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The time evolution of the dissociation fraction in a pulsed radio frequency (rf) CO2 discharge is studied by infrared absorption. A large parametric study performed in a closed reactor brings valua...

It has been recently advocated that Mars has excellent conditions for oxygen and fuel production directly from atmospheric CO2 using non-equilibrium plasmas. The Martian conditions would be favorable for vibrational excitation and/or enhanced dissociation by electron impact, two important pathways for CO2 plasma dissociation. Herein we confirm these theoretical predictions by measuring, for the first time, the vibrational temperatures of CO2 and the CO and CO2 concentrations in realistic Martian conditions. In situ Fourier transform infrared spectroscopy (FTIR) measurements are performed in experiments conducted in DC glow discharges operating at pressures p=1-5 Torr, discharge currents I=10-50 mA, initial gas temperatures of 220 K and 300 K, both in pure CO2 and in the synthetic Martian atmosphere 96% CO2-2% Ar-2% N2. To analyse and interpret the experimental results, we develop a detailed self-consistent kinetic model for pure CO2 plasmas, describing the coupled electron and heavy-particle kinetics. The simulation results are in very good agreement with the experimental data. It is shown that the low-temperature conditions may enhance the degree of vibrational non-equilibrium and that the Martian atmospheric composition has a positive effect on CO2 decomposition. Accordingly, the present investigation confirms the potential of plasma technologies for in-situ resource utilization (ISRU) on Mars.

International audience; Oxygen atom densities were measured in situ in a CO2 glow discharge, at pressures between 0.2 and 5 Torr (26.7?666.6 Pa). Two measurement techniques were compared, namely optical emission actinometry (using Ar as the actinometer) and high-resolution two-photon absorption laser induced fluorescence normalised to Xe, and were found to give consistent results. The variation of the atomic oxygen density with gas pressure shows two different regimes with a transition around 1 Torr. Measurements of the O atom loss frequency under plasma exposure showed that this behaviour is caused by a change in the O atom loss mechanisms, which are dominated by surface processes in our experimental conditions. The corresponding recombination probabilities on Pyrex ? O are found to vary with the gas temperature near the wall for a constant surface temperature, similarly to what has recently been obtained in pure O2. However, the measured values are more than two times lower than ? O obtained in a O2 plasma in similar conditions. The O atom densities are also compared to the dissociation fraction of CO2 determined by infra-red absorption. The obtained CO and O densities show different behaviour as a function of the energy input. The simultaneous measurement of gas temperature, electric field, O, CO and CO2 densities and O atoms loss frequency in the same conditions provides an ideal set of constraints for validating CO2 plasma kinetic models.

International audience; The excitation and relaxation of the vibrations of CO2 as well as the reduction of CO2 to CO are studied in a pulsed glow discharge. Two diagnostics are employed, being (1) time-resolved in situ Fourier transform infrared (FTIR) spectroscopy and (2) spatiotemporally resolved in situ rotational Raman spectroscopy. Experiments are conducted within a pressure range of 1.3-6.7 mbar and a current range of 10-50 mA. In the afterglow, the rate of exponential decay from the asymmetric stretch temperature (T3) to the rotational temperature (Trot) is found to be only dependent on Trot, in the conditions under study. The decay rate ρT3-Trot follows the relation ρT3-Trot = 388 s-1 exp((Trot - 273 K)/(154 K)). Pressure and varying concentrations of CO and (presumably) atomic oxygen did not show to be of significant influence. In the active part of the discharge the excitation of T3 showed to be positively related to current and negatively to pressure. However, the contribution of current to vibrational excitation is ambiguous: the conversion of CO2 and therefore the fraction of CO in the discharge, is found to be strongly dependent on the current, with a conversion factor of 0.05 to 0.18 for 10 mA to 50 mA, while CO can contribute to the excitation through near-resonant collisions. A clear relation between the elevation of T3 and the dissociation of CO2 could not be confirmed, though conversion peaks are observed in the near afterglow, which motivate future experiments on vibrational ladder-climbing directly after termination of the discharge.

The implementation of in situ rotational Raman spectroscopy is realized for a pulsed glow discharge in CO2 in the mbar range and is used to study the rotational temperature and molecular number densities of CO2, CO, and O2. The polarizability anisotropy of these molecules is required for extracting number densities from the recorded spectra and is determined for incident photons of 532 nm. The spatiotemporally-resolved measurements are performed in the same reactor and at equal discharge conditions (5-10 ms on-off cycle, 50 mA plasma current, 6.7 mbar pressure) as in recently published work employing in situ Fourier transform infrared (FTIR) spectroscopy. The rotational temperature ranges from 394 to 809 K from start to end of the discharge pulse and is constant over the length of the reactor. The discharge is demonstrated to be spatially uniform in gas composition, with a CO2 conversion factor of 0.15 ± 0.02. Rotational temperatures and molecular composition agree well with the FTIR results, while the spatial uniformity confirms the assumption made for the FTIR analysis of a homogeneous medium over the line-of-sight of absorption. Furthermore, the rotational Raman spectra of CO2 are related to vibrational temperatures through the vibrationally averaged nuclear spin degeneracy, which is expressed in the intensity ratio between even and odd numbered Raman peaks. The elevation of the odd averaged degeneracy above thermal conditions agrees well with the elevation of vibrational temperatures of CO2, acquired in the FTIR study.

Time-resolved in situ FTIR spectroscopy and spatiotemporally resolved in situ Raman spectroscopy are used to study the excitation and relaxation of the vibrations of CO 2 and the reduction of CO 2 to CO in a pulsed glow discharge.

Vibrational temperatures of CO2 are studied in a pulsed glow discharge by means of time-resolved in situ Fourier transform infrared spectroscopy, with a 10 μs temporal resolution. A method to analyze the infrared transmittance through vibrationally excited CO2 is presented and validated on a previously published CO2 spectrum, showing good agreement between fit and data. The discharge under study is pulsed with a typical duty cycle of 5-10 ms on-off, at 50 mA and 6.7 mbar. A rapid increase of the temperature of the asymmetric stretch vibration (T 3) is observed at the start of the pulse, reaching 1050 K, which is an elevation of 550 K above the rotational temperature () of 500 K. After the plasma pulse, the characteristic relaxation time of T 3 to strongly depends on the rotational temperature. By adjusting the duty cycle, the rotational temperature directly after the discharge is varied from 530 to 860 K, resulting in relaxation times between 0.4 and 0.1 ms. Equivalently, as the gas heats up during the plasma pulse, the elevation of T 3 above decreases strongly.

This work explores the effect of nitrogen addition on CO2 dissociation under various non-equilibrium plasma conditions. Experiments are performed in non-thermal plasmas sustained by DC pulsed discharges, for pressure and current ranges of 1 to 5 Torr and 20 to 50 mA, respectively. A self-consistent model, previously validated for pure CO2 discharges, is further extended to take into account e-V, V-T and V-V reactions involving N2. Both model predictions and experimental data reveal a maximum of the asymmetric vibrational temperature T3 at 5 Torr during the discharge around 1 ms, while no such maximum is visible at 1 Torr before the saturation occurs. It is shown that V-T deactivation by O atoms can have a strong influence on the vibrational kinetics, by affecting directly the relaxation of N2 vibrational excited states and, as a consequence, the very important energy transfers between vibrationally excited N2 and CO2 molecules. The experimental results show a twice larger CO2-conversion rate when N2 gas is added to the plasma. The simulations suggest this effect cannot be the result of an increased dissociation by direct electron impact due to modifications in the reduced electric field, but rather of some other contribution to dissociation and/or inhibition of reactions giving back CO2.