Photocatalytic CO2 reduction with aminoanthraquinone organic dyes

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Abstract

Summary

The photochemical reduction of CO2 to CO was shown using the iron complex Fe(DHPP)Cl in combination with the aminoanthraquinone photosensitizers xx-xx. Turnover numbers (TONs) of up to 21616 and a selectivity of >99.9% for CO were reached in DMF after 48 h of irradiation. The experiments were conducted under visible-light irradiation (λ > 400 nm) with BIH (see section SEDs below) as sacrificial electron donor.

Advances and special progress

The authors present an efficient photocatalytic system with naturally abundant photosensitizers and without rare metals in which both the photosensitizer and catalyst show a high activity.

Additional remarks

For the most efficient system investigated in this study, a TON of 21616 per mole of catalyst and a TON of 6012 per mole of photosensitizer was obtained.

Content of the published article in detail

The article contains results of a study for the reduction of CO2 to CO using an iron complex and different aminoanthraquinone-based photosensitizers. The catalytic system performs best (referring to the TON of CO production) in DMF with photosensitizer xx.

Catalyst

Fe(DHPP)Cl

Photosensitizer

100929 [Show R-Groups]

Investigation

catcat conc [µM]PSPS conc [mM]e-De-D conc [M]solvent Aλexc [nm].TON CO..
1.

Fe(DHPP)Cl

0.0006

Molecule:100930

0.02

BIH

0.06

DMF

>4002395
2.

Fe(DHPP)Cl

0.0006

Molecule:100958

0.02

BIH

0.06

DMF

>4002738
3.

Fe(DHPP)Cl

0.0006

Molecule:100959

0.02

BIH

0.06

DMF

>4003551
4.

Fe(DHPP)Cl

0.0006

Molecule:100931

0.02

BIH

0.06

DMF

>4008360
5.

Fe(DHPP)Cl

0.0006

Molecule:100932

0.02

BIH

0.06

DMF

>40021616
6.

Fe(DHPP)Cl

0.0006

Molecule:100933

0.02

BIH

0.06

DMF

>400907
catcat conc [µM]PSPS conc [mM]e-De-D conc [M]solvent Aλexc [nm]TON CO.
1.

Fe(DHPP)Cl

0.0005

Molecule:100932

0.0005

BIH

0.06

DMF

> 4003174
2.

Fe(DHPP)Cl

0.001

Molecule:100932

0.001

BIH

0.06

DMF

> 4003587
3.

Fe(DHPP)Cl

0.002

Molecule:100932

0.002

BIH

0.06

DMF

> 4003817
4.

Fe(DHPP)Cl

0.005

Molecule:100932

0.005

BIH

0.06

DMF

> 4004978
5.

Fe(DHPP)Cl

0.01

Molecule:100932

0.01

BIH

0.06

DMF

> 4004028
6.

Fe(DHPP)Cl

0.0005

Molecule:100932

0.02

BIH

0.06

DMF

> 40019158
7.

Fe(DHPP)Cl

0.0006

Molecule:100932

0.02

BIH

0.06

DMF

> 40021616
8.

Fe(DHPP)Cl

0.001

Molecule:100932

0.02

BIH

0.06

DMF

> 40017020
9.

Fe(DHPP)Cl

0.002

Molecule:100932

0.02

BIH

0.06

DMF

> 40011250
10.

Fe(DHPP)Cl

0.01

Molecule:100932

0.02

BIH

0.06

DMF

> 4003942
11.

Fe(DHPP)Cl

0.02

Molecule:100932

0.02

BIH

0.06

DMF

> 4002134
12.

Fe(DHPP)Cl

0.05

Molecule:100932

0.02

BIH

0.06

DMF

> 400891
13.

Fe(DHPP)Cl

0.002

Molecule:100932

0.015

BIH

0.06

DMF

> 4008772
14.

Fe(DHPP)Cl

0.002

Molecule:100932

0.01

BIH

0.06

DMF

> 4005593
15.

Fe(DHPP)Cl

0.005

Molecule:100932

0.01

BIH

0.06

DMF

> 4004128
16.

Fe(DHPP)Cl

0.01

Molecule:100932

0.01

BIH

0.06

DMF

> 4004028
17.

Fe(DHPP)Cl

0.02

Molecule:100932

0.01

BIH

0.06

DMF

> 4002325
18.

Fe(DHPP)Cl

0.002

Molecule:100932

0.005

BIH

0.06

DMF

> 4008780
19.

Fe(DHPP)Cl

0.005

Molecule:100932

0.005

BIH

0.06

DMF

> 4005258
20.

Fe(DHPP)Cl

0.01

Molecule:100932

0.005

BIH

0.06

DMF

> 4002576
21.

Fe(DHPP)Cl

0.02

Molecule:100932

0.005

BIH

0.06

DMF

> 4001539

Sacrificial electron donor

In this study, the experiments were done with the sacrificial electron donor BIH (100508).

Additives

In this study, the addition of Hg(0) was tested.

Investigations