Bimetallic Metal Sites in Metal-Organic Frameworks Facilitate the Production of 1-Butene from Electrosynthesized Ethylene

Mi Gyoung Lee; Sharath Kandambeth; Xiao Yan Li; Osama Shekhah; Adnan Ozden; Joshua Wicks; Pengfei Ou; Sasa Wang; Roham Dorakhan; Sungjin Park; Prashant M. Bhatt; Vinayak S. Kale; David Sinton; Mohamed Eddaoudi; Edward H. Sargent

doi:10.1021/jacs.4c03806

Bimetallic Metal Sites in Metal-Organic Frameworks Facilitate the Production of 1-Butene from Electrosynthesized Ethylene

Mi Gyoung Lee, Sharath Kandambeth, Xiao Yan Li, Osama Shekhah, Adnan Ozden, Joshua Wicks, Pengfei Ou, Sasa Wang, Roham Dorakhan, Sungjin Park, Prashant M. Bhatt, Vinayak S. Kale, David Sinton, Mohamed Eddaoudi^*, Edward H. Sargent^*

^*Corresponding author for this work

Chemistry

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

8 Scopus citations

Abstract

Converting CO₂ to synthetic hydrocarbon fuels is of increasing interest. In light of progress in electrified CO₂ to ethylene, we explored routes to dimerize to 1-butene, an olefin that can serve as a building block to ethylene longer-chain alkanes. With goal of selective and active dimerization, we investigate a series of metal-organic frameworks having bimetallic catalytic sites. We find that the tunable pore structure enables optimization of selectivity and that periodic pore channels enhance activity. In a tandem system for the conversion of CO₂ to 1-C₄H₈, wherein the outlet cathodic gas from a CO₂-to-C₂H₄ electrolyzer is fed directly (via a dehumidification stage) into the C₂H₄ dimerizer, we study the highest-performing MOF found herein: M′ = Ru and M″ = Ni in the bimetallic two-dimensional M′₂(OAc)₄M″(CN)₄ MOF. We report a 1-C₄H₈ production rate of 1.3 mol g_cat^-1 h^-1 and a C₂H₄ conversion of 97%. From these experimental data, we project an estimated cradle-to-gate carbon intensity of −2.1 kg-CO₂e/kg-1-C₄H₈ when CO₂ is supplied from direct air capture and when the required energy is supplied by electricity having the carbon intensity of wind.

Original language	English (US)
Pages (from-to)	14267-14277
Number of pages	11
Journal	Journal of the American Chemical Society
Volume	146
Issue number	20
DOIs	https://doi.org/10.1021/jacs.4c03806
State	Published - May 22 2024

Funding

All DFT calculations were performed on the Niagara supercomputer of the SciNet HPC Consortium. SciNet is funded by the Canada Foundation for Innovation, the Government of Ontario, Ontario Research Fund Research Excellence Program, and the University of Toronto. M.G.L. is supported by a research grant (2023-0387) from Incheon National University.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

UN SDGs

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

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10.1021/jacs.4c03806

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Lee, M. G., Kandambeth, S., Li, X. Y., Shekhah, O., Ozden, A., Wicks, J., Ou, P., Wang, S., Dorakhan, R., Park, S., Bhatt, P. M., Kale, V. S., Sinton, D., Eddaoudi, M., & Sargent, E. H. (2024). Bimetallic Metal Sites in Metal-Organic Frameworks Facilitate the Production of 1-Butene from Electrosynthesized Ethylene. Journal of the American Chemical Society, 146(20), 14267-14277. https://doi.org/10.1021/jacs.4c03806

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title = "Bimetallic Metal Sites in Metal-Organic Frameworks Facilitate the Production of 1-Butene from Electrosynthesized Ethylene",

abstract = "Converting CO2 to synthetic hydrocarbon fuels is of increasing interest. In light of progress in electrified CO2 to ethylene, we explored routes to dimerize to 1-butene, an olefin that can serve as a building block to ethylene longer-chain alkanes. With goal of selective and active dimerization, we investigate a series of metal-organic frameworks having bimetallic catalytic sites. We find that the tunable pore structure enables optimization of selectivity and that periodic pore channels enhance activity. In a tandem system for the conversion of CO2 to 1-C4H8, wherein the outlet cathodic gas from a CO2-to-C2H4 electrolyzer is fed directly (via a dehumidification stage) into the C2H4 dimerizer, we study the highest-performing MOF found herein: M′ = Ru and M″ = Ni in the bimetallic two-dimensional M′2(OAc)4M″(CN)4 MOF. We report a 1-C4H8 production rate of 1.3 mol gcat-1 h-1 and a C2H4 conversion of 97%. From these experimental data, we project an estimated cradle-to-gate carbon intensity of −2.1 kg-CO2e/kg-1-C4H8 when CO2 is supplied from direct air capture and when the required energy is supplied by electricity having the carbon intensity of wind.",

author = "Lee, {Mi Gyoung} and Sharath Kandambeth and Li, {Xiao Yan} and Osama Shekhah and Adnan Ozden and Joshua Wicks and Pengfei Ou and Sasa Wang and Roham Dorakhan and Sungjin Park and Bhatt, {Prashant M.} and Kale, {Vinayak S.} and David Sinton and Mohamed Eddaoudi and Sargent, {Edward H.}",

note = "Publisher Copyright: {\textcopyright} 2024 American Chemical Society.",

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Lee, MG, Kandambeth, S, Li, XY, Shekhah, O, Ozden, A, Wicks, J, Ou, P, Wang, S, Dorakhan, R, Park, S, Bhatt, PM, Kale, VS, Sinton, D, Eddaoudi, M & Sargent, EH 2024, 'Bimetallic Metal Sites in Metal-Organic Frameworks Facilitate the Production of 1-Butene from Electrosynthesized Ethylene', Journal of the American Chemical Society, vol. 146, no. 20, pp. 14267-14277. https://doi.org/10.1021/jacs.4c03806

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T1 - Bimetallic Metal Sites in Metal-Organic Frameworks Facilitate the Production of 1-Butene from Electrosynthesized Ethylene

AU - Lee, Mi Gyoung

AU - Kandambeth, Sharath

AU - Li, Xiao Yan

AU - Shekhah, Osama

AU - Ozden, Adnan

AU - Wicks, Joshua

AU - Ou, Pengfei

AU - Wang, Sasa

AU - Dorakhan, Roham

AU - Park, Sungjin

AU - Bhatt, Prashant M.

AU - Kale, Vinayak S.

AU - Sinton, David

AU - Eddaoudi, Mohamed

AU - Sargent, Edward H.

PY - 2024/5/22

Y1 - 2024/5/22

N2 - Converting CO2 to synthetic hydrocarbon fuels is of increasing interest. In light of progress in electrified CO2 to ethylene, we explored routes to dimerize to 1-butene, an olefin that can serve as a building block to ethylene longer-chain alkanes. With goal of selective and active dimerization, we investigate a series of metal-organic frameworks having bimetallic catalytic sites. We find that the tunable pore structure enables optimization of selectivity and that periodic pore channels enhance activity. In a tandem system for the conversion of CO2 to 1-C4H8, wherein the outlet cathodic gas from a CO2-to-C2H4 electrolyzer is fed directly (via a dehumidification stage) into the C2H4 dimerizer, we study the highest-performing MOF found herein: M′ = Ru and M″ = Ni in the bimetallic two-dimensional M′2(OAc)4M″(CN)4 MOF. We report a 1-C4H8 production rate of 1.3 mol gcat-1 h-1 and a C2H4 conversion of 97%. From these experimental data, we project an estimated cradle-to-gate carbon intensity of −2.1 kg-CO2e/kg-1-C4H8 when CO2 is supplied from direct air capture and when the required energy is supplied by electricity having the carbon intensity of wind.

AB - Converting CO2 to synthetic hydrocarbon fuels is of increasing interest. In light of progress in electrified CO2 to ethylene, we explored routes to dimerize to 1-butene, an olefin that can serve as a building block to ethylene longer-chain alkanes. With goal of selective and active dimerization, we investigate a series of metal-organic frameworks having bimetallic catalytic sites. We find that the tunable pore structure enables optimization of selectivity and that periodic pore channels enhance activity. In a tandem system for the conversion of CO2 to 1-C4H8, wherein the outlet cathodic gas from a CO2-to-C2H4 electrolyzer is fed directly (via a dehumidification stage) into the C2H4 dimerizer, we study the highest-performing MOF found herein: M′ = Ru and M″ = Ni in the bimetallic two-dimensional M′2(OAc)4M″(CN)4 MOF. We report a 1-C4H8 production rate of 1.3 mol gcat-1 h-1 and a C2H4 conversion of 97%. From these experimental data, we project an estimated cradle-to-gate carbon intensity of −2.1 kg-CO2e/kg-1-C4H8 when CO2 is supplied from direct air capture and when the required energy is supplied by electricity having the carbon intensity of wind.

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ER -

Bimetallic Metal Sites in Metal-Organic Frameworks Facilitate the Production of 1-Butene from Electrosynthesized Ethylene

Abstract

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