Electrocatalytic reduction of CO2 by a complex of rhenium in thin polymeric films

O’Toole, Terrence R.; Sullivan, B. Patrick; Bruce, Mitchell R. M.; Margerum, Lawrence D.; Murray, Royce W.; Meyer, Thomas J.

doi:10.1016/0022-0728(89)80049-x

Cited by 117 publications

(74 citation statements)

References 22 publications

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“…27 This behavior is also distinct from that displayed by vinyl substituted Re-bipyridine complexes that can be electrodeposited on electrode surfaces. 45,46 The rapid deposition of Re(BB2)(CO)3Cl onto the working electrode may be due to formation of π−π interactions between the large, planar BODIPY units of the BB2 ligand the glassy carbon surface.…”

Section: Resultsmentioning

confidence: 99%

Reduction of CO2 using a rhenium bipyridine complex containing ancillary BODIPY moieties

et al. 2014

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The reduction of carbon dioxide to chemical fuels such as carbon monoxide is an important challenge in the field of renewable energy conversion. Given the thermodynamic stability of carbon dioxide, it is difficult to efficiently activate this substrate in a selective fashion and the development of new electrocatalysts for CO2 reduction is of prime importance. To this end, we have prepared and studied a new fac-ReI(CO)3 complex supported by a bipyridine ligand containing ancillary BODIPY moieties ([Re(BB2)(CO)3Cl]). Voltammetry experiments revealed that this system displays a rich redox chemistry under N2, as [Re(BB2)(CO)3Cl] can be reduced by up to four electrons at modest potentials. These redox events have been characterized as the ReI/0 couple, and three ligand based reductions – two of which are localized on the BODIPY units. The ability of the BB2 ligand to serve as a non-innocent redox reservoir is manifest in an enhanced electrocatalysis with CO2 as compared to an unsubstituted Re-bipyridine complex lacking BODIPY units ([Re(bpy)(CO)3Cl]). The second order rate constant for reduction of CO2 by [Re(BB2)(CO)3Cl] was measured to be k = 3400 M−1s−1 at an applied potential of −2.0 V versus SCE, which is roughly three times greater than the corresponding unsubstituted Re-bipyridine homologue. Photophysical and photochemical studies were also carried out to determine if [Re(BB2)(CO)3Cl] was a competent platform for CO2 reduction using visible light. These experiments showed that this complex supports unusual excited state dynamics that precludes efficient CO2 reduction and are distinct from those that are typically observed for fac-ReI(CO)3 complexes.

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Section: Resultsmentioning

confidence: 99%

Reduction of CO2 using a rhenium bipyridine complex containing ancillary BODIPY moieties

et al. 2014

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“…In previous studies, several mechanisms were separately suggested by Lehn [26], Sullivan, Meyer [30] and Christensen [31] for the electroreduction of CO 2 by Re complexes. Also, Johnson et al investigated CO 2 electroreduction via some metal complexes by the IR spectroelectrochemical technique [32].…”

Section: Catalytic Activity Of the Complex As A Homogenous Catalystmentioning

confidence: 97%

Electrocatalytic reduction of CO2 using the dinuclear rhenium(I) complex [ReCl(CO)3(μ-tptzH)Re(CO)3]

et al. 2015

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“…Depending on the methodo fi mmobilization, the heterogenized molecular catalystc an be removed from the electrode surfacea nd reused, whichi sn ecessary for energy-converting applications. Covalent attachment, [22][23][24][25] electropolymerization, [26][27][28][29][30] and adsorption/noncovalent attachment of metal complexes [31][32][33][34][35] are methods of heterogenizing molecular catalysts for energy-conversion applications and were reviewed elsewhere. [36][37][38] …”

Section: Molecular Electrocatalysts For Energy Conversionmentioning

confidence: 99%

Electrocatalytic Metal–Organic Frameworks for Energy Applications

2017

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With the global energy demand expected to increase drastically over the next several decades, the development of a sustainable energy system to meet this increase is paramount. Renewable energy sources can be coupled with electrochemical conversion processes to store energy in chemical bonds. To promote these difficult transformations, electrocatalysts that operate at high conversion rates and efficiency are required. Metal–organic frameworks (MOFs) have emerged as a promising class of materials; however, the insulating nature of MOFs has limited their application as electrocatalysts. The recent development of conductive MOFs has led to several electrocatalytic MOFs that display activity comparable to that of the best‐performing heterogeneous catalysts. Although many electrocatalytic MOFs exhibit low activity and stability, the few successful examples highlight the possibility of MOF electrocatalysts as replacements for noble‐metal‐based catalysts in commercial energy‐converting devices. We review herein the use of pristine MOFs as electrocatalysts to facilitate important energy‐related reactions.

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Electrocatalytic reduction of CO2 by a complex of rhenium in thin polymeric films

Cited by 117 publications

References 22 publications

Reduction of CO2 using a rhenium bipyridine complex containing ancillary BODIPY moieties

Reduction of CO2 using a rhenium bipyridine complex containing ancillary BODIPY moieties

Electrocatalytic reduction of CO2 using the dinuclear rhenium(I) complex [ReCl(CO)3(μ-tptzH)Re(CO)3]

Electrocatalytic Metal–Organic Frameworks for Energy Applications

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