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Highly Dispersed Zn Sites on ZrO2 by Flame Spray Pyrolysis for CO2 Hydrogenation to Methanol

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Abstract

In this study, we synthesized xZnO–ZrO2 (x = 14–40 at%) by flame spray pyrolysis under a lean-fuel condition. The optimal ZnO content was investigated to obtain a ZnO–ZrO2 solid solution with high specific surface area for CO2-to-methanol hydrogenation. The Zn species in ZnO–ZrO2 were highly dispersed and hexagonal ZnO was not detected by X-ray diffraction (XRD). After heating the particles in Ar at 400 °C for 3 h, hexagonal ZnO particles were observed at x = 40 at%, while below x = 28 at%, the Zn species remained high dispersion state. A fraction of the Zn species was substituted into the bulk of the ZrO2 particles, as evidenced by the shift of the ZrO2 (101) peak in the XRD patterns. The elemental mapping of Zn and Zr in 28 at% ZnO–ZrO2 showed that the Zn species on the surface were uniformly distributed. The presence of partially reduced Zrδ+ state (δ < 4) was confirmed by X-ray photoelectron spectroscopy. The Zrδ+ state in the ZnO–ZrO2 particles was prominent when ZnO content was below 28 at%. The catalytic activity of 28 at% ZnO–ZrO2 for CO2-to-methanol hydrogenation was higher than that of 40 at% ZnO–ZrO2. At 300 °C and 1.0 MPa, the CO2 conversion and the selectivity to methanol over 28 at% ZnO–ZrO2 were 9 and 48%, respectively, resulting in the high yield of methanol (4.3%).

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Acknowledgements

This work was supported by Leading Initiative for Excellent Young Researchers (LEADER) of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan. STEM measurements were supported by the microstructural characterization platform at Osaka University (JPMXP09A21OS0012) in a nanotechnology platform project sponsored by MEXT, Japan. XPS measurements were performed at Industrial Technology Institute, Miyagi Prefectural Government.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Engineering, Yamagata University, 4-3-6 Jonan, Yonezawa, Yamagata, 992–8510, Japan

    Kakeru Fujiwara & Taiki Akutsu

  2. Flexible 3D System Integration Laboratory, Sanken, Osaka University, 8–1 Mihogaoka, Ibaraki, Osaka, 567-0047, Japan

    Masahiko Nishijima

  3. Division of Applied Chemistry, Graduate School of Engineering, Hokkaido University, N13 W8, Kita-Ku, Sapporo, Hokkaido, 060-8628, Japan

    Shohei Tada

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  1. Kakeru Fujiwara
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Correspondence to Kakeru Fujiwara or Shohei Tada.

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Fujiwara, K., Akutsu, T., Nishijima, M. et al. Highly Dispersed Zn Sites on ZrO2 by Flame Spray Pyrolysis for CO2 Hydrogenation to Methanol. Top Catal 66, 1492–1502 (2023). https://doi.org/10.1007/s11244-023-01803-w

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