Tunneling effects in confined gold nanoparticle hydrogenation catalysts

Luza, Leandro; Gual, Aitor; Fernandes, Jesum Alves; Eberhardt, Dario; Dupont, Jaı̈rton

doi:10.1039/c9cp03012c

Cited by 6 publications

(6 citation statements)

References 44 publications

(63 reference statements)

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“…Importantly, our experiments allow the direct observation of the effect of conning the active sites on the Arrhenius plot. 51 The reaction rates decrease, yet the slopes (i.e., the activation energies, Fig. 5, table inset) remain nearly identical in each case.…”

Section: Resultsmentioning

confidence: 83%

An experimental approach for controlling confinement effects at catalyst interfaces

et al. 2020

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Section: Resultsmentioning

confidence: 83%

An experimental approach for controlling confinement effects at catalyst interfaces

et al. 2020

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Section: Discussionmentioning

confidence: 99%

“…The same group investigated the potential of confinement effects in catalytic systems composed of Au NPs immobilized on Al 2 O 3 -based SILPs in the hydrogenation of trans -cinnamaldehyde. From kinetic studies and the determination of kinetic isotopic effects, the authors concluded that the dynamic chemisorbed IL layers act as nanocontainers for the Au NPs and play a key role in controlling the mode of activation of H 2 (homolytic vs heterolytic) …”

Section: Discussionmentioning

confidence: 99%

“…From kinetic studies and the determination of kinetic isotopic effects, the authors concluded that the dynamic chemisorbed IL layers act as nanocontainers for the Au NPs and play a key role in controlling the mode of activation of H 2 (homolytic vs heterolytic). 38 Rossi and co-workers synthesized Pd NPs on silica surfaces modified with primary amine-functionalized ligands (propylamine, propylethylenediamine, propyldiethylenetriamine). In the presence of excess amine ligands, the Pd NPs were more stable and selective for the semihydrogenation of alkynes to alkenes than on bare SiO 2 , while the production of alkane was suppressed.…”

Section: Reactivity: Activation Of Dihydrogen For the Conversion Of U...mentioning

confidence: 99%

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Metal Nanoparticles Immobilized on Molecularly Modified Surfaces: Versatile Catalytic Systems for Controlled Hydrogenation and Hydrogenolysis

Bordet

Leitner

2021

Acc. Chem. Res.

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Conspectus The synthesis and use of supported metal nanoparticle catalysts have a long-standing tradition in catalysis, typically associated with the field of heterogeneous catalysis. More recently, the development and understanding of catalytic systems composed of metal nanoparticles (NPs) that are synthesized from organometallic precursors on molecularly modified surfaces (MMSs) have opened a conceptually new approach to the design of multifunctional catalysts (NPs@MMS). These complex yet fascinating materials bridge molecular (“homogeneous”) and material (“heterogeneous”) approaches to catalysis and provide access to catalytic systems with tailor-made reactivity through judicious combinations of supports, molecular modifiers, and nanoparticle precursors. A particularly promising field of application is the controlled activation and transfer of dihydrogen, enabling highly selective hydrogenation and hydrogenolysis reactions as relevant for the conversion of biogenic feedstocks and platform chemicals as well as for novel synthetic pathways to fine chemicals and even pharmaceuticals. Consequently, the topic offers an emerging field for interdisciplinary research activities involving organometallic chemists, material scientists, synthetic organic chemists, and catalysis experts. This Account will provide a brief overview of the historical background and cover examples from the most recent developments in the field. A coherent account on the methodological and experimental basis will be given from the long-standing experience in our laboratories. MMSs are widely accessible via chemisorption and physisorption methods for the generation of stable molecular environments on solid surfaces, whereby a special emphasis is given here to ionic liquid-type molecules as modifiers (supported ionic liquid phases, SILPs) and silica as support material. Metal nanoparticles are synthesized following an organometallic approach, allowing the controlled formation of small and uniformly dispersed monometallic or multimetallic NPs in defined composition. A combination of techniques from molecular and material characterization provides a detailed insight into the structure of the resulting materials across various scales (electron microscopy, solid-state NMR, XPS, XAS, etc.). The molecular functionalities grafted on the silica surface have a pronounced influence on the formation, stabilization, and reactivity of the NPs. The complementary and synergistic fine-tuning of the metal and its molecular environment in NPs@MMSs allow in particular the control of the activation of hydrogen and its transfer to substrates. Monometallic (Ru, Rh, Pd) monofunctional NPs@MMSs possess excellent activities for the hydrogenation of alkenes, alkynes, and arenes for which a nonpolarized (homolytic) activation of H 2 is predominant. The incorporation of 3d metals in noble metal NPs to give bimetallic (FeRu, CoRh, etc.) monofunctional NPs@MMSs favors a more polarized H 2 ...

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“…These observations are supported by several theoretical and experimental studies. 380,384 For example, the hydrogenation of benzene by bimetallic Ru@Pt NPs in [C 4 C 1 Im][PF 6 ]/hydrocarbon leads to the isolation of 1,3-cyclohexadiene in relatively high selectivity (21%) at low substrate conversion (5%). These results suggest that metal NPs in highly organized ILs can operate far from equilibrium.…”

Section: The Il-effect In Catalysismentioning

confidence: 99%

Ionic Liquids in Metal, Photo-, Electro-, and (Bio) Catalysis

Dupont,

Leal,

Lozano

et al. 2024

Chem. Rev.

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Tunneling effects in confined gold nanoparticle hydrogenation catalysts

Abstract: H2 activation proceeds via homolytic activation over AuNPs confined in ionic liquid hybrid supports and display high kinetic isotope effects and convex curves in the Arrhenius plots, which suggests the possible involvement of a tunneling pathway.

Cited by 6 publications

References 44 publications

An experimental approach for controlling confinement effects at catalyst interfaces

An experimental approach for controlling confinement effects at catalyst interfaces

Metal Nanoparticles Immobilized on Molecularly Modified Surfaces: Versatile Catalytic Systems for Controlled Hydrogenation and Hydrogenolysis

Ionic Liquids in Metal, Photo-, Electro-, and (Bio) Catalysis

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