Visible-Light Photocatalytic Conversion of Carbon Dioxide by Ni(II) Complexes with N4S2 Coordination: Highly Efficient and Selective Production of Formate: Difference between revisions
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{{DOI|doi=10.1021/jacs.0c08145}} | |||
===Abstract=== | |||
====Summary==== | |||
A photochemical reduction of CO<sub>2</sub> to formate was shown using the nickel complexes {{#moleculelink:|link=CLQAFMRCKIGWOF-UHFFFAOYSA-L|image=false|width=300|height=200}} or {{#moleculelink:|link=BDPUYSVREMMVBP-UHFFFAOYSA-L|image=false|width=300|height=200}} as catalysts in combination with the organic photosensitizer {{#moleculelink:|link=SEACYXSIPDVVMV-UHFFFAOYSA-L|image=false|width=300|height=200}}. Turnover numbers (TONs) of up to 14000 and a selectivity of >99% for formate were reached in ethanol/water. The experiments were conducted under visible-light irradiation (λ > 400 nm) using TEOA as sacrificial electron donor (see section SEDs below). | |||
====Advances and special progress==== | |||
A set of bioinspired nickel complexes have been developed and shown to possess remarkably high efficiencies and selectivities as catalysts in CO<sub>2</sub> reduction, being the (at that time) best early transition metal complexes for photocatalytic CO<sub>2</sub> conversion. | |||
==== | ====Additional remarks==== | ||
{{# | The nickel complexes were also active catalysts for hydrogen photoreduction under argon atmosphere. | ||
===Content of the published article in detail=== | |||
The article contains results for the reduction of CO<sub>2</sub> to formate under visible-light catalysis using nickel complexes and an organic photosensitizer. The catalytic system performs best (referring to the TON of formate production) in ethanol/water with complex {{#moleculelink:|link=CLQAFMRCKIGWOF-UHFFFAOYSA-L|image=false|width=300|height=200}} as a catalyst. | |||
==== Catalyst ==== | ==== Catalyst ==== | ||
<chemform smiles="C1C=CC=N2[Ni]3( | <chemform smiles="C1C=CC=N2[Ni+2]3([S-]C4N3=CC=CC=4)3([S-]C4=CC=CC=N43)N3=C(NC4C=CC=CC=43)C=12" inchikey="CLQAFMRCKIGWOF-UHFFFAOYSA-L" inchi="1S/C12H9N3.2C5H5NS.Ni/c1-2-6-10-9(5-1)14-12(15-10)11-7-3-4-8-13-11;2*7-5-3-1-2-4-6-5;/h1-8H,(H,14,15);2*1-4H,(H,6,7);/q;;;+2/p-2" float="none" width="300" height="200"> | ||
-INDIGO- | -INDIGO-11302312462D | ||
0 0 0 0 0 0 0 0 0 0 0 V3000 | 0 0 0 0 0 0 0 0 0 0 0 V3000 | ||
| Line 12: | Line 21: | ||
M V30 COUNTS 30 37 0 0 0 | M V30 COUNTS 30 37 0 0 0 | ||
M V30 BEGIN ATOM | M V30 BEGIN ATOM | ||
M V30 1 C | M V30 1 C 4.22629 -7.80601 0.0 0 | ||
M V30 2 N 5. | M V30 2 N 5.90948 -7.56855 0.0 0 | ||
M V30 3 C 4. | M V30 3 C 4.96703 -7.24549 0.0 0 | ||
M V30 4 C | M V30 4 C 6.08213 -8.50205 0.0 0 | ||
M V30 5 C | M V30 5 C 4.36141 -8.74382 0.0 0 | ||
M V30 6 C | M V30 6 C 5.29809 -9.11534 0.0 0 | ||
M V30 7 C 4. | M V30 7 C 4.92207 -6.38756 0.0 0 | ||
M V30 8 N 4. | M V30 8 N 4.11814 -5.81174 0.0 0 | ||
M V30 9 C 4. | M V30 9 C 4.47217 -4.9117 0.0 0 | ||
M V30 10 C 5. | M V30 10 C 5.45493 -4.93524 0.0 0 | ||
M V30 11 N 5. | M V30 11 N 5.71267 -5.91607 0.0 0 | ||
M V30 12 C 3. | M V30 12 C 3.95563 -4.10265 0.0 0 | ||
M V30 13 C 4. | M V30 13 C 4.43773 -3.2562 0.0 0 | ||
M V30 14 C 5. | M V30 14 C 5.97573 -4.1409 0.0 0 | ||
M V30 15 C 5. | M V30 15 C 5.46132 -3.25564 0.0 0 | ||
M V30 16 C | M V30 16 C 8.19043 -5.02095 0.0 0 | ||
M V30 17 C 9. | M V30 17 C 9.64906 -4.15013 0.0 0 | ||
M V30 18 C 8. | M V30 18 C 8.6395 -4.13871 0.0 0 | ||
M V30 19 C | M V30 19 C 10.0934 -5.02704 0.0 0 | ||
M V30 20 N 8. | M V30 20 N 8.55109 -5.74026 0.0 0 | ||
M V30 21 C 9. | M V30 21 C 9.5156 -5.85055 0.0 0 | ||
M V30 22 N 8. | M V30 22 N 8.5589 -7.14296 0.0 0 | ||
M V30 23 C | M V30 23 C 10.2084 -7.55589 0.0 0 | ||
M V30 24 C 9. | M V30 24 C 9.5038 -6.86005 0.0 0 | ||
M V30 25 C 9. | M V30 25 C 9.92498 -8.50582 0.0 0 | ||
M V30 26 C 8. | M V30 26 C 8.33576 -7.91156 0.0 0 | ||
M V30 27 C 8. | M V30 27 C 8.93402 -8.69908 0.0 0 | ||
M V30 28 S 7. | M V30 28 S 7.12277 -8.08302 0.0 0 CHG=-1 | ||
M V30 29 | M V30 29 Ni 7.04952 -6.51544 0.0 0 CHG=2 | ||
M V30 30 | M V30 30 S 6.97788 -5.00244 0.0 0 CHG=-1 | ||
M V30 END ATOM | M V30 END ATOM | ||
M V30 BEGIN BOND | M V30 BEGIN BOND | ||
| Line 73: | Line 82: | ||
M V30 28 2 26 27 | M V30 28 2 26 27 | ||
M V30 29 1 27 25 | M V30 29 1 27 25 | ||
M V30 30 1 | M V30 30 1 26 28 | ||
M V30 31 | M V30 31 10 20 29 | ||
M V30 32 10 | M V30 32 10 11 29 | ||
M V30 33 | M V30 33 10 2 29 | ||
M V30 34 10 | M V30 34 10 22 29 | ||
M V30 35 10 | M V30 35 10 28 29 | ||
M V30 36 | M V30 36 1 16 30 | ||
M V30 37 | M V30 37 10 30 29 | ||
M V30 END BOND | M V30 END BOND | ||
M V30 END CTAB | M V30 END CTAB | ||
| Line 165: | Line 174: | ||
</chemform> | </chemform> | ||
==== Photosensitizer ==== | ====Photosensitizer==== | ||
{{#moleculelink:|link=SEACYXSIPDVVMV-UHFFFAOYSA-L}} | {{#moleculelink:|link=SEACYXSIPDVVMV-UHFFFAOYSA-L|image=true|width=300|height=200}} | ||
====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 TEOA ([[Molecule:100507|triethanolamine]]). | |||
==== | ==== Additives ==== | ||
In this study, no additives were tested. | |||
[[Category:Photocatalytic CO2 conversion to HCOOH]] | [[Category:Photocatalytic CO2 conversion to HCOOH]][[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 formate was shown using the nickel complexes Ni(pbi)(pyS)2 or Ni(pbt)(pyS)2 as catalysts in combination with the organic photosensitizer Eosin Y. Turnover numbers (TONs) of up to 14000 and a selectivity of >99% for formate were reached in ethanol/water. The experiments were conducted under visible-light irradiation (λ > 400 nm) using TEOA as sacrificial electron donor (see section SEDs below).
Advances and special progress[edit | edit source]
A set of bioinspired nickel complexes have been developed and shown to possess remarkably high efficiencies and selectivities as catalysts in CO2 reduction, being the (at that time) best early transition metal complexes for photocatalytic CO2 conversion.
Additional remarks[edit | edit source]
The nickel complexes were also active catalysts for hydrogen photoreduction under argon atmosphere.
Content of the published article in detail[edit | edit source]
The article contains results for the reduction of CO2 to formate under visible-light catalysis using nickel complexes and an organic photosensitizer. The catalytic system performs best (referring to the TON of formate production) in ethanol/water with complex Ni(pbi)(pyS)2 as a catalyst.
Catalyst[edit | edit source]
Photosensitizer[edit | edit source]
Investigation[edit | edit source]
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | e-D conc [M] | solvent A | . | . | . | . | TON HCOOH | . | . | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 0.004 | 2 | 0.4 | 14000 | |||||||||||
| 2. | 0.004 | 2 | 0.4 | 13100 |
Investigation-Name: Table 1
Sacrificial Electron Donor[edit | edit source]
In this study, the experiments were done with the sacrificial electron donor TEOA (triethanolamine).
Additives[edit | edit source]
In this study, no additives were tested.
Investigations
- Table 1 (Molecular process, Photocatalytic CO2 conversion experiments)
