Highly Efficient and Selective Photocatalytic CO2 Reduction by Iron and Cobalt Quaterpyridine Complexes: Difference between revisions

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DOI 10.1021/jacs.6b06002
Authors Zhenguo Guo, Siwei Cheng, Claudio Cometto, Elodie Anxolabéhère-Mallart, Siu-Mui Ng, Chi-Chiu Ko, Guijian Liu, Lingjing Chen, Marc Robert, Tai-Chu Lau,
Submitted 22.07.2016
Published online 26.07.2016
Licenses -
Subjects Colloid and Surface Chemistry, Biochemistry, General Chemistry, Catalysis
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{{#doiinfobox: 10.1021/jacs.6b06002}}
{{DOI|doi=10.1021/jacs.6b06002}}  
[[Category:Photocatalytic CO2 conversion to CO]]
[[Category:Photocatalytic CO2 conversion to CO]]
{{BaseTemplate}}
{{BaseTemplate}}
===Abstract===
====Summary====
A photochemical reduction of CO<sub>2</sub> to CO was shown using the cobalt complex {{#moleculelink:|link=NLKWUAXOGCKGEY-UHFFFAOYSA-L|image=false|width=300|height=200}} or the iron complex {{#moleculelink:|link=OZQYFMFOIFRRLI-UHFFFAOYSA-L|image=false|width=300|height=200}} as catalysts in combination with the ruthenium-based photosensitizer {{#moleculelink:|link=SJFYGUKHUNLZTK-UHFFFAOYSA-L|image=false|width=300|height=200}}. Turnover numbers (TONs) up to 2660 and a selectivity of 98% for CO using the cobalt catalyst and TONs of >3000 and a selectivity of 95% for CO using the iron catalyst were reached in acetonitrile/triethanolamine. When swapping the ruthenium photosensitizer for the organic dye sensitizer {{#moleculelink:|link=BBNQQADTFFCFGB-UHFFFAOYSA-N|image=false|width=300|height=200}}, TONs of 790 and 1365 in DMF were obtained for the cobalt and iron catalysts, respectively. The experiments were conducted under visible-light irradiation (λ = 460 nm) using BIH as sacrificial reductant (see section SEDs below). 
==== Advances and special progress====
The photocatalytic reduction of CO<sub>2</sub> to CO by cobalt and iron complexes was shown with some of the highest TONs for homogeneous photocatalytic CO<sub>2</sub> reduction at that time and the (back then) highest TON for a system of fully earth-abundant materials was achieved.
====Additional remarks====
===Content of the published article in detail===
The article contains results for the reduction of CO<sub>2</sub> to CO under visible-light catalysis using cobalt and iron quaterpyridine complexes as catalysts. The catalytic system performs best (referring to the TON of CO production) in acetonitrile/triethanolamine using the cobalt complex {{#moleculelink:|link=OZQYFMFOIFRRLI-UHFFFAOYSA-L|image=false|width=300|height=200}} and the ruthenium photosensitizer.
==== Catalysts ====
<chemform smiles="C1C2C3C=CC=C4C5C=CC=C6C7C=CC=CN=7[Fe+2](O)(O)(N=34)(N=56)N=2C=CC=1.Cl([O-])(=O)(=O)=O.Cl([O-])(=O)(=O)=O" inchi="1S/C20H14N4.2ClHO4.Fe.2H2O/c1-3-13-21-15(7-1)17-9-5-11-19(23-17)20-12-6-10-18(24-20)16-8-2-4-14-22-16;2*2-1(3,4)5;;;/h1-14H;2*(H,2,3,4,5);;2*1H2/q;;;+2;;/p-2" inchikey="NLKWUAXOGCKGEY-UHFFFAOYSA-L" height="200px" width="300px" float="none">
  -INDIGO-08112312532D
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M  V30 2 C 8.56515 -2.97459 0.0 0
M  V30 3 C 7.70164 -2.47497 0.0 0
M  V30 4 C 8.56515 -3.97553 0.0 0
M  V30 5 C 6.83485 -3.98002 0.0 0
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M  V30 16 C 5.12026 -8.98303 0.0 0
M  V30 17 C 4.24559 -7.49007 0.0 0
M  V30 18 C 4.25515 -8.4901 0.0 0
M  V30 19 C 6.85288 -8.97643 0.0 0
M  V30 20 C 8.58317 -8.96906 0.0 0
M  V30 21 N 7.71768 -8.47288 0.0 0
M  V30 22 C 8.58715 -9.97 0.0 0
M  V30 23 C 6.85688 -9.98136 0.0 0
M  V30 24 C 7.72781 -10.4729 0.0 0
M  V30 25 Fe 7.72882 -6.42503 0.0 0 CHG=2
M  V30 26 O 9.04485 -5.57503 0.0 0
M  V30 27 O 9.11985 -7.27503 0.0 0
M  V30 28 Cl 11.8 -4.275 0.0 0
M  V30 29 O 10.8 -4.275 0.0 0
M  V30 30 O 11.8088 -3.28407 0.0 0
M  V30 31 O 12.8659 -4.28382 0.0 0
M  V30 32 O 11.8 -5.275 0.0 0 CHG=-1
M  V30 33 Cl 11.88 -7.54538 0.0 0
M  V30 34 O 10.8629 -7.54538 0.0 0
M  V30 35 O 11.889 -6.53745 0.0 0
M  V30 36 O 12.8621 -7.55478 0.0 0
M  V30 37 O 11.88 -8.56255 0.0 0 CHG=-1
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M  V30 29 10 25 21
M  V30 30 10 15 25
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M  V30 32 10 25 26
M  V30 33 10 25 27
M  V30 34 2 28 29
M  V30 35 2 28 30
M  V30 36 2 28 31
M  V30 37 1 28 32
M  V30 38 2 33 34
M  V30 39 2 33 35
M  V30 40 2 33 36
M  V30 41 1 33 37
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform><chemform smiles="C1C2C3C=CC=C4C5C=CC=C6C7C=CC=CN=7[Co+2](O)(O)(N=34)(N=56)N=2C=CC=1.Cl([O-])(=O)(=O)=O.Cl([O-])(=O)(=O)=O" inchi="1S/C20H14N4.2ClHO4.Co.2H2O/c1-3-13-21-15(7-1)17-9-5-11-19(23-17)20-12-6-10-18(24-20)16-8-2-4-14-22-16;2*2-1(3,4)5;;;/h1-14H;2*(H,2,3,4,5);;2*1H2/q;;;+2;;/p-2" inchikey="OZQYFMFOIFRRLI-UHFFFAOYSA-L" height="200px" width="300px" float="none">
  -INDIGO-08112312532D
  0  0  0  0  0  0  0  0  0  0  0 V3000
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M  V30 2 C 9.46221 25.0731 0.0 0
M  V30 3 C 8.6977 25.5155 0.0 0
M  V30 4 C 9.46221 24.187 0.0 0
M  V30 5 C 7.93029 24.183 0.0 0
M  V30 6 N 8.69963 23.7447 0.0 0
M  V30 7 C 7.16484 23.7381 0.0 0
M  V30 8 C 6.40399 22.4085 0.0 0
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M  V30 10 C 5.63495 22.8488 0.0 0
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M  V30 12 C 5.63011 23.7303 0.0 0
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M  V30 17 C 5.63789 21.0754 0.0 0
M  V30 18 C 5.64635 20.19 0.0 0
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M  V30 20 C 9.47817 19.7659 0.0 0
M  V30 21 N 8.7119 20.2052 0.0 0
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M  V30 23 C 7.94979 18.8697 0.0 0
M  V30 24 C 8.72087 18.4345 0.0 0
M  V30 25 Co 8.72177 22.0183 0.0 0 CHG=2
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M  V30 28 Cl 12.3262 23.9218 0.0 0
M  V30 29 O 11.4408 23.9218 0.0 0
M  V30 30 O 12.334 24.7992 0.0 0
M  V30 31 O 13.2699 23.914 0.0 0
M  V30 32 O 12.3262 23.0365 0.0 0 CHG=-1
M  V30 33 Cl 12.397 21.0264 0.0 0
M  V30 34 O 11.4965 21.0264 0.0 0
M  V30 35 O 12.405 21.9188 0.0 0
M  V30 36 O 13.2665 21.0181 0.0 0
M  V30 37 O 12.397 20.1258 0.0 0 CHG=-1
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M  V30 37 1 28 32
M  V30 38 2 33 34
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M  V30 40 2 33 36
M  V30 41 1 33 37
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform><chemform smiles="Cl([O-])(=O)(=O)=O.Cl([O-])(=O)(=O)=O.[Co+2]" inchi="1S/2ClHO4.Co/c2*2-1(3,4)5;/h2*(H,2,3,4,5);/q;;+2/p-2" inchikey="BSUSEPIPTZNHMN-UHFFFAOYSA-L" height="200px" width="300px" float="none">
  -INDIGO-08112313202D
  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 11 8 0 0 0
M  V30 BEGIN ATOM
M  V30 1 Cl 5.85991 -4.47939 0.0 0
M  V30 2 O 5.02832 -4.47939 0.0 0
M  V30 3 O 5.86723 -3.65532 0.0 0
M  V30 4 O 6.74625 -4.48672 0.0 0
M  V30 5 O 5.85991 -5.31088 0.0 0 CHG=-1
M  V30 6 Cl 10.3764 -4.54882 0.0 0
M  V30 7 O 9.53063 -4.54882 0.0 0
M  V30 8 O 10.3839 -3.71065 0.0 0
M  V30 9 O 11.1931 -4.55661 0.0 0
M  V30 10 O 10.3764 -5.39468 0.0 0 CHG=-1
M  V30 11 Co 7.8 -4.45 0.0 0 CHG=2
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 2 1 2
M  V30 2 2 1 3
M  V30 3 2 1 4
M  V30 4 1 1 5
M  V30 5 2 6 7
M  V30 6 2 6 8
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M  V30 END BOND
M  V30 END CTAB
M  END
</chemform>
==== Photosensitizers ====
<chemform smiles="C1C2C3C=CC=CN=3[Ru+2]3(N4C=CC=CC=4C4N3=CC=CC=4)3(N4C=CC=CC=4C4N3=CC=CC=4)N=2C=CC=1.[Cl-].[Cl-]" inchi="1S/3C10H8N2.2ClH.Ru/c3*1-3-7-11-9(5-1)10-6-2-4-8-12-10;;;/h3*1-8H;2*1H;/q;;;;;+2/p-2" inchikey="SJFYGUKHUNLZTK-UHFFFAOYSA-L" height="200px" width="300px" float="none">
  -INDIGO-08112312492D
  0  0  0  0  0  0  0  0  0  0  0 V3000
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M  V30 35 C 11.5203 -4.88241 0.0 0
M  V30 36 C 11.5101 -3.88239 0.0 0
M  V30 37 Ru 8.05382 -5.85003 0.0 0 CHG=2
M  V30 38 Cl 10.05 -2.325 0.0 0 CHG=-1
M  V30 39 Cl 3.975 -5.9 0.0 0 CHG=-1
M  V30 END ATOM
M  V30 BEGIN BOND
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M  V30 END BOND
M  V30 END CTAB
M  END
</chemform><chemform smiles="C1C=CC2C(=O)C3C(O)=CC(O)=C(O)C=3C(=O)C=2C=1" inchi="1S/C14H8O5/c15-8-5-9(16)14(19)11-10(8)12(17)6-3-1-2-4-7(6)13(11)18/h1-5,15-16,19H" inchikey="BBNQQADTFFCFGB-UHFFFAOYSA-N" height="200px" width="300px" float="none">
  -INDIGO-08112312542D
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M  V30 END CTAB
M  END
</chemform>
==== Investigations ====
{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Optimizations of conditions for Co(qpy)(H2O)2(ClO4)2 and Ru(bpy)3Cl2}}
{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Optimizations of conditions for Fe(qpy)(H2O)2(ClO4)2 and Ru(bpy)3Cl2}}
{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Optimizations of conditions for Co(qpy)(H2O)2(ClO4)2 and purpurin}}
{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Optimizations of conditions for Fe(qpy)(H2O)2(ClO4)2}}
==== Sacrificial electron donor ====
In this study, the experiments were done with the sacrificial reductant BIH ([[Molecule:100508|100508]]).
==== Additives====
In this study, control experiments were conducted under an argon atmosphere.[[Category:Publication]]

Latest revision as of 09:55, 22 May 2024


Abstract[edit | edit source]

Summary[edit | edit source]

A photochemical reduction of CO2 to CO was shown using the cobalt complex [Fe(qpy)(H2O)2][ClO4]2 or the iron complex [Co(qpy)(H2O)2][ClO4]2 as catalysts in combination with the ruthenium-based photosensitizer Ru(bpy)3Cl2. Turnover numbers (TONs) up to 2660 and a selectivity of 98% for CO using the cobalt catalyst and TONs of >3000 and a selectivity of 95% for CO using the iron catalyst were reached in acetonitrile/triethanolamine. When swapping the ruthenium photosensitizer for the organic dye sensitizer purpurin, TONs of 790 and 1365 in DMF were obtained for the cobalt and iron catalysts, respectively. The experiments were conducted under visible-light irradiation (λ = 460 nm) using BIH as sacrificial reductant (see section SEDs below).

Advances and special progress[edit | edit source]

The photocatalytic reduction of CO2 to CO by cobalt and iron complexes was shown with some of the highest TONs for homogeneous photocatalytic CO2 reduction at that time and the (back then) highest TON for a system of fully earth-abundant materials was achieved.

Additional remarks[edit | edit source]

Content of the published article in detail[edit | edit source]

The article contains results for the reduction of CO2 to CO under visible-light catalysis using cobalt and iron quaterpyridine complexes as catalysts. The catalytic system performs best (referring to the TON of CO production) in acetonitrile/triethanolamine using the cobalt complex [Co(qpy)(H2O)2][ClO4]2 and the ruthenium photosensitizer.

Catalysts[edit | edit source]

[Fe(qpy)(H2O)2][ClO4]2 [Co(qpy)(H2O)2][ClO4]2 Co(ClO4)2

Photosensitizers[edit | edit source]

Ru(bpy)3Cl2 purpurin

Investigations[edit | edit source]

catcat conc [µM]PSPS conc [mM]e-De-D conc [M]..solvent Aadditivesλexc [nm].TON COTON H2TON HCOOH.
1.

[Co(qpy)(H2O)2][ClO4]2

0.005

Ru(bpy)3Cl2

0.3

BIH

0.1

MeCN

460 (LED)26602335
2.

[Co(qpy)(H2O)2][ClO4]2

0

Ru(bpy)3Cl2

0.3

BIH

0.1

MeCN

460 (LED)021
3.

[Co(qpy)(H2O)2][ClO4]2

0.005

Ru(bpy)3Cl2

0.3

BIH

0.1

MeCN

Argon atmosphere460 (LED)0330
4.

[Co(qpy)(H2O)2][ClO4]2

0.005

Ru(bpy)3Cl2

0.3

BIH

0.1

MeCN

460 (LED)182011
5.

[Co(qpy)(H2O)2][ClO4]2

0.005

Ru(bpy)3Cl2

0.3


MeCN

460 (LED)1142525
6.

[Co(qpy)(H2O)2][ClO4]2

0.01

Ru(bpy)3Cl2

0.3

BIH

0.1

MeCN

460 (LED)18751118
7.

[Co(qpy)(H2O)2][ClO4]2

0.2

Ru(bpy)3Cl2

0.3

BIH

0.1

MeCN

460 (LED)1262723
8.

[Co(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.3

BIH

0.1

MeCN

460 (LED)49753
9.

[Co(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.3


MeCN

460 (LED)011
10.

[Co(qpy)(H2O)2][ClO4]2

0.1

Ru(bpy)3Cl2

0.3

BIH

0.1

MeCN

460 (LED)466222
11.

[Co(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.5

BIH

0.1

MeCN

460 (LED)521496
12.

[Co(qpy)(H2O)2][ClO4]2

0

Ru(bpy)3Cl2

0.5

BIH

0.1

MeCN

460 (LED)136435
13.

[Co(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.2

BIH

0.1

MeCN

460 (LED)366154
14.

[Co(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.2

BIH

0.1

MeCN

Argon atmosphere460 (LED)031
15.

[Co(qpy)(H2O)2][ClO4]2

0

Ru(bpy)3Cl2

0.2

BIH

0.1

MeCN

460 (LED)061
16.

Co(ClO4)2

0.05

Ru(bpy)3Cl2

0.3

BIH

0.1

MeCN

460 (LED)33111
17.

[Co(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.3


MeCN

460 (LED)011
catcat conc [µM]PSPS conc [mM]e-De-D conc [M]solvent A..additivesλexc [nm].TON COTON H2TON HCOOH.
1.

[Fe(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.2

BIH

0.1

MeCN

460 (LED)18791548
2.

[Fe(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.2

BIH

0.1

MeCN

Argon atmosphere460 (LED)013
3.

[Fe(qpy)(H2O)2][ClO4]2

0

Ru(bpy)3Cl2

0.2

BIH

0.1

MeCN

460 (LED)000
4.

[Fe(qpy)(H2O)2][ClO4]2

0.02

Ru(bpy)3Cl2

0.2

BIH

0.1

MeCN

460 (LED)26602951
5.

[Fe(qpy)(H2O)2][ClO4]2

0.02

Ru(bpy)3Cl2

0.2

BIH

0.1

MeCN

Argon atmosphere460 (LED)000
6.

[Fe(qpy)(H2O)2][ClO4]2

0.01

Ru(bpy)3Cl2

0.2

BIH

0.1

MeCN

460 (LED)308712135
7.

[Fe(qpy)(H2O)2][ClO4]2

0.01

Ru(bpy)3Cl2

0.2

BIH

0.1

MeCN

Argon atmosphere460 (LED)000
8.

[Fe(qpy)(H2O)2][ClO4]2

0.005

Ru(bpy)3Cl2

0.2

BIH

0.1

MeCN

460 (LED)3844118534
9.

[Fe(qpy)(H2O)2][ClO4]2

0.005

Ru(bpy)3Cl2

0.2

BIH

0.1

MeCN

Argon atmosphere460 (LED)010
10.

[Fe(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.05

BIH

0.1

MeCN

460 (LED)13361034
11.

[Fe(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.05

BIH

0.1

MeCN

460 (LED)000
12.

[Fe(qpy)(H2O)2][ClO4]2

0

Ru(bpy)3Cl2

0.05

BIH

0.1

MeCN

460 (LED)010
13.

[Fe(qpy)(H2O)2][ClO4]2

0.005

Ru(bpy)3Cl2

0.2


MeCN

460 (LED)160822
catcat conc [µM]PSPS conc [mM]e-De-D conc [M]solvent Aadditivesλexc [nm].TON COTON H2TON HCOOH.
1.

[Co(qpy)(H2O)2][ClO4]2

0.05

purpurin

2

BIH

0.1

DMF

460 (LED)19719
2.

[Co(qpy)(H2O)2][ClO4]2

0.05

purpurin

2

BIH

0.1

DMF

Argon atmosphere460 (LED)0786
3.

[Co(qpy)(H2O)2][ClO4]2

0

purpurin

2

BIH

0.1

DMF

460 (LED)0090
4.

[Co(qpy)(H2O)2][ClO4]2

0.05

purpurin

0

BIH

0.1

DMF

460 (LED)2704
5.

[Co(qpy)(H2O)2][ClO4]2

0.05

purpurin

2


DMF

460 (LED)003
6.

[Co(qpy)(H2O)2][ClO4]2

0.005

purpurin

2

BIH

0.1

DMF

460 (LED)7901178
7.

[Co(qpy)(H2O)2][ClO4]2

0.005

purpurin

2

BIH

0.1

DMF

Argon atmosphere460 (LED)0226167
8.

[Co(qpy)(H2O)2][ClO4]2

0.005

purpurin

2


DMF

Argon atmosphere460 (LED)0026
9.

Co(ClO4)2

0.05

purpurin

2

BIH

0.1

DMF

460 (LED)003
catcat conc [µM]PSPS conc [mM]e-De-D conc [M]solvent Aadditivesλexc [nm].TON COTON H2TON HCOOH.
1.

[Fe(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.02

BIH

0.1

DMF

460 (LED)520014
2.

[Fe(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.02

BIH

0.1

DMF

Argon atmosphere460 (LED)0321
3.

[Fe(qpy)(H2O)2][ClO4]2

0

Ru(bpy)3Cl2

0.02

BIH

0.1

DMF

460 (LED)01390
4.

[Fe(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.05

BIH

0.1

DMF

460 (LED)520021
5.

[Fe(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.05

BIH

0.1

DMF

Argon atmosphere460 (LED)008
6.

[Fe(qpy)(H2O)2][ClO4]2

0

Ru(bpy)3Cl2

0.05

BIH

0.1

DMF

460 (LED)0010
7.

[Fe(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.2

BIH

0.1

DMF

460 (LED)350123
8.

[Fe(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.2

BIH

0.1

DMF

Argon atmosphere460 (LED)05420
9.

[Fe(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0

BIH

0.1

DMF

460 (LED)0024
10.

[Fe(qpy)(H2O)2][ClO4]2

0.05

Ru(bpy)3Cl2

0.02

BIH

0.1

DMF

460 (LED)008
11.

[Fe(qpy)(H2O)2][ClO4]2

0.005

Ru(bpy)3Cl2

0.02

BIH

0.1

DMF

460 (LED)13650115
12.

[Fe(qpy)(H2O)2][ClO4]2

0.005

Ru(bpy)3Cl2

0.02

BIH

0.1

DMF

Argon atmosphere460 (LED)05288

Sacrificial electron donor[edit | edit source]

In this study, the experiments were done with the sacrificial reductant BIH (100508).

Additives[edit | edit source]

In this study, control experiments were conducted under an argon atmosphere.

Investigations