Shunan Zhang,Xiaofang Liu,Zilong Shao,Hui Wang,Yuhan Sun
Direct CO 2 hydrogenation to ethanol is one of the promising and emerging routes for the transformation of CO 2 into value-added chemicals, but it remains a major challenge because of low ethanol selectivity and catalytic stability. In this work, Na-promoted cobalt catalysts supported on different materials (Al 2 O 3 , ZnO, AC, TiO 2 , SiO 2 , and Si 3 N 4 ) were evaluated to elucidate the effects of supports. The SiO 2 - and Si 3 N 4 -supported catalysts exhibited efficient generation of ethanol with 18% CO 2 conversion and 62% selectivity in the alcohol distribution at 250 °C, whereas CH 4 was predominantly produced on other supported catalysts. Characterization results indicated that the Co 2 C active phase only remained intact on SiO 2 and Si 3 N 4 supports during reaction and exhibited excellent durability for 300 h, which was attributed to the existence of a strong metal–support interaction (SMSI) obtained by Si O Co bond formation. In situ DRIFTS results revealed that CO produced on Co 2 C inserted into CH x intermediates to form ethanol. Moreover, CO as the reactive intermediate could induce the regeneration and reconstruction of decomposed Co 2 C on the surface for catalytic sustainability.
The reasons for the too high CO2 selectivity (near 50 C %) in Co2C-based Fischer–Tropsch to olefins (FTO) are not clear. Water–gas-shift (WGS) side reaction is thought to be responsible for this, but in-depth research is lacking. Here, we revealed the mechanism of the too high CO2 selectivity in Co2C-based FTO. Kinetic studies showed that WGS reaction was more likely to occur than the hydrocarbon production reaction. In addition, a too severe WGS reaction would result in the formation of an H2-enriched and CO-deficient environment on the catalyst surface, which was not favorable for the generation of light olefins. Catalyst characterization results proved that the severe WGS reaction could also lead to the transformation of prismatic Co2C to spherical Co2C. Theoretical calculations demonstrated that prismatic Co2C (020) and Co2C (101) facets were dominant crystal facets for both FTO and WGS reactions. Furthermore, in situ diffuse reflectance infrared Fourier transform spectroscopy experiments found that the H2O produced in FTO completely participated in the WGS reaction. This clearly revealed why the CO2 selectivity was close to 50 C % in FTO. Therefore, we believed that accelerating the desorption of H2O on the catalyst surface and preventing its readsorption are the key elements for inhibiting CO2 formation in FTO.
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