A highly active non-precious transition metal catalyst for the hydrogenation of carbon dioxide to formates

Abstract

Herein a highly active non-precious transition metal catalyst for the homogeneous hydrogenation of carbon dioxide to formate is presented. Detailed ligand optimisation enabled the development of a nickel-based catalytic system with exceptional productivity.

Matching emerging formic acid synthesis processes with application requirements

“…3 Lifetimes of several thousands of hours are needed before the electrolysers are commercially viable. 35 CO 2 can also be converted by catalytic hydrogenation with either homogeneous catalysts such as Ir (III)-pincer complexes 36 and non-precious Ni(II)-tris(2-(diphenylphosphino)ethyl)amine complexes 37 or heterogeneous catalysts, as recently summarized by Sun et al 38 Some routes even combine carbon capture and conversion into one process, such as the hydrogenation of CO 2 in polyethyleneimine and Rh/monophosphine systems. 39 Although rapid progress is being made in these routes, they are still plagued with a need for expensive catalyst complexes and rather high temperatures and pressures.…”

Carbon Dioxide Hydrogenation to Formate Catalyzed by a Bench-Stable, Non-Pincer-Type Mn(I) Alkylcarbonyl Complex

“…In the case of earth-abundant metals, in recent years, the attention has been focused principally on Fe, although interesting results were reported also with Co, Ni, and Cu . Very recently, Klankermayer and co-workers established the new state-of-the-art for 3d metal-catalyzed CO 2 hydrogenation with the system obtained in situ by the combination of Ni­(BF 4 ) 2 ·6H 2 O (0.002 μmol) and the tetradentate ligand tris-[2-(diphenylphosphino)­ethyl]­amine (NP 3 , 1 equiv to Ni) in CH 3 CN . In the presence of DBU as a base, 90 bar H 2 /CO 2 (2:1), 120 °C, 72 h, unsurpassed TON = 4 650 710 and TOF = 64 593 h –1 were achieved, showing that earth-abundant metals can efficiently compete with noble-metal counterparts.…”

Computational Study of Triphosphine-Ligated Cu(I) Catalysts for Hydrogenation of CO2 to Formate

“…The use of transition-metal catalysts for CO 2 hydrogenation to formate has been refined over the past few decades, resulting in turnover numbers exceeding 3 500 000 and turnover frequencies exceeding 10 6 h –1 . − Catalysts that can reach these numbers are typically complexes of ruthenium or iridium. Once made sufficiently catalytic, cheaper, first-row transition metals, like Cu, would be advantageous for large-scale productions of fuels.…”

“…Once made sufficiently catalytic, cheaper, first-row transition metals, like Cu, would be advantageous for large-scale productions of fuels. Neighboring first-row transition metals such as Fe, − Co, ,− and Ni − are reported to be active in CO 2 reduction.…”