An integrated Re(I) photocatalyst and sensitizer that activates the formation of formic acid from reduction of CO2: Difference between revisions

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DOI 10.1039/c9cc03943k
Authors Yasmeen Hameed, Patrick Berro, Bulat Gabidullin, Darrin Richeson,
Submitted 16.08.2019
Published online 2019
Licenses http://rsc.li/journals-terms-of-use,
Subjects Materials Chemistry, Metals and Alloys, Surfaces, Coatings and Films, General Chemistry, Ceramics and Composites, Electronic, Optical and Magnetic Materials, Catalysis
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{{#doiinfobox: 10.1039/c9cc03943k}}
{{DOI|doi=10.1039/c9cc03943k}}
[[Category:Photocatalytic CO2 conversion to HCOOH]]
[[Category:Photocatalytic CO2 conversion to HCOOH]]
{{BaseTemplate}}
{{BaseTemplate}}
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===Abstract===
===Abstract===
====Summary====
====Summary====
A photochemical reduction of CO<sub>2</sub> to CO was shown using the nickel complex {{#moleculelink:|link=SOBXSEUOEROXNJ-UHFFFAOYSA-L|image=false|width=300|height=200}} as catalyst in combination with the ruthenium-based photosensitizer {{#moleculelink:|link=SJFYGUKHUNLZTK-UHFFFAOYSA-L|image=false|width=300|height=200}}. Turnover numbers (TONs) over 700 and a selectivity of >99% for CO were reached in dimethylacetamide/water. The experiments were conducted under visible-light irradiation (λ = 450 nm) using BIH as sacrificial reductants (see section SEDs below).
A photochemical reduction of CO<sub>2</sub> to formic acid was shown using the rhenium catalyst and sensitizer {{#moleculelink:|link=SQEHJZNRDJMTCB-UHFFFAOYSA-M|image=false|width=300|height=200}} in combination with the supplemental photosensitizer {{#moleculelink:|link=KLDYQWXVZLHTKT-UHFFFAOYSA-N|image=false|width=300|height=200}}. Turnover numbers (TONs) up to 2750 for formic acid were reached in dimethylacetamide. The experiments were conducted under visible-light irradiation (λ = 405 nm) with TEOA (see section SEDs below) as sacrificial electron donor.
 
====Advances and special progress====
====Advances and special progress====
A nickel catalyst inspired by the CODH enzyme (carbon monoxide dehydrogenase) was employed for the photocatalytic reduction of CO<sub>2</sub> with the back then highest reported TON values among nickel complexes in systems with [Ru(bpy)<sub>3</sub>]<sup>2+</sup>.
An unprecedented rhenium complex was used as an integrated photosensitizer/catalyst to generate formic acid from CO<sub>2</sub>; other rhenium catalysts only allow for the formation of CO as the reduction product.
 
====Additional remarks====
====Additional remarks====
The binding of CO<sub>2</sub> to the nickel(0) species was identified as the potential rate-determining step of the reduction.
The complex {{#moleculelink:|link=SQEHJZNRDJMTCB-UHFFFAOYSA-M|image=false|width=300|height=200}} can act both as a photocatalyst and sensitizer, but its performance is considerably enhanced by the addition of {{#moleculelink:|link=KLDYQWXVZLHTKT-UHFFFAOYSA-N|image=false|width=300|height=200}} as supplemental photosensitizer. The variation of the catalyst concentration also showed a drastic influence on the performance of the catalytic system.
 
=== 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 a nickel complex as a catalyst. The catalytic system performs best (referring to the TON of CO production) in dimethylacetamide/water.
The article contains results for the reduction of CO<sub>2</sub> to formic acid under visible-light catalysis using a rhenium complex as a catalyst. The catalytic system performs best (referring to the TON of formic acid production) in dimethylacetamide.
 
=== Catalyst===
=== Catalyst===
<chemform smiles="C1C=C2C3C=CC=CN=3[Re+]([C-]#[O+])([C-]#[O+])3(N4C=CC=CC=4C4N3=CC=CC=4)N2=CC=1.S(C(F)(F)F)([O-])(=O)=O" inchi="1S/2C10H8N2.CHF3O3S.2CO.Re/c2*1-3-7-11-9(5-1)10-6-2-4-8-12-10;2-1(3,4)8(5,6)7;2*1-2;/h2*1-8H;(H,5,6,7);;;/q;;;;;+1/p-1" inchikey="SQEHJZNRDJMTCB-UHFFFAOYSA-M" height="200px" width="300px" float="none">
<chemform smiles="C1C=C2C3C=CC=CN=3[Re+]([C-]#[O+])([C-]#[O+])3(N4C=CC=CC=4C4N3=CC=CC=4)N2=CC=1.S(C(F)(F)F)([O-])(=O)=O" inchi="1S/2C10H8N2.CHF3O3S.2CO.Re/c2*1-3-7-11-9(5-1)10-6-2-4-8-12-10;2-1(3,4)8(5,6)7;2*1-2;/h2*1-8H;(H,5,6,7);;;/q;;;;;+1/p-1" inchikey="SQEHJZNRDJMTCB-UHFFFAOYSA-M" height="200px" width="300px" float="none">
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M  END
M  END
</chemform>
</chemform>
===Photosensitizer===
<chemform smiles="" inchi="" inchikey="KLDYQWXVZLHTKT-UHFFFAOYSA-N" height="200px" width="300px" float="none"></chemform>


===Investigations===
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Solvent effect study between DMA DMF and acetonitrile|importFile=}}
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Time profile in DMF|importFile=}}
{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Study on the concentration of catalyst}}


Toller Artikel über das Molekül {{#moleculelink:|link=KLDYQWXVZLHTKT-UHFFFAOYSA-N|image=false|width=300|height=200}}, das total tolle Dinge kann.
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Effect of proton donor|importFile=}}


===Photosensitizer===
<chemform smiles="" inchi="" inchikey="KLDYQWXVZLHTKT-UHFFFAOYSA-N" height="200px" width="300px" float="none"></chemform>
===Investigation===
{{#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 donor TEOA ([[Molecule:100507|100507]]).
In this study, the experiments were done with the sacrificial electron donor TEOA ([[Molecule:100507|100507]]).
====Additives====
====Additives====
In this study, no additives were tested.
In this study, the experiments were done with the additives water ({{#moleculelink:|link=XLYOFNOQVPJJNP-UHFFFAOYSA-N|image=false|width=300|height=200}}) and phenol ({{#moleculelink:|link=ISWSIDIOOBJBQZ-UHFFFAOYSA-N|image=false|width=300|height=200}}).[[Category:Publication]]

Latest revision as of 19:39, 15 March 2025


Abstract[edit | edit source]

Summary[edit | edit source]

A photochemical reduction of CO2 to formic acid was shown using the rhenium catalyst and sensitizer [Re(bpy)2(CO)2][OTf] in combination with the supplemental photosensitizer [Ru(bpy)3][PF6]. Turnover numbers (TONs) up to 2750 for formic acid were reached in dimethylacetamide. The experiments were conducted under visible-light irradiation (λ = 405 nm) with TEOA (see section SEDs below) as sacrificial electron donor.

Advances and special progress[edit | edit source]

An unprecedented rhenium complex was used as an integrated photosensitizer/catalyst to generate formic acid from CO2; other rhenium catalysts only allow for the formation of CO as the reduction product.

Additional remarks[edit | edit source]

The complex [Re(bpy)2(CO)2][OTf] can act both as a photocatalyst and sensitizer, but its performance is considerably enhanced by the addition of [Ru(bpy)3][PF6] as supplemental photosensitizer. The variation of the catalyst concentration also showed a drastic influence on the performance of the catalytic system.

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 a rhenium complex as a catalyst. The catalytic system performs best (referring to the TON of formic acid production) in dimethylacetamide.

Catalyst[edit | edit source]

[Re(bpy)2(CO)2][OTf]

Photosensitizer[edit | edit source]

[Ru(bpy)3][PF6]

Investigations[edit | edit source]

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


[Ru(bpy)3][PF6]

0.008

TEOA

DMA

405 nm1.7512.5
2.


[Ru(bpy)3][PF6]

0.008

TEOA

DMF

405 nm215
3.


[Ru(bpy)3][PF6]

0.008

TEOA

MeCN

405 nm1.52.5
4.

[Re(bpy)2(CO)2][OTf]

8


TEOA

DMA

405 nm10.3
5.

[Re(bpy)2(CO)2][OTf]

8

[Ru(bpy)3][PF6]

0.008

TEOA

DMA

405 nm1.552
6.

[Re(bpy)2(CO)2][OTf]

8


TEOA

DMF

405 nm0.810.8
7.

[Re(bpy)2(CO)2][OTf]

8

[Ru(bpy)3][PF6]

0.008

TEOA

DMF

405 nm2.866
8.

[Re(bpy)2(CO)2][OTf]

8

[Ru(bpy)3][PF6]

0.008

TEOA

MeCN

405 nm
9.

[Re(bpy)2(CO)2][OTf]

8

[Ru(bpy)3][PF6]

0.008

TEOA

MeCN

405 nm2.811.5
catcat conc [µM]PSPS conc [mM]e-Dsolvent A..λexc [nm].TON H2TON HCOOH.
1.

[Re(bpy)2(CO)2][OTf]

0.2

[Ru(bpy)3][PF6]

0.0002

TEOA

DMF

405 nm00
2.

[Re(bpy)2(CO)2][OTf]

0.2

[Ru(bpy)3][PF6]

0.0002

TEOA

DMF

405 nm112.5
3.

[Re(bpy)2(CO)2][OTf]

0.2

[Ru(bpy)3][PF6]

0.0002

TEOA

DMF

405 nm2.519.5
4.

[Re(bpy)2(CO)2][OTf]

0.2

[Ru(bpy)3][PF6]

0.0002

TEOA

DMF

405 nm4.550.5
5.

[Re(bpy)2(CO)2][OTf]

0.2

[Ru(bpy)3][PF6]

0.0002

TEOA

DMF

405 nm659.5
6.

[Re(bpy)2(CO)2][OTf]

0.2

[Ru(bpy)3][PF6]

0.0002

TEOA

DMF

405 nm8.569.25
Investigation-Name: Time profile in DMF
Investigation-Name: Study on the concentration of catalyst
Investigation-Name: Effect of proton donor

Sacrificial electron donor[edit | edit source]

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

Additives[edit | edit source]

In this study, the experiments were done with the additives water (H2O) and phenol (PhOH).

Investigations