Integrated CO2 Capture and Conversion to Formate with a Molecular Platinum Bis(diphosphine) Electrocatalyst

Gillis, Ciara N.; Pauker, Hunter; Ross, R. Dominic; Hahn, Christopher; Nielsen, Robert J.; Yang, Jenny Y.

doi:10.1021/jacsau.5c00801

Title: Integrated CO₂ Capture and Conversion to Formate with a Molecular Platinum Bis(diphosphine) Electrocatalyst

Journal Article · Thu Oct 23 00:00:00 UTC 2025 · JACS Au

DOI: https://doi.org/10.1021/jacsau.5c00801 · OSTI ID:3005652

Gillis, Ciara N. ^[1]; Pauker, Hunter ^[1];

^[2];

^[2]; Nielsen, Robert J. ^[1];

^[1]

Univ. of California, Irvine, CA (United States)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Carbon dioxide is a potentially valuable feedstock for carbon-based fuels or commodities but is only available in dilute streams. Many studies have focused on either the capture and concentration of CO₂ or the reduction of pure CO₂ streams. The direct reduction of sorbent-captured CO₂ in an integrated process would skip the energy-intensive CO₂ concentration and sorbent regeneration step. Herein, we report the electrocatalytic reduction of 1,3-bis(2,6-diisopropylphenyl)imidazolium-2-carboxylate (IPr·CO₂), which forms quantitatively from the reaction of sorbent 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) with 10% and 0.04% CO₂ streams, by catalyst [Pt(dmpe)₂](PF₆)₂ (dmpe = 1,2-bis(dimethylphosphino)ethane) to formate with >70% Faradaic efficiencies. Unexpectedly, experimental studies indicate that the proton source phenol facilitates rapid decarboxylation of IPr·CO₂ to release CO₂, which is the substrate for reduction. Kinetic studies determined the rate of hydride transfer from a catalytic intermediate [HPt(dmpe)₂](PF₆) to form the C–H bond in formate to be 0.22 M^–1s^–1. Further details on the mechanism, transition state energy, and structure for hydride transfer to CO₂, a common step in CO₂ reduction, were explored using computational methods.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Closing the Carbon Cycle; Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Univ. of California, Irvine, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC52-07NA27344; SC0023427

OSTI ID:: 3005652

Report Number(s):: LLNL-JRNL-2007805

Journal Information:: JACS Au, Journal Name: JACS Au Journal Issue: 11 Vol. 5; ISSN 2691-3704

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Integrated CO2 Capture and Conversion to Formate with a Molecular Platinum Bis(diphosphine) Electrocatalyst

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Title: Integrated CO₂ Capture and Conversion to Formate with a Molecular Platinum Bis(diphosphine) Electrocatalyst