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Title: Structural Identification of ZnxZryOz Catalysts for Cascade Aldolization and Self-Deoxygenation Reactions

Abstract

Here, complementary characterizations, such as nitrogen sorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), visible Raman, scanning transmission electron microscopy (STEM) coupled with elemental mapping, NH3/CO2 temperature programmed desorption (NH3/CO2-TPD), infrared spectroscopic analysis of adsorbed pyridine (Py-IR), and CO2-IR, have been employed to identify the structure and surface chemistry (i.e., acid-base) of mixed ZnxZryOz oxide catalysts of varied ratios of Zn/Zr. Atomically dispersed Zn2+ species are present in the framework within a thin surface shell (1.5-2.0 nm) of ZrO2 particles when the Zn/Zr ratio is smaller than 1/10; when the ratio is above this, both atomically dispersed Zn2+ and ZnO clusters coexist in mixed ZnxZryOz oxide catalysts. The presence of ZnO clusters shows no significant side effect but only a slight increase of selectivity to CO2, caused by steam reforming. The incorporation of atomic Zn2+ into the ZrO2 framework was found to not only passivate strong Lewis acid sites (i.e., Zr-O-Zr) on ZrO2, but to also generate new Lewis acid-base site pairs with enhanced Lewis basicity on the bridged O (i.e., Zr—o$$\curvearrowleft\atop{e\atop—}$$Zn). In the mixed ketone (i.e., acetone and methyl ethyl ketone (MEK)) reactions, while the passivation of strong acid sites can be correlated to the inhibition of side reactions, such as ketone decomposition and coking, the new Lewis acid-base pairs introduced enhance the cascade aldolization and self-deoxygenation reactions involved in olefin (C3=-C6=) production. More importantly, the surface acid-base properties change with varying Zn/Zr ratios, which in turn affect the cross- and self-condensation reactivity and subsequent distribution of olefins.

Authors:
 [1];  [1];  [2];  [2];  [1];  [1];  [3];  [4]
  1. Washington State Univ., Pullman, WA (United States). The Gene and Linda Voiland School of Chemical Engineering and Bioengineering
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis and Environmental Molecular Sciences Lab.
  3. Archer Daniels Midland Company, Chicago, IL (United States)
  4. Washington State Univ., Pullman, WA (United States). The Gene and Linda Voiland School of Chemical Engineering and Bioengineering; Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1434662
Alternate Identifier(s):
OSTI ID: 1591649
Report Number(s):
PNNL-SA-134337
Journal ID: ISSN 0926-3373; PII: S0926337318303801; TRN: US1802344
Grant/Contract Number:  
AC05-76RL01830; FWP-47319; WSU002206; AC05-RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Applied Catalysis B: Environmental
Additional Journal Information:
Journal Volume: 234; Journal ID: ISSN 0926-3373
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 09 BIOMASS FUELS; 10 SYNTHETIC FUELS; 36 MATERIALS SCIENCE; Lewis acid-base pairs; aldolization; ketonization; mixed-metal oxide; oxygenates; olefins

Citation Formats

Baylon, Rebecca A. L., Sun, Junming, Kovarik, Libor, Engelhard, Mark, Li, Houqian, Winkelman, Austin D., Martin, Kevin J., and Wang, Yong. Structural Identification of ZnxZryOz Catalysts for Cascade Aldolization and Self-Deoxygenation Reactions. United States: N. p., 2018. Web. https://doi.org/10.1016/j.apcatb.2018.04.051.
Baylon, Rebecca A. L., Sun, Junming, Kovarik, Libor, Engelhard, Mark, Li, Houqian, Winkelman, Austin D., Martin, Kevin J., & Wang, Yong. Structural Identification of ZnxZryOz Catalysts for Cascade Aldolization and Self-Deoxygenation Reactions. United States. https://doi.org/10.1016/j.apcatb.2018.04.051
Baylon, Rebecca A. L., Sun, Junming, Kovarik, Libor, Engelhard, Mark, Li, Houqian, Winkelman, Austin D., Martin, Kevin J., and Wang, Yong. Sun . "Structural Identification of ZnxZryOz Catalysts for Cascade Aldolization and Self-Deoxygenation Reactions". United States. https://doi.org/10.1016/j.apcatb.2018.04.051. https://www.osti.gov/servlets/purl/1434662.
@article{osti_1434662,
title = {Structural Identification of ZnxZryOz Catalysts for Cascade Aldolization and Self-Deoxygenation Reactions},
author = {Baylon, Rebecca A. L. and Sun, Junming and Kovarik, Libor and Engelhard, Mark and Li, Houqian and Winkelman, Austin D. and Martin, Kevin J. and Wang, Yong},
abstractNote = {Here, complementary characterizations, such as nitrogen sorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), visible Raman, scanning transmission electron microscopy (STEM) coupled with elemental mapping, NH3/CO2 temperature programmed desorption (NH3/CO2-TPD), infrared spectroscopic analysis of adsorbed pyridine (Py-IR), and CO2-IR, have been employed to identify the structure and surface chemistry (i.e., acid-base) of mixed ZnxZryOz oxide catalysts of varied ratios of Zn/Zr. Atomically dispersed Zn2+ species are present in the framework within a thin surface shell (1.5-2.0 nm) of ZrO2 particles when the Zn/Zr ratio is smaller than 1/10; when the ratio is above this, both atomically dispersed Zn2+ and ZnO clusters coexist in mixed ZnxZryOz oxide catalysts. The presence of ZnO clusters shows no significant side effect but only a slight increase of selectivity to CO2, caused by steam reforming. The incorporation of atomic Zn2+ into the ZrO2 framework was found to not only passivate strong Lewis acid sites (i.e., Zr-O-Zr) on ZrO2, but to also generate new Lewis acid-base site pairs with enhanced Lewis basicity on the bridged O (i.e., Zr—o$\curvearrowleft\atop{e\atop—}$Zn). In the mixed ketone (i.e., acetone and methyl ethyl ketone (MEK)) reactions, while the passivation of strong acid sites can be correlated to the inhibition of side reactions, such as ketone decomposition and coking, the new Lewis acid-base pairs introduced enhance the cascade aldolization and self-deoxygenation reactions involved in olefin (C3=-C6=) production. More importantly, the surface acid-base properties change with varying Zn/Zr ratios, which in turn affect the cross- and self-condensation reactivity and subsequent distribution of olefins.},
doi = {10.1016/j.apcatb.2018.04.051},
journal = {Applied Catalysis B: Environmental},
number = ,
volume = 234,
place = {United States},
year = {2018},
month = {4}
}

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    journal, January 2018

    • Liu, Yang; Xia, Chengjie; Wang, Qi
    • Catalysis Science & Technology, Vol. 8, Issue 19
    • DOI: 10.1039/c8cy01420e

    Real-time monitoring of surface acetone enolization and aldolization
    journal, January 2020

    • Li, Houqian; Sun, Junming; Li, Gengnan
    • Catalysis Science & Technology, Vol. 10, Issue 4
    • DOI: 10.1039/c9cy02339a