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Plasma-assisted dry reforming of methane has attracted much research attention because this process simultaneously utilizes greenhouse, methane and carbon dioxide, to produce hydrogen-rich syngas at a relative low temperature. Although it is generally recognized that the gas composition of reactant has great effect on the methane conversion and products distribution, systematic studies that clarify the roles that electron-induced chemistry and thermochemistry play are needed for a full understanding of reactant effect. Here, we compared the reforming performance by varying the ratio of CO2/CH4 or O2/CH4 at the similar reduced field intensity (E/N) in a temperature-controlled dielectric barrier discharge reactor to elaborate the role of electron-induced chemistry and thermo-chemistry in the dry reforming process. By conducting optical emission spectrum measurement, the enrichment of O atoms was observed at the increased CO2/CH4 or O2/CH4 ratios. At T = 293 K, methane conversion was only dependent on the electron-induced chemistry regardless of the specific reactant gas composition. At a relative high temperature condition, however, thermochemistry could become pronounce when sufficient O atoms were added into the dry reforming process. In contrast, the chemical pathways to the products were overall controlled by the thermochemistry at the tested background temperatures. Due to the conversion of carbon-based products into the carbon dioxide, the conversion of carbon dioxide was influenced by the thermochemistry when the concentration of O atoms was high. Our findings may improve the understanding of reactant effect and the designs of plasma-reformer.

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