The role of surface hydroxyls on ZnZrOx solid solution catalyst in CO2 hydrogenation to methanol

doi:10.1016/S1872-2067(22)64176-7

Abstract

Abstract:

ZnZrO_x solid solution catalyst is an excellent catalyst in methanol synthesis from CO₂ hydrogenation. It is still highly aspiration to make any further improvement in catalytic performance. In this work, ZnZrO_x solid solution catalyst is prepared with different methods, resulting in different surface property. The ZnZrO_x solid solution catalyst prepared by reflux ammonia (ZnZrO_x-RA) exhibits higher methanol selectivity of 95.2% and CO₂ conversion of 3.3% than that of the catalyst obtained via co-precipitation (ZnZrO_x-CP) at 280 °C, 5 MPa. Subsequent kinetics analysis shows that ZnZrO_x-RA, in comparison to ZnZrO_x-CP, shows a decreased activation energy for methanol synthesis, an increased reaction order in H₂, and a similar reaction order in CO₂. Structural characterizations indicate that these two catalysts are in solid solution state, while ZnZrO_x-RA possesses more Zn-OH species on the surface. The surface Zn-OH species enhance the activation and adsorption of CO₂ and H₂, and improve the generation and stability of HCOO* species, which promote CO₂ hydrogenation to methanol.

Key words: Surface hydroxyl, ZnZrOx solid solution, CO2 hydrogenation, Methanol synthesis, Preparation method

Feng Sha, Shan Tang, Chizhou Tang, Zhendong Feng, Jijie Wang, Can Li. The role of surface hydroxyls on ZnZrO_x solid solution catalyst in CO₂ hydrogenation to methanol[J]. Chinese Journal of Catalysis, 2023, 45: 162-173.

Figures/Tables 9

Fig. 1. CO2 conversion and methanol selectivity (a), and methanol STY (b) over different catalysts. (c) Stability test of ZnZrOx-RA at 320 °C. Reaction conditions: 280-340 °C, 5 MPa, H2/CO2 = 3:1, and 24000 mL·gcat-1·h-1.

Fig. 2. CO2 conversion (a), methanol selectivity (b), and methanol STY (c) as a function of the molar ratio of H2/CO2 in the feed gas over ZnZrOx-RA catalyst. Reaction conditions: 260-340 °C, 5 MPa, and 24000 mL·gcat-1·h-1.

Fig. 3. CO2 conversion (a), methanol selectivity (b), and methanol STY (c) as a function of space velocity over ZnZrOx-RA catalyst. Reaction conditions: 290 °C, 5 MPa, H2/CO2=6:1, and 24000 mL·gcat-1·h-1.

Fig. 4. Arrhenius plot for CO2 hydrogenation to methanol (a) and the RWGS reaction (b), and dependence of methanol formation rate on H2 partial pressure (c) and CO2 partial pressure (d) over ZnZrOx-RA and ZnZrOx-CP catalysts.

Fig. 5. XRD patterns of ZnZrOx-RA and ZnZrOx-CP catalysts.

Fig. 6. HRTEM and EDX element mapping of ZnZrOx-RA (a-c) and ZnZrOx-CP (d-f) catalysts.

Fig. 7. UV-vis (a), XPS of Zn 2p (b), FT-IR spectra (c), and CO-TPD profiles (d) for ZnZrOx-RA and ZnZrOx-CP catalysts.

Fig. 8. H2-TPR (a), H2-D2 exchange (b), H2-TPD (c), and CO2-TPD (d) profiles for ZnZrOx-RA and ZnZrOx-CP catalysts.

Fig. 9. In situ DRIFT spectra of ZnZrOx-RA and ZnZrOx-CP in the range of 3200-2700 cm-1 under different atmosphere H2 + CO2 (a), H2 (b), and 1 MPa H2 (c), and variation of IR peak intensities of HCOO* (d), CH3O* (e), and dynamic change of the HCOO*/CH3O ratio (f) over ZnZrOx-RA and ZnZrOx-CP catalysts.

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The role of surface hydroxyls on ZnZrO_x solid solution catalyst in CO₂ hydrogenation to methanol

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