Visible-Light Photocatalytic Reduction of CO2 to Formic Acid with a Ru Catalyst Supported by N,N’- Bis(diphenylphosphino)-2,6-diaminopyridine Ligands: Difference between revisions

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DOI 10.1002/cssc.201901326
Authors Yasmeen Hameed, Gyandshwar Kumar Rao, Jeffrey S. Ovens, Bulat Gabidullin, Darrin Richeson,
Submitted 11.06.2019
Published online 03.07.2019
Licenses http://onlinelibrary.wiley.com/termsAndConditions#vor, http://doi.wiley.com/10.1002/tdm_license_1.1,
Subjects General Energy, General Materials Science, General Chemical Engineering, Environmental Chemistry
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{{#doiinfobox: 10.1002/cssc.201901326}}
{{DOI|doi=10.1002/cssc.201901326}}
[[Category:Photocatalytic CO2 conversion to HCOOH]]
[[Category:Photocatalytic CO2 conversion to HCOOH]]
===Abstract===
====Summary====
A photochemical reduction of CO<sub>2</sub> to formic acid was shown using the ruthenium pincer complexes {{#moleculelink: |link=RQVVTEHURKEOIA-UHFFFAOYSA-M|image=false|width=300|height=200}} and {{#moleculelink: |link=XNTONGVEYKVCNE-UHFFFAOYSA-M|image=false|width=300|height=200}} as catalyst in combination with the ruthenium-based photosensitizer {{#moleculelink:|link=KLDYQWXVZLHTKT-UHFFFAOYSA-N|image=false|width=300|height=200}}. Turnover numbers (TONs) of 380 for formic acid were reached in dimethylformamide with complex {{#moleculelink: |link=XNTONGVEYKVCNE-UHFFFAOYSA-M|image=false|width=300|height=200}}. The experiments were conducted under visible-light irradiation (λ = 405 nm) using TEOA as sacrificial electron donor (see section SEDs below).
====Advances and special progress====
The authors report a novel molecular architecture for a ruthenium photocatalyst active in the reduction of CO<sub>2</sub> to formic acid, displaying competitive TONs and quantum yields up to 14%.


====Additional remarks====
===Content of the published article in detail===
The article contains results for the reduction of CO<sub>2</sub> to formic acid under visible-light catalysis using ruthenium complexes as catalysts. The catalytic system performs best (referring to the TON of formic acid production) with complex {{#moleculelink: |link=XNTONGVEYKVCNE-UHFFFAOYSA-M|image=false|width=300|height=200}} in dimethylformamide.
==== Catalyst====
==== Catalyst====
<chemform smiles="C1C2N([*])P([Ru]3(P(C4C=CC=CC=4)(C4C=CC=CC=4)N([*])C(N=23)=CC=1)(Cl)(C#O)C#O)(C1C=CC=CC=1)C1C=CC=CC=1" inchi="" inchikey="" height="200px" width="300px" float="none" r1="H,Me">
<chemform smiles="C1C2N([*])P(C3C=CC=CC=3)(C3C=CC=CC=3)[Ru+]([C-]#[O+])([C-]#[O+])3P(C4C=CC=CC=4)(C4C=CC=CC=4)N([*])C(N=23)=CC=1.[Cl-]" inchikey="" inchi="" float="none" width="200" height="200" r1="H,Me">
   -INDIGO-02132315442D
   -INDIGO-01112413302D


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M  V30 000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 -
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M  V30 000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 -
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M  V30 000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 -
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M  V30 END SGROUP
M  V30 END CTAB
M  V30 END CTAB
M  END
M  END
</chemform> <chemform smiles="C1C2N([*])P([Ru+]3(P(C4C=CC=CC=4)(C4C=CC=CC=4)N([*])C(N=23)=CC=1)(~Cl)([C-]#[O+])[C-]#[O+])(C1C=CC=CC=1)C1C=CC=CC=1.[Cl-]" inchi="" inchikey="" height="200px" width="300px" float="none" r1="H,Me">
</chemform>
   -INDIGO-07122316072D
 
====Photosensitizer====
<chemform smiles="C1C=CN2[Ru+2]3(N4=CC=CC=C4C4=CC=CC=N43)(N3=CC=CC=C3C=2C=1)1N2C(C3N1=CC=CC=3)=CC=CC=2.[P-](F)(F)(F)(F)(F)F.[P-](F)(F)(F)(F)(F)F" inchi="1S/3C10H8N2.2F6P.Ru/c3*1-3-7-11-9(5-1)10-6-2-4-8-12-10;2*1-7(2,3,4,5)6;/h3*1-8H;;;/q;;;2*-1;+2" inchikey="KLDYQWXVZLHTKT-UHFFFAOYSA-N" height="200px" width="300px" float="none">
   -INDIGO-11272316292D


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M  V30 END BOND
M  V30 END BOND
M  V30 BEGIN SGROUP
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M  V30 000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 -
M  V30 0.000000) LABEL=Ph
M  V30 2 SUP 2 ATOMS=(6 16 28 29 30 31 32) BRKXYZ=(9 0.000000 0.000000 0.0000-
M  V30 00 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000) BRKXYZ=(9 0.-
M  V30 000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 -
M  V30 0.000000) LABEL=Ph
M  V30 3 SUP 3 ATOMS=(6 13 33 34 35 36 37) BRKXYZ=(9 0.000000 0.000000 0.0000-
M  V30 00 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000) BRKXYZ=(9 0.-
M  V30 000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 -
M  V30 0.000000) LABEL=Ph
M  V30 4 SUP 4 ATOMS=(6 14 38 39 40 41 42) BRKXYZ=(9 0.000000 0.000000 0.0000-
M  V30 00 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000) BRKXYZ=(9 0.-
M  V30 000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 -
M  V30 0.000000) LABEL=Ph
M  V30 END SGROUP
M  V30 END CTAB
M  V30 END CTAB
M  END
M  END
</chemform>
</chemform>
====Photosensitizer====
{{#moleculelink:|link=HNVRWFFXWFXICS-UHFFFAOYSA-N|image=true}}


====Investigation====
====Investigation====
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}}
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}}
 
==== Sacrificial electron donor ====
====Sacrificial electron donor====
In this study, the experiments were done with the sacrificial electron donors TEOA ([[Molecule:100507|100507]]).
{{#moleculelink:|link=GSEJCLTVZPLZKY-UHFFFAOYSA-N|image=true}}
====Additives====
In this study, no additives were tested.[[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 formic acid was shown using the ruthenium pincer complexes Ru(py)-(HNdpp)2(CO)2Cl and Ru(py)-(MeNdpp)2(CO)2Cl as catalyst in combination with the ruthenium-based photosensitizer [Ru(bpy)3][PF6]. Turnover numbers (TONs) of 380 for formic acid were reached in dimethylformamide with complex Ru(py)-(MeNdpp)2(CO)2Cl. The experiments were conducted under visible-light irradiation (λ = 405 nm) using TEOA as sacrificial electron donor (see section SEDs below).

Advances and special progress[edit | edit source]

The authors report a novel molecular architecture for a ruthenium photocatalyst active in the reduction of CO2 to formic acid, displaying competitive TONs and quantum yields up to 14%.

Additional remarks[edit | edit source]

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

The article contains results for the reduction of CO2 to formic acid under visible-light catalysis using ruthenium complexes as catalysts. The catalytic system performs best (referring to the TON of formic acid production) with complex Ru(py)-(MeNdpp)2(CO)2Cl in dimethylformamide.

Catalyst[edit | edit source]

100772 [Show R-Groups]

Photosensitizer[edit | edit source]

[Ru(bpy)3][PF6]

Investigation[edit | edit source]

catcat conc [µM]PSPS conc [mM]e-Dsolvent A.λexc [nm].TON H2TON HCOOH.
1.

Ru(py)-(MeNdpp)2(CO)2Cl

0.025

[Ru(bpy)3][PF6]

0.025

TEOA

DMF

405380
2.

Ru(py)-(MeNdpp)2(CO)2Cl

0.05

[Ru(bpy)3][PF6]

0.05

TEOA

DMF

405210
3.

Ru(py)-(MeNdpp)2(CO)2Cl

0.1

[Ru(bpy)3][PF6]

0.1

TEOA

DMF

40557.5363
4.

Ru(py)-(MeNdpp)2(CO)2Cl

0.5

[Ru(bpy)3][PF6]

1

TEOA

DMF

40514162
5.

Ru(py)-(MeNdpp)2(CO)2Cl

1

[Ru(bpy)3][PF6]

1

TEOA

DMF

40513.390.5
6.

Ru(py)-(HNdpp)2(CO)2Cl

0.5

[Ru(bpy)3][PF6]

1

TEOA

DMF

4051470.5
7.

Ru(py)-(HNdpp)2(CO)2Cl

1

[Ru(bpy)3][PF6]

1

TEOA

DMF

4051244.5
8.

Ru(py)-(HNdpp)2(CO)2Cl

2

[Ru(bpy)3][PF6]

1

TEOA

DMF

4059.341.5
Investigation-Name: Table 1

Sacrificial electron donor[edit | edit source]

In this study, the experiments were done with the sacrificial electron donors TEOA (100507).

Additives[edit | edit source]

In this study, no additives were tested.

Investigations

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