Phenoxazine-Sensitized CO2-to-CO Reduction with an Iron Porphyrin Catalyst: A Redox Properties-Catalytic Performance Study: Difference between revisions

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DOI 10.1002/cptc.202200009
Authors Martin Kientz, Grace Lowe, Blaine G. McCarthy, Garret M. Miyake, Julien Bonin, Marc Robert,
Submitted 11.03.2022
Published online 29.03.2022
Licenses http://creativecommons.org/licenses/by/4.0/, http://doi.wiley.com/10.1002/tdm_license_1.1,
Subjects Organic Chemistry, Physical and Theoretical Chemistry, Analytical Chemistry
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{{#doiinfobox: 10.1002/cptc.202200009}}
{{DOI|doi=10.1002/cptc.202200009}}
[[Category:Photocatalytic CO2 conversion to CO]]
[[Category:Photocatalytic CO2 conversion to CO]]
{{BaseTemplate}}
{{BaseTemplate}}
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===Abstract===
===Abstract===
====Summary====
====Summary====
A photochemical reduction of CO<sub>2</sub> to CO was shown using the iron porphyrin complex {{#moleculelink:|link=FAKQJSUSUXMEFI-NGWNFTKISA-M|image=false|width=300|height=200}} as catalyst, screening the effect of different phenoxazine-based photosensitizers on the CO production. Turnover numbers (TONs) of 115 for CO were reached in acetonitrile in combination with the photosensitizer {{#moleculelink:|link=HDOFYEULLIFSQY-UHFFFAOYSA-N|image=false|width=300|height=200}}. The experiments were conducted under visible-light irradiation (λ > 400 nm) using BIH as sacrificial electron donor (see section SEDs below).
A photochemical reduction of CO<sub>2</sub> to CO was shown using the iron porphyrin complex {{#moleculelink:|link=FAKQJSUSUXMEFI-NGWNFTKISA-M|image=false|width=300|height=200}} as catalyst, screening the effect of different phenoxazine-based photosensitizers on the CO production. Turnover numbers (TONs) of 115 and a selectivity of 100% for CO were reached in acetonitrile in combination with the photosensitizer {{#moleculelink:|link=HDOFYEULLIFSQY-UHFFFAOYSA-N|image=false|width=300|height=200}}. The experiments were conducted under visible-light irradiation (λ > 400 nm) using BIH as sacrificial electron donor (see section SEDs below).
====Advances and special progress====
====Advances and special progress====
In this study, the authors showed a strong relation between the oxidation potential of the photosensitizer and the CO production whereas no correlation between the CO production and the excited state potential of the photosensitizer was discovered.  
In this study, the authors showed a strong relation between the oxidation potential of the photosensitizer and the CO production whereas no correlation between the CO production and the excited state potential of the photosensitizer was discovered. This identifies the electron transfer to regenerate the photosensitizer as a determining step and demonstrates the importance of improving the interaction between the photosensitizer and the sacrificial electron donor for optimization of the CO<sub>2</sub> reduction.  
====Additional remarks====
====Additional remarks====
The tested phenoxazine-based photosensitizers performed similarly in combination with the iron porphyrin complex and allowed for TONs of 88-115 and selectivities of 80-100% apart from complex {{#moleculelink:|link=JUDLWUDCWSBXOA-UHFFFAOYSA-N|image=false|width=300|height=200}} that showed both a lower TON (32) and decreased selectivity (36%).
===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 an iron complex and different phenoxazine-based photosensitizers . The catalytic system performs best (referring to the TON of CO production) in acetonitrile.
The article contains results for the reduction of CO<sub>2</sub> to CO under visible-light catalysis using an iron complex and different phenoxazine-based photosensitizers. The catalytic system performs best (referring to the TON of CO production) in acetonitrile.
====Catalyst====
====Catalyst====
<chemform smiles="C12C(C3C=CC([N+](C)(C)C)=CC=3)=C3N4~[Fe+3]([Cl-])56~N7C(=C(C8C=CC([N+](C)(C)C)=CC=8)C8N~5C(C(C5C=CC([N+](C)(C)C)=CC=5)=C(N=1~6)C=C2)=CC=8)C=CC=7C(C1C=CC([N+](C)(C)C)=CC=1)=C4C=C3.[P-](F)(F)(F)(F)(F)F.[P-](F)(F)(F)(F)(F)F.[P-](F)(F)(F)(F)(F)F.[P-](F)(F)(F)(F)(F)F" inchi="1S/C56H60N8.ClH.4F6P.Fe/c1-61(2,3)41-21-13-37(14-22-41)53-45-29-31-47(57-45)54(38-15-23-42(24-16-38)62(4,5)6)49-33-35-51(59-49)56(40-19-27-44(28-20-40)64(10,11)12)52-36-34-50(60-52)55(48-32-30-46(53)58-48)39-17-25-43(26-18-39)63(7,8)9;;4*1-7(2,3,4,5)6;/h13-36H,1-12H3;1H;;;;;/q+2;;4*-1;+5/p-1/b53-45-,53-46-,54-47-,54-49-,55-48-,55-50-,56-51-,56-52-;;;;;;" inchikey="FAKQJSUSUXMEFI-NGWNFTKISA-M" height="200px" width="300px" float="none">
<chemform smiles="C12C(C3C=CC([N+](C)(C)C)=CC=3)=C3N4~[Fe+3]([Cl-])56~N7C(=C(C8C=CC([N+](C)(C)C)=CC=8)C8N~5C(C(C5C=CC([N+](C)(C)C)=CC=5)=C(N=1~6)C=C2)=CC=8)C=CC=7C(C1C=CC([N+](C)(C)C)=CC=1)=C4C=C3.[P-](F)(F)(F)(F)(F)F.[P-](F)(F)(F)(F)(F)F.[P-](F)(F)(F)(F)(F)F.[P-](F)(F)(F)(F)(F)F" inchi="1S/C56H60N8.ClH.4F6P.Fe/c1-61(2,3)41-21-13-37(14-22-41)53-45-29-31-47(57-45)54(38-15-23-42(24-16-38)62(4,5)6)49-33-35-51(59-49)56(40-19-27-44(28-20-40)64(10,11)12)52-36-34-50(60-52)55(48-32-30-46(53)58-48)39-17-25-43(26-18-39)63(7,8)9;;4*1-7(2,3,4,5)6;/h13-36H,1-12H3;1H;;;;;/q+2;;4*-1;+5/p-1/b53-45-,53-46-,54-47-,54-49-,55-48-,55-50-,56-51-,56-52-;;;;;;" inchikey="FAKQJSUSUXMEFI-NGWNFTKISA-M" height="200px" width="300px" float="none">
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In this study, the experiments were done with the sacrificial electron donor BIH ({{#moleculelink:|link=VDFIVJSRRJXMAU-UHFFFAOYSA-N|image=false|width=300|height=200}}).
In this study, the experiments were done with the sacrificial electron donor BIH ({{#moleculelink:|link=VDFIVJSRRJXMAU-UHFFFAOYSA-N|image=false|width=300|height=200}}).
==== Additives====
==== Additives====
In this study, {{#moleculelink:|link=RHQDFWAXVIIEBN-UHFFFAOYSA-N|image=false|width=300|height=200}} was used as an additive.
In this study, {{#moleculelink:|link=RHQDFWAXVIIEBN-UHFFFAOYSA-N|image=false|width=300|height=200}} was used as an additive.[[Category:Publication]]

Latest revision as of 10:37, 11 April 2024


Abstract[edit | edit source]

Summary[edit | edit source]

A photochemical reduction of CO2 to CO was shown using the iron porphyrin complex [Fe(pTMAPP)Cl][PF6]4 as catalyst, screening the effect of different phenoxazine-based photosensitizers on the CO production. Turnover numbers (TONs) of 115 and a selectivity of 100% for CO were reached in acetonitrile in combination with the photosensitizer 100762. The experiments were conducted under visible-light irradiation (λ > 400 nm) using BIH as sacrificial electron donor (see section SEDs below).

Advances and special progress[edit | edit source]

In this study, the authors showed a strong relation between the oxidation potential of the photosensitizer and the CO production whereas no correlation between the CO production and the excited state potential of the photosensitizer was discovered. This identifies the electron transfer to regenerate the photosensitizer as a determining step and demonstrates the importance of improving the interaction between the photosensitizer and the sacrificial electron donor for optimization of the CO2 reduction.

Additional remarks[edit | edit source]

The tested phenoxazine-based photosensitizers performed similarly in combination with the iron porphyrin complex and allowed for TONs of 88-115 and selectivities of 80-100% apart from complex 4-[7-[4-(diphenylamino)phenyl]-10-naphthalen-2-yl-phenoxazin-3-yl]-N,N-diphenyl-aniline that showed both a lower TON (32) and decreased selectivity (36%).

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 an iron complex and different phenoxazine-based photosensitizers. The catalytic system performs best (referring to the TON of CO production) in acetonitrile.

Catalyst[edit | edit source]

[Fe(pTMAPP)Cl][PF6]4

Photosensitizer[edit | edit source]

3,7-Di((1,1'-biphenyl)-4-yl)-10-(naphthalen-1-yl)-10H-phenoxazine 1007611007621007634-[7-[4-(diphenylamino)phenyl]-10-naphthalen-2-yl-phenoxazin-3-yl]-N,N-diphenyl-aniline10-naphthalen-2-yl-3,7-di(pyren-1-yl)phenoxazine

Investigation[edit | edit source]

catcat conc [µM]PSPS conc [mM]e-De-D conc [M]solvent Aadditives.λexc [nm].TON COTON H2.
1.

[Fe(pTMAPP)Cl][PF6]4

0.002

Molecule:100493

0.2

BIH

0.005

MeCN

TFE> 40010325
2.

[Fe(pTMAPP)Cl][PF6]4

0.002

Molecule:100761

0.2

BIH

0.005

MeCN

TFE> 4008812
3.

[Fe(pTMAPP)Cl][PF6]4

0.002

Molecule:100762

0.2

BIH

0.005

MeCN

TFE> 400115
4.

[Fe(pTMAPP)Cl][PF6]4

0.002

Molecule:100763

0.2

BIH

0.005

MeCN

TFE> 40011212
5.

[Fe(pTMAPP)Cl][PF6]4

0.002

Molecule:100764

0.2

BIH

0.005

MeCN

TFE> 4003257
6.

[Fe(pTMAPP)Cl][PF6]4

0.002

Molecule:100765

0.2

BIH

0.005

MeCN

TFE> 40089
Investigation-Name: Table 1

Sacrificial Electron Donor[edit | edit source]

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

Additives[edit | edit source]

In this study, TFE was used as an additive.

Investigations

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