Room-Temperature Formate Ester Transfer Hydrogenation Enables an Electrochemical/Thermal Organometallic Cascade for Methanol Synthesis from CO.

The reduction of CO to synthetic fuels is a valuable strategy for energy storage. However, the formation of energy-dense liquid fuels such as methanol remains rare, particularly under low-temperature and low-pressure conditions that can be coupled to renewable electricity sources via electrochemistry. Here, a multicatalyst system pairing an electrocatalyst with a thermal organometallic catalyst is introduced, which enables the reduction of CO to methanol at ambient temperature and pressure.

Molecular catalyst coordinatively bonded to organic semiconductors for selective light-driven CO reduction in water.

The selective photoreduction of CO in aqueous media based on earth-abundant elements only, is today a challenging topic. Here we present the anchoring of discrete molecular catalysts on organic polymeric semiconductors via covalent bonding, generating molecular hybrid materials with well-defined active sites for CO photoreduction, exclusively to CO in purely aqueous media. The molecular catalysts are based on aryl substituted Co phthalocyanines that can be coordinated by dangling pyridyl attached to a polymeric covalent triazine framework that acts as a light absorber.

Circumventing Kinetic Barriers to Metal Hydride Formation with Metal-Ligand Cooperativity.

We report the two-electron, one-proton mechanism of cobalt hydride formation for the conversion of [CoCp(PN)(CHCN)] to [HCoCp(PN)]. This complex catalytically converts CO to formate under CO reduction conditions, with hydride formation as a key elementary step. Through a combination of electrochemical measurements, digital simulations, theoretical calculations, and additional mechanistic and thermochemical studies, we outline the explicit role of the PN ligand in the proton-coupled electron transfer (PCET) reactivity that leads to hydride formation.