High catalytic performance of Al–Pd–(Ru, Fe) icosahedral approximants for acetylene semi-hydrogenation

Abe, Keishi; Tsukuda, Ryota; Fujita, Nobuhisa; Kameoka, Satoshi

doi:10.1039/d1ra01958a

“…Additionally, Ru@Pd catalysts showed comparable stability with Pd under long‐term operation of 19 hours (Figure S14), also corroborating the stability against segregation found by the calculations. We note that ternary Al−Pd−Ru cubic crystalline icosahedral approximants demonstrated high activity and selectivity for acetylene semihydrogenation [29] …”

Section: Resultsmentioning

confidence: 82%

“…We note that ternary AlÀ PdÀ Ru cubic crystalline icosahedral approximants demonstrated high activity and selectivity for acetylene semihydrogenation. [29] In contrast to the highly efficient bimetallic core-shell Ru@Pd catalysts, Ru(5.1 nm)/SiO 2 did not show any activity up to 200 °C. We did not observe color change for the used Ru catalysts, accordingly, coke formation for the inactivity is excluded.…”

Section: Resultsmentioning

confidence: 85%

Molecule Saturation Boosts Acetylene Semihydrogenation Activity and Selectivity on a Core‐Shell Ruthenium@Palladium Catalyst

Zhu

¹

,

Xu

²

,

Liu

³

et al. 2023

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Increasing selectivity without the expense of activity is desired but challenging in heterogeneous catalysis. By revealing the molecule saturation and adsorption sensitivity on overlayer thickness, strain, and coordination of Pd-based catalysts from first-principles calculations, we designed a stable Pd monolayer (ML) catalyst on a Ru terrace to boost both activity and selectivity of acetylene semihydrogenation. The least saturated molecule is most sensitive to the change in catalyst electronic and geometric properties. By simultaneously compressing the Pd ML and exposing the high coordination sites, the adsorption of more saturated ethylene is considerably weakened to facilitate the desorption for high selectivity. The even stronger weakening to the least saturated acetylene drives its hydrogenation such that it is more exothermic, thereby boosting the activity. Tailoring the molecule saturation and its sensitivity to structure and composition provides a tool for rational design of efficient catalysts.

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“…Several studies on the catalytic properties of quasicrystals and related materials have been performed so far, and much attention has been paid to new catalysts originating from their unique structures. [7][8][9][10][11][12][13][14][15][16] In this work, materials composed of the Tsai-type cluster are chosen for the investigation of catalytic properties: The Tsai-type cluster is a type of icosahedral cluster where rare earth elements occupy the vertices of the inner icosahedron shell among various concentric shells, and many compounds composed of the Tsai-type cluster have been discovered in recent years. 17) The objective of this study is to evaluate the catalytic properties of Pd-containing Al-Pd-Sc and Ga-Pd-Sc compounds, which are classified as Tsai-type 1/1 ACs.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Properties and Their Relation with Adsorption Energies Calculated by Density Functional Theory in Pd-Containing 1/1 Approximant Crystals

Yoshikawa

¹

,

Labib

²

,

Xu

³

et al. 2023

Mater. Trans.

0

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Quasicrystals and approximant crystals (ACs) have a unique complex structure with many crystallographically non-equivalent sites. In order to apply this characteristic potential to catalysts, we investigated catalytic properties of Pd-containing Tsai-type 1/1 ACs, i.e., Al-Pd-Sc and Ga-Pd-Sc, in the acetylene hydrogenation reaction and also performed density functional theory calculations of adsorption energies of reactants and products. The catalytic properties are found to significantly depend on the kind of the semimetal element such as Al and Ga, where the Al-Pd-Sc 1/1 AC shows higher catalytic activity and selectivity. The adsorption energy of reactant acetylene is smaller in the Al-Pd-Sc 1/1 AC whereas the amount of product ethylene are comparable for both ACs. Therefore, the adsorption rate of reactants is increased while the desorption rate of products remains almost the same in the Al-Pd-Sc 1/1 AC. Furthermore, the adsorption energies are found to differ significantly from site to site, implying a superior potential of ACs for designation of active sites using many non-equivalent crystallographic sites for high catalytic performance.

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Molecule Saturation Boosts Acetylene Semihydrogenation Activity and Selectivity on a Core‐Shell Ruthenium@Palladium Catalyst

Zhu

¹

,

Xu

²

,

Liu

³

et al. 2023

View full text Add to dashboard Cite

Increasing selectivity without the expense of activity is desired but challenging in heterogeneous catalysis. By revealing the molecule saturation and adsorption sensitivity on overlayer thickness, strain, and coordination of Pd-based catalysts from first-principles calculations, we designed a stable Pd monolayer (ML) catalyst on a Ru terrace to boost both activity and selectivity of acetylene semihydrogenation. The least saturated molecule is most sensitive to the change in catalyst electronic and geometric properties. By simultaneously compressing the Pd ML and exposing the high coordination sites, the adsorption of more saturated ethylene is considerably weakened to facilitate the desorption for high selectivity. The even stronger weakening to the least saturated acetylene drives its hydrogenation such that it is more exothermic, thereby boosting the activity. Tailoring the molecule saturation and its sensitivity to structure and composition provides a tool for rational design of efficient catalysts.

show abstract

High catalytic performance of Al–Pd–(Ru, Fe) icosahedral approximants for acetylene semi-hydrogenation

Abstract: The Al–Pd–(Ru, Fe) icosahedral approximants exhibited high catalytic ethylene selectivity and stability for semi-hydrogenation of acetylene.

Cited by 5 publications

References 37 publications

Molecule Saturation Boosts Acetylene Semihydrogenation Activity and Selectivity on a Core‐Shell Ruthenium@Palladium Catalyst

Molecule Saturation Boosts Acetylene Semihydrogenation Activity and Selectivity on a Core‐Shell Ruthenium@Palladium Catalyst

Catalytic Properties and Their Relation with Adsorption Energies Calculated by Density Functional Theory in Pd-Containing 1/1 Approximant Crystals

Molecule Saturation Boosts Acetylene Semihydrogenation Activity and Selectivity on a Core‐Shell Ruthenium@Palladium Catalyst

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