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

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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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mNo edit summary
(added corrected molecule)
Line 151: Line 151:
M  V30 END CTAB
M  V30 END CTAB
M  END
M  END
</chemform><chemform smiles="C1C=CN2~[Ru](~C#O)(~O([H])[H])3(~N4C=CC=CC=4C4N~3=CC=CC=4)~N3C=CC=CC=3C=2C=1" inchi="1S/2C10H8N2.CHO.H2O.Ru/c2*1-3-7-11-9(5-1)10-6-2-4-8-12-10;1-2;;/h2*1-8H;1H;1H2;" inchikey="FMDXTMDWVPGKIR-UHFFFAOYSA-N" height="200px" width="300px" float="none">
</chemform><chemform smiles="C1C=CN2[Ru+2]([C-]#[O+])(O([H])[H])(N3=CC=CC=C3C=2C=1)1N2C=CC=CC=2C2C=CC=CN=21.F[P-](F)(F)(F)(F)F.F[P-](F)(F)(F)(F)F" inchi="1S/2C10H8N2.CO.2F6P.H2O.Ru/c2*1-3-7-11-9(5-1)10-6-2-4-8-12-10;1-2;2*1-7(2,3,4,5)6;;/h2*1-8H;;;;1H2;/q;;;2*-1;;+2" inchikey="CPFZZAZNEQBLAC-UHFFFAOYSA-N" height="200px" width="300px" float="none">
   -INDIGO-12122214222D
   -INDIGO-08012316222D


   0  0  0  0  0  0  0  0  0  0  0 V3000
   0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 BEGIN CTAB
M  V30 COUNTS 30 35 0 0 0
M  V30 COUNTS 44 47 0 0 0
M  V30 BEGIN ATOM
M  V30 BEGIN ATOM
M  V30 1 C 4.88353 -4.01367 0.0 0
M  V30 1 C 3.00985 -3.67507 0.0 0
M  V30 2 C 6.49467 -4.14508 0.0 0
M  V30 2 C 4.74015 -3.67459 0.0 0
M  V30 3 C 5.65227 -3.62021 0.0 0
M  V30 3 C 3.87664 -3.17497 0.0 0
M  V30 4 N 6.59022 -5.14567 0.0 0
M  V30 4 N 4.74015 -4.67553 0.0 0
M  V30 5 C 4.85996 -4.97527 0.0 0
M  V30 5 C 3.00985 -4.68002 0.0 0
M  V30 6 C 5.77142 -5.58913 0.0 0
M  V30 6 C 3.87882 -5.17503 0.0 0
M  V30 7 C 7.02354 -2.8684 0.0 0
M  V30 7 C 5.60641 -3.17499 0.0 0
M  V30 8 C 8.59272 -2.82698 0.0 0
M  V30 8 C 6.47083 -1.67609 0.0 0
M  V30 9 C 7.73189 -2.39265 0.0 0
M  V30 9 C 5.60649 -2.17428 0.0 0
M  V30 10 C 8.69857 -3.84084 0.0 0
M  V30 10 C 7.33778 -2.17638 0.0 0
M  V30 11 C 7.09288 -3.79375 0.0 0
M  V30 11 N 6.47682 -3.67729 0.0 0
M  V30 12 N 8.03247 -4.33342 0.0 0
M  V30 12 C 7.3399 -3.17207 0.0 0
M  V30 13 C 7.38633 -7.34736 0.0 0
M  V30 13 C 3.03485 -6.65007 0.0 0
M  V30 14 C 5.9367 -7.55656 0.0 0
M  V30 14 N 4.76515 -6.64959 0.0 0
M  V30 15 C 6.74404 -7.90844 0.0 0
M  V30 15 C 3.90164 -6.14997 0.0 0
M  V30 16 C 5.83442 -6.56452 0.0 0
M  V30 16 C 4.76515 -7.65053 0.0 0
M  V30 17 N 7.19184 -6.19665 0.0 0
M  V30 17 C 3.03485 -7.65502 0.0 0
M  V30 18 C 6.56743 -5.9679 0.0 0
M  V30 18 C 3.90382 -8.15003 0.0 0
M  V30 19 C 8.07224 -7.64104 0.0 0
M  V30 19 C 5.63166 -8.1497 0.0 0
M  V30 20 C 9.73101 -7.40193 0.0 0
M  V30 20 C 7.36196 -8.14639 0.0 0
M  V30 21 N 8.69266 -7.00028 0.0 0
M  V30 21 N 6.49763 -7.64818 0.0 0
M  V30 22 C 9.81611 -8.45063 0.0 0
M  V30 22 C 7.36359 -9.14733 0.0 0
M  V30 23 C 8.18872 -8.58778 0.0 0
M  V30 23 C 5.6333 -9.15464 0.0 0
M  V30 24 C 9.00146 -8.99698 0.0 0
M  V30 24 C 6.50308 -9.64824 0.0 0
M  V30 25 Ru 7.94968 -5.63386 0.0 0
M  V30 25 Ru 6.48118 -5.65053 0.0 0 CHG=2
M  V30 26 O 9.14992 -5.06621 0.0 0
M  V30 26 O 7.4971 -4.94171 0.0 0
M  V30 27 C 8.91539 -6.04352 0.0 0
M  V30 27 C 7.4972 -6.22553 0.0 0 CHG=-1
M  V30 28 O 9.8811 -6.45318 0.0 0
M  V30 28 O 8.36323 -6.72553 0.0 0 CHG=1
M  V30 29 H 9.37348 -4.08653 0.0 0
M  V30 29 H 8.42404 -5.425 0.0 0
M  V30 30 H 9.92585 -5.60144 0.0 0
M  V30 30 H 7.55801 -3.925 0.0 0
M  V30 31 F 10.517 -3.85 0.0 0
M  V30 32 P 11.383 -3.35 0.0 0 CHG=-1
M  V30 33 F 12.249 -3.85 0.0 0
M  V30 34 F 11.383 -2.35 0.0 0
M  V30 35 F 10.517 -2.85 0.0 0
M  V30 36 F 12.249 -2.85 0.0 0
M  V30 37 F 11.383 -4.35 0.0 0
M  V30 38 F 11.209 -6.95 0.0 0
M  V30 39 P 12.075 -6.45 0.0 0 CHG=-1
M  V30 40 F 12.941 -6.95 0.0 0
M  V30 41 F 12.075 -5.45 0.0 0
M  V30 42 F 11.209 -5.95 0.0 0
M  V30 43 F 12.941 -5.95 0.0 0
M  V30 44 F 12.075 -7.45 0.0 0
M  V30 END ATOM
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 BEGIN BOND
Line 196: Line 210:
M  V30 5 2 5 6
M  V30 5 2 5 6
M  V30 6 1 6 4
M  V30 6 1 6 4
M  V30 7 2 9 7
M  V30 7 1 2 7
M  V30 8 2 10 8
M  V30 8 2 9 7
M  V30 9 1 7 11
M  V30 9 2 10 8
M  V30 10 1 8 9
M  V30 10 1 7 11
M  V30 11 2 11 12
M  V30 11 1 8 9
M  V30 12 1 12 10
M  V30 12 2 11 12
M  V30 13 2 15 13
M  V30 13 1 12 10
M  V30 14 2 16 14
M  V30 14 2 15 13
M  V30 15 1 13 17
M  V30 15 2 16 14
M  V30 16 1 14 15
M  V30 16 1 13 17
M  V30 17 2 17 18
M  V30 17 1 14 15
M  V30 18 1 18 16
M  V30 18 2 17 18
M  V30 19 2 21 19
M  V30 19 1 18 16
M  V30 20 2 22 20
M  V30 20 1 16 19
M  V30 21 1 19 23
M  V30 21 2 21 19
M  V30 22 1 20 21
M  V30 22 2 22 20
M  V30 23 2 23 24
M  V30 23 1 19 23
M  V30 24 1 24 22
M  V30 24 1 20 21
M  V30 25 1 13 19
M  V30 25 2 23 24
M  V30 26 1 2 11
M  V30 26 1 24 22
M  V30 27 8 4 25
M  V30 27 10 4 25
M  V30 28 8 12 25
M  V30 28 10 25 14
M  V30 29 8 17 25
M  V30 29 10 25 21
M  V30 30 8 21 25
M  V30 30 10 25 11
M  V30 31 8 25 26
M  V30 31 10 25 26
M  V30 32 8 25 27
M  V30 32 10 25 27
M  V30 33 3 27 28
M  V30 33 3 27 28
M  V30 34 1 26 29
M  V30 34 1 26 30
M  V30 35 1 26 30
M  V30 35 1 26 29
M  V30 36 1 31 32
M  V30 37 1 32 33
M  V30 38 1 32 34
M  V30 39 1 32 35
M  V30 40 1 32 36
M  V30 41 1 32 37
M  V30 42 1 38 39
M  V30 43 1 39 40
M  V30 44 1 39 41
M  V30 45 1 39 42
M  V30 46 1 39 43
M  V30 47 1 39 44
M  V30 END BOND
M  V30 END BOND
M  V30 END CTAB
M  V30 END CTAB

Revision as of 15:23, 1 August 2023


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Catalysts

Ru(bpy)2CO3 [Ru(bpy)(H2O)(CO)][PF6]

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