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Copper-zirconia interfaces in UiO-66 enable selective catalytic hydrogenation of CO₂ to methanol.

ABSTRACT: Molecular interactions with both oxides and metals are essential for heterogenous catalysis, leading to remarkable synergistic impacts on activity and selectivity. Here, we show that the direct link between the two phases (and not merely being together) is required to selectively hydrogenate CO₂ to methanol on catalysts containing Cu and ZrO₂. Materials consisting of isolated Cu particles or atomically dispersed Cu-O-Zr sites only catalyze the reverse water-gas shift reaction. In contrast, a metal organic framework structure (UiO-66) with Cu nanoparticles occupying missing-linker defects maximizes the fraction of metallic Cu interfaced to ZrO₂ nodes leading to a material with high adsorption capacity for CO₂ and high activity and selectivity for low-temperature methanol synthesis.

SUBMITTER: Zhu Y

PROVIDER: S-EPMC7674450 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Copper-zirconia interfaces in UiO-66 enable selective catalytic hydrogenation of CO2 to methanol.

Zhu Yifeng Y Zheng Jian J Ye Jingyun J Cui Yanran Y Koh Katherine K Kovarik Libor L Camaioni Donald M DM Fulton John L JL Truhlar Donald G DG Neurock Matthew M Cramer Christopher J CJ Gutiérrez Oliver Y OY Lercher Johannes A JA

Nature communications 20201118 1

Molecular interactions with both oxides and metals are essential for heterogenous catalysis, leading to remarkable synergistic impacts on activity and selectivity. Here, we show that the direct link between the two phases (and not merely being together) is required to selectively hydrogenate CO2 to methanol on catalysts containing Cu and ZrO2. Materials consisting of isolated Cu particles or atomically dispersed Cu-O-Zr sites only catalyze the reverse water-gas shift reacti ...[more]

PMID: 33208734

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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

Copper-zirconia interfaces in UiO-66 enable selective catalytic hydrogenation of CO₂ to methanol.

Publications

Copper-zirconia interfaces in UiO-66 enable selective catalytic hydrogenation of CO<sub>2</sub> to methanol.

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