Molecular Catalysis of the Electrochemical and Photochemical Reduction of CO2 with Earth-Abundant Metal Complexes. Selective Production of CO vs HCOOH by Switching of the Metal Center: Difference between revisions

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DOI 10.1021/jacs.5b06535
Authors Lingjing Chen, Zhenguo Guo, Xi-Guang Wei, Charlotte Gallenkamp, Julien Bonin, Elodie Anxolabéhère-Mallart, Kai-Chung Lau, Tai-Chu Lau, Marc Robert,
Submitted 12.08.2015
Published online 19.08.2015
Licenses -
Subjects Colloid and Surface Chemistry, Biochemistry, General Chemistry, Catalysis
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{{#doiinfobox: 10.1021/jacs.5b06535}}
{{DOI|doi=10.1021/jacs.5b06535}}
[[Category:Photocatalytic CO2 conversion to HCOOH]]
[[Category:Photocatalytic CO2 conversion to HCOOH]]
{{BaseTemplate}}{{MissingInvestigation}}
{{BaseTemplate}}
===Abstract===
==== Summary====
A photochemical reduction of CO<sub>2</sub> to CO or formic acid was shown using the iron complex {{#moleculelink:|link=XTLBRFNUSVMBAM-DQIPMIPLSA-K|image=false|width=300|height=200}} or the cobalt complex {{#moleculelink:|link=UEQRGEGBADTDNK-YBRXSBAKSA-L|image=false|width=300|height=200}} as catalysts in combination with the iridium-based photosensitizer {{#moleculelink:|link=NSABRUJKERBGOU-UHFFFAOYSA-N|image=false|width=300|height=200}}. Turnover numbers (TONs) of 270 for CO with the cobalt complex and 5 for formic acid with the iron complex were reached in acetonitrile. The experiments were conducted under visible-light irradiation (λ > 460 nm) using TEA as sacrificial electron donor (see section SEDs below).
====Advances and special progress====
The authors could demonstrate that switching the metal center has a major influence on the outcome of CO<sub>2</sub> reduction, enabling the generation of either CO or formic acid depending on the employed metal. For the cobalt complex, CO<sub>2</sub> reduction was possible both under electrochemical conditions and photochemically with a photosensitizer under visible light.


==== Investigation ====
====Additional remarks====
In electrocatalytic experiments with the cobalt catalyst {{#moleculelink:|link=UEQRGEGBADTDNK-YBRXSBAKSA-L|image=false|width=300|height=200}} and E = -1.5 V vs SCE, CO formation with high faradaic yields of 82% was possible.


==== Catalyst ====
===Content of the published article in detail===
The article contains results for the reduction of CO<sub>2</sub> to CO and formic acid under visible-light catalysis using iron or cobalt complexes as catalysts. The catalytic system performs best (referring to the TON of CO production) in acetonitrile with the cobalt catalyst.
====Catalyst====
<chemform smiles="C1C2C(C)=N3[Fe+3]([Cl-])([Cl-])456N(CCN4CCN5CC3)=C(C)C(N=26)=CC=1.Cl([O-])(=O)(=O)=O" inchi="1S/C15H23N5.ClHO4.2ClH.Fe/c1-12-14-4-3-5-15(20-14)13(2)19-11-9-17-7-6-16-8-10-18-12;2-1(3,4)5;;;/h3-5,16-17H,6-11H2,1-2H3;(H,2,3,4,5);2*1H;/q;;;;+3/p-3/b18-12+,19-13+;;;;" inchikey="XTLBRFNUSVMBAM-DQIPMIPLSA-K" height="200px" width="300px" float="none">
<chemform smiles="C1C2C(C)=N3[Fe+3]([Cl-])([Cl-])456N(CCN4CCN5CC3)=C(C)C(N=26)=CC=1.Cl([O-])(=O)(=O)=O" inchi="1S/C15H23N5.ClHO4.2ClH.Fe/c1-12-14-4-3-5-15(20-14)13(2)19-11-9-17-7-6-16-8-10-18-12;2-1(3,4)5;;;/h3-5,16-17H,6-11H2,1-2H3;(H,2,3,4,5);2*1H;/q;;;;+3/p-3/b18-12+,19-13+;;;;" inchikey="XTLBRFNUSVMBAM-DQIPMIPLSA-K" height="200px" width="300px" float="none">
   -INDIGO-05172314152D
   -INDIGO-05172314152D
Line 78: Line 86:
M  V30 END CTAB
M  V30 END CTAB
M  END
M  END
</chemform>
</chemform><chemform smiles="C1C2C(C)=N3[Co+2]456N(CCN4CCN5=C(C)C(N=26)=CC=1)CC3.Cl([O-])(=O)(=O)=O.Cl(=O)(=O)(=O)[O-]" inchi="1S/C15H23N5.2ClHO4.Co/c1-12-14-4-3-5-15(20-14)13(2)19-11-9-17-7-6-16-8-10-18-12;2*2-1(3,4)5;/h3-5,16-17H,6-11H2,1-2H3;2*(H,2,3,4,5);/q;;;+2/p-2/b18-12+,19-13+;;;" inchikey="UEQRGEGBADTDNK-YBRXSBAKSA-L" height="200px" width="300px" float="none">
 
   -INDIGO-05192309532D
==== Photosensitizer ====
<chemform smiles="C1C=C2C3C=CC=CN=3[Ir]3(C4=CC=CC=C4C4=CC=CC=N43)3(C4=CC=CC=C4C4N3=CC=CC=4)C2=CC=1" inchi="1S/3C11H9N.Ir/c3*1-2-6-10(7-3-1)11-8-4-5-9-12-11;/h3*1-9H;" inchikey="UEEXRMUCXBPYOV-UHFFFAOYSA-N" height="200px" width="300px" float="none">
   -INDIGO-05172314172D


   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 37 45 0 0 0
M  V30 COUNTS 31 34 0 0 0
M  V30 BEGIN ATOM
M  V30 BEGIN ATOM
M  V30 1 C 4.28485 -3.02507 0.0 0
M  V30 1 C 7.28485 -4.85007 0.0 0
M  V30 2 C 6.01515 -3.02459 0.0 0
M  V30 2 C 9.01515 -4.84959 0.0 0
M  V30 3 C 5.15164 -2.52497 0.0 0
M  V30 3 C 8.15164 -4.34997 0.0 0
M  V30 4 C 6.01515 -4.02553 0.0 0
M  V30 4 C 9.01515 -5.85053 0.0 0
M  V30 5 C 4.28485 -4.03002 0.0 0
M  V30 5 C 7.28485 -5.85502 0.0 0
M  V30 6 C 5.15382 -4.52503 0.0 0
M  V30 6 N 8.15382 -6.35003 0.0 0
M  V30 7 C 5.15382 -5.52503 0.0 0
M  V30 7 C 6.41882 -6.35502 0.0 0
M  V30 8 C 6.0204 -7.0227 0.0 0
M  V30 8 N 6.41882 -7.35502 0.0 0
M  V30 9 N 6.02066 -6.02506 0.0 0
M  V30 9 C 9.88118 -6.35053 0.0 0
M  V30 10 C 5.15389 -7.52375 0.0 0
M  V30 10 N 9.88118 -7.35053 0.0 0
M  V30 11 C 4.28385 -6.02809 0.0 0
M  V30 11 C 5.5528 -5.85502 0.0 0
M  V30 12 C 4.29031 -7.02814 0.0 0
M  V30 12 C 10.7472 -5.85053 0.0 0
M  V30 13 C 6.85985 -1.65007 0.0 0
M  V30 13 N 7.15 -8.625 0.0 0
M  V30 14 C 8.59015 -1.64959 0.0 0
M  V30 14 N 8.925 -8.625 0.0 0
M  V30 15 C 7.72664 -1.14997 0.0 0
M  V30 15 C 5.71172 -8.06213 0.0 0
M  V30 16 C 8.59015 -2.65053 0.0 0
M  V30 16 C 6.21172 -8.92815 0.0 0
M  V30 17 C 6.85985 -2.65502 0.0 0
M  V30 17 C 9.86602 -8.95 0.0 0
M  V30 18 N 7.72882 -3.15003 0.0 0
M  V30 18 C 10.3812 -8.21656 0.0 0
M  V30 19 C 9.45618 -3.15053 0.0 0
M  V30 19 C 7.40882 -9.59093 0.0 0
M  V30 20 C 11.1865 -3.14889 0.0 0
M  V30 20 C 8.66618 -9.59093 0.0 0
M  V30 21 C 10.3226 -2.64984 0.0 0
M  V30 21 Co 8.125 -7.45 0.0 0 CHG=2
M  V30 22 C 11.1871 -4.14983 0.0 0
M  V30 22 Cl 12.975 -3.075 0.0 0
M  V30 23 C 9.45685 -4.15548 0.0 0
M  V30 23 O 12.975 -4.075 0.0 0
M  V30 24 C 10.3262 -4.64991 0.0 0
M  V30 24 O 13.975 -3.075 0.0 0
M  V30 25 N 9.33485 -5.87507 0.0 0
M  V30 25 O 11.975 -3.075 0.0 0
M  V30 26 C 11.0652 -5.87459 0.0 0
M  V30 26 O 12.975 -2.075 0.0 0 CHG=-1
M  V30 27 C 10.2016 -5.37497 0.0 0
M  V30 27 Cl 13.925 -5.1 0.0 0
M  V30 28 C 11.0652 -6.87553 0.0 0
M  V30 28 O 13.925 -4.1 0.0 0 CHG=-1
M  V30 29 C 9.33485 -6.88002 0.0 0
M  V30 29 O 14.925 -5.1 0.0 0
M  V30 30 C 10.2038 -7.37503 0.0 0
M  V30 30 O 13.925 -6.1 0.0 0
M  V30 31 C 8.46882 -7.38002 0.0 0
M  V30 31 O 12.925 -5.1 0.0 0
M  V30 32 C 7.6051 -8.87933 0.0 0
M  V30 33 C 8.46921 -8.38073 0.0 0
M  V30 34 C 6.73792 -8.37944 0.0 0
M  V30 35 C 7.59818 -6.87813 0.0 0
M  V30 36 C 6.73534 -7.38375 0.0 0
M  V30 37 Ir 7.8 -4.975 0.0 0
M  V30 END ATOM
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 BEGIN BOND
Line 133: Line 132:
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 1 6 7
M  V30 7 1 5 7
M  V30 8 2 9 7
M  V30 8 2 7 8
M  V30 9 2 10 8
M  V30 9 1 4 9
M  V30 10 1 7 11
M  V30 10 2 9 10
M  V30 11 1 8 9
M  V30 11 1 7 11
M  V30 12 2 11 12
M  V30 12 1 9 12
M  V30 13 1 12 10
M  V30 13 1 8 15
M  V30 14 2 15 13
M  V30 14 1 15 16
M  V30 15 2 16 14
M  V30 15 1 16 13
M  V30 16 1 13 17
M  V30 16 1 14 17
M  V30 17 1 14 15
M  V30 17 1 10 18
M  V30 18 2 17 18
M  V30 18 1 17 18
M  V30 19 1 18 16
M  V30 19 1 13 19
M  V30 20 1 16 19
M  V30 20 1 14 20
M  V30 21 2 21 19
M  V30 21 1 20 19
M  V30 22 2 22 20
M  V30 22 10 6 21
M  V30 23 1 19 23
M  V30 23 10 8 21
M  V30 24 1 20 21
M  V30 24 10 10 21
M  V30 25 2 23 24
M  V30 25 10 14 21
M  V30 26 1 24 22
M  V30 26 10 13 21
M  V30 27 2 27 25
M  V30 27 2 22 23
M  V30 28 2 28 26
M  V30 28 2 22 24
M  V30 29 1 25 29
M  V30 29 2 22 25
M  V30 30 1 26 27
M  V30 30 1 22 26
M  V30 31 2 29 30
M  V30 31 1 27 28
M  V30 32 1 30 28
M  V30 32 2 27 29
M  V30 33 1 29 31
M  V30 33 2 27 30
M  V30 34 2 33 31
M  V30 34 2 27 31
M  V30 35 2 34 32
M  V30 36 1 31 35
M  V30 37 1 32 33
M  V30 38 2 35 36
M  V30 39 1 36 34
M  V30 40 10 4 37
M  V30 41 10 9 37
M  V30 42 10 18 37
M  V30 43 10 23 37
M  V30 44 10 25 37
M  V30 45 10 35 37
M  V30 END BOND
M  V30 END BOND
M  V30 END CTAB
M  V30 END CTAB
Line 177: Line 165:
</chemform>
</chemform>


==== Sacrificial electron donor ====
====Photosensitizer====
{{#moleculelink: |link=NSABRUJKERBGOU-UHFFFAOYSA-N|image=true}}
 
====Investigation====
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}}
====Sacrificial electron donor====
In this study, the experiments were done with the sacrificial electron donor TEA ([[Molecule:100505|100505]]).
====Additives====
In this study, no additives were tested.[[Category:Publication]]

Latest revision as of 09:57, 22 May 2024


Abstract[edit | edit source]

Summary[edit | edit source]

A photochemical reduction of CO2 to CO or formic acid was shown using the iron complex [Fe(pabop)Cl2][CLO4] or the cobalt complex [Co(pabop)][ClO4]2 as catalysts in combination with the iridium-based photosensitizer Ir(ppy)3. Turnover numbers (TONs) of 270 for CO with the cobalt complex and 5 for formic acid with the iron complex were reached in acetonitrile. The experiments were conducted under visible-light irradiation (λ > 460 nm) using TEA as sacrificial electron donor (see section SEDs below).

Advances and special progress[edit | edit source]

The authors could demonstrate that switching the metal center has a major influence on the outcome of CO2 reduction, enabling the generation of either CO or formic acid depending on the employed metal. For the cobalt complex, CO2 reduction was possible both under electrochemical conditions and photochemically with a photosensitizer under visible light.

Additional remarks[edit | edit source]

In electrocatalytic experiments with the cobalt catalyst [Co(pabop)][ClO4]2 and E = -1.5 V vs SCE, CO formation with high faradaic yields of 82% was possible.

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

The article contains results for the reduction of CO2 to CO and formic acid under visible-light catalysis using iron or cobalt complexes as catalysts. The catalytic system performs best (referring to the TON of CO production) in acetonitrile with the cobalt catalyst.

Catalyst[edit | edit source]

[Fe(pabop)Cl2][CLO4] [Co(pabop)][ClO4]2

Photosensitizer[edit | edit source]

Ir(ppy)3

Investigation[edit | edit source]

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

[Co(pabop)][ClO4]2

0.05

Ir(ppy)3

0.2

TEA

MeCN

>460270
2.

[Fe(pabop)Cl2][CLO4]

0.05

Ir(ppy)3

0.2

TEA

MeCN

>4205
Investigation-Name: Table 1

Sacrificial electron donor[edit | edit source]

In this study, the experiments were done with the sacrificial electron donor TEA (100505).

Additives[edit | edit source]

In this study, no additives were tested.

Investigations

  • Table 1 (Molecular process, Photocatalytic CO2 conversion experiments)
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