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Title: Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C3+ Olefin Formation from Ethanol

Abstract

Direct and selective production of C3+ olefins from bioethanol remains a critical challenge and important for the production of renewable transportation fuels such as aviation biofuels. In this study, we report a Cu–Zn–Y/Beta catalyst for selective ethanol conversion to butene-rich C3+ olefins (88% selectivity at 100% ethanol conversion, 623 K), where the Cu, Zn, and Y sites are all highly dispersed. The ethanol-to-butene reaction network includes ethanol dehydrogenation, aldol condensation to crotonaldehyde, and hydrogenation to butyraldehyde, followed by further hydrogenation and dehydration reactions to form butenes. Cu sites play a critical role in promoting hydrogenation of the crotonaldehyde C═C bond to form butyraldehyde in the presence of hydrogen, making this a distinctive pathway from crotyl alcohol-based ethanol-to-butadiene reaction. Reaction rate measurements in the presence of ethanol and acetaldehyde (543 K, 12 kPa ethanol, 1.2 kPa acetaldehyde, 101.9 kPa H2) over monometallic Zn/Beta and Y/Beta catalysts indicate that Y sites have higher C–C coupling rates than over Zn sites (initial C–C coupling rate, 6.1 × 10–3 mol molY–1 s–1 vs 1.2 × 10–3 mol molZn–1 s–1). Further, Lewis-acidic Y-site densities over Cu–Zn–Y/Beta with varied Y loadings are linearly correlated with the initial C–C coupling rates, suggesting that Lewis-acidic Y sites aremore » the predominant sites that catalyze C–C coupling in Cu–Zn–Y/Beta catalysts. Control experiments show that the dealuminated Beta support is important to form higher density of Lewis-acidic Y sites in comparison with other supports such as silica, or deboronated MWW despite similar atomic dispersion of Y sites and Y–O coordination numbers over these supports, leading to more than 9 times higher C–C coupling rate per mole Y over dealuminated Beta relative to other supports. This study highlights the significance of unique combination of metal sites in contributing to the selective valorization of ethanol to C3+ olefins, motivating for exploring multifunctional zeolite catalysts, where the presence of multiple sites with varying reactivities and functions allows for controlling the predominant molecular fluxes toward the desired products in complex reactions.« less

Authors:
 [1];  [2];  [3]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [4];  [4]; ORCiD logo [5];  [2];  [6]; ORCiD logo [6]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [4]
+ Show Author Affiliations
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Maryland, College Park, MD (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Univ. of Alabama, Tuscaloosa, AL (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  5. Purdue Univ., West Lafayette, IN (United States)
  6. Univ. of Maryland, College Park, MD (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Science Foundation (NSF)
OSTI Identifier:
1813166
Grant/Contract Number:  
AC05-00OR22725; AC02-06CH11357; EEC‐1647722
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 11; Journal Issue: 15; 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; butenes; olefins; Lewis acid zeolites; single-atom catalysts

Citation Formats

Zhang, Junyan, Wegener, Evan C., Samad, Nohor River, Harris, James W., Unocic, Kinga A., Allard, Lawrence F., Purdy, Stephen, Adhikari, Shiba, Cordon, Michael J., Miller, Jeffrey T., Krause, Theodore R., Cheng, Sichao, Liu, Dongxia, Li, Meijun, Jiang, Xiao, Wu, Zili, and Li, Zhenglong. Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C3+ Olefin Formation from Ethanol. United States: N. p., 2021. Web. doi:10.1021/acscatal.1c02177.
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Zhang, Junyan, Wegener, Evan C., Samad, Nohor River, Harris, James W., Unocic, Kinga A., Allard, Lawrence F., Purdy, Stephen, Adhikari, Shiba, Cordon, Michael J., Miller, Jeffrey T., Krause, Theodore R., Cheng, Sichao, Liu, Dongxia, Li, Meijun, Jiang, Xiao, Wu, Zili, & Li, Zhenglong. Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C3+ Olefin Formation from Ethanol. United States. https://doi.org/10.1021/acscatal.1c02177
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Zhang, Junyan, Wegener, Evan C., Samad, Nohor River, Harris, James W., Unocic, Kinga A., Allard, Lawrence F., Purdy, Stephen, Adhikari, Shiba, Cordon, Michael J., Miller, Jeffrey T., Krause, Theodore R., Cheng, Sichao, Liu, Dongxia, Li, Meijun, Jiang, Xiao, Wu, Zili, and Li, Zhenglong. Thu . "Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C3+ Olefin Formation from Ethanol". United States. https://doi.org/10.1021/acscatal.1c02177. https://www.osti.gov/servlets/purl/1813166.
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@article{osti_1813166,
title = {Isolated Metal Sites in Cu–Zn–Y/Beta for Direct and Selective Butene-Rich C3+ Olefin Formation from Ethanol},
author = {Zhang, Junyan and Wegener, Evan C. and Samad, Nohor River and Harris, James W. and Unocic, Kinga A. and Allard, Lawrence F. and Purdy, Stephen and Adhikari, Shiba and Cordon, Michael J. and Miller, Jeffrey T. and Krause, Theodore R. and Cheng, Sichao and Liu, Dongxia and Li, Meijun and Jiang, Xiao and Wu, Zili and Li, Zhenglong},
abstractNote = {Direct and selective production of C3+ olefins from bioethanol remains a critical challenge and important for the production of renewable transportation fuels such as aviation biofuels. In this study, we report a Cu–Zn–Y/Beta catalyst for selective ethanol conversion to butene-rich C3+ olefins (88% selectivity at 100% ethanol conversion, 623 K), where the Cu, Zn, and Y sites are all highly dispersed. The ethanol-to-butene reaction network includes ethanol dehydrogenation, aldol condensation to crotonaldehyde, and hydrogenation to butyraldehyde, followed by further hydrogenation and dehydration reactions to form butenes. Cu sites play a critical role in promoting hydrogenation of the crotonaldehyde C═C bond to form butyraldehyde in the presence of hydrogen, making this a distinctive pathway from crotyl alcohol-based ethanol-to-butadiene reaction. Reaction rate measurements in the presence of ethanol and acetaldehyde (543 K, 12 kPa ethanol, 1.2 kPa acetaldehyde, 101.9 kPa H2) over monometallic Zn/Beta and Y/Beta catalysts indicate that Y sites have higher C–C coupling rates than over Zn sites (initial C–C coupling rate, 6.1 × 10–3 mol molY–1 s–1 vs 1.2 × 10–3 mol molZn–1 s–1). Further, Lewis-acidic Y-site densities over Cu–Zn–Y/Beta with varied Y loadings are linearly correlated with the initial C–C coupling rates, suggesting that Lewis-acidic Y sites are the predominant sites that catalyze C–C coupling in Cu–Zn–Y/Beta catalysts. Control experiments show that the dealuminated Beta support is important to form higher density of Lewis-acidic Y sites in comparison with other supports such as silica, or deboronated MWW despite similar atomic dispersion of Y sites and Y–O coordination numbers over these supports, leading to more than 9 times higher C–C coupling rate per mole Y over dealuminated Beta relative to other supports. This study highlights the significance of unique combination of metal sites in contributing to the selective valorization of ethanol to C3+ olefins, motivating for exploring multifunctional zeolite catalysts, where the presence of multiple sites with varying reactivities and functions allows for controlling the predominant molecular fluxes toward the desired products in complex reactions.},
doi = {10.1021/acscatal.1c02177},
journal = {ACS Catalysis},
number = 15,
volume = 11,
place = {United States},
year = {Thu Jul 22 00:00:00 EDT 2021},
month = {Thu Jul 22 00:00:00 EDT 2021}
}
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https://doi.org/10.1021/acscatal.1c02177
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