Photochemical reduction of carbon dioxide to formate mediated by ruthenium bipyridine complexes as homogeneous catalysts

Hawecker, Jeannot; Lehn, Jean-Maríe; Ziessel, Raymond

doi:10.1039/c39850000056

Cited by 140 publications

(90 citation statements)

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“…Meyer 6a,9a proposed an alternative mechanism for the formation of formic acid, based on earlier work by Hawecker et al 13 Conversion of CO 2 to hydrocarbons and oxygenates beyond formic acid and CO is seldom achieved. As the search for even more efficient light or electrochemically driven catalysts continues, another approach to increase CO 2 reduction efficiency is to vastly increase the reactant concentration.…”

Section: Amentioning

confidence: 99%

Photoreduction of CO₂ Using [Ru(bpy)₂(CO)L]ⁿ⁺ Catalysts in Biphasic Solution/Supercritical CO₂ Systems

et al. 2013

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The reduction of CO 2 in a biphasic liquid-condensed gas system was investigated as a function of the CO 2 pressure. Using 1-benzyl-1,4-dihydronicotinamide (BNAH) as sacrificial electron donor dissolved in a dimethylformamide−water mixture and [Ru(bpy) 2 (CO)L]n+ as a catalyst and [Ru(bpy) 3 ]2+ as a photosensitizer, the reaction was found to produce a mixture of CO and formate, in total about 250 μmol after just 2 h. As CO 2 pressure increases, CO formation is greatly favored, being four times greater than that of formate in aqueous systems. In contrast, formate production was independent of CO 2 pressure, present at about 50 μmol. Using TEOA as a solvent instead of water created a single-phase supercritical system and greatly favored formate synthesis, but similarly increasing CO 2 concentration favored the CO catalytic cycle. Under optimum conditions, a turnover number (TON) of 125 was obtained. Further investigations of the component limits led to an unprecedented TON of over 1000, and an initial turnover frequency (TOF) of 1600 h −1.

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Section: Amentioning

confidence: 99%

Photoreduction of CO₂ Using [Ru(bpy)₂(CO)L]ⁿ⁺ Catalysts in Biphasic Solution/Supercritical CO₂ Systems

et al. 2013

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“…In the second system based onfuc-[Re(bpy) (CO),Cl], high yields of CO were obtained [38]. In the third system, based on Ru complexes, catalytic amounts of formate were formed [39].…”

Section: *)mentioning

confidence: 99%

Photochemical and Electrochemical Reduction of Carbon Dioxide to Carbon Monoxide Mediated by (2,2′‐Bipyridine)tricarbonylchlororhenium(I) and Related Complexes as Homogeneous Catalysts

Hawecker¹,

Lehn²,

Ziessel³

1986

Helvetica Chimica Acta

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647

441

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Wac-Re(bpy) (CO),Cl] (bpy = 2,2'-bipyridine) is an efficient homogeneous catalyst for the selective and sustained photochemical or electrochemical reduction of CO, to CO. A quantum yield of 14% and a faradic efficiency of 98 % were measured in the presence of excess C1-ions.The photochemical process took place under visible-light irradiation and consumed a tertiary amine as electron donor. A formato-rhenium complex was isolated in the absence ofexcess CI-ions. Substitution by CI-ion generated free formate, but no CO was detected. Luminescence measurements showed that the tertiary amine quenches the metal-to-ligand charge-transfer excited state of the rhenium complex via a reductive mechanism, with a rate constant of 3.4 x lo7M-'S-'. The 19e-complex [Re(bpy) (CO),X]-produced either photochemically or electrochemically appears to be the active precursor in the CO-generation process. Detailed spectroscopic studies on I3C-enriched carbonyl-rhenium and formato-rhenium complexes derived from I3C-enriched C 0 2 were performed in order to confirm the origin of the products and to study the exchange of the ligands. A mechanism for the present C 0 2 photoreduction process is presented; it involves separate pathways for CO and formate generation, in which the [Re(bpy) (CO),X] complex plays the role of boih rhephotoactivr and fhe catalytic center.

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“…The re port methods using solar photoenergy can be divided into two categories. One is using semiconductors [7][8][9][10][11] and the other using metal complexes [12][13][14] as a photosensitizer. The latter has the advantage of using visible light, while the former is more advanta geous from viewpoint of energy transfer efficiency.…”

Section: Introductionmentioning

confidence: 99%

“…Reduction of carbon dioxide to formate was reported in the system using Ru(bpy)3 + as photosensitizer and triethanolamine as Reprint requests to Prof. Naoki Toshima. sacrificial reagent in a mixed solution of dimethylformamide and water [13].…”

Section: Introductionmentioning

confidence: 99%

Photosensitized Reduction of Carbon Dioxide in Solution Using Noble-Metal Clusters for Electron Transfer

Toshima

Yamaji

Teranishi

et al. 1995

Zeitschrift Für Naturforschung A

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Dedicated to Prof. Hitoshi Ohtaki on the occasion of his 60th birthday Carbon dioxide was reduced to methane by visible-light irradiation of a solution composed of tris(bipyridine)ruthenium(III) as photosensitizer, ethylenediaminetetraacetic acid disodium salt as sacrificial reagent, methyl viologen as electron relay, and a colloidal dispersion of polymer-protected noble-metal clusters, prepared by alcohol-reduction, as catalyst. Among the noble-metal clusters examined, Pt clusters showed the highest activity for the formation of methane as well as hydrogen. In order to improve the activity, oxidized clusters and bimetallic clusters were also applied. For example, the CH4 yield in 3-h irradiation increased from 51 x 10"3 |xmol with unoxidized Pt clusters to 72 x 10" 3 pmol with partially oxidized ones. In the case of Pt/Ru bimetalic systems, the improve ment of the catalytic activity by air treatment was much greater than in case of monometallic clusters.

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Photochemical reduction of carbon dioxide to formate mediated by ruthenium bipyridine complexes as homogeneous catalysts

Cited by 140 publications

References 3 publications

Photoreduction of CO₂ Using [Ru(bpy)₂(CO)L]ⁿ⁺ Catalysts in Biphasic Solution/Supercritical CO₂ Systems

Photoreduction of CO₂ Using [Ru(bpy)₂(CO)L]ⁿ⁺ Catalysts in Biphasic Solution/Supercritical CO₂ Systems

Photochemical and Electrochemical Reduction of Carbon Dioxide to Carbon Monoxide Mediated by (2,2′‐Bipyridine)tricarbonylchlororhenium(I) and Related Complexes as Homogeneous Catalysts

Photosensitized Reduction of Carbon Dioxide in Solution Using Noble-Metal Clusters for Electron Transfer

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Photochemical reduction of carbon dioxide to formate mediated by ruthenium bipyridine complexes as homogeneous catalysts

Cited by 140 publications

References 3 publications

Photoreduction of CO2 Using [Ru(bpy)2(CO)L]n+ Catalysts in Biphasic Solution/Supercritical CO2 Systems

Photoreduction of CO2 Using [Ru(bpy)2(CO)L]n+ Catalysts in Biphasic Solution/Supercritical CO2 Systems

Photochemical and Electrochemical Reduction of Carbon Dioxide to Carbon Monoxide Mediated by (2,2′‐Bipyridine)tricarbonylchlororhenium(I) and Related Complexes as Homogeneous Catalysts

Photosensitized Reduction of Carbon Dioxide in Solution Using Noble-Metal Clusters for Electron Transfer

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Photoreduction of CO₂ Using [Ru(bpy)₂(CO)L]ⁿ⁺ Catalysts in Biphasic Solution/Supercritical CO₂ Systems

Photoreduction of CO₂ Using [Ru(bpy)₂(CO)L]ⁿ⁺ Catalysts in Biphasic Solution/Supercritical CO₂ Systems