No abstract

We propose and demonstrate an integrated electrified plasma-assisted chemical looping (PACL) process that yields supra-equilibrium CO 2 conversions unattainable with conventional catalysis at temperatures ≪3000 K. CO 2 is first dissociated inside plasma into CO/O at supra-equilibrium conversions (up to 60%) at a bulk gas temperature of 773 K and a 403 kJ/mol energy cost. Supra-equilibrium CO 2 conversions (29% on average) are achieved at the reactor outlet by placing a nanostructured CeO 2 /Fe 2 O 3 oxygen scavenger, prereduced by H 2 plasma, downstream of the plasma zone, to capture produced oxygen species and suppress CO/O recombination. Without plasma-material synergy, such an average CO 2 conversion can only be attained at temperatures ≥ 2775 K, according to chemical equilibrium calculations. This concept of plasma-assisted chemical looping allows reaching 3-fold higher conversions than state-of-the-art plasma technologies.

The plasma dry reforming reaction of methane with carbon dioxide is investigated in a nanosecond repetitively pulsed discharge, a type of plasma that offers some of the highest performance and non-equilibrium characteristics. The experiment's purpose was to examine the effect of varying the sequence of high-voltage pulses. We find that when successive pulses are closer than 500 μs, a memory-dominated regime gradually develops, which influences subsequent breakdown events. While reactant conversions increase with the plasma energy, both energy efficiency and conversions increase by shortening the inter-pulse time at the same plasma energy. This finding suggests that plasma power is not the only thing that matters to achieve better performance. How it is delivered can make a significant difference, in particular for CO2, whose conversion doubles at the maximum energy for molecule investigated, 1.6 eV molecule -1 .

Power-to-chemical technologies with CO2 as feedstock recycle CO2 and store energy into value-added compounds. Plasma discharges fed by renewable electricity are a promising approach to CO2 conversion. However, controlling the mechanisms of plasma dissociation is crucial to improving the efficiency of the technology. We have investigated pulsed nanosecond discharges, showing that while most of the energy is deposited in the breakdown phase, CO2 dissociation only occurs after an order of microsecond delay, leaving the system in a quasi-metastable condition in the intervening time. These findings indicate the presence of delayed dissociation mechanisms mediated by CO2 excited states rather than direct electron impact. This “metastable” condition, favorable for an efficient CO2 dissociation, can be prolonged by depositing more energy in the form of additional pulses and critically depends on a sufficiently short interpulse time.