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

J Am Chem Soc. 2024 May 22;146(20):14267-14277. doi: 10.1021/jacs.4c03806. Epub 2024 May 8.

Authors

Mi Gyoung Lee^{1

2}, Sharath Kandambeth³, Xiao-Yan Li^{1

4}, Osama Shekhah³, Adnan Ozden⁵, Joshua Wicks¹, Pengfei Ou^{1

4}, Sasa Wang¹, Roham Dorakhan¹, Sungjin Park¹, Prashant M Bhatt³, Vinayak S Kale³, David Sinton⁵, Mohamed Eddaoudi³, Edward H Sargent^{1

4

6}

Affiliations

¹ Department of Electrical and Computer Engineering, University of Toronto, Toronto, ON M5S 1A4, Canada.
² Department of Materials Science and Engineering, Incheon National University, Incheon 22012, Republic of Korea.
³ Functional Materials Design, Discovery, and Development (FMD3) research group, Advanced Membranes and Porous Materials (AMPM), Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia.
⁴ Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.
⁵ Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, ON M5S 3G8, Canada.
⁶ Department of Electrical and Computer Engineering, Northwestern University, Evanston, Illinois 60208, United States.

PMID: 38717595
DOI: 10.1021/jacs.4c03806

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.