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Title: Molecular Orientations Change Reaction Kinetics and Mechanism: A Review on Catalytic Alcohol Oxidation in Gas Phase and Liquid Phase on Size-Controlled Pt Nanoparticles

Abstract

Catalytic oxidation of alcohols is an essential process for energy conversion, production of fine chemicals and pharmaceutical intermediates. Although it has been broadly utilized in industry, the basic understanding for catalytic alcohol oxidations at a molecular level, especially under both gas and liquid phases, is still lacking. In this paper, we systematically summarized our work on catalytic alcohol oxidation over size-controlled Pt nanoparticles. The studied alcohols included methanol, ethanol, 1-propanol, 2-propanol, and 2-butanol. The turnover rates of different alcohols on Pt nanoparticles and also the apparent activation energy in gas and liquid phase reactions were compared. The Pt nanoparticle size dependence of reaction rates and product selectivity was also carefully examined. Water showed very distinct effects for gas and liquid phase alcohol oxidations, either as an inhibitor or as a promoter depending on alcohol type and reaction phase. A deep understanding of different alcohol molecular orientations on Pt surface in gas and liquid phase reactions was established using sum-frequency generation spectroscopy analysis for in situ alcohol oxidations, as well as density functional theory calculation. This approach can not only explain the entirely different behaviors of alcohol oxidations in gas and liquid phases, but can also provide guidance for future catalyst/processmore » design.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [2];  [2];  [1];  [1];  [1]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1489656
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Catalysts
Additional Journal Information:
Journal Volume: 8; Journal Issue: 6; Journal ID: ISSN 2073-4344
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalytic alcohol oxidation; gas phase; liquid phase; Pt nanoparticles; sum-frequency generation spectroscopy; surface molecular orientation; density functional theory calculation

Citation Formats

Liu, Fudong, Wang, Hailiang, Sapi, Andras, Tatsumi, Hironori, Zherebetskyy, Danylo, Han, Hui-Ling, Carl, Lindsay, and Somorjai, Gabor. Molecular Orientations Change Reaction Kinetics and Mechanism: A Review on Catalytic Alcohol Oxidation in Gas Phase and Liquid Phase on Size-Controlled Pt Nanoparticles. United States: N. p., 2018. Web. doi:10.3390/catal8060226.
Liu, Fudong, Wang, Hailiang, Sapi, Andras, Tatsumi, Hironori, Zherebetskyy, Danylo, Han, Hui-Ling, Carl, Lindsay, & Somorjai, Gabor. Molecular Orientations Change Reaction Kinetics and Mechanism: A Review on Catalytic Alcohol Oxidation in Gas Phase and Liquid Phase on Size-Controlled Pt Nanoparticles. United States. doi:10.3390/catal8060226.
Liu, Fudong, Wang, Hailiang, Sapi, Andras, Tatsumi, Hironori, Zherebetskyy, Danylo, Han, Hui-Ling, Carl, Lindsay, and Somorjai, Gabor. Sun . "Molecular Orientations Change Reaction Kinetics and Mechanism: A Review on Catalytic Alcohol Oxidation in Gas Phase and Liquid Phase on Size-Controlled Pt Nanoparticles". United States. doi:10.3390/catal8060226. https://www.osti.gov/servlets/purl/1489656.
@article{osti_1489656,
title = {Molecular Orientations Change Reaction Kinetics and Mechanism: A Review on Catalytic Alcohol Oxidation in Gas Phase and Liquid Phase on Size-Controlled Pt Nanoparticles},
author = {Liu, Fudong and Wang, Hailiang and Sapi, Andras and Tatsumi, Hironori and Zherebetskyy, Danylo and Han, Hui-Ling and Carl, Lindsay and Somorjai, Gabor},
abstractNote = {Catalytic oxidation of alcohols is an essential process for energy conversion, production of fine chemicals and pharmaceutical intermediates. Although it has been broadly utilized in industry, the basic understanding for catalytic alcohol oxidations at a molecular level, especially under both gas and liquid phases, is still lacking. In this paper, we systematically summarized our work on catalytic alcohol oxidation over size-controlled Pt nanoparticles. The studied alcohols included methanol, ethanol, 1-propanol, 2-propanol, and 2-butanol. The turnover rates of different alcohols on Pt nanoparticles and also the apparent activation energy in gas and liquid phase reactions were compared. The Pt nanoparticle size dependence of reaction rates and product selectivity was also carefully examined. Water showed very distinct effects for gas and liquid phase alcohol oxidations, either as an inhibitor or as a promoter depending on alcohol type and reaction phase. A deep understanding of different alcohol molecular orientations on Pt surface in gas and liquid phase reactions was established using sum-frequency generation spectroscopy analysis for in situ alcohol oxidations, as well as density functional theory calculation. This approach can not only explain the entirely different behaviors of alcohol oxidations in gas and liquid phases, but can also provide guidance for future catalyst/process design.},
doi = {10.3390/catal8060226},
journal = {Catalysts},
issn = {2073-4344},
number = 6,
volume = 8,
place = {United States},
year = {2018},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 4 works
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Figures / Tables:

Figure 1 Figure 1: Turnover rates of alcohol oxidation to carbonyl compounds in gas and liquid phases over 6 nm Pt/MCF-17 (4.5 nm Pt/MCF-17 for 1-PrOH oxidation). Gas phase reaction: 1.33 kPa alcohol, 6.67 kPaO2, 94.66 kPa He, 60 °C reaction temperature for MeOH, EtOH, 1-PrOH, 2-PrOH and 80 °C reaction temperaturemore » for 2-BuOH. Liquid phase reaction: 15 mL alcohol, dissolved oxygen under 100 kPa for MeOH, EtOH, 1-PrOH, 2-PrOH (60 °C reaction temperature) and 300 kPa for 2-BuOH (80 °C reaction temperature). Liquid phase reaction (1000 times diluted): 15 mL heptane, 15 μL alcohol with dissolved oxygen under 100 kPa for MeOH, EtOH, 1-PrOH, 2-PrOH at 60 °C reaction temperature. The vapor pressure of MeOH, EtOH, 1-PrOH, 2-PrOH at 20 and 60 °C is also presented herein. (TOF data for MeOH, EtOH, 1-PrOH, 2-PrOH, 2-BuOH oxidations were reported in [9,19–22], respectively).« less

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