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Title: The role of CO2 as a soft oxidant for dehydrogenation of ethylbenzene to styrene over a high-surface-area ceria catalyst

Abstract

Catalytic performance and the nature of surface adsorbates were investigated for high-surface-area ceria during the ethylbenzene oxidative dehydrogenation (ODH) reaction using CO2 as a soft oxidant. The high surface area ceria material was synthesized using a template-assisted method. The interactions among ethylbenzene, styrene, and CO2 on the surface of ceria and the role of CO2 for the ethylbenzene ODH reaction have been investigated in detail by using activity test, in situ diffuse reflectance infrared and Raman spectroscopy. CO2 as an oxidant not only favored the higher yield of styrene but also inhibited the deposition of coke during the ethylbenzene ODH reaction. Ethylbenzene ODH reaction over ceria followed a two-step pathway: ethylbenzene is first dehydrogenated to styrene with H2 formed simultaneously, and then CO2 reacts with H2 via the reverse water gas shift. The produced styrene can easily undergo polymerization to form polystyrene, which is a key intermediate for coke formation. Furthermore, in the absence of CO2, the produced polystyrene transforms into graphite-like coke at temperatures above 500°C, which leads to catalyst deactivation. In the presence of CO2, the coke deposition can be effectively removed via oxidation with CO2.

Authors:
 [1];  [1];  [2];  [2];  [2];  [1]
+ Show Author Affiliations
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Iowa State Univ., Ames, IA (United States); Ames Lab., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1222559
Alternate Identifier(s):
OSTI ID: 1234459; OSTI ID: 1287018
Report Number(s):
IS-J-8866
Journal ID: ISSN 2155-5435; ED2801000; CEED500
Grant/Contract Number:  
AC05-00OR22725; AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 5; Journal Issue: 10; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; high-surface-area ceria; oxidative dehydrogenation; ethylbenzene; styrene; CO2; infrared spectroscopy; Raman spectroscopy; coking; CO2

Citation Formats

Zhang, Li, Wu, Zili, Nelson, Nicholas, Sadow, Aaron D., Slowing, Igor I., and Overbury, Steven H. The role of CO2 as a soft oxidant for dehydrogenation of ethylbenzene to styrene over a high-surface-area ceria catalyst. United States: N. p., 2015. Web. doi:10.1021/acscatal.5b01519.
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Zhang, Li, Wu, Zili, Nelson, Nicholas, Sadow, Aaron D., Slowing, Igor I., & Overbury, Steven H. The role of CO2 as a soft oxidant for dehydrogenation of ethylbenzene to styrene over a high-surface-area ceria catalyst. United States. https://doi.org/10.1021/acscatal.5b01519
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Zhang, Li, Wu, Zili, Nelson, Nicholas, Sadow, Aaron D., Slowing, Igor I., and Overbury, Steven H. Tue . "The role of CO2 as a soft oxidant for dehydrogenation of ethylbenzene to styrene over a high-surface-area ceria catalyst". United States. https://doi.org/10.1021/acscatal.5b01519. https://www.osti.gov/servlets/purl/1222559.
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@article{osti_1222559,
title = {The role of CO2 as a soft oxidant for dehydrogenation of ethylbenzene to styrene over a high-surface-area ceria catalyst},
author = {Zhang, Li and Wu, Zili and Nelson, Nicholas and Sadow, Aaron D. and Slowing, Igor I. and Overbury, Steven H.},
abstractNote = {Catalytic performance and the nature of surface adsorbates were investigated for high-surface-area ceria during the ethylbenzene oxidative dehydrogenation (ODH) reaction using CO2 as a soft oxidant. The high surface area ceria material was synthesized using a template-assisted method. The interactions among ethylbenzene, styrene, and CO2 on the surface of ceria and the role of CO2 for the ethylbenzene ODH reaction have been investigated in detail by using activity test, in situ diffuse reflectance infrared and Raman spectroscopy. CO2 as an oxidant not only favored the higher yield of styrene but also inhibited the deposition of coke during the ethylbenzene ODH reaction. Ethylbenzene ODH reaction over ceria followed a two-step pathway: ethylbenzene is first dehydrogenated to styrene with H2 formed simultaneously, and then CO2 reacts with H2 via the reverse water gas shift. The produced styrene can easily undergo polymerization to form polystyrene, which is a key intermediate for coke formation. Furthermore, in the absence of CO2, the produced polystyrene transforms into graphite-like coke at temperatures above 500°C, which leads to catalyst deactivation. In the presence of CO2, the coke deposition can be effectively removed via oxidation with CO2.},
doi = {10.1021/acscatal.5b01519},
journal = {ACS Catalysis},
number = 10,
volume = 5,
place = {United States},
year = {Tue Sep 22 00:00:00 EDT 2015},
month = {Tue Sep 22 00:00:00 EDT 2015}
}
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https://doi.org/10.1021/acscatal.5b01519
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