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

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/?-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/?-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.

SUBMITTER: Kobayashi H

PROVIDER: S-EPMC6429599 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

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

Kobayashi Hirokazu H Taylor Jared M JM Mitsuka Yuko Y Ogiwara Naoki N Yamamoto Tomokazu T Toriyama Takaaki T Matsumura Syo S Kitagawa Hiroshi H

Chemical science 20190206 11

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 replaceme ...[more]

PMID: 30996914

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Project description:In catalysts for CO2 hydrogenation, the interface between metal nanoparticles (NPs) and the support material is of high importance for the activity and reaction selectivity. In Pt NP-containing UiO Zr-metal-organic frameworks (MOFs), key intermediates in methanol formation are adsorbed at open Zr-sites at the Pt-MOF interface. In this study, we investigate the dynamic role of the Zr-node and the influence of H2O on the CO2 hydrogenation reaction at 170 °C, through steady state and transient isotope exchange experiments, H2O cofeed measurements, and density functional theory (DFT) calculations. The study revealed that an increased number of Zr-node defects increase the formation rates to both methanol and methane. Transient experiments linked the increase to a higher number of surface intermediates for both products. Experiments involving either dehydrated or prehydrated Zr-nodes showed higher methanol and methane formation rates over the dehydrated Zr-node. Transient experiments suggested that the difference is related to competitive adsorption between methanol and water. DFT calculations and microkinetic modeling support this conclusion and give further insight into the equilibria involved in the competitive adsorption process. The calculations revealed weaker adsorption of methanol in defective or dehydrated nodes, in agreement with the larger gas phase concentration of methanol observed experimentally. The microkinetic model shows that [Zr2(μ-O)2]4+ and [Zr2(μ-OH)(μ-O)(OH)(H2O)]4+ are the main surface species when the concentration of water is lower than the number of defect sites. Lastly, although addition of water was found to promote methanol desorption, water does not change the methanol steady state reaction rate, while it has a substantial inhibiting effect on CH4 formation. These results indicate that water can be used to increase the reaction selectivity to methanol and encourages further detailed investigations of the catalyst system.

Dataset Information

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

Publications

Charge transfer dependence on CO<sub>2</sub> hydrogenation activity to methanol in Cu nanoparticles covered with metal-organic framework systems.

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