plasma-surface interaction

In this work, we present the results of simulations carried out for N2-H2 capacitively coupled radio-frequency discharges, running at low pressure (0.3-0.9 mbar), low power (5-20 W), and for amounts of H2 up to 5%. Simulations are performed using a hybrid code that couples a two-dimensional time-dependent fluid module, describing the dynamics of the charged particles in the discharge, to a zero-dimensional kinetic module, that solves the Boltzmann equation and describes the production and destruction of neutral species. The model accounts for the production of several vibrationally and electronic excited states, and contains a detailed surface chemistry that includes recombination processes and the production of NH x molecules. The results obtained highlight the relevance of the interactions between plasma and surface, given the role of the secondary electron emission in the electrical parameters of the discharge and the critical importance of the surface production of ammonia to the neutral and ionic chemistry of the discharge.The Portuguese Foundation sponsored this research for Science and Technology (FCT) in the framework of the Strategic Funding UID/FIS/04650/2019

The 2020 plasma catalysis roadmap

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N2-H2 capacitively coupled radio-frequency discharges at low pressure. Part I. Experimental results: Effect of the H2 amount on electrons, positive ions and ammonia formation

The mixing of N2 with H2 leads to very different plasmas from pure N2 and H2 plasma discharges. Numerous issues are therefore raised involving the processes leading to ammonia (NH3) formation. The aim of this work is to better characterize capacitively-coupled radiofrequency plasma discharges in N2 with few percents of H2 (up to 5%), at low pressure (0.3-1 mbar) and low coupled power (3-13 W). Both experimental measurements and numerical simulations are performed. For clarity, we separated the results in two complementary parts. The actual one (first part), presents the details on the experimental measurements, while the second focuses on the simulation, a hybrid model combining a 2D fluid module and a 0D kinetic module. Electron density is measured by a resonant cavity method. It varies from 0.4 to 5 109 cm-3, corresponding to ionization degrees from 2 10-8 to 4 10-7. Ammonia density is quantified by combining IR absorption and mass spectrometry. It increases linearly with the amount of H2 (up to 3 1013 cm-3 at 5% H2). On the contrary, it is constant with pressure, which suggests the dominance of surface processes on the formation of ammonia. Positive ions are measured by mass spectrometry. Nitrogen-bearing ions are hydrogenated by the injection of H2, N2H+ being the major ion as soon as the amount of H2 is >1%. The increase of pressure leads to an increase of secondary ions formed by ion/radical-neutral collisions (ex: N2H+, NH4 +, H3 +), while an increase of the coupled power favours ions formed by direct ionization (ex: N2 +, NH3 +, H2 +).N. Carrasco acknowledges the financial support of the European Research Council (ERC Starting Grant PRIMCHEM, Grant agreement no. 636829). A. Chatain acknowledges ENS Paris-Saclay Doctoral Program. A. Chatain is grateful to Gilles Cartry and Thomas Gautier for fruitful discussions on the MS calibration. L.L. Alves acknowledges the financial support of the Portuguese Foundation for Science and Technology (FCT) through the project UID/FIS/50010/2019. L. Marques and M. J. Redondo acknowledge the financial support of the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding UIDB/04650/2019

Meta-analysis of CO2 conversion, energy efficiency, and other performance data of plasma-catalysis reactors with the open access PIONEER database

This paper brings the comparison of performances of CO2 conversion by plasma and plasma-assisted catalysis based on the data collected from literature in this field, organised in an open access online database. This tool is open to all users to carry out their own analyses, but also to contributors who wish to add their data to the database in order to improve the relevance of the comparisons made, and ultimately to improve the efficiency of CO2 conversion by plasma-catalysis. The creation of this database and database user interface is motivated by the fact that plasma-catalysis is a fast-growing field for all CO2 conversion processes, be it methanation, dry reforming of methane, methanolisation, or others. As a result of this rapid increase, there is a need for a set of standard procedures to rigorously compare performances of different systems. However, this is currently not possible because the fundamental mechanisms of plasma-catalysis are still too poorly understood to define these standard procedures. Fortunately however, the accumulated data within the CO2 plasma-catalysis community has become large enough to warrant so-called “big data” studies more familiar in the fields of medicine and the social sciences. To enable comparisons between multiple data sets and make future research more effective, this work proposes the first database on CO2 conversion performances by plasma-catalysis open to the whole community. This database has been initiated in the framework of a H2020 European project and is called the “PIONEER DataBase”. The database gathers a large amount of CO2 conversion performance data such as conversion rate, energy efficiency, and selectivity for numerous plasma sources coupled with or without a catalyst. Each data set is associated with metadata describing the gas mixture, the plasma source, the nature of the catalyst, and the form of coupling with the plasma. Beyond the database itself, a data extraction tool with direct visualisation features or advanced filtering functionalities has been developed and is available online to the public. The simple and fast visualisation of the state of the art puts new results into context, identifies literal gaps in data, and consequently points towards promising research routes. More advanced data extraction illustrates the impact that the database can have in the understanding of plasma-catalyst coupling. Lessons learned from the review of a large amount of literature during the setup of the database lead to best practice advice to increase comparability between future CO2 plasma-catalytic studies. Finally, the community is strongly encouraged to contribute to the database not only to increase the visibility of their data but also the relevance of the comparisons allowed by this tool

Plasma/surface interaction: example of air plasmas and plasma bullets

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Nature de la synergie plasma-photocatalyseur pour la destruction d'un composé organique volatil type : l'acétylène.

The procedures coupling a catalyst and a plasma at atmospheric pressure present a promising solution for atmospheric depolluting; more specifically for the processing of VOCs. In particular, the low energetic cost of this technique is highly interesting for minor concentrations (odor treatments), which are difficult to treat with usual methods. Among the catalysts available for the given purpose, TiO2 (a photocatalyst) is of advantage thanks to its low cost, its non toxicity and especially thank to its excellent selectivity in CO2. The combination with plasma could improve the processing speed which is slow using photocatalysis alone. The plasma/TiO2 synergy has just been studied since 2000. The aim of this work consists in the identification of the mechanisms responsible for this phenomenon. The physical and chemical contributions from the discharge, from porosity and from TiO2's photocatalytic activity were therefore separately scrutinized. In order to accomplish this, an non conventional approach was adopted to study a discharge at atmospheric pressure (DBD) as well as a discharge at low pressure (pulsed DC) permitting the use of infrared laser diagnosctics for in situ measurements resolved in time.Les procédés de couplage d'un plasma à pression atmosphérique et d'un catalyseur représentent une solution prometteuse pour la dépollution atmosphérique, ou plus spécifiquement pour le traitement des Composés Organiques Volatils. En particulier, le faible coût énergétique de cette technique la rend très intéressante pour les petites concentrations (traitement d'odeurs), difficiles à traiter avec les techniques habituelles. Parmi les catalyseurs qui peuvent être employés, le TiO2 (photocatalyseur) est avantageux pour son faible coût, sa non toxicité, et surtout son excellente sélectivité en CO2. Le couplage avec un plasma pourrait améliorer la vitesse de traitement qui est très lente en photocatalyse seule. La synergie plasma/TiO2 est étudiée depuis 2000 seulement. Le but de ce travail est d'identifier les mécanismes responsables de cette synergie en séparant les contributions de la décharge, de la porosité et de l'activité photocatalytique du TiO2. Pour y parvenir, une approche originale à été utilisée en étudiant à la fois une décharge à pression atmosphérique (DBD) et une décharge à basse pression (DC pulsée) autorisant l'utilisation de diagnostics lasers infra-rouge pour effectuer des mesures in situ résolues en temps