Highly Efficient and Robust Photocatalytic Systems for CO2 Reduction Consisting of a Cu(I) Photosensitizer and Mn(I) Catalysts

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DOI 10.1021/jacs.8b10619
Authors Hiroyuki Takeda, Hiroko Kamiyama, Kouhei Okamoto, Mina Irimajiri, Toshihide Mizutani, Kazuhide Koike, Akiko Sekine, Osamu Ishitani,
Submitted 27.11.2018
Published online 27.11.2018
Licenses http://pubs.acs.org/page/policy/authorchoice_termsofuse.html,
Subjects Colloid and Surface Chemistry, Biochemistry, General Chemistry, Catalysis
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Abstract

Summary

A photochemical reduction of CO2 to CO or formic acid was shown using the manganese complexes Mn(bpy)(CO)3Br, 100845 or Mn(oMesbpy)(CO)2Br as catalyst in combination with the copper-based photosensitizer [Cu(phen)-(dPPh-Bu)2]2[PF6]2. Turnover numbers (TONs) over 1300 for CO were reached in dimethylacetamide/TEOA for complex 100845. The highest selectivity for CO (96%) was obtained for catalyst Mn(oMesbpy)(CO)2Br while catalyst Mn(bpy)(CO)3Br allowed for the reduction of CO2 to formic acid with a selectivity of 74%. The experiments were conducted under visible-light irradiation (λ = 436 nm) using BIH as sacrificial reductants (see section SEDs below).

Advances and special progress

Employing catalyst 100845, the highest quantum yield for CO2 reduction using abundant elements (57%) at that time was achieved.

Additional remarks

The authors could show that the substituents on the manganese complexes largely influenced the photocatalytic efficiency and product selectivity.

Content of the published article in detail

The article contains results for the reduction of CO2 to CO and formic acid under visible-light catalysis using manganese complexes as catalysts. The catalytic system performs best (referring to the TON of CO production) in DMA/TEOA.

Catalyst

100751 [Show R-Groups] Mn(oMesbpy)(CO)2Br

Photosensitizer

[Cu(phen)-(dPPh-Bu)2]2[PF6]2

Investigation

Investigation-Name: Table 1

Sacrificial electron donor

In this study, the experiments were done with the sacrificial electron donors TEOA (100507) and BIH (100508).

Additives

In this study, no additives were tested.

Investigations