Fluorine-modified Cu/Zn/Al/Zr catalysts via hydrotalcite-like precursors for CO2 hydrogenation to methanol

• Fluorine-modified catalyst was prepared derived from the fluorine-containing HTlcs.
• The exposed Cu surface area decreased with the introduction of fluorine.
• The proportion of strongly basic sites to total basic sites increased remarkably.
• The CO2 conversion decreased slightly and the CH3OH selectivity increased markedly.
• The presence of fluorine is beneficial for the production of methanol.

Fluorine-modified Cu/Zn/Al/Zr catalysts were prepared by calcination of the fluorine-containing Cu/Zn/Al/Zr hydrotalcite-like compounds and tested for CO2 hydrogenation to methanol. The results revealed that the CH3OH selectivity was greatly improved by the remarkable increase of the proportion of strongly basic sites, while the CO2 conversion decreased slightly. It is also found that the activity of catalysts is closely related to the synergy between the Cu and basic sites. The CH3OH yield for the fluorine-modified Cu/Zn/Al/Zr catalysts was higher than that for the fluorine-free catalysts; thus, the introduction of fluorine favored the methanol formation.

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