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

Abstract

Summary

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

A 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

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

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

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

Photosensitizer

[Ru(bpy)3][PF6]

Investigation

1. REDIRECT Study on the concentration of catalyst

Investigation-Name: Table 1Export

Sacrificial electron donor

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

Additives

No additives were tested in this study.