Phenoxazine-Sensitized CO2-to-CO Reduction with an Iron Porphyrin Catalyst: A Redox Properties-Catalytic Performance Study: Difference between revisions
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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"> |
Revision as of 15:47, 22 January 2024
Abstract
Summary
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
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
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
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
Photosensitizer
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
cat | cat conc [µM] | PS | PS conc [mM] | e-D | e-D conc [M] | solvent A | additives | . | λexc [nm] | . | TON CO | TON H2 | . | |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
1. | 0.002 | 0.2 | 0.005 | TFE | > 400 | 103 | 25 | |||||||
2. | 0.002 | 0.2 | 0.005 | TFE | > 400 | 88 | 12 | |||||||
3. | 0.002 | 0.2 | 0.005 | TFE | > 400 | 115 | ||||||||
4. | 0.002 | 0.2 | 0.005 | TFE | > 400 | 112 | 12 | |||||||
5. | 0.002 | 0.2 | 0.005 | TFE | > 400 | 32 | 57 | |||||||
6. | 0.002 | 0.2 | 0.005 | TFE | > 400 | 89 |
Sacrificial Electron Donor
In this study, the experiments were done with the sacrificial electron donor BIH (BIH).
Additives
In this study, TFE was used as an additive.
Investigations
- Table 1 (Molecular process, Photocatalytic CO2 conversion experiments)