Electrocatalysis in CO₂-Binding Organic Liquids with an Iron Porphyrin

ACS electrochemistry., Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 22, 2025

Language: Английский

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Cambered Bipyridyl Ligand with Extended Aryl System Enables Electrochemical Reduction of Carbon Dioxide and Bicarbonate by Mn(bpy)(CO)₃Br-type Catalyst Immobilized on Carbon Nanotubes

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(9), P. 7411 - 7422

Published: Feb. 24, 2025

Heterogeneous materials containing molecular catalytic sites show promise for electrocatalytic reduction of CO2 to energy-enriched carbon products. Interactions between the catalyst and heterogeneous support increasingly are recognized as important in governing product selectivity rate. Recent work on Mn(R-bpy)(CO)3Br type catalysts immobilized multiwalled nanotubes (MWCNT) demonstrated control behavior with steric modification catalyst. Phenyl groups installed 4,4' positions bipyridine ligand (ph-bpy) maximized performance through π-π interactions MWCNT support. Herein we report outcome extending π system Mn(nap-bpy)(CO)3Br (nap-bpy = 4,4'-di(naphthalen-1-yl)-2,2'-bipyridine) Mn(pyr-bpy)(CO)3Br (pyr-bpy 4,4'-di(pyren-1-yl)-2,2'-bipyridine) MWCNT. We demonstrate exceptional electrocatalysis Mn(nap-bpy)(CO)3Br/MWCNT (FECO > 92%; JCO 16.5 mA/cm2) find that this electrochemically reduces bicarbonate absence deliberately added at a remarkable overall >80% products (FEHCOO- 52% FECO 29%). diminishing returns simply adding aromatic character bipyridyl Mn(pyr-bpy)(CO)3Br/MWCNT observe unique cambering believe enables selective catalysis. Mechanistic studies were carried out using novel thin-film infrared spectroelectrochemical (IR-SEC) technique. These experiments undergo single electron Mn-centered radical binds reduction-coupled process.

Language: Английский

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Electrosynthesis of CO from an electrically pH-shifted DAC post-capture liquid using a catalyst:support amide linkage

Joule, Journal Year: 2025, Volume and Issue: unknown, P. 101883 - 101883

Published: March 1, 2025

Language: Английский

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The Role of Metal–Organic Framework Induced Confinement Effects on Molecular Electrocatalysts Relevant to the Energy Transition

ChemSusChem, Journal Year: 2025, Volume and Issue: unknown

Published: April 24, 2025

Metal organic frameworks (MOFs) are promising materials for (electro)catalysis as they can improve stability, reusability, and catalytic current densities of molecular catalysts, thereby combining the advantages homogeneous‐ heterogeneous catalysts. However, much is unknown about effects confinement a catalyst within an MOF on overall behavior. The performance series electrocatalysts confined in MOFs compared to that corresponding homogeneous catalysts evaluate what extend site affected by terms activity, selectivity. Together examples discuss depict happens when it incorporated into MOF, recommendations made how electrochemical activity way allows description such performance. It noted limiting factor reaction found 1) slow electron transport, 2) mass transport reactants products, or 3) low itself. Understanding changes mass‐ resulting mechanism essential be able bring systems practical applications.

Language: Английский

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Electrostatic versus Hydrogen Bonding Control of Selectivity in CO₂ Reduction by Iron Porphyrins

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3595 - 3610

Published: Feb. 13, 2025

Language: Английский

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