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

Junyan Zhang; Evan C. Wegener; Nohor River Samad; James W. Harris; Kinga A. Unocic; Lawrence F. Allard; Stephen Purdy; Shiba Adhikari; Michael J. Cordon; Jeffrey T. Miller; Theodore R. Krause; Sichao Cheng; Dongxia Liu; Meijun Li; Xiao Jiang; Zili Wu; Zhenglong Li

doi:10.1021/acscatal.1c02177

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

Junyan Zhang, Evan C. Wegener, Nohor River Samad, James W. Harris, Kinga A. Unocic, Lawrence F. Allard, Stephen Purdy, Shiba Adhikari, Michael J. Cordon, Jeffrey T. Miller, Theodore R. Krause, Sichao Cheng, Dongxia Liu, Meijun Li, Xiao Jiang, Zili Wu, Zhenglong Li

Research output: Contribution to journal › Article › peer-review

33 Scopus citations

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. Here, 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.

Original language	English
Pages (from-to)	9885-9897
Number of pages	13
Journal	ACS Catalysis
Volume	11
Issue number	15
DOIs	https://doi.org/10.1021/acscatal.1c02177
State	Published - Aug 6 2021

Funding

This research is sponsored by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, BioEnergy Technologies Office, under contract DE-AC05-00OR22725 with UT-Battelle, LLC, and in collaboration with the Chemical Catalysis for Bioenergy (ChemCatBio) Consortium, a member of the Energy Materials Network. J.T.M was supported in part by the National Science Foundation under Cooperative Agreement No. EEC-1647722. N.R.S. and J.W.H. were supported in part by The University of Alabama Office of Research and Economic Development’s Small Grants Program. Argonne National Laboratory’s work was supported by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office, under contract DE-AC02-06CH11357. This work used the resources of the Advanced Photon Sources, which is a U.S. Department of Energy, Office of Science User Facility supported under contract DE AC02 06CH11357. MRCAT operations are supported by the Department of Energy and its member institutions. The work of X.J. and Z.W. was supported by the Center for Understanding and Control of Acid Gas-Induced Evolution of Materials for Energy (UNCAGE-ME), an Energy Frontier Research Center funded by U.S. Department of Energy, Office of Science, Basic Energy Sciences. A portion of the research was conducted at Center for Nanophase Materials Sciences, a US DOE Office of Science User Facility. The views and opinions of the authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. This manuscript has been authored in part by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). Acknowledgments

Funders	Funder number
Center for Understanding and Control of Acid
Chemical Catalysis for Bioenergy
Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office	DE-AC02-06CH11357
National Science Foundation	EEC-1647722
U.S. Department of Energy
Office of Science	DE AC02 06CH11357
Office of Energy Efficiency and Renewable Energy
Basic Energy Sciences
University of Alabama
Bioenergy Technologies Office	DE-AC05-00OR22725

Keywords

Lewis acid zeolites
butenes
ethanol
olefins
single-atom catalysts

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1021/acscatal.1c02177

Cite this

Zhang, J., Wegener, E. C., Samad, N. R., Harris, J. W., Unocic, K. A., Allard, L. F., Purdy, S., Adhikari, S., Cordon, M. J., Miller, J. T., Krause, T. R., Cheng, S., Liu, D., Li, M., Jiang, X., Wu, Z., & Li, Z. (2021). Isolated Metal Sites in Cu-Zn-Y/Beta for Direct and Selective Butene-Rich C₃₊Olefin Formation from Ethanol. ACS Catalysis, 11(15), 9885-9897. https://doi.org/10.1021/acscatal.1c02177

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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. Here, 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.",

keywords = "Lewis acid zeolites, butenes, ethanol, olefins, single-atom catalysts",

author = "Junyan Zhang and Wegener, {Evan C.} and Samad, {Nohor River} and Harris, {James W.} and Unocic, {Kinga A.} and Allard, {Lawrence F.} and Stephen Purdy and Shiba Adhikari and Cordon, {Michael J.} and Miller, {Jeffrey T.} and Krause, {Theodore R.} and Sichao Cheng and Dongxia Liu and Meijun Li and Xiao Jiang and Zili Wu and Zhenglong Li",

note = "Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

month = aug,

day = "6",

doi = "10.1021/acscatal.1c02177",

language = "English",

volume = "11",

pages = "9885--9897",

journal = "ACS Catalysis",

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publisher = "American Chemical Society",

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Zhang, J, Wegener, EC, Samad, NR, Harris, JW, Unocic, KA, Allard, LF , Purdy, S, Adhikari, S, Cordon, MJ, Miller, JT, Krause, TR, Cheng, S, Liu, D, Li, M, Jiang, X, Wu, Z & Li, Z 2021, 'Isolated Metal Sites in Cu-Zn-Y/Beta for Direct and Selective Butene-Rich C₃₊Olefin Formation from Ethanol', ACS Catalysis, vol. 11, no. 15, pp. 9885-9897. https://doi.org/10.1021/acscatal.1c02177

TY - JOUR

T1 - Isolated Metal Sites in Cu-Zn-Y/Beta for Direct and Selective Butene-Rich C3+Olefin Formation from Ethanol

AU - Zhang, Junyan

AU - Wegener, Evan C.

AU - Samad, Nohor River

AU - Harris, James W.

AU - Unocic, Kinga A.

AU - Allard, Lawrence F.

AU - Purdy, Stephen

AU - Adhikari, Shiba

AU - Cordon, Michael J.

AU - Miller, Jeffrey T.

AU - Krause, Theodore R.

AU - Cheng, Sichao

AU - Liu, Dongxia

AU - Li, Meijun

AU - Jiang, Xiao

AU - Wu, Zili

AU - Li, Zhenglong

PY - 2021/8/6

Y1 - 2021/8/6

N2 - 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. Here, 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.

AB - 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. Here, 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.

KW - Lewis acid zeolites

KW - butenes

KW - ethanol

KW - olefins

KW - single-atom catalysts

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U2 - 10.1021/acscatal.1c02177

DO - 10.1021/acscatal.1c02177

M3 - Article

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