Local Proton Source in Electrocatalytic CO<sub>2</sub> Reduction with [Mn(bpy–R)(CO)<sub>3</sub>Br] Complexes

Franco, Federico; Cometto, Claudio; Nencini, L.; Barolo, Claudia; Sordello, Fabrizio; Minero, Claudio; Fiedler, Jan; Robert, Marc; Gobetto, Roberto; Nervi, Carlo

doi:10.1002/chem.201605546

Cited by 131 publications

(186 citation statements)

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“…This assignment is corroborated by the excellent correlation between the experimental and DFT‐calculated IR spectra of 1 − . The growth of a broad visible band ( λ max =527 nm) in a UV/Vis SEC experiment is in agreement with the formation of 1 − as the main species (Figures S22–S24 and Table S2) 4a, 4d…”

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confidence: 80%

A Highly Active N‐Heterocyclic Carbene Manganese(I) Complex for Selective Electrocatalytic CO₂ Reduction to CO

et al. 2018

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We report here the first purely organometallic fac‐[MnI(CO)3(bis‐MeNHC)Br] complex with unprecedented activity for the selective electrocatalytic reduction of CO2 to CO, exceeding 100 turnovers with excellent faradaic yields (η CO≈95 %) in anhydrous CH3CN. Under the same conditions, a maximum turnover frequency (TOFmax) of 2100 s−1 was measured by cyclic voltammetry, which clearly exceeds the values reported for other manganese‐based catalysts. Moreover, the addition of water leads to the highest TOFmax value (ca. 320 000 s−1) ever reported for a manganese‐based catalyst. A MnI tetracarbonyl intermediate was detected under catalytic conditions for the first time.

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confidence: 80%

A Highly Active N‐Heterocyclic Carbene Manganese(I) Complex for Selective Electrocatalytic CO₂ Reduction to CO

et al. 2018

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“…Currently, much of the literature regarding molecular electrochemical activation of CO 2 still continues to explore the catalytic properties of the heavier members of Group‐7 (Re), Group‐8 (Ru and Os) and Group‐9 (Rh, and Ir) triads. These “first‐generation” electrocatalysts must be phased out; encouragingly, cheaper alternatives exist within the same groups – Mn substituting Re, Fe substituting Ru and Os, and Co substituting Rh and Ir . However, the community's focus on late transition metals is leaving the Group‐6 metals (Cr, Mo, W) rather neglected, despite the high potential for the comparatively abundant metal triad to function as both high‐performance alternatives to the noble metals and photostable alternatives to the hot‐topic manganese carbonyls .…”

Section: Methodsmentioning

confidence: 99%

Solvent and Ligand Substitution Effects on the Electrocatalytic Reduction of CO₂ with [Mo(CO)₄(x,x′‐dimethyl‐2,2′‐bipyridine)] (x=4–6) Enhanced at a Gold Cathodic Surface

2018

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A series of molybdenum tetracarbonyl complexes with dimethyl‐substituted 2,2′‐bipyridine (dmbipy) ligands were investigated by cyclic voltammetry (CV) combined with infrared spectroelectrochemistry (IR‐SEC) in tetrahydrofuran (THF) and N‐methyl‐2‐pyrrolidone (NMP) to explore their potential in a reduced state to trigger electrocatalytic CO2 reduction to CO. Addressed is their ability to take advantage of a low‐energy, CO‐dissociation two‐electron ECE pathway available only at an Au cathode. A comparison is made with the reference complex bearing unsubstituted 2,2′‐bipyridine (bipy). The methyl substitution in the 6,6′ position has a large positive impact on the catalytic efficiency. This behavior is ascribed to the advantageous positioning of the steric bulk of the methyl groups, which further facilitate CO dissociation from the one‐electron‐reduced parent radical anion. On the contrary, the substitution in the 4,4′ position appears to have a negative impact on the catalytic performance, exerting a strong stabilizing effect on the π‐accepting CO ligands and, in THF, preventing exploitation of the low‐energy dissociative pathway.

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“…[32,92,[105][106][107] Work by Sampson et al pushed the boundaries of manganese bipyridine aided electro-reduction; the team synthesized, for the first time in reported literature, Mn(mesbpy)-(CO) 3 Br and [Mn(mesbpy)(CO) 3 (MeCN)]-(OTf) molecular catalysts (Figure 40) (mesbpy = Br6,6′-dimesityl-2,2′-bipyridine). [32,92,[105][106][107] Work by Sampson et al pushed the boundaries of manganese bipyridine aided electro-reduction; the team synthesized, for the first time in reported literature, Mn(mesbpy)-(CO) 3 Br and [Mn(mesbpy)(CO) 3 (MeCN)]-(OTf) molecular catalysts (Figure 40) (mesbpy = Br6,6′-dimesityl-2,2′-bipyridine).…”

Section: Other Metal-based Catalystsmentioning

confidence: 99%

Recent Trends, Benchmarking, and Challenges of Electrochemical Reduction of CO₂ by Molecular Catalysts

Elouarzaki

Kannan

Jose

et al. 2019

Advanced Energy Materials

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provides a promising alternative to hydrocarbon sources for petrochemical feedstock. Thanks to the electrochemical nature of the CO 2 conversion to fuels and chemicals, the electrical energy invested to convert CO 2 in the form of a chemical fuel can be stored and redistributed using established supply chains for future use. Additionally, the integration of renewable energy systems (green electricity) into the grid can potentially create a carbon neutral energy cycle, and when driven by solar energy, offers a completely renewable energy cycle or negative carbon technology. Converting CO 2 electrochemically into compounds with high energy densities, such as alcohols (methanol, ethanol), formates, and CO, represents a form of energy storage and is also adaptable to demand response or energy arbitrage technologies. [3][4][5][6][7] The recoverable energy density of the chemicals that can be converted from CO 2 is substantially higher than most battery technologies.Given CO 2 electroreduction's immense economic and environmental potential, it has been the subject of much research activity over the past decades. [8][9][10][11] One of the greatest challenges of reducing CO 2 in an electrochemical cell is overcoming the immense energy barrier required to do so; the single electron reduction of CO 2 to CO 2 −˙, a common step in many CO 2 reduction mechanisms, requires an applied potential of −1.97 V measured versus standard hydrogen electrode (SHE). To alleviate this problem, many catalytic cathodes have been developed to avoid this intermediate and to reroute the reduction mechanism through alternate pathways requiring much lower applied potentials (a necessity if CO 2 electroreduction is to be implemented at industrial scale). [12][13][14] However, despite the low potentials offered by catalytic electrodes, the cost of electrodes is not always viable when upscaled to industrial levels. [15,16] Therefore, recent research trends in electrocatalytic reduction of CO 2 have been shifting toward the development of molecular catalysts that can exist as either solutes in electrolytes or can be surface-confined on electrodes. [13,16] The tunable nature and electronic characteristics of molecular catalysts give access to a large variety of catalysts with high activity, selectivity, and durability, as well as their ability to be integrated into sophisticated nanoassemblies. [17][18][19] Thanks to the aforementioned proprieties, performing CO 2 reduction using molecularly defined compounds offer several advantages compared to classical solid-state counterparts. Molecular catalysts usually exhibit well-defined homogeneous and/or CO 2 reduction using molecular catalysts is a key area of study for achieving electrical-to-chemical energy storage and feedstock chemical synthesis. Compared to classical metallic solid-state catalysts, these molecular catalysts often result in high performance and selectivity, even under unfavorable aqueous environments. This review considers the recent state-of-the-art molecular catalysts for CO 2 electro...

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Local Proton Source in Electrocatalytic CO₂ Reduction with [Mn(bpy–R)(CO)₃Br] Complexes

Cited by 131 publications

References 70 publications

A Highly Active N‐Heterocyclic Carbene Manganese(I) Complex for Selective Electrocatalytic CO₂ Reduction to CO

A Highly Active N‐Heterocyclic Carbene Manganese(I) Complex for Selective Electrocatalytic CO₂ Reduction to CO

Solvent and Ligand Substitution Effects on the Electrocatalytic Reduction of CO₂ with [Mo(CO)₄(x,x′‐dimethyl‐2,2′‐bipyridine)] (x=4–6) Enhanced at a Gold Cathodic Surface

Recent Trends, Benchmarking, and Challenges of Electrochemical Reduction of CO₂ by Molecular Catalysts

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Local Proton Source in Electrocatalytic CO2 Reduction with [Mn(bpy–R)(CO)3Br] Complexes

Cited by 131 publications

References 70 publications

A Highly Active N‐Heterocyclic Carbene Manganese(I) Complex for Selective Electrocatalytic CO2 Reduction to CO

A Highly Active N‐Heterocyclic Carbene Manganese(I) Complex for Selective Electrocatalytic CO2 Reduction to CO

Solvent and Ligand Substitution Effects on the Electrocatalytic Reduction of CO2 with [Mo(CO)4(x,x′‐dimethyl‐2,2′‐bipyridine)] (x=4–6) Enhanced at a Gold Cathodic Surface

Recent Trends, Benchmarking, and Challenges of Electrochemical Reduction of CO2 by Molecular Catalysts

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Local Proton Source in Electrocatalytic CO₂ Reduction with [Mn(bpy–R)(CO)₃Br] Complexes

A Highly Active N‐Heterocyclic Carbene Manganese(I) Complex for Selective Electrocatalytic CO₂ Reduction to CO

A Highly Active N‐Heterocyclic Carbene Manganese(I) Complex for Selective Electrocatalytic CO₂ Reduction to CO

Solvent and Ligand Substitution Effects on the Electrocatalytic Reduction of CO₂ with [Mo(CO)₄(x,x′‐dimethyl‐2,2′‐bipyridine)] (x=4–6) Enhanced at a Gold Cathodic Surface

Recent Trends, Benchmarking, and Challenges of Electrochemical Reduction of CO₂ by Molecular Catalysts