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Title: Mechanistic Study on the Lewis Acid Catalyzed Synthesis of 1,3-Butadiene over Ta-BEA Using Modulated Operando DRIFTS-MS

Abstract

In recent years, the on-purpose production of 1,3-butadiene (BD) from renewable resources such as ethanol has received increased attention. In that context, Lewis acid catalysts play an important role, especially in the two-step process, i.e. when a mixture of acetaldehyde and ethanol is used as substrate. As the reaction mechanism consists of many intermediates and occurs over different catalytic functionalities, it is notoriously difficult to gain molecular-level insights into the mechanism. Here, we present a study on Lewis acidic Ta-BEA and propose a plausible reaction mechanism. We developed an operando DRIFTS-MS setup that allows for precise control and analysis of changes in the gas-phase composition as well as surface species. Using this tool, we found a surface intermediate with a vibrational frequency at 1690 cm–1 that is only formed in the presence of both ethanol and crotonaldehyde and that is likely involved in the production of BD. Our data further suggests that a subtle control of the ratio of ethanol to acetaldehyde is crucial to keep a high ethoxy coverage and to desorb the intermediate crotyl alcohol in order to achieve high BD productivity. To the best of our knowledge, this is the first dynamic operando spectroscopic study on thismore » re-emerging reaction.« less

Authors:
 [1];  [1];  [1];  [1];  [2];  [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering
  2. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering; ETH Zurich (Switzerland)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1332571
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 6; Journal Issue: 10; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ethanol; Mixtures; Catalysts; Infrared light; Chemical reactions

Citation Formats

Müller, Philipp, Burt, Samuel P., Love, Alyssa M., McDermott, William P., Wolf, Patrick, and Hermans, Ive. Mechanistic Study on the Lewis Acid Catalyzed Synthesis of 1,3-Butadiene over Ta-BEA Using Modulated Operando DRIFTS-MS. United States: N. p., 2016. Web. doi:10.1021/acscatal.6b01642.
Müller, Philipp, Burt, Samuel P., Love, Alyssa M., McDermott, William P., Wolf, Patrick, & Hermans, Ive. Mechanistic Study on the Lewis Acid Catalyzed Synthesis of 1,3-Butadiene over Ta-BEA Using Modulated Operando DRIFTS-MS. United States. https://doi.org/10.1021/acscatal.6b01642
Müller, Philipp, Burt, Samuel P., Love, Alyssa M., McDermott, William P., Wolf, Patrick, and Hermans, Ive. 2016. "Mechanistic Study on the Lewis Acid Catalyzed Synthesis of 1,3-Butadiene over Ta-BEA Using Modulated Operando DRIFTS-MS". United States. https://doi.org/10.1021/acscatal.6b01642. https://www.osti.gov/servlets/purl/1332571.
@article{osti_1332571,
title = {Mechanistic Study on the Lewis Acid Catalyzed Synthesis of 1,3-Butadiene over Ta-BEA Using Modulated Operando DRIFTS-MS},
author = {Müller, Philipp and Burt, Samuel P. and Love, Alyssa M. and McDermott, William P. and Wolf, Patrick and Hermans, Ive},
abstractNote = {In recent years, the on-purpose production of 1,3-butadiene (BD) from renewable resources such as ethanol has received increased attention. In that context, Lewis acid catalysts play an important role, especially in the two-step process, i.e. when a mixture of acetaldehyde and ethanol is used as substrate. As the reaction mechanism consists of many intermediates and occurs over different catalytic functionalities, it is notoriously difficult to gain molecular-level insights into the mechanism. Here, we present a study on Lewis acidic Ta-BEA and propose a plausible reaction mechanism. We developed an operando DRIFTS-MS setup that allows for precise control and analysis of changes in the gas-phase composition as well as surface species. Using this tool, we found a surface intermediate with a vibrational frequency at 1690 cm–1 that is only formed in the presence of both ethanol and crotonaldehyde and that is likely involved in the production of BD. Our data further suggests that a subtle control of the ratio of ethanol to acetaldehyde is crucial to keep a high ethoxy coverage and to desorb the intermediate crotyl alcohol in order to achieve high BD productivity. To the best of our knowledge, this is the first dynamic operando spectroscopic study on this re-emerging reaction.},
doi = {10.1021/acscatal.6b01642},
url = {https://www.osti.gov/biblio/1332571}, journal = {ACS Catalysis},
issn = {2155-5435},
number = 10,
volume = 6,
place = {United States},
year = {Tue Sep 13 00:00:00 EDT 2016},
month = {Tue Sep 13 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
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Citation Metrics:
Cited by: 51 works
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Figures / Tables:

Figure 1 Figure 1: Diffuse Reflectance UV-VIS spectra of Ta-BEA and bulk tantalum oxide.

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Works referencing / citing this record:

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Surface chemistry of MgO/SiO 2 catalyst during the ethanol catalytic conversion to 1,3-butadiene: in-situ DRIFTS and DFT study
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1,3-Butadiene production from ethanol–water mixtures over Zn–La–Zr–Si oxide catalyst
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Design, modelling, and application of a low void-volume in situ diffuse reflectance spectroscopic reaction cell for transient catalytic studies
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Ag- and Cu-Promoted Mesoporous Ta-SiO2 Catalysts Prepared by Non-Hydrolytic Sol-Gel for the Conversion of Ethanol to Butadiene
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Porous metallosilicates for heterogeneous, liquid-phase catalysis: perspectives and pertaining challenges
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Application of modulation excitation-phase sensitive detection-DRIFTS for in situ /operando characterization of heterogeneous catalysts
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Recent Breakthroughs in the Conversion of Ethanol to Butadiene
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