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Open AccessArticle

Mechanistic Study of Silane Alcoholysis Reactions with Self-Assembled Monolayer-Functionalized Gold Nanoparticle Catalysts

1
Institute for Chemical Research, Kyoto University, Gokasyo, Uji, Kyoto 611-0011, Japan
2
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyoku, Kyoto 615-8510, Japan
3
National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
4
Department of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8571, Japan
5
Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
6
Department of Electrical Materials and Engineering, Graduate School of Engineering, University of Hyogo, Shosya 2167, Himeji, Hyogo 671-2280, Japan
*
Authors to whom correspondence should be addressed.
Catalysts 2020, 10(8), 908; https://doi.org/10.3390/catal10080908
Received: 13 July 2020 / Revised: 31 July 2020 / Accepted: 7 August 2020 / Published: 9 August 2020
(This article belongs to the Special Issue New Insights into Heterogeneous Catalysis)
The self-assembled monolayer (SAM)-modified metallic nanoparticles (MNPs) often exhibit improved chemoselectivity in various catalytic reactions by controlling the reactants’ orientations adsorbed in the SAM; however, there have been a few examples showing that the reaction rate, i.e., catalytic activity, is enhanced by the SAM-modification of MNP catalysts. The critical parameters that affect the catalytic activity, such as the supports, nanoparticle size, and molecular structures of the SAM components, remain uninvestigated in these sporadic literature precedents. Here, we report the mechanistic investigation on the effects of those parameters on the catalytic activity of alkanethiolate SAM-functionalized gold nanoparticles (AuNPs) toward silane alcoholysis reactions. The evaluation of the catalytic reaction over two-dimensionally arrayed dodecanethiolate SAM-functionalized AuNPs with different supports revealed the electronic interactions between AuNPs and the supports contributing to the rate enhancement. Additionally, an unprecedented size effect appeared—the AuNP with a 20 nm radius showed higher catalytic activity than those at 10 and 40 nm. Infrared reflection–absorption spectroscopy revealed that the conformational change of alkyl chains of the SAM affects the entrapment of reactants and products inside the SAM, and therefore brings about the acceleration effect. These findings provide a guideline for further applying the SAM-functionalization technique to stereoselective organic transformations with designer MNP catalysts. View Full-Text
Keywords: gold nanoparticle; catalysts; self-assembled monolayer; silane alcoholysis; size effect; support effect; molecular recognition; IR reflection-absorption spectroscopy gold nanoparticle; catalysts; self-assembled monolayer; silane alcoholysis; size effect; support effect; molecular recognition; IR reflection-absorption spectroscopy
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MDPI and ACS Style

Isozaki, K.; Taguchi, T.; Ishibashi, K.; Shimoaka, T.; Kurashige, W.; Negishi, Y.; Hasegawa, T.; Nakamura, M.; Miki, K. Mechanistic Study of Silane Alcoholysis Reactions with Self-Assembled Monolayer-Functionalized Gold Nanoparticle Catalysts. Catalysts 2020, 10, 908. https://doi.org/10.3390/catal10080908

AMA Style

Isozaki K, Taguchi T, Ishibashi K, Shimoaka T, Kurashige W, Negishi Y, Hasegawa T, Nakamura M, Miki K. Mechanistic Study of Silane Alcoholysis Reactions with Self-Assembled Monolayer-Functionalized Gold Nanoparticle Catalysts. Catalysts. 2020; 10(8):908. https://doi.org/10.3390/catal10080908

Chicago/Turabian Style

Isozaki, Katsuhiro; Taguchi, Tomoya; Ishibashi, Kosuke; Shimoaka, Takafumi; Kurashige, Wataru; Negishi, Yuichi; Hasegawa, Takeshi; Nakamura, Masaharu; Miki, Kazushi. 2020. "Mechanistic Study of Silane Alcoholysis Reactions with Self-Assembled Monolayer-Functionalized Gold Nanoparticle Catalysts" Catalysts 10, no. 8: 908. https://doi.org/10.3390/catal10080908

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