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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Line 365: Line 365:
</chemform>
</chemform>
=== Photosensitizer ===
=== Photosensitizer ===
<chemform smiles="C1C2C3C=CC=CC=3~[Ir]3(~C4C=CC=CC=4C4C=CC=CN=4~3)3(~N4=C(C5N~3=CC=CC=5)C=CC=C4)~N=2C=CC=1.P(F)(F)(F)(F)(F)F" inchi="1S/2C11H9N.C10H8N2.F6P.Ir/c2*1-2-6-10(7-3-1)11-8-4-5-9-12-11;1-3-7-11-9(5-1)10-6-2-4-8-12-10;1-7(2,3,4,5)6;/h2*1-9H;1-8H;;" inchikey="YLYRMTZQAOANTD-UHFFFAOYSA-N" height="200px" width="300px" float="none">
<chemform smiles="C1C=C[C-]2[Ir+3]3([C-]4C=CC=CC=4C4C=CC=CN=43)3(N4=CC=CC=C4C4C=CC=CN=43)N3=CC=CC=C3C=2C=1.[P-](F)(F)(F)(F)(F)F" inchi="1S/2C11H8N.C10H8N2.F6P.Ir/c2*1-2-6-10(7-3-1)11-8-4-5-9-12-11;1-3-7-11-9(5-1)10-6-2-4-8-12-10;1-7(2,3,4,5)6;/h2*1-6,8-9H;1-8H;;/q2*-1;;-1;+3" inchikey="RJJGJTKSOSSNNL-UHFFFAOYSA-N" height="200px" width="300px" float="none">
  -INDIGO-12122214422D
 
  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 44 51 0 0 0
M  V30 BEGIN ATOM
M  V30 1 C 6.86521 -4.85135 0.0 0
M  V30 2 C 8.41771 -4.69374 0.0 0
M  V30 3 C 7.49611 -4.29588 0.0 0
M  V30 4 C 8.59253 -5.83511 0.0 0
M  V30 5 C 7.08033 -5.78282 0.0 0
M  V30 6 N 8.11488 -6.23567 0.0 0
M  V30 7 C 4.87789 -6.03109 0.0 0
M  V30 8 C 6.55161 -6.17412 0.0 0
M  V30 9 C 5.65652 -5.63903 0.0 0
M  V30 10 C 6.70386 -7.1489 0.0 0
M  V30 11 C 4.86086 -7.04446 0.0 0
M  V30 12 C 5.78608 -7.65601 0.0 0
M  V30 13 C 8.0594 -9.2927 0.0 0
M  V30 14 C 9.54214 -8.78128 0.0 0
M  V30 15 N 8.79341 -8.63647 0.0 0
M  V30 16 C 9.81309 -9.84419 0.0 0
M  V30 17 C 8.29341 -10.2043 0.0 0
M  V30 18 C 9.12893 -10.5036 0.0 0
M  V30 19 C 9.10181 -5.24617 0.0 0
M  V30 20 C 10.8976 -5.28114 0.0 0
M  V30 21 C 10.0549 -4.75542 0.0 0
M  V30 22 C 10.8699 -6.15407 0.0 0
M  V30 23 N 9.1085 -6.4053 0.0 0
M  V30 24 C 10.0024 -6.72701 0.0 0
M  V30 25 C 10.2008 -7.25568 0.0 0
M  V30 26 C 11.7569 -8.07717 0.0 0
M  V30 27 C 11.2664 -7.30936 0.0 0
M  V30 28 C 11.2618 -8.93626 0.0 0
M  V30 29 N 9.55862 -7.95889 0.0 0
M  V30 30 C 10.1287 -8.92474 0.0 0
M  V30 31 Ir 8.17869 -7.44217 0.0 0
M  V30 32 C 5.79321 -8.64181 0.0 0
M  V30 33 C 7.16286 -8.04741 0.0 0
M  V30 34 C 6.53603 -7.81358 0.0 0
M  V30 35 C 7.38389 -9.10258 0.0 0
M  V30 36 C 6.06915 -9.51366 0.0 0
M  V30 37 C 6.79378 -9.63661 0.0 0
M  V30 38 P 14.3 -3.6 0.0 0
M  V30 39 F 14.3 -2.6 0.0 0
M  V30 40 F 15.3 -3.6 0.0 0
M  V30 41 F 13.3 -3.6 0.0 0
M  V30 42 F 14.3 -4.6 0.0 0
M  V30 43 F 15.0071 -4.30711 0.0 0
M  V30 44 F 13.5929 -2.89289 0.0 0
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 2 3 1
M  V30 2 2 4 2
M  V30 3 1 1 5
M  V30 4 1 2 3
M  V30 5 2 5 6
M  V30 6 1 6 4
M  V30 7 2 9 7
M  V30 8 2 10 8
M  V30 9 1 7 11
M  V30 10 1 8 9
M  V30 11 2 11 12
M  V30 12 1 12 10
M  V30 13 2 15 13
M  V30 14 2 16 14
M  V30 15 1 13 17
M  V30 16 1 14 15
M  V30 17 2 17 18
M  V30 18 1 18 16
M  V30 19 2 21 19
M  V30 20 2 22 20
M  V30 21 1 19 23
M  V30 22 1 20 21
M  V30 23 2 23 24
M  V30 24 1 24 22
M  V30 25 2 27 25
M  V30 26 2 28 26
M  V30 27 1 25 29
M  V30 28 1 26 27
M  V30 29 2 29 30
M  V30 30 1 30 28
M  V30 31 1 8 5
M  V30 32 1 24 25
M  V30 33 8 6 31
M  V30 34 8 10 31
M  V30 35 8 15 31
M  V30 36 8 31 29
M  V30 37 8 23 31
M  V30 38 2 34 32
M  V30 39 2 35 33
M  V30 40 1 32 36
M  V30 41 1 33 34
M  V30 42 2 36 37
M  V30 43 1 37 35
M  V30 44 1 35 13
M  V30 45 8 33 31
M  V30 46 1 38 39
M  V30 47 1 38 40
M  V30 48 1 38 41
M  V30 49 1 38 42
M  V30 50 1 38 43
M  V30 51 1 38 44
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform><chemform smiles="C1C=C[C-]2[Ir+3]3([C-]4C=CC=CC=4C4C=CC=CN=43)3(N4=CC=CC=C4C4C=CC=CN=43)N3=CC=CC=C3C=2C=1.[P-](F)(F)(F)(F)(F)F" inchi="1S/2C11H8N.C10H8N2.F6P.Ir/c2*1-2-6-10(7-3-1)11-8-4-5-9-12-11;1-3-7-11-9(5-1)10-6-2-4-8-12-10;1-7(2,3,4,5)6;/h2*1-6,8-9H;1-8H;;/q2*-1;;-1;+3" inchikey="RJJGJTKSOSSNNL-UHFFFAOYSA-N" height="200px" width="300px" float="none">
   -INDIGO-08012317142D
   -INDIGO-08012317142D



Revision as of 16:19, 1 August 2023


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Catalysts

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

Photosensitizer

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

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
Experiment-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
Experiment-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
Experiment-Name: Table 3 - CV

Investigations