The effect of the compensating cation on the catalytic performances of Ni/USY zeolites towards CO2 methanation

- CO2 methanation performed on alkaline and alkaline earth-exchanged NiY zeolites.
- Compensation cations do not strongly affect Ni reducibility.
- Larger size alkaline compensation cations enhance CO2 adsorption and methanation.
- Mg2+ shows the best catalytic results among alkaline earth metals.
- Tuning the zeolite compensating cation can favour CO2 methanation.

In the present work, monovalent (Cs+, K+, Na+, Li+) and divalent (Ba2+, Ca2+, Mg2+) cations have been exchanged in a HUSY zeolite and impregnated with 15% of Ni, in order to be used as catalysts for CO2 methanation reaction. The results showed that the order of improvement of the catalytic performances is Cs+ > Na+ > Li+ > K+ > H+ for the monovalent cations and Mg2+ > Ca2+ > Ba2+ for the divalent. No important differences were observed in terms of Ni reducibility followed by H2-TPR and textural properties determined by N2 adsorption experiments. In addition, similar Ni particles sizes were observed for Cs+, Na+, Li+ and H+ and much bigger Ni particles were found on K+ sample. The differences in the performances of these monovalent exchanged samples were thus attributed to the reported enhancement of the CO2 adsorption capacity and framework basicity of the zeolites containing these cations. In terms of divalent cations, Mg2+ sample presented both the lower Ni particle size and the better performances, while no relevant differences were observed in terms of Ni species reducibility and textural properties among all the divalent samples. Thus, Mg2+ induces not only an enhancement of the CO2 activation, but also of the Ni dispersion. To conclude, this work constitutes a crucial advance in the use of zeolites as supports for CO2 conversion into CH4 by tuning the catalyst properties through the exchanged cation, as almost no studies on this subject have been published.

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