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

Converting CO 2 to synthetic hydrocarbon fuels is of increasing interest. In light of progress in electrified CO 2 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 CO 2 to 1-C 4 H 8 , wherein the outlet cathodic gas from a CO 2 -to-C 2 H 4 electrolyzer is fed directly (via a dehumidification stage) into the C 2 H 4 dimerizer, we study the highest-performing MOF found herein: M' = Ru and M″ = Ni in the bimetallic two-dimensional M' 2 (OAc) 4 M″(CN) 4 MOF. We report a 1-C 4 H 8 production rate of 1.3 mol g cat -1 h -1 and a C 2 H 4 conversion of 97%. From these experimental data, we project an estimated cradle-to-gate carbon intensity of -2.1 kg-CO 2 e/kg-1-C 4 H 8 when CO 2 is supplied from direct air capture and when the required energy is supplied by electricity having the carbon intensity of wind.