A manganese complex on a gas diffusion electrode for selective CO<sub>2</sub> to CO reduction

Eagle, Catherine; Neri, Gaia; Piercy, Verity L; Younis, Khadija; Siritanaratkul, Bhavin; Cowan, Alexander J.

doi:10.1039/d3se00236e

Cited by 9 publications

(5 citation statements)

References 49 publications

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“…We attribute the shoulder peaks to the formation of the solvento species, where the Br – ligand is substituted for an aquo or IPA ligand. This aligns well with observations from the Cowan group on XPS of Mn(bpy)(CO) 3 Br on MWCNT in a gas diffusion electrode . Additionally, the solvent species was reported to form spontaneously in the case of the Re(bpy- t Bu) on MWCNT .…”

Section: Resultssupporting

confidence: 89%

“…This aligns well with observations from the Cowan group on XPS of Mn(bpy)(CO) 3 Br on MWCNT in a gas diffusion electrode. 20 Additionally, the solvent species was reported to form spontaneously in the case of the Re(bpy-t Bu) on MWCNT. 8 There are evident shifts in the positions of the Mn 2p, N 1s (Figure 2), and Br 3d (Figure S20) peaks across catalysts 1−5.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Steric Effects on CO₂ Reduction with Substituted Mn(bpy)(CO)₃X-Type Catalysts on Multiwalled Carbon Nanotubes Reveal Critical Mechanistic Details

DeLuca,

Chan,

Taylor

et al. 2024

ACS Catal.

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A series of Mn(bpy-R)(CO) 3 Br (bpy-R = 4,4′-R-2,2′-bipyridine) complexes with systematic substituent variations (R = H, −Me, −Et, t Bu, and −Ph) are immobilized on multiwalled carbon nanotubes (MWCNTs) and investigated as electrocatalysts for CO 2 reduction to study substituent effects on heterogenized molecular electrocatalysis. The electrochemical response and catalytic activity of each heterogenized complex are characterized, unveiling clear trends across the series investigated. Mn(bpy-Ph)(CO) 3 Br/MWCNT exhibited the best catalytic performance, producing CO with a Faradaic efficiency of 72% and a current density (J CO ) of 7.0 mA/cm 2 at low overpotential (η = 0.65 V). Adding steric bulk to the bpy ligands is shown to restrict Mn 0 − Mn 0 dimerization and cause a shift to two-electron reduction occurring at less negative potentials. The apparent quantity of electroactive catalyst scales inversely with steric bulk, where Mn(bpy-Ph)(CO) 3 Br exhibits no distinguishable Faradaic features in CV under normal conditions. These results indicate that catalytic performance is optimized by the confinement of electroactive species to the MWCNT interface.

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Section: Resultssupporting

confidence: 89%

Section: ■ Results and Discussionmentioning

confidence: 99%

Steric Effects on CO₂ Reduction with Substituted Mn(bpy)(CO)₃X-Type Catalysts on Multiwalled Carbon Nanotubes Reveal Critical Mechanistic Details

DeLuca,

Chan,

Taylor

et al. 2024

ACS Catal.

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“…A challenge here was that the system gradually lost its selectivity for CO within 2 h. An improvement was made with a subsequent generation of Mn carbonyl complexes in a similar setup, in which CO was produced with 70% selectivity and partial current densities of 35 mA cm −2 . 75 However, the FE for CO decreased from 60% to 20% within 5 h.…”

Section: Extended Classes Of Molecular Catalystsmentioning

confidence: 96%

Electrocatalysis with molecules and molecular assemblies within gas diffusion electrodes

Bemana,

McKee,

Kornienko

2023

Chem. Sci.

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“…Hence, a wide-range of ligands have been attached to a manganese tricarbonyl halide core [24][25][26], including N-heterocyclic carbene [27,28], non-aromatic diamine [29], pincer ligands [30], and P-coordinating ligands [31]. There are a wide range of recent examples exploring structure-activity and mechanistic questions of these organomanganese electrocatalysts [32][33][34][35][36][37][38][39].…”

Section: Introductionmentioning

confidence: 99%

Manganese(I) Diamine Electrocatalysts: Electrochemical Carbon Dioxide Reduction to Carbon Monoxide

Dhakal,

Corbin,

Sosa Parada

et al. 2023

Inorganics

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Novel organometallic complexes Mn(benzene-1,2-diamine)(CO)3Br, Mn-1, Mn(3-methylbenzene-1,2-diamine)(CO)3Br, Mn-2, and Re(benzene-1,2-diamine)(CO)3Cl, Re-1, have been synthesized and characterized by IR, UV/Vis, 1H-NMR, EA and HRMS. The structures of Mn-2 and Re-1 were confirmed by X-ray crystallography. The three novel compounds were studied for their electrocatalytic reduction of carbon dioxide to carbon monoxide using cyclic voltammetry in acetonitrile solutions. Controlled potential electrolysis was used to obtain information on faradaic yield, with product formation being confirmed by GC. Using earth-abundant manganese, compounds Mn-1 and Mn-2 display turnover frequencies of 108 s−1 and 82 s−1, respectively, amid selective production of carbon monoxide (faradaic yields ~85%), with minimal co-production of dihydrogen (<2%), and low overpotential of 0.18 V. The rhenium congener, Re-1, displays no activity as an electrocatalyst for carbon dioxide reduction under identical conditions.

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A manganese complex on a gas diffusion electrode for selective CO₂ to CO reduction

Abstract: Manganese carbonyl complexes have been studied extensively in solution as low cost, selective electrocatalysts with a low overpotential for CO2 reduction but experiments are typically at low current densities. In...

Cited by 9 publications

References 49 publications

Steric Effects on CO₂ Reduction with Substituted Mn(bpy)(CO)₃X-Type Catalysts on Multiwalled Carbon Nanotubes Reveal Critical Mechanistic Details

Steric Effects on CO₂ Reduction with Substituted Mn(bpy)(CO)₃X-Type Catalysts on Multiwalled Carbon Nanotubes Reveal Critical Mechanistic Details

Electrocatalysis with molecules and molecular assemblies within gas diffusion electrodes

Manganese(I) Diamine Electrocatalysts: Electrochemical Carbon Dioxide Reduction to Carbon Monoxide

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A manganese complex on a gas diffusion electrode for selective CO2 to CO reduction

Abstract: Manganese carbonyl complexes have been studied extensively in solution as low cost, selective electrocatalysts with a low overpotential for CO2 reduction but experiments are typically at low current densities. In...

Cited by 9 publications

References 49 publications

Steric Effects on CO2 Reduction with Substituted Mn(bpy)(CO)3X-Type Catalysts on Multiwalled Carbon Nanotubes Reveal Critical Mechanistic Details

Steric Effects on CO2 Reduction with Substituted Mn(bpy)(CO)3X-Type Catalysts on Multiwalled Carbon Nanotubes Reveal Critical Mechanistic Details

Electrocatalysis with molecules and molecular assemblies within gas diffusion electrodes

Manganese(I) Diamine Electrocatalysts: Electrochemical Carbon Dioxide Reduction to Carbon Monoxide

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Product

Resources

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A manganese complex on a gas diffusion electrode for selective CO₂ to CO reduction

Steric Effects on CO₂ Reduction with Substituted Mn(bpy)(CO)₃X-Type Catalysts on Multiwalled Carbon Nanotubes Reveal Critical Mechanistic Details

Steric Effects on CO₂ Reduction with Substituted Mn(bpy)(CO)₃X-Type Catalysts on Multiwalled Carbon Nanotubes Reveal Critical Mechanistic Details