The structure of Pd-functionalized UiO-67 during CO<sub>2</sub> hydrogenation

Skorynina, Alina A.; Lazzarini, Andrea; Sannes, Dag Kristian; Kozyr, Elizaveta G.; Ahoba-Sam, Christian; Bordiga, Silvia; Olsbye, Unni; Bugaev, Aram L.

doi:10.1039/d3tc04175a

J. Mater. Chem. C

2024

DOI: 10.1039/d3tc04175a

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The structure of Pd-functionalized UiO-67 during CO₂ hydrogenation

Alina A. Skorynina,

Andrea Lazzarini,

Dag Kristian Sannes

et al.

Abstract: Multi-technique operando investigation reveals the detailed evolution of UiO-67 MOF with embedded Pd nanoparticles under CO2 hydrogenation reaction conditions at elevated pressures and temperatures.

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Cited by 3 publications

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High‐Pressure Cell for In Situ Grazing Incidence XAS Characterization of Model Catalysts on Planar Supports

Phadke,

Coroa,

Abbas

et al. 2024

Chemistry Methods

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The growing interest in physically deposited model catalysts for uncovering complex structure‐activity relationships is spurred by the possibility of depositing nanoparticles of precise atomic structure and composition using cluster‐beam sources. However, the limitations accompanying these synthesis techniques, such as low deposition rates and flat sample geometry, present a challenge for in situ structural characterization using bulk‐sensitive methods, such as X‐ray absorption spectroscopy (XAS), especially at elevated pressures (1–100 bar). To overcome this challenge, we constructed an in situ XAS cell operating in a grazing incidence (GI) geometry. The GIXAS cell was used to investigate the structure of cluster‐beam‐generated Pd and Au0.3Ag0.7 nanoparticles under CO2‐to‐methanol hydrogenation conditions (230 °C, 20 bar, CO2:H2=1 : 3). These nanoparticles, with metal loading of 0.96–10 μg cm−2, demonstrated stability and resistance to sintering upon activation in H2 at 120 °C and catalytic conditions, revealed by in situ XAS. The promising results from our work will help bridge the gap in the investigation of model catalytic materials produced by gas‐phase cluster deposition at industrially relevant pressures and temperatures, which is vital for a mechanistic understanding of catalytic processes.

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High‐Pressure Cell for In Situ Grazing Incidence XAS Characterization of Model Catalysts on Planar Supports

Phadke,

Coroa,

Abbas

et al. 2024

Chemistry Methods

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Restructuring of Palladium Nanoparticles during Oxidation by Molecular Oxygen

Usoltsev,

Stoian,

Skorynina

et al. 2024

Small

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An interplay between Pd and PdO and their spatial distribution inside the particles are relevant for numerous catalytic reactions. Using in situ time‐resolved X‐ray absorption spectroscopy (XAS) supported by theoretical simulations, a mechanistic picture of the structural evolution of 2.3 nm palladium nanoparticles upon their exposure to molecular oxygen is provided. XAS analysis revealed the restructuring of the fcc‐like palladium surface into the 4‐coordinated structure of palladium oxide upon absorption of oxygen from the gas phase and formation of core@shell Pd@PdO structures. The reconstruction starts from the low‐coordinated sites at the edges of palladium nanoparticles. Formation of the PdO shell does not affect the average Pd‒Pd coordination numbers, since the decrease of the size of the metallic core is compensated by a more spherical shape of the oxidized nanoparticles due to a weaker interaction with the support. The metallic core is preserved below 200 °C even after continuous exposure to oxygen, with its size decreasing insignificantly upon increasing the temperature, while above 200 °C, bulk oxidation proceeds. The Pd‒Pd distances in the metallic phase progressively decrease upon increasing the fraction of the Pd oxide due to the alignment of the cell parameters of the two phases.

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Anchoring Cu on Zirconium-oxo nodes in a pore-confined metal-organic framework for CO2 hydrogenation to methanol

Bao,

Huo,

et al. 2025

Chemical Engineering Journal

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The structure of Pd-functionalized UiO-67 during CO₂ hydrogenation

Abstract: Multi-technique operando investigation reveals the detailed evolution of UiO-67 MOF with embedded Pd nanoparticles under CO2 hydrogenation reaction conditions at elevated pressures and temperatures.

Cited by 3 publications

References 70 publications

High‐Pressure Cell for In Situ Grazing Incidence XAS Characterization of Model Catalysts on Planar Supports

High‐Pressure Cell for In Situ Grazing Incidence XAS Characterization of Model Catalysts on Planar Supports

Restructuring of Palladium Nanoparticles during Oxidation by Molecular Oxygen

Anchoring Cu on Zirconium-oxo nodes in a pore-confined metal-organic framework for CO2 hydrogenation to methanol

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About

The structure of Pd-functionalized UiO-67 during CO2 hydrogenation

Abstract: Multi-technique operando investigation reveals the detailed evolution of UiO-67 MOF with embedded Pd nanoparticles under CO2 hydrogenation reaction conditions at elevated pressures and temperatures.

Cited by 3 publications

References 70 publications

High‐Pressure Cell for In Situ Grazing Incidence XAS Characterization of Model Catalysts on Planar Supports

High‐Pressure Cell for In Situ Grazing Incidence XAS Characterization of Model Catalysts on Planar Supports

Restructuring of Palladium Nanoparticles during Oxidation by Molecular Oxygen

Anchoring Cu on Zirconium-oxo nodes in a pore-confined metal-organic framework for CO2 hydrogenation to methanol

Contact Info

Product

Resources

About

The structure of Pd-functionalized UiO-67 during CO₂ hydrogenation