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

Revision as of 12:11, 12 January 2024

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Abstract

Summary

A photochemical reduction of CO₂ to formic acid was shown using a system containing an iridium-based photosensitizer, ruthenium photocatalyst and triethanolamine as the electron donor. Turnover numbers up to 526 and a selectivity of 80% towards formic acid were observed if the reaction was performed with [Ir(ppy)₂(bpy)]PF₆ ([Ir(ppy)2(bpy)][PF6]) as the photosensitizer and [Ru(bpy)₂(Cl)(CO)]PF₆ (100837) as the catalyst. The experiments were conducted under irradiation with Hg-lamp equipped with a λ=400–700 nm filter.

Advances and special progress

The employed photocatalytic system showed activity for the photoreduction of Na₂CO₃ to formic acid as well. A TON of 53 was observed after 5h reaction time.

Additional remarks

Experiments using different electron and proton donors such as triethylamine (TEA) and 1-benzyl-1,4-dihydronicotinamide (BNAH) were unsuccessful as the observed activities were lower than those obtained in the presence of TEOA.

Content of the published article in detail

The article contains results for the reduction of CO2 to formic under visible-light catalysis using ruthenium complexes as catalysts, the iridium complex [Ir(ppy)₂(bpy)]PF₆ ([Ir(ppy)2(bpy)][PF6]) as a photosensitizer and triethanolamine as the electron donor. The catalytic system performs best (referring to the TON of HCOOH production) with [Ru(bpy)₂(Cl)(CO)]PF₆ (100837) as photocatalyst.

Catalysts

Ru(bpy)2CO3

Photosensitizer

[Ir(ppy)2(bpy)][PF6]

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 1

	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 2

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

Investigation-Name: Table 3 - CV

Sacrificial electron donor

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

Additives

No additives were used in the described experiments.

Investigations

CO2 reduction experiments (Molecular process, Photocatalytic CO2 conversion experiments)
Optimization of concentrations (Molecular process, Photocatalytic CO2 conversion experiments)
Table 1 (Molecular process, Photocatalytic CO2 conversion experiments)
Table 2 (Molecular process, Photocatalytic CO2 conversion experiments)
Table 3 - CV (Assay, Cyclic Voltammetry experiments)

DOI	10.1002/cctc.201500494
Authors	Alonso Rosas-Hernández, Henrik Junge, Matthias Beller,
Submitted	26.08.2015
Published online	26.08.2015
Licenses	http://doi.wiley.com/10.1002/tdm_license_1.1,
Subjects	Inorganic Chemistry, Organic Chemistry, Physical and Theoretical Chemistry, Catalysis
Go to literature page

@@ Line 18: / Line 18: @@
 ==== Catalysts ====
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-M  V30 3 C 7.64012 -3.3494 0.0 0
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-M  V30 4 N 8.38676 -4.64689 0.0 0
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-M  V30 5 C 6.89063 -4.65077 0.0 0
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-M  V30 6 C 7.642 -5.07879 0.0 0
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-M  V30 8 C 9.88323 -2.05337 0.0 0
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-M  V30 17 C 6.91225 -7.22316 0.0 0
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-M  V30 19 C 9.15762 -7.65089 0.0 0
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-M  V30 21 N 9.9064 -7.21724 0.0 0
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-M  V30 22 C 10.6552 -8.51351 0.0 0
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-M  V30 23 C 9.15904 -8.51983 0.0 0
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-M  V30 24 C 9.91111 -8.94663 0.0 0
+M  V30 24 C 8.77162 -7.93243 0.0 0
-M  V30 25 Ru 9.93164 -5.38338 0.0 0 CHG=2
+M  V30 25 Ru 7.51723 -4.8062 0.0 0 CHG=2
-M  V30 26 Cl 11.3477 -4.48338 0.0 0 CHG=-1
-M  V30 27 Cl 11.4477 -6.20838 0.0 0 CHG=-1
 M  V30 END ATOM
 M  V30 BEGIN BOND
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Photochemical Reduction of Carbon Dioxide to Formic Acid using Ruthenium(II)-Based Catalysts and Visible Light: Difference between revisions

Revision as of 12:11, 12 January 2024

Contents

Abstract

Summary

Advances and special progress

Additional remarks

Content of the published article in detail

Catalysts

Photosensitizer

Investigations

Sacrificial electron donor

Additives

Investigations

Topics

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

Revision as of 12:11, 12 January 2024

Abstract

Summary

Advances and special progress

Additional remarks

Content of the published article in detail

Catalysts

Photosensitizer

Investigations

Sacrificial electron donor

Additives

Investigations

Current site

Topics