Photochemical Reduction of Carbon Dioxide to Formic Acid using Ruthenium(II)-Based Catalysts and Visible Light

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publication
About
DOI 10.1002/cctc.201500494
Authors Alonso Rosas-Hernández, Henrik Junge, Matthias Beller,
Submitted 26.08.2015
Published online 26.08.2015
Licenses http://doi.wiley.com/10.1002/tdm_license_1.1,
Subjects Inorganic Chemistry, Organic Chemistry, Physical and Theoretical Chemistry, Catalysis
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Catalysts

Ru(bpy)2CO3

Photosensitizer

Sacrificial electron donor

TEOA

Investigations

catcat conc [µM]PSPS conc [mM]e-Dsolvent A.λexc [nm]TON COTON H2TON HCOOH.
1.

Ru(bpy)2Cl2

0.025

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7001213
2.

Ru(bpy)2CO3

0.025

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7002421
3.

[Ru(bpy)2ClCO][PF6]

0.025

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 70013862
4.

[Ru(bpy)2HCO][PF6]

0.025

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7008834
5.

[Ru(bpy)(H2O)(CO)][PF6]

0.025

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7007940
6.

[Ru(bpy)(AcMe)2][PF6]

0.025

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7003427
Investigation-Name: Table 1
catcat conc [µM]PSPS conc [mM]e-Dsolvent A.λexc [nm]TON COTON H2TON HCOOH.
1.

Ru(bpy)2Cl2

0.0062

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7003926
2.

Ru(bpy)2CO3

0.0062

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 70031139
3.

[Ru(bpy)2ClCO][PF6]

0.0062

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7001919117
4.

[Ru(bpy)2HCO][PF6]

0.0062

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7002116107
5.

[Ru(bpy)(H2O)(CO)][PF6]

0.0062

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 700211475
6.

[Ru(bpy)(AcMe)2][PF6]

0.0062

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 70041264
7.

[Ru(bpy)2ClCO][PF6]

0.0031

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7003633296
8.

[Ru(bpy)2HCO][PF6]

0.0031

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7001629145
9.

[Ru(bpy)(H2O)(CO)][PF6]

0.0031

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7003428211
10.

[Ru(bpy)2ClCO][PF6]

0.0016

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7004067419
11.

[Ru(bpy)2HCO][PF6]

0.0016

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7002562225
12.

[Ru(bpy)(H2O)(CO)][PF6]

0.0016

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 7004565335
13.

[Ru(bpy)(AcMe)2][PF6]

0.0016

[Ir(ppy)2(bpy)][PF6]

0.025

TEOA

NMP

400 - 70044475
Investigation-Name: Table 2
analytereduction potentialsolventelectrolyte..WE..RE.
1.

Ru(bpy)2Cl2

0,-2.11

MeCN

TBABF4

glassy carbonAg/AgNO3 in MeCN
2.

Ru(bpy)2CO3

0.45,-1.97

MeCN

TBABF4

glassy carbonAg/AgNO3 in MeCN
3.

[Ru(bpy)2ClCO][PF6]

1.22,-1.75

MeCN

TBABF4

glassy carbonAg/AgNO3 in MeCN
4.

[Ru(bpy)2HCO][PF6]

1.20,-1.61

MeCN

TBABF4

glassy carbonAg/AgNO3 in MeCN
Investigation-Name: Table 3 - CV

Investigations