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

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Catalysts

Photosensitizer

Sacrificial electron donor

TEOA

Investigations

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

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

	analyte	E0,0 [V]	E1,2 [V]	Ered1 [V]	Eox1 [V]	Ered2 [V]	Eox2 [V]	Ered3 [V]	Eox3 [V]	solvent	electrolyte	.	.	WE	.	.	RE	.
1.	Ru(bpy)2Cl2	0	0, -2.11;	0	0	0	0	0	0	MeCN	TBABF4			glassy carbon			Ag/AgNO3 in MeCN
2.	Ru(bpy)2CO3	0	0.45, -1.97;	0	0	0	0	0	0	MeCN	TBABF4			glassy carbon			Ag/AgNO3 in MeCN
3.	[Ru(bpy)2ClCO][PF6]	0	1.22, -1.75;	0	0	0	0	0	0	MeCN	TBABF4			glassy carbon			Ag/AgNO3 in MeCN
4.	[Ru(bpy)2HCO][PF6]	0	1.2, -1.61;	0	0	0	0	0	0	MeCN	TBABF4			glassy carbon			Ag/AgNO3 in MeCN

Investigation-Name: Table 3 - CVExportRefresh