Selective and Efficient Photocatalytic CO2 Reduction to CO Using Visible Light and an Iron-Based Homogeneous Catalyst: Difference between revisions

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DOI 10.1021/ja510290t
Authors Julien Bonin, Marc Robert, Mathilde Routier,
Submitted 14.11.2014
Published online 20.11.2014
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===Abstract===
===Abstract===
====Summary====
====Summary====
The photochemical reduction of CO<sub>2</sub> to CO was shown using the iron complex {{#moleculelink:|link=JQYRTQVHCKLBTL-YQGGSDPOSA-M|image=false|width=300|height=200}} in combination with the photosensitizers xx or xx. Turnover numbers (TONs) of up to 140 and a selectivity of xx for CO were reached in acetonitrile after xx h of irradiation. The experiments were conducted under visible-light irradiation (λ > 400 nm) with TEA (see section SEDs below) as sacrificial electron donor.
The photochemical reduction of CO<sub>2</sub> to CO was shown using the iron complex {{#moleculelink:|link=JQYRTQVHCKLBTL-YQGGSDPOSA-M|image=false|width=300|height=200}} in combination with the photosensitizers {{#moleculelink:|link=NSABRUJKERBGOU-UHFFFAOYSA-N|image=false|width=300|height=200}} or {{#moleculelink:|link=KEQZHLAEKAVZLY-UHFFFAOYSA-N|image=false|width=300|height=200}}. Turnover numbers (TONs) of up to 140 and a selectivity of 93% for CO were reached in acetonitrile after 55 h of irradiation. The experiments were conducted under visible-light irradiation (λ > 400 nm) with TEA (see section SEDs below) as sacrificial electron donor.
====Advances and special progress====
====Advances and special progress====
The authors reported one of the highest TONs in homogeneous photocatalysis at that time in this study without detecting significant degradation of the catalyst or sensitizer. In addition, they reported the use of a cheap organic photosensitizer for CO<sub>2</sub> conversion with a slightly lower TON (60), but higher selectivity (100%).
====Additional remarks====
====Additional remarks====
===Content of the published article in detail===
===Content of the published article in detail===
The article contains results of a study for the reduction of CO<sub>2</sub> to CO using an iron complex and an iridium-based photosensitizer. The catalytic system performs best (referring to the TON of CO production) in acetonitrile with photosensitizer xx.
The article contains results of a study for the reduction of CO<sub>2</sub> to CO using an iron complex and an iridium-based or organic photosensitizer. The catalytic system performs best (referring to the TON of CO production) in acetonitrile with photosensitizer {{#moleculelink:|link=NSABRUJKERBGOU-UHFFFAOYSA-N|image=false|width=300|height=200}}.
====Catalyst====
====Catalyst====
<chemform smiles="C1C2C(C3C(O)=CC=CC=3O)=C3N4[Fe](Cl)56~N7C(=C(C8C(O)=CC=CC=8O)C8N5C(C(C5C(O)=CC=CC=5O)=C(N=2~6)C=1)=CC=8)C=CC=7C(=C4C=C3)C1C(O)=CC=CC=1O" inchi="1S/C44H28N4O8.ClH.Fe/c49-29-5-1-6-30(50)41(29)37-21-13-15-23(45-21)38(42-31(51)7-2-8-32(42)52)25-17-19-27(47-25)40(44-35(55)11-4-12-36(44)56)28-20-18-26(48-28)39(24-16-14-22(37)46-24)43-33(53)9-3-10-34(43)54;;/h1-20H,(H8-2,45,46,47,48,49,50,51,52,53,54,55,56);1H;/q-2;;+3/p-1/b37-21+,37-22+,38-23+,38-25+,39-24+,39-26+,40-27+,40-28+;;" inchikey="JQYRTQVHCKLBTL-YQGGSDPOSA-M" height="200px" width="300px" float="none">
<chemform smiles="C1C2C(C3C(O)=CC=CC=3O)=C3N4[Fe](Cl)56~N7C(=C(C8C(O)=CC=CC=8O)C8N5C(C(C5C(O)=CC=CC=5O)=C(N=2~6)C=1)=CC=8)C=CC=7C(=C4C=C3)C1C(O)=CC=CC=1O" inchi="1S/C44H28N4O8.ClH.Fe/c49-29-5-1-6-30(50)41(29)37-21-13-15-23(45-21)38(42-31(51)7-2-8-32(42)52)25-17-19-27(47-25)40(44-35(55)11-4-12-36(44)56)28-20-18-26(48-28)39(24-16-14-22(37)46-24)43-33(53)9-3-10-34(43)54;;/h1-20H,(H8-2,45,46,47,48,49,50,51,52,53,54,55,56);1H;/q-2;;+3/p-1/b37-21+,37-22+,38-23+,38-25+,39-24+,39-26+,40-27+,40-28+;;" inchikey="JQYRTQVHCKLBTL-YQGGSDPOSA-M" height="200px" width="300px" float="none">
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</chemform>
</chemform>
====Photosensitizer====
====Photosensitizer====
<chemform smiles="C1C=CN2~[Ir]3(~N4C(C5C3=CC=CC=5)=CC=CC=4)3(~N4C(C5C3=CC=CC=5)=CC=CC=4)C3=CC=CC=C3C=2C=1" inchi="1S/3C11H8N.Ir/c3*1-2-6-10(7-3-1)11-8-4-5-9-12-11;/h3*1-6,8-9H;" inchikey="QKBWDYLFYVXTGE-UHFFFAOYSA-N" height="200px" width="300px" float="none">
<chemform smiles="" inchi="" inchikey="NSABRUJKERBGOU-UHFFFAOYSA-N " height="200px" width="300px" float="none"></chemform><chemform smiles="C1C=CC2C=C3C=CC=CC3=C(C#N)C=2C=1" inchi="1S/C15H9N/c16-10-15-13-7-3-1-5-11(13)9-12-6-2-4-8-14(12)15/h1-9H" inchikey="KEQZHLAEKAVZLY-UHFFFAOYSA-N" height="200px" width="300px" float="none">
   -INDIGO-05102413182D
   -INDIGO-05102413272D


   0  0  0  0  0  0  0  0  0  0  0 V3000
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M  V30 BEGIN CTAB
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M  V30 COUNTS 16 18 0 0 0
M  V30 BEGIN ATOM
M  V30 BEGIN ATOM
M  V30 1 C 6.70037 -3.65079 0.0 0
M  V30 1 C 4.38485 -6.0 0.0 0
M  V30 2 C 7.56594 -5.14904 0.0 0
M  V30 2 C 6.11515 -5.99959 0.0 0
M  V30 3 C 7.56687 -4.1514 0.0 0
M  V30 3 C 5.25164 -5.49997 0.0 0
M  V30 4 N 6.6991 -5.64951 0.0 0
M  V30 4 C 6.11515 -7.00053 0.0 0
M  V30 5 C 5.83006 -4.15327 0.0 0
M  V30 5 C 4.38485 -7.00502 0.0 0
M  V30 6 C 5.83586 -5.15333 0.0 0
M  V30 6 C 5.25382 -7.50003 0.0 0
M  V30 7 C 8.43174 -5.64944 0.0 0
M  V30 7 C 6.97965 -5.50121 0.0 0
M  V30 8 C 10.162 -5.6478 0.0 0
M  V30 8 C 7.84683 -6.00155 0.0 0
M  V30 9 C 9.29819 -5.14875 0.0 0
M  V30 9 C 6.9858 -7.50287 0.0 0
M  V30 10 C 10.1627 -6.64874 0.0 0
M  V30 10 C 7.84903 -6.99746 0.0 0
M  V30 11 C 8.43241 -6.65439 0.0 0
M  V30 11 C 8.70588 -5.50378 0.0 0
M  V30 12 C 9.30171 -7.14882 0.0 0
M  V30 12 C 9.56981 -5.99969 0.0 0
M  V30 13 N 8.13485 -8.07507 0.0 0
M  V30 13 C 8.71641 -7.49535 0.0 0
M  V30 14 C 9.86515 -8.07459 0.0 0
M  V30 14 C 9.57419 -6.99059 0.0 0
M  V30 15 C 9.00164 -7.57497 0.0 0
M  V30 15 C 6.97982 -4.50121 0.0 0
M  V30 16 C 9.86515 -9.07553 0.0 0
M  V30 16 N 6.97982 -3.50121 0.0 0
M  V30 17 C 8.13485 -9.08002 0.0 0
M  V30 18 C 9.00382 -9.57503 0.0 0
M  V30 19 C 7.27028 -9.58253 0.0 0
M  V30 20 C 6.40655 -11.0818 0.0 0
M  V30 21 C 7.27066 -10.5832 0.0 0
M  V30 22 C 5.53937 -10.5819 0.0 0
M  V30 23 C 6.39963 -9.08064 0.0 0
M  V30 24 C 5.53679 -9.58626 0.0 0
M  V30 25 C 3.25985 -8.32507 0.0 0
M  V30 26 N 4.99015 -8.32459 0.0 0
M  V30 27 C 4.12664 -7.82497 0.0 0
M  V30 28 C 4.99015 -9.32553 0.0 0
M  V30 29 C 3.25985 -9.33002 0.0 0
M  V30 30 C 4.12882 -9.82503 0.0 0
M  V30 31 C 4.12725 -6.82497 0.0 0
M  V30 32 C 3.26067 -5.32731 0.0 0
M  V30 33 C 3.26041 -6.32494 0.0 0
M  V30 34 C 4.12718 -4.82625 0.0 0
M  V30 35 C 4.99722 -6.32191 0.0 0
M  V30 36 C 4.99076 -5.32186 0.0 0
M  V30 37 Ir 6.375 -7.4 0.0 0
M  V30 END ATOM
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 BEGIN BOND
Line 203: Line 184:
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 2 7
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M  V30 16 1 13 17
M  V30 16 1 14 12
M  V30 17 1 14 15
M  V30 17 1 7 15
M  V30 18 2 17 18
M  V30 18 3 15 16
M  V30 19 1 18 16
M  V30 20 1 17 19
M  V30 21 2 21 19
M  V30 22 2 22 20
M  V30 23 1 19 23
M  V30 24 1 20 21
M  V30 25 2 23 24
M  V30 26 1 24 22
M  V30 27 2 27 25
M  V30 28 2 28 26
M  V30 29 1 25 29
M  V30 30 1 26 27
M  V30 31 2 29 30
M  V30 32 1 30 28
M  V30 33 1 27 31
M  V30 34 2 33 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 1 35 37
M  V30 41 1 23 37
M  V30 42 1 37 11
M  V30 43 8 26 37
M  V30 44 8 4 37
M  V30 45 8 37 13
M  V30 END BOND
M  V30 END BOND
M  V30 END CTAB
M  V30 END CTAB
Line 248: Line 202:


====Investigation====
====Investigation====
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=photocatalytic conversion of CO2 to CO|importFile=}}
====Sacrificial electron donor====
====Sacrificial electron donor====
In this study, the experiments were done with the sacrificial electron donor TEA ({{#moleculelink:|link=ZMANZCXQSJIPKH-UHFFFAOYSA-N|image=false|width=300|height=200}}).
In this study, the experiments were done with the sacrificial electron donor TEA ({{#moleculelink:|link=ZMANZCXQSJIPKH-UHFFFAOYSA-N|image=false|width=300|height=200}}).
====Additives====
====Additives====
In this study, ....
In this study, no additives were tested.

Latest revision as of 12:43, 15 May 2024


Abstract[edit | edit source]

Summary[edit | edit source]

The photochemical reduction of CO2 to CO was shown using the iron complex Fe(DHPP)Cl in combination with the photosensitizers Ir(ppy)3 or 9-Anthracenecarbonitrile. Turnover numbers (TONs) of up to 140 and a selectivity of 93% for CO were reached in acetonitrile after 55 h of irradiation. The experiments were conducted under visible-light irradiation (λ > 400 nm) with TEA (see section SEDs below) as sacrificial electron donor.

Advances and special progress[edit | edit source]

The authors reported one of the highest TONs in homogeneous photocatalysis at that time in this study without detecting significant degradation of the catalyst or sensitizer. In addition, they reported the use of a cheap organic photosensitizer for CO2 conversion with a slightly lower TON (60), but higher selectivity (100%).

Additional remarks[edit | edit source]

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

The article contains results of a study for the reduction of CO2 to CO using an iron complex and an iridium-based or organic photosensitizer. The catalytic system performs best (referring to the TON of CO production) in acetonitrile with photosensitizer Ir(ppy)3.

Catalyst[edit | edit source]

Fe(DHPP)Cl

Photosensitizer[edit | edit source]

Ir(ppy)3 9-Anthracenecarbonitrile

Investigation[edit | edit source]

catcat conc [µM]PSPS conc [mM]e-De-D conc [M]solvent A..TON CO.
1.

Fe(DHPP)Cl

0.002

Ir(ppy)3

0.2

TEA

0.36

MeCN

140
2.

Fe(DHPP)Cl

0.002

Molecule:100936

0.2

TEA

0.36

MeCN

40
3.

Fe(DHPP)Cl

0.002

Molecule:100936

0.2

TEA

0.05

MeCN

60
Investigation-Name: photocatalytic conversion of CO2 to CO

Sacrificial electron donor[edit | edit source]

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

Additives[edit | edit source]

In this study, no additives were tested.

Investigations

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