Photochemical Reduction of Carbon Dioxide to Formic Acid using Ruthenium(II)-Based Catalysts and Visible Light

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Catalysts

Ru(bpy)2CO3 (100482) [Ru(bpy)(H2O)(CO)][PF6] (100836)

Photosensitizer

Sacrificial electron donor

TEOA (100507)

Investigations

		cat	cat conc [µM]	PS	PS conc [mM]	e-D	solvent A	.	λexc [nm]	TON CO	TON H2	TON HCOOH	.	.
(edit)	1.	Ru(bpy)2Cl2	0.025	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	1	2	13
(edit)	2.	Ru(bpy)2CO3	0.025	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	2	4	21
(edit)	3.	[Ru(bpy)2ClCO][PF6]	0.025	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	13	8	62
(edit)	4.	[Ru(bpy)2HCO][PF6]	0.025	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	8	8	34
(edit)	5.	[Ru(bpy)(H2O)(CO)][PF6]	0.025	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	7	9	40
(edit)	6.	[Ru(bpy)(AcMe)2][PF6]	0.025	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	3	4	27

Investigation-Name: Table 1

		cat	cat conc [µM]	PS	PS conc [mM]	e-D	solvent A	.	λexc [nm]	TON CO	TON H2	TON HCOOH	.	.
(edit)	1.	Ru(bpy)2Cl2	0.0062	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	3	9	26
(edit)	2.	Ru(bpy)2CO3	0.0062	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	3	11	39
(edit)	3.	[Ru(bpy)2ClCO][PF6]	0.0062	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	19	19	117
(edit)	4.	[Ru(bpy)2HCO][PF6]	0.0062	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	21	16	107
(edit)	5.	[Ru(bpy)(H2O)(CO)][PF6]	0.0062	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	21	14	75
(edit)	6.	[Ru(bpy)(AcMe)2][PF6]	0.0062	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	4	12	64
(edit)	7.	[Ru(bpy)2ClCO][PF6]	0.0031	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	36	33	296
(edit)	8.	[Ru(bpy)2HCO][PF6]	0.0031	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	16	29	145
(edit)	9.	[Ru(bpy)(H2O)(CO)][PF6]	0.0031	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	34	28	211
(edit)	10.	[Ru(bpy)2ClCO][PF6]	0.0016	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	40	67	419
(edit)	11.	[Ru(bpy)2HCO][PF6]	0.0016	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	25	62	225
(edit)	12.	[Ru(bpy)(H2O)(CO)][PF6]	0.0016	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	45	65	335
(edit)	13.	[Ru(bpy)(AcMe)2][PF6]	0.0016	[Ir(ppy)2(bpy)][PF6]	0.025	TEOA	NMP		400 - 700	4	44	75

Investigation-Name: Table 2

		analyte	reduction potential	solvent	electrolyte	.	.	WE	.	.	RE	.
(edit)	1.	Ru(bpy)2Cl2	0,-2.11	MeCN	TBABF4			glassy carbon			Ag/AgNO3 in MeCN
(edit)	2.	Ru(bpy)2CO3	0.45,-1.97	MeCN	TBABF4			glassy carbon			Ag/AgNO3 in MeCN
(edit)	3.	[Ru(bpy)2ClCO][PF6]	1.22,-1.75	MeCN	TBABF4			glassy carbon			Ag/AgNO3 in MeCN
(edit)	4.	[Ru(bpy)2HCO][PF6]	1.20,-1.61	MeCN	TBABF4			glassy carbon			Ag/AgNO3 in MeCN

Investigation-Name: Table 3 - CV