Charge transfer dependence on CO2 hydrogenation activity to methanol in Cu nanoparticles covered with metal–organic framework systems

Hirokazu Kobayashi; Jared M. Taylor; Yuko Mitsuka; Naoki Ogiwara; Tomokazu Yamamoto; Takaaki Toriyama; Syo Matsumura; Hiroshi Kitagawa

doi:10.1039/C8SC05441J

Charge transfer dependence on CO₂ hydrogenation activity to methanol in Cu nanoparticles covered with metal–organic framework systems†

Hirokazu Kobayashi,*^ab Jared M. Taylor,‡^a Yuko Mitsuka,^c Naoki Ogiwara,^a Tomokazu Yamamoto,^de Takaaki Toriyama,^e Syo Matsumura^def and Hiroshi Kitagawa

*^afg

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* Corresponding authors

^a Division of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto, Japan
E-mail: hkobayashi@kuchem.kyoto-u.ac.jp, kitagawa@kuchem.kyoto-u.ac.jp

^b JST, PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama, Japan

^c Shoei Chemical Inc., 5-3, Aza-wakazakura Fujinoki-machi, Tosu-shi, Saga 841-0048, Japan

^d Department of Applied Quantum Physics and Nuclear Engineering, Graduate School of Engineering, Kyushu University, Motooka 744, Nishi-ku, Fukuoka, Japan

^e The Ultramicroscopy Research Center, Kyushu University, Motooka 744, Nishi-ku, Fukuoka, Japan

^f Inamori Frontier Research Center, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, Japan

^g Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University, Yoshida, Sakyo-ku, Kyoto, Japan

Abstract

We report the synthesis and characterization of highly active Cu nanoparticles covered with zirconium/hafnium-based metal–organic frameworks for CO₂ hydrogenation to methanol. Compared to Cu/γ-Al₂O₃, Cu/ZIF-8, Cu/MIL-100 and Cu/UiO-66 composites, UiO-66 acts as the most active support, with Cu/Zr-UiO-66 producing methanol at a rate 70 times higher than that of Cu/γ-Al₂O₃. In addition, the replacement of Zr⁴⁺ with Hf⁴⁺ in UiO-66 tripled in the rate of methanol production. Furthermore, we describe a substituent effect on the catalytic activity, with Cu/Zr-UiO66-COOH providing a three-fold enhancement of methanol production, compared to that of Zr-UiO-66 or Zr-UiO66-NH₂. The enhanced catalytic activity of Cu nanoparticles depends on the charge transfer degree from Cu nanoparticles to UiO-66 at the interface between Cu nanoparticles and UiO-66.

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DOI: https://doi.org/10.1039/C8SC05441J
Article type: Edge Article
Submitted: 05 Dec 2018
Accepted: 30 Jan 2019
First published: 06 Feb 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry

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Chem. Sci., 2019,10, 3289-3294

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Charge transfer dependence on CO₂ hydrogenation activity to methanol in Cu nanoparticles covered with metal–organic framework systems

H. Kobayashi, J. M. Taylor, Y. Mitsuka, N. Ogiwara, T. Yamamoto, T. Toriyama, S. Matsumura and H. Kitagawa, Chem. Sci., 2019, 10, 3289 DOI: 10.1039/C8SC05441J

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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Charge transfer dependence on CO₂ hydrogenation activity to methanol in Cu nanoparticles covered with metal–organic framework systems†

Abstract

Supplementary files

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Charge transfer dependence on CO₂ hydrogenation activity to methanol in Cu nanoparticles covered with metal–organic framework systems

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