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2. HYDROGEN RADICAL ASSISTED METHANATION 2.4. DISCUSSION Figure 2.8: Schematic representation of possible reaction mechanisms at surface. A and B can be any of the surface species listed in table 2.2 while C is a gas phase species. a) starting surface b) and c) ending surface states. affected by a copper surface (figure 2.4). The experiments with an Al surfaces clearly indicate that just adding the sheets did not alter the reaction conditions; for example, change in wall temperature. The qualitative features of the trends of all the measured species remained similar with Cu as surface but with excessive soot deposition (carbon- aceous deposits) at the surface and slightly reduced levels of CO and CH4 (figure 2.4). X-ray photoelectron spectroscopy and Raman spectroscopy of the soot covered copper confirmed that the deposits are primarily carbon based. The carbon soot deposited can alter the rate of any of the five steps involved in CH4 production thus reducing its total yield. Jones et al [114] show with the help of DFT calculations - in contrast to what is observed in EPJ - that CO dissociation is not favored by copper. The most difficult step in CH4 formation in chain reactions (S1, S2 and S7, S8) on a copper surface is to dissociate CO (S1), once carbon is available all the subsequent reactions to form methane are favor- able. In other words, copper is not expected to bind carbon and to build an appreciable surface coverage. Disproportionation reaction of carbon monoxide on copper surface could be another possible pathway [115] for carbon production. Copper electrodes were known for carbon deposition in CO lasers [116] from disproportionation reaction which have non-thermal conditions like in EPJ. The unexpected behavior of copper in plasma conditions show that conventional catalysts are not suitable in EPJ like environments and new candidates have to be found if plasma has to become viable. 34PDF Image | Understanding CO2 containing non-equilibrium plasmas
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