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Plasma catalysis is gaining increasing interest for various gas conversion applications, such as CO2 conversion into value-added chemicals and fuels, CH4 activation into hydrogen, higher hydrocarbons or oxygenates, and NH3 synthesis. Other applications are already more established, such as for air pollution control, e.g. volatile organic compound remediation, particulate matter and NOx removal. In addition, plasma is also very promising for catalyst synthesis and treatment. Plasma catalysis clearly has benefits over ‘conventional’ catalysis, as outlined in the Introduction. However, a better insight into the underlying physical and chemical processes is crucial. This can be obtained by experiments applying diagnostics, studying both the chemical processes at the catalyst surface and the physicochemical mechanisms of plasma-catalyst interactions, as well as by computer modeling. The key challenge is to design cost-effective, highly active and stable catalysts tailored to the plasma environment. Therefore, insight from thermal catalysis as well as electro- and photocatalysis is crucial. All these aspects are covered in this Roadmap paper, written by specialists in their field, presenting the state-of-the-art, the current and future challenges, as well as the advances in science and technology needed to meet these challenges.

Dry reforming of methane over a Ni/Al2O3 catalyst in a coaxial dielectric barrier discharge reactor. AbstractA coaxial double dielectric barrier discharge (DBD) reactor has been developed for plasmacatalytic conversion of CH 4 and CO 2 into syngas and other valuable products. A supported metal catalyst (Ni/Al 2 O 3 ) reduced in a methane discharge is fully packed into the discharge region. The influence of the Ni/Al 2 O 3 catalyst packed into the gas gap on the electrical characteristics of the discharge has been investigated. The introduction of the catalyst pellets leads to a transition in discharge behaviour from a typical filamentary microdischarge to a combination of spatially-limited microdischarges and a predominant surface discharge on the catalyst surface. It is also found that the breakdown voltage of the CH 4 /CO 2 discharge significantly decreases when the reduced catalyst is fully packed in the discharge area.Conductive Ni active sites dispersed on the catalyst surface contribute to the expansion of the discharge and enhancement of charge transfer. In addition, plasma-catalytic dry reforming of CH 4 has been carried out with the reduced Ni/Al 2 O 3 catalyst using a mixing ratio of CH 4 /CO 2 = 1 and a total flow rate of 50 ml min -1 . An increase in H 2 selectivity is observed compared to dry CH 4 reforming with no catalyst, while the H 2 /CO molar ratio greatly increases from 0.84 to 2.53 when the catalyst is present.

A cylindrical dielectric barrier discharge (DBD) reactor has been developed for the conversion of undiluted CO2 into CO and O2 at atmospheric pressure and low temperatures. Both the physical and chemical effects on reaction performance have been investigated for the addition of BaTiO3 and glass beads into the discharge gap. The presence of these packing materials in the DBD reactor changes the physical characteristics of the discharge and leads to a shift of the discharge mode from a typical filamentary discharge with no packing to a combination of filamentary discharge and surface discharge with packing. Highest CO2 conversion and energy efficiency are achieved when the BaTiO3 beads are fully packed into the discharge gap. It is found that adding the BaTiO3 beads into the plasma system enhances the average electric field and mean electron energy of the CO2 discharge by a factor of 2, which significantly contributes to the enhancement of CO2 conversion, CO yield and energy efficiency of the plasma process. In addition, highly energetic electrons (> 3.0 eV) generated by the discharge could activate BaTiO3 photocatalyst to form electron-hole pairs on its surface, which contributes to the enhanced conversion of CO2.

We present a computational study for the conversion of CH4 and CO2 into value-added chemicals, i.e., the so-called “dry reforming of methane”, in a dielectric barrier discharge reactor. A zero-dimensional chemical kinetics model is applied to study the plasma chemistry in a 1:1 CH4/CO2 mixture. The calculations are first performed for one microdischarge pulse and its afterglow, to study in detail the chemical pathways of the conversion. Subsequently, long time-scale simulations are carried out, corresponding to real residence times in the plasma, assuming a large number of consecutive microdischarge pulses, to mimic the conditions of the filamentary discharge regime in a dielectric barrier discharge (DBD) reactor. The conversion of CH4 and CO2 as well as the selectivity of the formed products and the energy cost and energy efficiency of the process are calculated and compared to experiments for a range of different powers and gas flows, and reasonable agreement is reached.