Photocatalytic CO2 Reduction Mediated by Electron Transfer via the Excited Triplet State of Zn(II) Porphyrin

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Abstract

Summary

A photochemical reduction of CO2 to CO was shown using the zinc porphyrin dyad with a connected rhenium complex (Zn(tBuPP))-(Re(Phen)Br(CO)3) as a combined catalyst and photosensitizer molecule. Turnover numbers (TONs) of >1300 and a selectivity of >99.9% for CO were reached in DMA. The experiments were conducted under visible-light irradiation (λ = 420 nm) using BIH as sacrificial electron donor (see section SEDs below).

Advances and special progress

A selective method for the reduction of CO2 to CO with a porphyrin-rhenium complex dyad was presented, effectively linking the catalyst and photosensitizer in one molecule.

Additional remarks

Content of the published article in detail

The article contains results for the reduction of CO2 to CO under visible-light catalysis using (Zn(tBuPP))-(Re(Phen)Br(CO)3) as a catalyst and photosensitizer. The catalytic system performs best (referring to the TON of CO production) in DMA.

Catalyst and Photosensitizer

(Zn(tBuPP))-(Re(Phen)Br(CO)3)

Investigation

catcat conc [µM]e-De-D conc [M]solvent Aadditives..λexc [nm].TON CO....
1.

(Zn(tBuPP))-(Re(Phen)Br(CO)3)

0.05

BIH

0.05

DMA

phenol420 nm910
2.

(Zn(tBuPP))-(Re(Phen)Br(CO)3)

0.075

BIH

0.05

DMA

phenol420 nm1340
3.

(Zn(tBuPP))-(Re(Phen)Br(CO)3)

0.05

BIH

0.05

DMA

420 nm520
Investigation-Name: photocatalytic CO2 conversion

Sacrificial electron donor

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

Additives

In this study, phenol was used as an additive.

Investigations