Photocatalytic reduction of CO2 to CO and formate by a novel Co(ii) catalyst containing a cis-oxygen atom: photocatalysis and DFT calculations

Dalton Transactions : an International Journal of Inorganic Chemistry
Cheng-Yi ZhuFeng Wang

Abstract

The conversion of carbon dioxide (CO2) to fuels or value-added chemicals by a photocatalytic system has recently been of growing research interest. One of the challenges is the development of new catalysts with high activity and low cost. Cobalt complexes have long been used as catalysts for the reduction of CO2 in either electrochemical or photochemical systems. Recently, a series of cis-CoII complexes of tetradentate pyridine-amine ligands (N4-ligands) exhibited high activity in the reduction of CO2 in homogeneous photocatalytic systems. However, only CO was obtained as the reduction product. In this regard, herein, we report a novel cis-CoII complex C1 supported by an N4 ligand derivatized with TPA (TPA = tris(2-pyridylmethyl)amine). In contrast to the aforementioned CoII catalysts, which contain two halogen atoms at cis-positions, C1 contains one oxygen atom at one cis-coordination site. The structure of C1 was fully characterized by MS, elemental analysis, and single-crystal X-ray diffraction. Experiments on the photocatalytic reduction of CO2 revealed that C1 is able to convert CO2 to not only CO but also formate in a homogeneous system containing C1 as a catalyst, Ir(ppy)3 as a photosensitizer, and triethylamine as an el...Continue Reading

References

Sep 14, 2010·Journal of the American Chemical Society·Hui-Wen ShihDavid W C MacMillan
Dec 25, 2013·Chemical Communications : Chem Comm·Hiroyuki TakedaOsamu Ishitani
Jan 30, 2014·Chemical Society Reviews·Serena BerardiAntoni Llobet
Nov 15, 2014·Journal of the American Chemical Society·Julien BoninMathilde Routier
Mar 19, 2015·Chemical Communications : Chem Comm·Sharon Lai-Fung ChanNga Man Cheng
May 1, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Rong-Zhen LiaoPer E M Siegbahn
Dec 8, 2016·ChemSusChem·Ying-Ying LiRong-Zhen Liao
Jan 14, 2017·Chemical Society Reviews·Noémie ElgrishiMarc Fontecave
Jan 1, 2015·Chemical Science·James J Devery IiiCorey R J Stephenson

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Methods Mentioned

BETA
X-ray
column chromatography

Software Mentioned

Gaussian
SHELXTL

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