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Title: Mechanistic study of the ceria supported, re-catalyzed deoxydehydration of vicinal OH groups

Abstract

Deoxydehydration (DODH) is an emerging biomass deoxygenation process whereby vicinal OH groups are removed. Based on DFT calculations and microkinetic modeling, we seek to understand the mechanism of the Re-catalyzed deoxydehydration supported on CeO 2(111). In addition, we aim at understanding the promotional effect of Pd in a heterogeneous ReO x–Pd/CeO 2 DODH catalyst system. We disentangle the contribution of the oxide support, the oxide-supported single ReO x species, and a co-adsorbed Pd promoter that has no direct interaction with the Re species. In the absence of a nearby Pd cluster, a Re site is able to reduce subsurface Ce-ions of a hydroxylated CeO 2(111) surface, leading to a catalytically active Re +6 species. The effect of Pd is twofold: (i) Pd catalyzes the hydrogen dissociation and spillover onto CeO 2, which is an indispensable process for the regeneration of the Re catalyst, and (ii) Pd adsorbed in close proximity to Re on CeO2(111) facilitates the oxidation of Re to a +7 oxidation state, which leads to an even more active Re species than the Re +6 site present in the absence of Pd. The latter promotional effect of Pd (and change in oxidation state of Re) disappears with increasingmore » Pd–Re distance and in the presence of oxygen defects on the ceria support. Under these conditions, the ReO x–Pd/CeO 2 catalyst system exhibits appreciable activity consistent with recent experiments. The established mechanism and role of various species in the catalyst system help to better understand the deoxydehydration catalysis. Also, the importance of the Re oxidation state and the identified oxidation state modification mechanisms suggest a new pathway for tuning the properties of metal-oxide supported catalysts.« less

Authors:
 [1];  [1];  [1];  [1];  [2]; ORCiD logo [1]
  1. Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemical Engineering
  2. Univ. of Puerto Rico-Mayaguez Campus; Mayaguez (Puerto Rico). Dept. of Chemical Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543806
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 8; Journal Issue: 22; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry

Citation Formats

Xi, Yongjie, Yang, Wenqiang, Ammal, Salai Cheettu, Lauterbach, Jochen, Pagan-Torres, Yomaira, and Heyden, Andreas. Mechanistic study of the ceria supported, re-catalyzed deoxydehydration of vicinal OH groups. United States: N. p., 2018. Web. doi:10.1039/c8cy01782d.
Xi, Yongjie, Yang, Wenqiang, Ammal, Salai Cheettu, Lauterbach, Jochen, Pagan-Torres, Yomaira, & Heyden, Andreas. Mechanistic study of the ceria supported, re-catalyzed deoxydehydration of vicinal OH groups. United States. doi:10.1039/c8cy01782d.
Xi, Yongjie, Yang, Wenqiang, Ammal, Salai Cheettu, Lauterbach, Jochen, Pagan-Torres, Yomaira, and Heyden, Andreas. Mon . "Mechanistic study of the ceria supported, re-catalyzed deoxydehydration of vicinal OH groups". United States. doi:10.1039/c8cy01782d.
@article{osti_1543806,
title = {Mechanistic study of the ceria supported, re-catalyzed deoxydehydration of vicinal OH groups},
author = {Xi, Yongjie and Yang, Wenqiang and Ammal, Salai Cheettu and Lauterbach, Jochen and Pagan-Torres, Yomaira and Heyden, Andreas},
abstractNote = {Deoxydehydration (DODH) is an emerging biomass deoxygenation process whereby vicinal OH groups are removed. Based on DFT calculations and microkinetic modeling, we seek to understand the mechanism of the Re-catalyzed deoxydehydration supported on CeO2(111). In addition, we aim at understanding the promotional effect of Pd in a heterogeneous ReOx–Pd/CeO2 DODH catalyst system. We disentangle the contribution of the oxide support, the oxide-supported single ReOx species, and a co-adsorbed Pd promoter that has no direct interaction with the Re species. In the absence of a nearby Pd cluster, a Re site is able to reduce subsurface Ce-ions of a hydroxylated CeO2(111) surface, leading to a catalytically active Re +6 species. The effect of Pd is twofold: (i) Pd catalyzes the hydrogen dissociation and spillover onto CeO2, which is an indispensable process for the regeneration of the Re catalyst, and (ii) Pd adsorbed in close proximity to Re on CeO2(111) facilitates the oxidation of Re to a +7 oxidation state, which leads to an even more active Re species than the Re +6 site present in the absence of Pd. The latter promotional effect of Pd (and change in oxidation state of Re) disappears with increasing Pd–Re distance and in the presence of oxygen defects on the ceria support. Under these conditions, the ReOx–Pd/CeO2 catalyst system exhibits appreciable activity consistent with recent experiments. The established mechanism and role of various species in the catalyst system help to better understand the deoxydehydration catalysis. Also, the importance of the Re oxidation state and the identified oxidation state modification mechanisms suggest a new pathway for tuning the properties of metal-oxide supported catalysts.},
doi = {10.1039/c8cy01782d},
journal = {Catalysis Science and Technology},
issn = {2044-4753},
number = 22,
volume = 8,
place = {United States},
year = {2018},
month = {1}
}

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