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Supported Gold Nanoparticles from Quantum Dot to Mesoscopic Size Scale: Effect of Electronic and Structural Properties on Catalytic Hydrogenation of Conjugated Functional Groups

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TLDR
In this article, titania and zirconia-supported gold particles of 1−5 nm size were employed in the partial hydrogenation of acrolein, and their structural and electronic properties were characterized by electron microscopy, electron paramagnetic resonance, and optical absorption spectroscopy aimed at disclosing the nature of the active sites controlling the CO vs CC bonds.
Abstract
Titania- and zirconia-supported gold particles of 1−5 nm size, prepared by various routes of synthesis, were employed in the partial hydrogenation of acrolein. In-depth characterization of their structural and electronic properties by electron microscopy, electron paramagnetic resonance, and optical absorption spectroscopy aimed at disclosing the nature of the active sites controlling the hydrogenation of CO vs CC bonds. The structural characteristics of the catalysts, as mean particle size, size distribution, and dispersion, distinctly depend on the synthesis applied and the oxide support used whereby the highest gold dispersion (DAu = 0.78, Au/TiO2) results from a modified sol−gel technique. For extremely small gold particles on titania and zirconia (1.1 and 1.4 nm mean size), conduction electron spin resonance of the metal and paramagnetic F-centers (trapped electrons in oxygen vacancies) of the support were observed. Besides the influence of the surface geometry on the adsorption mode of the α,β-unsat...

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Citations
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Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology.

TL;DR: A review of gold nanoparticles can be found in this article, where the most stable metal nanoparticles, called gold colloids (AuNPs), have been used for catalysis and biology applications.
Journal ArticleDOI

Gold-Catalyzed Organic Reactions

TL;DR: Important vinylgold intermediates, the transmetalation from gold to other transition metals, the development of new ligands for gold catalysis, and significant contributions from computational chemistry are other crucial points for the field highlighted here.
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Nanoparticles as Recyclable Catalysts: The Frontier between Homogeneous and Heterogeneous Catalysis

TL;DR: The Review presents the recent developments and the use of NP catalysis in organic synthesis, for example, in hydrogenation and C--C coupling reactions, and the heterogeneous oxidation of CO on gold NPs.
Journal ArticleDOI

Recent advances in the liquid-phase syntheses of inorganic nanoparticles.

TL;DR: The development of novel materials is a fundamental focal point of chemical research; and this interest is mandated by advancements in all areas of industry and technology.
Journal ArticleDOI

Oxidation of Alcohols with Molecular Oxygen on Solid Catalysts

TL;DR: It is considered more feasible that the rate-deter-mining step is the cleavage of the C-H bond at the R-carbon atom, and the active site consists of an ensemble of metallic Auatoms and a cationic Au.
References
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Journal ArticleDOI

Onset of Catalytic Activity of Gold Clusters on Titania with the Appearance of Nonmetallic Properties

TL;DR: Results suggest that supported clusters, in general, may have unusual catalytic properties as one dimension of the cluster becomes smaller than three atomic spacings.
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Quantum size effects in metal particles

TL;DR: In this paper, a general review of experimental work is presented in order to permit a comprehensive evaluation of current understanding of the quantum size effect on the electronic spectrum including magnetic susceptibility, nuclear magnetic resonance, electron spin resonance, heat capacity, optical, and infrared absorption measurements.
Journal ArticleDOI

Optical absorption of small metallic particles

TL;DR: In this paper, a survey is given of recent results concerning particle-size dependences of the optical plasma resonance absorption and of the FIR absorption of small noble metal particles, and it is shown that the spectra are strongly changed if the particles of a sample interact with each other.
Journal ArticleDOI

Selective Hydrogenation of α,β-Unsaturated Aldehydes

TL;DR: In this paper, the authors mainly focused on the hydrogenation of α, β-unsaturated aldehydes into the corresponding unsaturated alcohols and showed that when a substituent is present on the carbon atom of the carbonyl group (i.e. with ketones), there is no chance to hydrogenate selectively the C═O bond, and saturated ketones are obtained with a high yield.
Book

Catalysis of organic reactions

TL;DR: A collection of 33 papers and posters from a conference in Boca Raton, Florida, May 1990, in which chemists from the chemical and pharmaceutical industries, and from academia, discuss their work on the use of catalysis in organic synthesis is presented in this article.
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