Electrocatalytic activity of electropolymerized films of bis(vinylterpyridine)cobalt(2+) for the reduction of carbon dioxide and oxygen

Hurrell, Helen C.; Mogstad, A. L.; Usifer, D. A.; Potts, K. T.; Abruña, Héctor D.

doi:10.1021/ic00305a016

Cited by 73 publications

(40 citation statements)

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“…We determined the concentration of dissolved carbon dioxide in DMF-0.10 M TBABF 4 at room temperature by treating a known volume of the carbon dioxide-saturated solvent-supporting electrolyte with an excess of aqueous barium hydroxide. From the mass of the resulting collected and dried barium carbonate precipitate, we calculated that the concentration of dissolved carbon dioxide was 0.20 ± 0.04 M under the conditions of our experiments; this value is comparable to previously reported results [14,18].…”

Section: Preparation Of Cobalt(ii) Salen Solutions; Determination Of supporting

confidence: 91%

“…2, the classic reversible cobalt(II) salen-cobalt(I) salen redox couple is seen (E pc = À0.52 V, E pa = À0.45 V). In addition, curve A displays a cathodic shoulder at approximately À2.00 V, which we attribute to reduction of carbon dioxide to formic acid, as reported by others [18,25,26]. Curve B, depicting the system in the absence of carbon dioxide, shows that the cathodic peak potential for the cobalt(II) salen-cobalt(I) salen couple again occurs at À0.52 V and that irreversible reduction of the salen ligand takes place at À1.89 V. On the positive-going potential sweep, the normal anodic peak for oxidation of cobalt(I) salen disappears; instead, a new anodic peak is seen at À0.61 V, which is probably due to oxidation of a ligand-reduced form of cobalt(I) salen.…”

Section: Cyclic Voltammetric Behavior Of Cobalt(ii) Salen In the Pressupporting

confidence: 87%

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Cyclic voltammetric and spectrophotometric investigation of the catalytic reduction of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) by electrogenerated cobalt(I) salen in dimethylformamide saturated with carbon dioxide

Skljarevski

Peverly

Peters

2011

Journal of Electroanalytical Chemistry

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Section: Preparation Of Cobalt(ii) Salen Solutions; Determination Of supporting

confidence: 91%

Section: Cyclic Voltammetric Behavior Of Cobalt(ii) Salen In the Pressupporting

confidence: 87%

Cyclic voltammetric and spectrophotometric investigation of the catalytic reduction of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) by electrogenerated cobalt(I) salen in dimethylformamide saturated with carbon dioxide

Skljarevski

Peverly

Peters

2011

Journal of Electroanalytical Chemistry

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“…0.009 s −1 ), suggesting that the polymeric scaffold does not impede catalysis. Similar kinetic limitations were previously observed for other Co bis(terpyridine) catalysts immobilized on electrodes in aqueous and MeCN electrolysis conditions, which could originate from the reduced degrees of freedom of the anchored catalyst or, in this case, from the limited diffusion of CO 2 within the porous electrodes.…”

Section: Figurementioning

confidence: 99%

Rational Design of Polymers for Selective CO₂ Reduction Catalysis

et al. 2019

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As eries of copolymers comprising at erpyridine ligand and various functional groups were synthesized toward integrating aC o-based molecular CO 2 reduction catalyst. Using porous metal oxide electrodes designed to host macromolecules,t he Co-coordinated polymers were readily immobilizedv ia phosphonate anchoring groups.W ithin the polymeric matrix, the outer coordination sphere of the Co terpyridine catalyst was engineered using hydrophobic functional moieties to improve CO 2 reduction selectivity in the presence of water.E lectrochemical and photoelectrochemical CO 2 reduction were demonstrated with the polymer-immobilized hybrid cathodes,with aCO:H 2 product ratio of up to 6:1 compared to 2:1f or ac orresponding "monomeric" Co terpyridine catalyst. This versatile platform of polymer design demonstrates promise in controlling the outer-sphere environment of synthetic molecular catalysts,a nalogous to CO 2 reductases.Electrocatalytic reduction of CO 2 selectively to CO remains am ajor goal toward realizing as ustainable,c losed carbon cycle. [1] To this end, molecular catalysts have been developed taking inspiration from natural archetypes such as CO and formate dehydrogenase enzymes. [2] While still dominated by precious metal-based complexes,t remendous efforts have recently been devoted to designing earth-abundant 3d transition metal-based catalysts. [3] Often limited by their low stability and solubility,aswell as the low concentration of CO 2 and competing H 2 evolution in water, examples of first-row transition metals performing aqueous CO 2 reduction remain scarce.Since early reports of Ni cyclam [4] and LehnsR e [5] catalysts,o ptimizing molecular design toward improved product selectivity has principally involved tailoring the metalsprimary coordination sphere. [3] Alternative strategies have incorporated catalysts almost exclusively with carbon materials to provide hybrid electrodes with ah ydrophobic environment conducive to CO 2 utilization, even in water. [6] Considering their facile preparation and stability in water, metal oxides represent an alternative class of promising materials,a nd have been successfully exploited both in photocatalytic colloidal schemes and as cathode substrates toward H 2 evolution. [7] However,t heir hydrophilicity and propensity toward hydrogen bonding generally promote H 2 evolution over CO 2 reduction.Herein we report rationally designed polymers for selective CO production and their incorporation into porous electrode architectures to produce precious metal-free CO 2 reduction cathodes.B uilding upon our recent utilization of ap hosphonated Co bis(tpy) catalyst (tpy = 2,2':6',2''-terpyridine), CotpyP (see the Supporting Information), toward photoelectrochemical reduction of CO 2 in aqueous environments, [8] we demonstrate that integrating the CO 2 reduction catalyst in ar ationally designed copolymer is ap romising strategy for engineering the outer-sphere environment around the metal center to achieve improved CO 2 reduction performance. [2a, 9] Copolymer scaffold...

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“…These new electrodes possess properties which may be exploited to lay a foundation for new and interesting applications and devices such as electrochromic displays and sensors (Green et. al 1983, Hurrell et. al 1989, Li et.…”

Section: Introductionmentioning

confidence: 98%

Cyclic Voltammetric Studies of Electropolymerized Films Based on Ruthenium(II/III) Bis(1,10 phenanthroline) (4-methyl-4’vinyl-2,2’-bipyridine)

Brown¹,

Gray²

2010

IJC

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A ruthenium complex of bis(1,10-phenanthroline)(4-methyl-4'vinyl-2,2'-bipyridine) was used to modify glassy carbon electrodes during cyclic voltammetry. The modification procedure is rapid and produces a polymer film on the glassy carbon electrode. Characterization cyclic voltammograms of the ruthenium-based polymer films in supporting electrolyte solutions are very similar to the electropolymerization cyclic voltammograms. The polymer thin films derived from the ruthenium complex exhibit Nernstian electron transfer with respect to the applied potential at low scan rates. This is shown by the small peak separation between the cathodic and anodic peaks during characterization. At scan rates greater than 1.00 V/sec, the films model the Randles-Sevcik equation for diffusion-controlled mass transfer processes. Surface coverage ranges from 9.42 x 10 -11 mol/cm 2 to 4.76 x 10 -10 mol/cm 2 and was calculated by integrating the area under the anodic peak of the characterization cyclic voltammograms.

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Electrocatalytic activity of electropolymerized films of bis(vinylterpyridine)cobalt(2+) for the reduction of carbon dioxide and oxygen

Cited by 73 publications

References 2 publications

Cyclic voltammetric and spectrophotometric investigation of the catalytic reduction of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) by electrogenerated cobalt(I) salen in dimethylformamide saturated with carbon dioxide

Cyclic voltammetric and spectrophotometric investigation of the catalytic reduction of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) by electrogenerated cobalt(I) salen in dimethylformamide saturated with carbon dioxide

Rational Design of Polymers for Selective CO₂ Reduction Catalysis

Cyclic Voltammetric Studies of Electropolymerized Films Based on Ruthenium(II/III) Bis(1,10 phenanthroline) (4-methyl-4’vinyl-2,2’-bipyridine)

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Electrocatalytic activity of electropolymerized films of bis(vinylterpyridine)cobalt(2+) for the reduction of carbon dioxide and oxygen

Cited by 73 publications

References 2 publications

Cyclic voltammetric and spectrophotometric investigation of the catalytic reduction of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) by electrogenerated cobalt(I) salen in dimethylformamide saturated with carbon dioxide

Cyclic voltammetric and spectrophotometric investigation of the catalytic reduction of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) by electrogenerated cobalt(I) salen in dimethylformamide saturated with carbon dioxide

Rational Design of Polymers for Selective CO2 Reduction Catalysis

Cyclic Voltammetric Studies of Electropolymerized Films Based on Ruthenium(II/III) Bis(1,10 phenanthroline) (4-methyl-4’vinyl-2,2’-bipyridine)

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Rational Design of Polymers for Selective CO₂ Reduction Catalysis