Photoreduction of CO2 using [Ru(bpy)(2)(CO)L](n+) catalysts in biphasic solution/supercritical CO2 systems

Chemistry

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https://doi.org/10.1021/ic401031j
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Keywords

CARBON-DIOXIDE REDUCTION, HIGH TURNOVER FREQUENCY, ELECTROCATALYTIC REDUCTION, ELECTROCHEMICAL REDUCTION, ARTIFICIAL PHOTOSYNTHESIS, PHOTOCATALYTIC REDUCTION, PHOTOCHEMICAL REDUCTION, HOMOGENEOUS CATALYSTS, SUPERCRITICAL CARBON-DIOXIDE, HIGH-PRESSURE

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Photoreduction of CO2 using [Ru(bpy)(2)(CO)L](n+) catalysts in biphasic solution/supercritical CO2 systems. / Voyame, Patrick; Toghill, Kathryn E.; Mendez, Manuel A. et al.
In: Inorganic Chemistry, Vol. 52, No. 19, 07.10.2013, p. 10949-10957.

Research output: Contribution to Journal/Magazine › Journal article › peer-review

Bibtex

@article{fe260dd3474d423eb685e29d7554da45,

title = "Photoreduction of CO2 using [Ru(bpy)(2)(CO)L](n+) catalysts in biphasic solution/supercritical CO2 systems",

abstract = "The reduction of CO2 in a biphasic liquid-condensed gas system was investigated as a function of the CO2 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 mu mol after just 2 h. As CO2 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 CO2 pressure, present at about 50 mu mol. Using TEOA as a solvent instead of water created a single-phase supercritical system and greatly favored formate synthesis, but similarly increasing CO2 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).",

keywords = "CARBON-DIOXIDE REDUCTION, HIGH TURNOVER FREQUENCY, ELECTROCATALYTIC REDUCTION, ELECTROCHEMICAL REDUCTION, ARTIFICIAL PHOTOSYNTHESIS, PHOTOCATALYTIC REDUCTION, PHOTOCHEMICAL REDUCTION, HOMOGENEOUS CATALYSTS, SUPERCRITICAL CARBON-DIOXIDE, HIGH-PRESSURE",

author = "Patrick Voyame and Toghill, {Kathryn E.} and Mendez, {Manuel A.} and Girault, {Hubert H.}",

year = "2013",

month = oct,

day = "7",

doi = "10.1021/ic401031j",

language = "English",

volume = "52",

pages = "10949--10957",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "19",

}

RIS

TY - JOUR

T1 - Photoreduction of CO2 using [Ru(bpy)(2)(CO)L](n+) catalysts in biphasic solution/supercritical CO2 systems

AU - Voyame, Patrick

AU - Toghill, Kathryn E.

AU - Mendez, Manuel A.

AU - Girault, Hubert H.

PY - 2013/10/7

Y1 - 2013/10/7

N2 - The reduction of CO2 in a biphasic liquid-condensed gas system was investigated as a function of the CO2 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 mu mol after just 2 h. As CO2 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 CO2 pressure, present at about 50 mu mol. Using TEOA as a solvent instead of water created a single-phase supercritical system and greatly favored formate synthesis, but similarly increasing CO2 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).

AB - The reduction of CO2 in a biphasic liquid-condensed gas system was investigated as a function of the CO2 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 mu mol after just 2 h. As CO2 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 CO2 pressure, present at about 50 mu mol. Using TEOA as a solvent instead of water created a single-phase supercritical system and greatly favored formate synthesis, but similarly increasing CO2 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).

KW - CARBON-DIOXIDE REDUCTION

KW - HIGH TURNOVER FREQUENCY

KW - ELECTROCATALYTIC REDUCTION

KW - ELECTROCHEMICAL REDUCTION

KW - ARTIFICIAL PHOTOSYNTHESIS

KW - PHOTOCATALYTIC REDUCTION

KW - PHOTOCHEMICAL REDUCTION

KW - HOMOGENEOUS CATALYSTS

KW - SUPERCRITICAL CARBON-DIOXIDE

KW - HIGH-PRESSURE

U2 - 10.1021/ic401031j

DO - 10.1021/ic401031j

M3 - Journal article

VL - 52

SP - 10949

EP - 10957

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 19

ER -

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