A Dinuclear Cobalt Cryptate as a Homogeneous Photocatalyst for Highly Selective and Efficient Visible-Light Driven CO2 Reduction to CO in CH3CN-H2O Solution

Abstract

Summary

In this article CO₂ was reduced to CO by using the dinuclear cobalt catalyst (100776) along with the photosensitizer [Ru(phen)3][PF6]2 (100777). The photoreaction displayed a high TON of 16896 under 450 nm LED irradiation in 10 h. These good results are attributed to the synergetic effect of the two close cobalt atoms.

Advances and Special progress

This new catalyst displays high efficiency and a very good selectivity of 98% towards CO.

Content of the published article in detail

This article emphasizes on the efficiency and selectivity of this new dinuclear complex as it is the first one with such good properties in photocatalysis, especially as it works in water containing conditions and shows good results also with only 10% CO₂ in atmosphere.

Catalyst

(100776)

Photosensitizer

[Ru(phen)3][PF6]2 (100777)

Investigation

		cat	cat conc [µM]	PS	PS conc [mM]	e-D	e-D conc [M]	solvent A	.	.	additives	.	.	λexc [nm]	.	TON CO	.	TON H2	.	.	.
(edit)	1.	Molecule:100776	0.000025	[Ru(phen)3][PF6]2	0.4	TEOA	300	MeCN						450 nm (LED, 100 mW.cm^-2)		16896		368
(edit)	2.	Molecule:100776	0.0005	[Ru(phen)3][PF6]2	0.4	TEOA	300	MeCN			CO2/Ar (10:90) atmosphere			450 nm (LED, 100 mW.cm^-2)		684		56
(edit)	3.			[Ru(phen)3][PF6]2	0.4	TEOA	300	MeCN						450 nm (LED, 100 mW.cm^-2)
(edit)	4.	Molecule:100776	0.000025			TEOA	300	MeCN						450 nm (LED, 100 mW.cm^-2)
(edit)	5.	Molecule:100776	0.000025	[Ru(phen)3][PF6]2	0.4			MeCN						450 nm (LED, 100 mW.cm^-2)
(edit)	6.	Molecule:100776	0.000025	[Ru(phen)3][PF6]2	0.4	TEOA	300	MeCN
(edit)	7.	Molecule:100776	0.000025	[Ru(phen)3][PF6]2	0.4	TEOA	300	MeCN			Argon atmosphere			450 nm (LED, 100 mW.cm^-2)

Investigation-Name: Best result and control experiments

Sacrificial electron donor

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