molecular sieve. The conversion of CO2 was simply defined as xCO/(xCO + xCO2), where xCO and xCO2 are the molar fractions of CO and CO2, respectively in the effluent gas.
2.3. CO2-TPD
The surface basicity of the catalysts was determined by the CO2-TPD in a micro reactor followed by a mass spectroscopy (Omni Star 200), and about 200mg catalyst was used per run. The catalyst sample was first heated up to 550◦C under nitrogen atmosphere and kept at this temperature for 1h, and then cooled down to 100◦C. The pulse of CO2 was then introduced until the adsorption of CO2 on the catalyst was saturated. After that, TPD was performed under nitrogen at 100–800◦C with a heating rate of 12◦C/min and the exhaust gases were detected by the mass spectrometry.
3. Results and discussion
3.1. Two pathways viewed on the basis of thermodynamic analysis
As proposed by Mimura and Saito [3], EB dehydrogenation in the presence of CO2 may proceed in two pathways, namely one-step and two-step pathways. For the one-step pathway, EB is oxidized to ST with CO2 through the direct interaction of CO2 and EB: C6H5–C2H5 +CO2 → C6H5–C2H3 +CO+H2O (1) while for the two-step pathway, EB is first dehydrogenated to ST with H2 formed simultaneously, and then CO2 reacts with H2 via the RWGS: C6H5–C2H5 → C6H5–C2H3 +H2 (2-1) H2 +CO2 → CO+H2O (2-2) Since H2 produced in the EB dehydrogenation is eliminated simultaneously by RWGS, the EB conversion can be then improved through the shift of dehydrogenation equilibrium. To examine the contribution of each pathway, the equilibrium conversions of EB and CO2 for the coupled EB dehydrogenation in the presence of CO2 in both one-step and two-step pathways were evaluated according to the method described elsewhere [2]. As shown in Fig. 1, the equilibrium conversions of EB with the coupling via either pathway are higher than those of EB dehydrogenation in the presence of N2 that has only dilution effect. EB conversion of the coupled dehydrogenation via the two-step pathway is a little higher than that via the one-step pathway at 350–600◦C; in contrast, the CO2 conversion via the two-step pathway is much lower at a temperature higher than 450◦C. Moreover, there will be no H2 in the effluent gas when the reaction follows solely the one-step pathway.