First-principles insight into CO hindered agglomeration of Rh and Pt single atoms on <i>m</i>-ZrO<sub>2</sub>

Kauppinen, Minttu M.; Melander, Marko; Honkala, Karoliina

doi:10.1039/d0cy00413h

Cited by 13 publications

(18 citation statements)

References 64 publications

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“…At high temperatures and a low CO pressure, bare clusters are the most stable for some sizes. Consistent with other computational work, 37 the clusters contain at least one CO under ultrahigh vacuum conditions (10 −11 bar) at lower temperatures (T < 700 K). Generally, low temperature favors more CO adsorption, but the CO loadings also depend on the cluster structure and the adsorption energy at each site.…”

Section: ■ Results and Discussionsupporting

confidence: 90%

Insights into Supported Subnanometer Catalysts Exposed to CO via Machine-Learning-Enabled Multiscale Modeling

Wang

Hensen

et al. 2022

Chem. Mater.

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Subnanometer catalysts offer high noble metal utilization and superior performance for several reactions. However, understanding their structures and properties on an atomic scale under working conditions is challenging due to the large configurational space. Here, we introduce an efficient multiscale framework to predict their stability exposed to an adsorbate. The framework integrates a comprehensive toolset including density functional theory (DFT) calculations, cluster expansion, machine learning, and structure optimization. The end-to-end machine-learning workflow guides DFT data generation and enables significant computational acceleration. We demonstrate the approach for CO-adsorbed Pd n (n = 1− 55) clusters on CeO 2 (111). Simulation results reveal that CO can facilitate restructuring by stabilizing smaller planar structures and bilayer structures of specific intermediate sizes, consistent with experimental reports. Metal−support interactions, preferential CO adsorption, and metal nuclearity and structure control catalyst stability. The framework allows automatic discovery of stable catalyst structures and a systematic strategy to exploit properties in the subnanometer scale.

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Section: ■ Results and Discussionsupporting

confidence: 90%

Insights into Supported Subnanometer Catalysts Exposed to CO via Machine-Learning-Enabled Multiscale Modeling

Wang

Hensen

et al. 2022

Chem. Mater.

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“…In effect, partially CO‐ligated intermediates such as Fe 3 (CO) 5 with a core‐level shift of ∼1 eV with respect to Fe−i are likely stabilized. Similar observations were previously made for systems based on clusters of Pt and Rh [26] …”

Section: Resultssupporting

confidence: 87%

“…Similar observations were previously made for systems based on clusters of Pt and Rh. [26] Thermogravimetric analysis of the iron precursors indicates virtually complete removal of the ligands at the annealing temperature (573 K), as expected from literature values. [27] Only for the dimeric complex, a second decomposition feature above that temperature corresponding to ca.…”

Section: Resultssupporting

confidence: 84%

Precursor Nuclearity and Ligand Effects in Atomically‐Dispersed Heterogeneous Iron Catalysts for Alkyne Semi‐Hydrogenation

et al. 2021

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Nanostructuring earth-abundant metals as single atoms or clusters of controlled size on suitable carriers opens new routes to develop high-performing heterogeneous catalysts, but resolving speciation trends remains challenging. Here, we investigate the potential of low-nuclearity iron catalysts in the continuous liquid-phase semi-hydrogenation of various alkynes. The activity depends on multiple factors, including the nuclearity and ligand sphere of the metal precursor and their evolution upon interaction with the mesoporous graphitic carbon nitride scaffold. Density functional theory predicts the favorable adsorption of the metal precursors on the scaffold without altering the nuclearity and preserving some ligands. Contrary to previous observations for palladium catalysts, single atoms of iron exhibit higher activity than larger clusters.Atomistic simulations suggest a central role of residual carbonyl species in permitting low-energy paths over these isolated metal centers.

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“…6 The oxide may also play an integral role in stabilizing the catalyst and in preventing catalyst sintering. 3,7 Given such diverse roles of metal oxides in catalysis, utilizing, modifying, and understanding their chemistry offers a powerful tool to tailor the performance of heterogeneous catalysts.…”

Section: Introductionmentioning

confidence: 99%

Reducing the Irreducible: Dispersed Metal Atoms Facilitate Reduction of Irreducible Oxides

2022

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Oxide reducibility is a central concept quantifying the role of the support in catalysis. While reducible oxides are often considered catalytically active, irreducible oxides are seen as inert supports. Enhancing the reducibility of irreducible oxides has, however, emerged as an effective way to increase their catalytic activity while retaining their inherent thermal stability. In this work, we focus on the prospect of using single metal atoms to increase the reducibility of a prototypical irreducible oxide, zirconia. Based on extensive self-consistent DFT+U calculations, we demonstrate that single metal atoms significantly improve and tune the surface reducibility of zirconia. Detailed analysis of the observed single atom induced reducibility allows us to attribute the enhanced reducibility to strong interactions between the metal atom and the electrons trapped in the vacancy and d−p orbital interactions between the metal atom and oxygen. This analysis enables transferring the obtained theoretical understanding to other irreducible oxides as well. The detailed understanding of how oxide reducibility can be tuned offers precise control over the catalytic properties of metal oxides.

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First-principles insight into CO hindered agglomeration of Rh and Pt single atoms on m-ZrO₂

Abstract: Kinetic and thermodynamic stability of single-atom and nanocluster catalysts is addressed under reaction conditions within a DFT-parametrised multi-scale thermodynamic framework combining atomistic, non-equilibrium, and nanothermodynamics.

Cited by 13 publications

References 64 publications

Insights into Supported Subnanometer Catalysts Exposed to CO via Machine-Learning-Enabled Multiscale Modeling

Insights into Supported Subnanometer Catalysts Exposed to CO via Machine-Learning-Enabled Multiscale Modeling

Precursor Nuclearity and Ligand Effects in Atomically‐Dispersed Heterogeneous Iron Catalysts for Alkyne Semi‐Hydrogenation

Reducing the Irreducible: Dispersed Metal Atoms Facilitate Reduction of Irreducible Oxides

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First-principles insight into CO hindered agglomeration of Rh and Pt single atoms on m-ZrO2

Abstract: Kinetic and thermodynamic stability of single-atom and nanocluster catalysts is addressed under reaction conditions within a DFT-parametrised multi-scale thermodynamic framework combining atomistic, non-equilibrium, and nanothermodynamics.

Cited by 13 publications

References 64 publications

Insights into Supported Subnanometer Catalysts Exposed to CO via Machine-Learning-Enabled Multiscale Modeling

Insights into Supported Subnanometer Catalysts Exposed to CO via Machine-Learning-Enabled Multiscale Modeling

Precursor Nuclearity and Ligand Effects in Atomically‐Dispersed Heterogeneous Iron Catalysts for Alkyne Semi‐Hydrogenation

Reducing the Irreducible: Dispersed Metal Atoms Facilitate Reduction of Irreducible Oxides

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First-principles insight into CO hindered agglomeration of Rh and Pt single atoms on m-ZrO₂