A Cu(I) Co(II) cryptate for the visible light-driven reduction of CO2

Abstract

Summary

Co^IICo^II 100905 and Zn^IICo^II 100901 cryptates were previously investigated as efficient photocatalysts. Herein, the group reported the synthesis of new {N^SN^N}_m ligands with Cu^IM^II (M^II = Co^II, Ni^II, Cu^II) to investigate on different metals and the addition of sulfur. Cu^ICo^II-{N^SN^N}_m showed high catalytic activity with a TON of 2305 and 98% selectivity towards CO. Further experiments showed that the activity can be attributed to the synergy between the metal centers, in particular, an increased distance between the metal atoms decreases activity.

Additional remarks

The syntheses of the catalysts were detailed in the following publication: [Aac21]

Content of the published article in detail

Catalyst

100799 100895 100903 100897 100900 100905 100901

Photosensitizer

[Ru(phen)3][PF6]2

Investigation

TOF is in min^-1.

	cat	cat conc [µM]	PS	PS conc [mM]	e-D	e-D conc [M]	solvent A	.	.	additives	.	λexc [nm]	.	TON CO	.	.	TON H2	.	.	.
1.	Molecule:100799	0.002	[Ru(phen)3][PF6]2	0.4	TEOA	0.3	MeCN					blue LED (450, 1200 mcd, 0.8 cm^2)		2305			47
2.			[Ru(phen)3][PF6]2	0.4	TEOA	0.3	MeCN					blue LED (450, 1200 mcd, 0.8 cm^2)		0			12.75
3.	Molecule:100799	0.002			TEOA	0.3	MeCN					blue LED (450, 1200 mcd, 0.8 cm^2)		0			2.22
4.	Molecule:100799	0.002	[Ru(phen)3][PF6]2	0.4			MeCN					blue LED (450, 1200 mcd, 0.8 cm^2)		0			2.05
5.	Molecule:100799	0.002	[Ru(phen)3][PF6]2	0.4	TEOA	0.3	MeCN							0			0
6.	Molecule:100799	0.002	[Ru(phen)3][PF6]2	0.4	TEOA	0.3	MeCN					blue LED (450, 1200 mcd, 0.8 cm^2)		0			0
7.	Molecule:100799	0.002	[Ru(phen)3][PF6]2	0.4	TEOA	0.3	MeCN					blue LED (450, 1200 mcd, 0.8 cm^2)		55.25			12.13
8.	Molecule:100799	0.002	[Ru(phen)3][PF6]2	0.4	TEOA	0.3	MeCN					blue LED (450, 1200 mcd, 0.8 cm^2)		1558			62.50
9.	Molecule:100799	0.002	[Ru(phen)3][PF6]2	0.4	TEOA	0.3	MeCN					blue LED (450, 1200 mcd, 0.8 cm^2)		19.78			5.55
10.	Molecule:100799	0.002	[Ru(phen)3][PF6]2	0.4	TEOA	0.3	MeCN			100 µL Hg(0)		blue LED (450, 1200 mcd, 0.8 cm^2)		1835			53.50
11.	Molecule:100895	0.002	[Ru(phen)3][PF6]2	0.4	TEOA	0.3	MeCN					blue LED (450, 1200 mcd, 0.8 cm^2)		11.60			6.975
12.	Molecule:100903	0.002	[Ru(phen)3][PF6]2	0.4	TEOA	0.3	MeCN					blue LED (450, 1200 mcd, 0.8 cm^2)		1425			33.75
13.	Molecule:100897	0.002	[Ru(phen)3][PF6]2	0.4	TEOA	0.3	MeCN					blue LED (450, 1200 mcd, 0.8 cm^2)		695			16.78
14.	Molecule:100799	0.0015	[Ru(phen)3][PF6]2	0.4	TEOA	0.3	MeCN					blue LED (450, 1200 mcd, 0.8 cm^2)		1623			28.37
15.	Molecule:100799	0.001	[Ru(phen)3][PF6]2	0.4	TEOA	0.3	MeCN					blue LED (450, 1200 mcd, 0.8 cm^2)		1565			31.30
16.	Molecule:100799	0.0005	[Ru(phen)3][PF6]2	0.4	TEOA	0.3	MeCN					blue LED (450, 1200 mcd, 0.8 cm^2)		1660			42.10
17.	Molecule:100905	0.002	[Ru(phen)3][PF6]2	0.4	TEOA	0.3	MeCN					blue LED (450, 1200 mcd, 0.8 cm^2)		2900			93.75
18.	Molecule:100900	0.002	[Ru(phen)3][PF6]2	0.4	TEOA	0.3	MeCN					blue LED (450, 1200 mcd, 0.8 cm^2)		1598			44.75
19.	Molecule:100901	0.002	[Ru(phen)3][PF6]2	0.4	TEOA	0.3	MeCN					blue LED (450, 1200 mcd, 0.8 cm^2)		1553			40

Investigation-Name: Photocatalytic reduction of CO2Export

Sacrificial electron donor

In this study, the experiments were done with the sacrificial electron donors TEOA.

Additives

In this study, the addition of Hg(0) was tested and control experiments under argon atmosphere were conducted.