Metal-free reduction of CO2 to formate using a photochemical organohydride-catalyst recycling strategy: Difference between revisions

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{{DOI|doi=10.1038/s41557-023-01157-6}}
{{DOI|doi=10.1038/s41557-023-01157-6}}
[[Category:Photocatalytic CO2 conversion to CH4]][[Category:Publication]]
[[Category:Publication]]
{{BaseTemplate}}
{{BaseTemplate}}
===Abstract===
===Abstract===
====Summary====
====Summary====
A photochemical reduction of CO<sub>2</sub> to CO was shown using the iron complexes {{#moleculelink: |link=VCSOHGDMTDAXCJ-UHFFFAOYSA-N|image=false|width=300|height=200}}, {{#moleculelink: |link=GNLSTNFUDXOKCD-UHFFFAOYSA-N|image=false|width=300|height=200}} and {{#moleculelink: |link=DJDQCCRAAYOAPK-UHFFFAOYSA-N|image=false|width=300|height=200}} as catalysts in combination with the organic photosensitizer {{#moleculelink:|link=PRWATGACIORDEL-UHFFFAOYSA-N|image=false|width=300|height=200}}. Turnover numbers (TONs) of 6320 and a selectivity of 99.4% for CO were reached in DMF/H<sub>2</sub>O with catalyst {{#moleculelink: |link=DJDQCCRAAYOAPK-UHFFFAOYSA-N|image=false|width=300|height=200}}. The experiments were conducted under visible-light irradiation (λ = 440 nm) using TEA as sacrificial electron donor (see section SEDs below).
A photochemical reduction of CO<sub>2</sub> to formic acid was shown using {{#moleculelink:|link=RDSICPYJALLFAN-UHFFFAOYSA-M|image=false|width=300|height=200}} as catalyst in combination with the organic carbazole-based photosensitizer {{#moleculelink:|link=SEAGXMGVRJVEBS-UHFFFAOYSA-N|image=false|width=300|height=200}}. Turnover numbers (TONs) of 6080 for the catalyst and 8820 for the photosensitizer and an exclusive selectivity for formic acid were reached in MeCN/H<sub>2</sub>O. The experiments were conducted under visible-light irradiation (λ = 400 nm) using ascorbic acid as sacrificial electron donor (see section SEDs below) and potassium carbonate as a base.
====Advances and special progress====
====Advances and special progress====
A transition-metal free process for the efficient photocatalytic reduction of CO<sub>2</sub> to formic acid was described. The use of an organohydride catalyst allowed for a high selectivity for formate without noteworthy formation of H<sub>2</sub> or CO.
====Additional remarks====
====Additional remarks====
Derivatives in which the carbazole and benzimidazolium moieties were covalently connected were tested as a combined catalyst/photosensitizer, but showed a lower activity in catalyzing CO<sub>2</sub> reduction.
===Content of the published article in detail===
===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 the iron complex {{#moleculelink: |link=DJDQCCRAAYOAPK-UHFFFAOYSA-N|image=false|width=300|height=200}} as a catalyst. The catalytic system performs best (referring to the TON of CO production) in DMF/H<sub>2</sub>O.
The article contains results for the reduction of CO<sub>2</sub> to HCOO<sup>-</sup> under visible-light catalysis using {{#moleculelink:|link=RDSICPYJALLFAN-UHFFFAOYSA-M|image=false|width=300|height=200}} as a catalyst. The catalytic system performs best (referring to the TON of formic acid production for the catalyst) in MeCN/H<sub>2</sub>O with photosensitizer {{#moleculelink:|link=SEAGXMGVRJVEBS-UHFFFAOYSA-N|image=false|width=300|height=200}}.
====Catalyst====
====Catalyst====
<chemform smiles="C1C=CC2N(C)C(C)=[N+](C)C=2C=1.[I-]" inchi="1S/C10H13N2.HI/c1-8-11(2)9-6-4-5-7-10(9)12(8)3;/h4-7H,1-3H3;1H/q+1;/p-1" inchikey="RDSICPYJALLFAN-UHFFFAOYSA-M" height="200px" width="300px" float="none">
  -INDIGO-05152410312D
  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 13 13 0 0 0
M  V30 BEGIN ATOM
M  V30 1 C 4.90985 -3.80007 0.0 0
M  V30 2 C 6.64015 -3.79959 0.0 0
M  V30 3 C 5.77664 -3.29997 0.0 0
M  V30 4 C 6.64015 -4.80053 0.0 0
M  V30 5 C 4.90985 -4.80502 0.0 0
M  V30 6 C 5.77882 -5.30003 0.0 0
M  V30 7 N 7.59213 -3.49022 0.0 0 CHG=1
M  V30 8 C 8.18049 -4.29999 0.0 0
M  V30 9 N 7.59212 -5.1098 0.0 0
M  V30 10 C 8.09213 -2.62419 0.0 0
M  V30 11 C 7.85094 -6.07572 0.0 0
M  V30 12 C 9.18049 -4.29998 0.0 0
M  V30 13 I 9.25 -3.225 0.0 0 CHG=-1
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 1 2 7
M  V30 8 2 7 8
M  V30 9 1 8 9
M  V30 10 1 9 4
M  V30 11 1 7 10
M  V30 12 1 9 11
M  V30 13 1 8 12
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform><chemform smiles="" inchi="" inchikey="VDFIVJSRRJXMAU-UHFFFAOYSA-N" height="200px" width="300px" float="none"></chemform>
====Photosensitizer====
====Photosensitizer====
<chemform smiles="N(C1C=CC=CC=1)1C2C=CC(N(C)C)=CC=2C2C=C(N(C)C)C=CC1=2" inchi="1S/C22H23N3/c1-23(2)17-10-12-21-19(14-17)20-15-18(24(3)4)11-13-22(20)25(21)16-8-6-5-7-9-16/h5-15H,1-4H3" inchikey="SEAGXMGVRJVEBS-UHFFFAOYSA-N" height="200px" width="300px" float="none">
<chemform smiles="N(C1C=CC=CC=1)1C2C=CC(N(C)C)=CC=2C2C=C(N(C)C)C=CC1=2" inchi="1S/C22H23N3/c1-23(2)17-10-12-21-19(14-17)20-15-18(24(3)4)11-13-22(20)25(21)16-8-6-5-7-9-16/h5-15H,1-4H3" inchikey="SEAGXMGVRJVEBS-UHFFFAOYSA-N" height="200px" width="300px" float="none">
Line 76: Line 120:
M  V30 END CTAB
M  V30 END CTAB
M  END
M  END
</chemform>
</chemform><chemform smiles="N1C2C=CC(N(C)C)=CC=2C2C=C(N(C)C)C=CC1=2" inchi="1S/C16H19N3/c1-18(2)11-5-7-15-13(9-11)14-10-12(19(3)4)6-8-16(14)17-15/h5-10,17H,1-4H3" inchikey="WRRDGZBKMQHXGG-UHFFFAOYSA-N" height="200px" width="300px" float="none">
  -INDIGO-05152410542D
 
  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 19 21 0 0 0
M  V30 BEGIN ATOM
M  V30 1 N 1.75 -6.28056 0.0 0
M  V30 2 C 2.55899 -6.86835 0.0 0
M  V30 3 C 2.24999 -7.81944 0.0 0
M  V30 4 C 1.25001 -7.81944 0.0 0
M  V30 5 C 0.94101 -6.86835 0.0 0
M  V30 6 C 0.58242 -8.55987 0.0 0
M  V30 7 C -0.396028 -8.35216 0.0 0
M  V30 8 C -0.0413505 -6.65981 0.0 0
M  V30 9 C -0.705564 -7.40653 0.0 0
M  V30 10 C 3.53428 -6.66167 0.0 0
M  V30 11 C 4.20381 -7.40479 0.0 0
M  V30 12 C 2.92221 -8.56553 0.0 0
M  V30 13 C 3.89846 -8.35178 0.0 0
M  V30 14 N 4.57069 -9.09212 0.0 0
M  V30 15 N -1.06425 -9.09612 0.0 0
M  V30 16 C -2.04265 -8.8894 0.0 0
M  V30 17 C -0.754073 -10.0468 0.0 0
M  V30 18 C 4.26565 -10.0445 0.0 0
M  V30 19 C 5.54796 -8.88013 0.0 0
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 1 1 2
M  V30 2 2 2 3
M  V30 3 1 3 4
M  V30 4 2 4 5
M  V30 5 1 5 1
M  V30 6 2 7 6
M  V30 7 1 5 8
M  V30 8 1 6 4
M  V30 9 2 8 9
M  V30 10 1 9 7
M  V30 11 2 11 10
M  V30 12 1 3 12
M  V30 13 1 10 2
M  V30 14 2 12 13
M  V30 15 1 13 11
M  V30 16 1 13 14
M  V30 17 1 7 15
M  V30 18 1 15 16
M  V30 19 1 15 17
M  V30 20 1 14 18
M  V30 21 1 14 19
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform><chemform smiles="N(C1C=CC=CC=1)1C2C=CC(N(C3C=CC=CC=3)C3C=CC=CC=3)=CC=2C2C=C(N(C3C=CC=CC=3)C3C=CC=CC=3)C=CC1=2" inchi="1S/C42H31N3/c1-6-16-32(17-7-1)43(33-18-8-2-9-19-33)37-26-28-41-39(30-37)40-31-38(27-29-42(40)45(41)36-24-14-5-15-25-36)44(34-20-10-3-11-21-34)35-22-12-4-13-23-35/h1-31H" inchikey="PJLYJWBAONHQFV-UHFFFAOYSA-N" height="200px" width="300px" float="none">
  -INDIGO-05152410562D
 
  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 45 52 0 0 0
M  V30 BEGIN ATOM
M  V30 1 N 7.825 -4.88056 0.0 0
M  V30 2 C 8.63399 -5.46835 0.0 0
M  V30 3 C 8.32499 -6.41944 0.0 0
M  V30 4 C 7.32501 -6.41944 0.0 0
M  V30 5 C 7.01601 -5.46835 0.0 0
M  V30 6 C 6.65742 -7.15987 0.0 0
M  V30 7 C 5.67897 -6.95216 0.0 0
M  V30 8 C 6.03365 -5.25981 0.0 0
M  V30 9 C 5.36944 -6.00653 0.0 0
M  V30 10 C 9.60928 -5.26167 0.0 0
M  V30 11 C 10.2788 -6.00479 0.0 0
M  V30 12 C 8.99721 -7.16553 0.0 0
M  V30 13 C 9.97346 -6.95178 0.0 0
M  V30 14 C 7.82537 -1.92579 0.0 0
M  V30 15 C 8.69094 -3.42404 0.0 0
M  V30 16 C 8.69187 -2.4264 0.0 0
M  V30 17 C 7.8241 -3.92451 0.0 0
M  V30 18 C 6.95506 -2.42827 0.0 0
M  V30 19 C 6.96086 -3.42833 0.0 0
M  V30 20 N 5.01075 -7.69612 0.0 0
M  V30 21 N 10.6457 -7.69212 0.0 0
M  V30 22 C 4.03235 -7.4894 0.0 0
M  V30 23 C 5.32093 -8.6468 0.0 0
M  V30 24 C 10.3406 -8.64446 0.0 0
M  V30 25 C 11.623 -7.48013 0.0 0
M  V30 26 C 2.36143 -7.93882 0.0 0
M  V30 27 C 3.32501 -8.19728 0.0 0
M  V30 28 C 2.10172 -6.97216 0.0 0
M  V30 29 C 3.7716 -6.51887 0.0 0
M  V30 30 C 2.80395 -6.26628 0.0 0
M  V30 31 C 6.5456 -9.86914 0.0 0
M  V30 32 C 6.28764 -8.90543 0.0 0
M  V30 33 C 5.8383 -10.5774 0.0 0
M  V30 34 C 4.6108 -9.35788 0.0 0
M  V30 35 C 4.87587 -10.3222 0.0 0
M  V30 36 C 10.7901 -10.3154 0.0 0
M  V30 37 C 11.0485 -9.3518 0.0 0
M  V30 38 C 9.82341 -10.5751 0.0 0
M  V30 39 C 9.37012 -8.90521 0.0 0
M  V30 40 C 9.11753 -9.87286 0.0 0
M  V30 41 C 12.8453 -6.25546 0.0 0
M  V30 42 C 11.8816 -6.51341 0.0 0
M  V30 43 C 13.5536 -6.96276 0.0 0
M  V30 44 C 12.334 -8.19026 0.0 0
M  V30 45 C 13.2983 -7.92518 0.0 0
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 1 1 2
M  V30 2 2 2 3
M  V30 3 1 3 4
M  V30 4 2 4 5
M  V30 5 1 5 1
M  V30 6 2 7 6
M  V30 7 1 5 8
M  V30 8 1 6 4
M  V30 9 2 8 9
M  V30 10 1 9 7
M  V30 11 2 11 10
M  V30 12 1 3 12
M  V30 13 1 10 2
M  V30 14 2 12 13
M  V30 15 1 13 11
M  V30 16 2 16 14
M  V30 17 2 17 15
M  V30 18 1 14 18
M  V30 19 1 15 16
M  V30 20 2 18 19
M  V30 21 1 19 17
M  V30 22 1 1 17
M  V30 23 1 7 20
M  V30 24 1 13 21
M  V30 25 1 20 22
M  V30 26 1 20 23
M  V30 27 1 21 24
M  V30 28 1 21 25
M  V30 29 2 27 22
M  V30 30 2 28 26
M  V30 31 1 22 29
M  V30 32 1 26 27
M  V30 33 2 29 30
M  V30 34 1 30 28
M  V30 35 2 32 23
M  V30 36 2 33 31
M  V30 37 1 23 34
M  V30 38 1 31 32
M  V30 39 2 34 35
M  V30 40 1 35 33
M  V30 41 2 37 24
M  V30 42 2 38 36
M  V30 43 1 24 39
M  V30 44 1 36 37
M  V30 45 2 39 40
M  V30 46 1 40 38
M  V30 47 2 42 25
M  V30 48 2 43 41
M  V30 49 1 25 44
M  V30 50 1 41 42
M  V30 51 2 44 45
M  V30 52 1 45 43
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform><chemform smiles="" inchi="" inchikey="NSABRUJKERBGOU-UHFFFAOYSA-N" height="200px" width="300px" float="none"></chemform>
====Investigation====
====Investigation====
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=photocatalytic CO2 conversion under different conditions|importFile=}}
====Sacrificial electron donor====
====Sacrificial electron donor====
In this study, the experiments were done with the sacrificial electron donor ascorbic acid {{#moleculelink:|link=PPASLZSBLFJQEF-UHFFFAOYSA-M|image=false|width=300|height=200}}. The use of BIH was tested, but found to yield worse results.
In this study, the experiments were done with the sacrificial electron donor ascorbic acid {{#moleculelink:|link=PPASLZSBLFJQEF-UHFFFAOYSA-M|image=false|width=300|height=200}}. The use of BIH was tested, but found to yield worse results.
====Additives====
====Additives====
In this study,
In this study, potassium carbonate was added as a base. Control experiments under argon and with other bases were performed.
[[Category:Photocatalytic CO2 conversion to HCOOH]]

Latest revision as of 12:49, 17 May 2024


Abstract[edit | edit source]

Summary[edit | edit source]

A photochemical reduction of CO2 to formic acid was shown using 1,2,3-Trimethylbenzimidazolium iodide as catalyst in combination with the organic carbazole-based photosensitizer 3,6-bis(dimethylamino)-9-phenyl-9H-carbazole. Turnover numbers (TONs) of 6080 for the catalyst and 8820 for the photosensitizer and an exclusive selectivity for formic acid were reached in MeCN/H2O. The experiments were conducted under visible-light irradiation (λ = 400 nm) using ascorbic acid as sacrificial electron donor (see section SEDs below) and potassium carbonate as a base.

Advances and special progress[edit | edit source]

A transition-metal free process for the efficient photocatalytic reduction of CO2 to formic acid was described. The use of an organohydride catalyst allowed for a high selectivity for formate without noteworthy formation of H2 or CO.

Additional remarks[edit | edit source]

Derivatives in which the carbazole and benzimidazolium moieties were covalently connected were tested as a combined catalyst/photosensitizer, but showed a lower activity in catalyzing CO2 reduction.

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

The article contains results for the reduction of CO2 to HCOO- under visible-light catalysis using 1,2,3-Trimethylbenzimidazolium iodide as a catalyst. The catalytic system performs best (referring to the TON of formic acid production for the catalyst) in MeCN/H2O with photosensitizer 3,6-bis(dimethylamino)-9-phenyl-9H-carbazole.

Catalyst[edit | edit source]

1,2,3-Trimethylbenzimidazolium iodide BIH

Photosensitizer[edit | edit source]

3,6-bis(dimethylamino)-9-phenyl-9H-carbazole 3,6-bis(dimethylamino)carbazole 3,6-Bis(diphenylamino)-9-phenyl-9H-carbazole Ir(ppy)3

Investigation[edit | edit source]

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

Molecule:100951

2.5

Molecule:100952

0.005

Molecule:100861

0.05

MeCN

4002750
2.

Molecule:100951

2.5

Molecule:100950

0.005

Molecule:100861

0.05

MeCN

4006510
3.

Molecule:100951

2.5

Molecule:100953

0.005

Molecule:100861

0.05

MeCN

4008820
4.

Molecule:100951

2.5

Ir(ppy)3

0.005

Molecule:100861

0.05

MeCN

4007380
5.

Molecule:100951

2.5


Molecule:100861

0.05

MeCN

4000
6.

Molecule:100951

0.05

Molecule:100950

0.5

Molecule:100861

0.05

MeCN

40061
7.


Molecule:100950

0.5

Molecule:100861

0.05

MeCN

4000
8.

Molecule:100951

0.05

Molecule:100950

0.05

Molecule:100861

0.05

MeCN

400710
9.

Molecule:100951

0.05

Molecule:100950

0.005

Molecule:100861

0.05

MeCN

400860
10.

Molecule:100951

0.005

Molecule:100950

0.005

Molecule:100861

0.05

MeCN

4000

Sacrificial electron donor[edit | edit source]

In this study, the experiments were done with the sacrificial electron donor ascorbic acid L-ascorbate, sodium. The use of BIH was tested, but found to yield worse results.

Additives[edit | edit source]

In this study, potassium carbonate was added as a base. Control experiments under argon and with other bases were performed.

Investigations

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