Highly Efficient and Selective Photocatalytic CO2 Reduction by Iron and Cobalt Quaterpyridine Complexes: Difference between revisions

Latest revision as of 09:55, 22 May 2024

A photochemical reduction of CO₂ to CO was shown using the cobalt complex [Fe(qpy)(H2O)2][ClO4]2 or the iron complex [Co(qpy)(H2O)2][ClO4]2 as catalysts in combination with the ruthenium-based photosensitizer Ru(bpy)3Cl2. Turnover numbers (TONs) up to 2660 and a selectivity of 98% for CO using the cobalt catalyst and TONs of >3000 and a selectivity of 95% for CO using the iron catalyst were reached in acetonitrile/triethanolamine. When swapping the ruthenium photosensitizer for the organic dye sensitizer purpurin, TONs of 790 and 1365 in DMF were obtained for the cobalt and iron catalysts, respectively. The experiments were conducted under visible-light irradiation (λ = 460 nm) using BIH as sacrificial reductant (see section SEDs below).

Advances and special progress[edit | edit source]

The photocatalytic reduction of CO₂ to CO by cobalt and iron complexes was shown with some of the highest TONs for homogeneous photocatalytic CO₂ reduction at that time and the (back then) highest TON for a system of fully earth-abundant materials was achieved.

Additional remarks[edit | edit source]

Content of the published article in detail[edit | edit source]

The article contains results for the reduction of CO₂ to CO under visible-light catalysis using cobalt and iron quaterpyridine complexes as catalysts. The catalytic system performs best (referring to the TON of CO production) in acetonitrile/triethanolamine using the cobalt complex [Co(qpy)(H2O)2][ClO4]2 and the ruthenium photosensitizer.

Catalysts[edit | edit source]

[Fe(qpy)(H2O)2][ClO4]2 [Co(qpy)(H2O)2][ClO4]2 Co(ClO4)2

Photosensitizers[edit | edit source]

Ru(bpy)3Cl2 purpurin

Investigations[edit | edit source]

	cat	cat conc [µM]	PS	PS conc [mM]	e-D	e-D conc [M]	solvent A	additives	λexc [nm]	TON CO	TON H2	TON HCOOH
1.	[Co(qpy)(H2O)2][ClO4]2	0.005	Ru(bpy)3Cl2	0.3	BIH	0.1	MeCN		460 (LED)	2660	23	35
2.	[Co(qpy)(H2O)2][ClO4]2	0	Ru(bpy)3Cl2	0.3	BIH	0.1	MeCN		460 (LED)	0	2	1
3.	[Co(qpy)(H2O)2][ClO4]2	0.005	Ru(bpy)3Cl2	0.3	BIH	0.1	MeCN	Argon atmosphere	460 (LED)	0	33	0
4.	[Co(qpy)(H2O)2][ClO4]2	0.005	Ru(bpy)3Cl2	0.3	BIH	0.1	MeCN		460 (LED)	182	0	11
5.	[Co(qpy)(H2O)2][ClO4]2	0.005	Ru(bpy)3Cl2	0.3			MeCN		460 (LED)	114	25	25
6.	[Co(qpy)(H2O)2][ClO4]2	0.01	Ru(bpy)3Cl2	0.3	BIH	0.1	MeCN		460 (LED)	1875	11	18
7.	[Co(qpy)(H2O)2][ClO4]2	0.2	Ru(bpy)3Cl2	0.3	BIH	0.1	MeCN		460 (LED)	1262	7	23
8.	[Co(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0.3	BIH	0.1	MeCN		460 (LED)	497	5	3
9.	[Co(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0.3			MeCN		460 (LED)	0	1	1
10.	[Co(qpy)(H2O)2][ClO4]2	0.1	Ru(bpy)3Cl2	0.3	BIH	0.1	MeCN		460 (LED)	466	2	22
11.	[Co(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0.5	BIH	0.1	MeCN		460 (LED)	521	49	6
12.	[Co(qpy)(H2O)2][ClO4]2	0	Ru(bpy)3Cl2	0.5	BIH	0.1	MeCN		460 (LED)	136	43	5
13.	[Co(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0.2	BIH	0.1	MeCN		460 (LED)	366	15	4
14.	[Co(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0.2	BIH	0.1	MeCN	Argon atmosphere	460 (LED)	0	3	1
15.	[Co(qpy)(H2O)2][ClO4]2	0	Ru(bpy)3Cl2	0.2	BIH	0.1	MeCN		460 (LED)	0	6	1
16.	Co(ClO4)2	0.05	Ru(bpy)3Cl2	0.3	BIH	0.1	MeCN		460 (LED)	33	11	1
17.	[Co(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0.3			MeCN		460 (LED)	0	1	1

Investigation-Name: Optimizations of conditions for Co(qpy)(H2O)2(ClO4)2 and Ru(bpy)3Cl2

	cat	cat conc [µM]	PS	PS conc [mM]	e-D	e-D conc [M]	solvent A	additives	λexc [nm]	TON CO	TON H2	TON HCOOH
1.	[Fe(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0.2	BIH	0.1	MeCN		460 (LED)	1879	15	48
2.	[Fe(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0.2	BIH	0.1	MeCN	Argon atmosphere	460 (LED)	0	1	3
3.	[Fe(qpy)(H2O)2][ClO4]2	0	Ru(bpy)3Cl2	0.2	BIH	0.1	MeCN		460 (LED)	0	0	0
4.	[Fe(qpy)(H2O)2][ClO4]2	0.02	Ru(bpy)3Cl2	0.2	BIH	0.1	MeCN		460 (LED)	2660	29	51
5.	[Fe(qpy)(H2O)2][ClO4]2	0.02	Ru(bpy)3Cl2	0.2	BIH	0.1	MeCN	Argon atmosphere	460 (LED)	0	0	0
6.	[Fe(qpy)(H2O)2][ClO4]2	0.01	Ru(bpy)3Cl2	0.2	BIH	0.1	MeCN		460 (LED)	3087	121	35
7.	[Fe(qpy)(H2O)2][ClO4]2	0.01	Ru(bpy)3Cl2	0.2	BIH	0.1	MeCN	Argon atmosphere	460 (LED)	0	0	0
8.	[Fe(qpy)(H2O)2][ClO4]2	0.005	Ru(bpy)3Cl2	0.2	BIH	0.1	MeCN		460 (LED)	3844	118	534
9.	[Fe(qpy)(H2O)2][ClO4]2	0.005	Ru(bpy)3Cl2	0.2	BIH	0.1	MeCN	Argon atmosphere	460 (LED)	0	1	0
10.	[Fe(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0.05	BIH	0.1	MeCN		460 (LED)	1336	10	34
11.	[Fe(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0.05	BIH	0.1	MeCN		460 (LED)	0	0	0
12.	[Fe(qpy)(H2O)2][ClO4]2	0	Ru(bpy)3Cl2	0.05	BIH	0.1	MeCN		460 (LED)	0	1	0
13.	[Fe(qpy)(H2O)2][ClO4]2	0.005	Ru(bpy)3Cl2	0.2			MeCN		460 (LED)	160	8	22

Investigation-Name: Optimizations of conditions for Fe(qpy)(H2O)2(ClO4)2 and Ru(bpy)3Cl2

	cat	cat conc [µM]	PS	PS conc [mM]	e-D	e-D conc [M]	solvent A	additives	λexc [nm]	TON CO	TON H2	TON HCOOH
1.	[Co(qpy)(H2O)2][ClO4]2	0.05	purpurin	2	BIH	0.1	DMF		460 (LED)	197	1	9
2.	[Co(qpy)(H2O)2][ClO4]2	0.05	purpurin	2	BIH	0.1	DMF	Argon atmosphere	460 (LED)	0	78	6
3.	[Co(qpy)(H2O)2][ClO4]2	0	purpurin	2	BIH	0.1	DMF		460 (LED)	0	0	90
4.	[Co(qpy)(H2O)2][ClO4]2	0.05	purpurin	0	BIH	0.1	DMF		460 (LED)	27	0	4
5.	[Co(qpy)(H2O)2][ClO4]2	0.05	purpurin	2			DMF		460 (LED)	0	0	3
6.	[Co(qpy)(H2O)2][ClO4]2	0.005	purpurin	2	BIH	0.1	DMF		460 (LED)	790	11	78
7.	[Co(qpy)(H2O)2][ClO4]2	0.005	purpurin	2	BIH	0.1	DMF	Argon atmosphere	460 (LED)	0	226	167
8.	[Co(qpy)(H2O)2][ClO4]2	0.005	purpurin	2			DMF	Argon atmosphere	460 (LED)	0	0	26
9.	Co(ClO4)2	0.05	purpurin	2	BIH	0.1	DMF		460 (LED)	0	0	3

Investigation-Name: Optimizations of conditions for Co(qpy)(H2O)2(ClO4)2 and purpurin

	cat	cat conc [µM]	PS	PS conc [mM]	e-D	e-D conc [M]	solvent A	additives	λexc [nm]	TON CO	TON H2	TON HCOOH
1.	[Fe(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0.02	BIH	0.1	DMF		460 (LED)	520	0	14
2.	[Fe(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0.02	BIH	0.1	DMF	Argon atmosphere	460 (LED)	0	3	21
3.	[Fe(qpy)(H2O)2][ClO4]2	0	Ru(bpy)3Cl2	0.02	BIH	0.1	DMF		460 (LED)	0	139	0
4.	[Fe(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0.05	BIH	0.1	DMF		460 (LED)	520	0	21
5.	[Fe(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0.05	BIH	0.1	DMF	Argon atmosphere	460 (LED)	0	0	8
6.	[Fe(qpy)(H2O)2][ClO4]2	0	Ru(bpy)3Cl2	0.05	BIH	0.1	DMF		460 (LED)	0	0	10
7.	[Fe(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0.2	BIH	0.1	DMF		460 (LED)	350	1	23
8.	[Fe(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0.2	BIH	0.1	DMF	Argon atmosphere	460 (LED)	0	54	20
9.	[Fe(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0	BIH	0.1	DMF		460 (LED)	0	0	24
10.	[Fe(qpy)(H2O)2][ClO4]2	0.05	Ru(bpy)3Cl2	0.02	BIH	0.1	DMF		460 (LED)	0	0	8
11.	[Fe(qpy)(H2O)2][ClO4]2	0.005	Ru(bpy)3Cl2	0.02	BIH	0.1	DMF		460 (LED)	1365	0	115
12.	[Fe(qpy)(H2O)2][ClO4]2	0.005	Ru(bpy)3Cl2	0.02	BIH	0.1	DMF	Argon atmosphere	460 (LED)	0	52	88

Investigation-Name: Optimizations of conditions for Fe(qpy)(H2O)2(ClO4)2

Sacrificial electron donor[edit | edit source]

In this study, the experiments were done with the sacrificial reductant BIH (100508).

Additives[edit | edit source]

In this study, control experiments were conducted under an argon atmosphere.

Investigations

Optimizations of conditions for Co(qpy)(H2O)2(ClO4)2 and Ru(bpy)3Cl2 (Molecular process, Photocatalytic CO2 conversion experiments)
Optimizations of conditions for Co(qpy)(H2O)2(ClO4)2 and purpurin (Molecular process, Photocatalytic CO2 conversion experiments)
Optimizations of conditions for Fe(qpy)(H2O)2(ClO4)2 (Molecular process, Photocatalytic CO2 conversion experiments)
Optimizations of conditions for Fe(qpy)(H2O)2(ClO4)2 and Ru(bpy)3Cl2 (Molecular process, Photocatalytic CO2 conversion experiments)

DOI	10.1021/jacs.6b06002
Authors	Zhenguo Guo, Siwei Cheng, Claudio Cometto, Elodie Anxolabéhère-Mallart, Siu-Mui Ng, Chi-Chiu Ko, Guijian Liu, Lingjing Chen, Marc Robert, Tai-Chu Lau,
Submitted	22.07.2016
Published online	26.07.2016
Licenses	-
Subjects	Colloid and Surface Chemistry, Biochemistry, General Chemistry, Catalysis
Go to literature page

@@ Line 1: / Line 1: @@
-==== {{#doiinfobox: 10.1021/jacs.6b06002}} [[Category:Photocatalytic CO2 conversion to CO]]
+{{DOI|doi=10.1021/jacs.6b06002}}
-{{BaseTemplate}} ====
+[[Category:Photocatalytic CO2 conversion to CO]]
+{{BaseTemplate}}
+===Abstract===
+====Summary====
+A photochemical reduction of CO<sub>2</sub> to CO was shown using the cobalt complex {{#moleculelink:|link=NLKWUAXOGCKGEY-UHFFFAOYSA-L|image=false|width=300|height=200}} or the iron complex {{#moleculelink:|link=OZQYFMFOIFRRLI-UHFFFAOYSA-L|image=false|width=300|height=200}} as catalysts in combination with the ruthenium-based photosensitizer {{#moleculelink:|link=SJFYGUKHUNLZTK-UHFFFAOYSA-L|image=false|width=300|height=200}}. Turnover numbers (TONs) up to 2660 and a selectivity of 98% for CO using the cobalt catalyst and TONs of >3000 and a selectivity of 95% for CO using the iron catalyst were reached in acetonitrile/triethanolamine. When swapping the ruthenium photosensitizer for the organic dye sensitizer {{#moleculelink:|link=BBNQQADTFFCFGB-UHFFFAOYSA-N|image=false|width=300|height=200}}, TONs of 790 and 1365 in DMF were obtained for the cobalt and iron catalysts, respectively. The experiments were conducted under visible-light irradiation (λ = 460 nm) using BIH as sacrificial reductant (see section SEDs below).
+==== Advances and special progress====
+The photocatalytic reduction of CO<sub>2</sub> to CO by cobalt and iron complexes was shown with some of the highest TONs for homogeneous photocatalytic CO<sub>2</sub> reduction at that time and the (back then) highest TON for a system of fully earth-abundant materials was achieved.
+====Additional remarks====
+===Content of the published article in detail===
+The article contains results for the reduction of CO<sub>2</sub> to CO under visible-light catalysis using cobalt and iron quaterpyridine complexes as catalysts. The catalytic system performs best (referring to the TON of CO production) in acetonitrile/triethanolamine using the cobalt complex {{#moleculelink:|link=OZQYFMFOIFRRLI-UHFFFAOYSA-L|image=false|width=300|height=200}} and the ruthenium photosensitizer.
 ==== Catalysts ====
 <chemform smiles="C1C2C3C=CC=C4C5C=CC=C6C7C=CC=CN=7[Fe+2](O)(O)(N=34)(N=56)N=2C=CC=1.Cl([O-])(=O)(=O)=O.Cl([O-])(=O)(=O)=O" inchi="1S/C20H14N4.2ClHO4.Fe.2H2O/c1-3-13-21-15(7-1)17-9-5-11-19(23-17)20-12-6-10-18(24-20)16-8-2-4-14-22-16;2*2-1(3,4)5;;;/h1-14H;2*(H,2,3,4,5);;2*1H2/q;;;+2;;/p-2" inchikey="NLKWUAXOGCKGEY-UHFFFAOYSA-L" height="200px" width="300px" float="none">
@@ Line 180: / Line 190: @@
 M  V30 40 2 33 36
 M  V30 41 1 33 37
+M  V30 END BOND
+M  V30 END CTAB
+M  END
+</chemform><chemform smiles="Cl([O-])(=O)(=O)=O.Cl([O-])(=O)(=O)=O.[Co+2]" inchi="1S/2ClHO4.Co/c2*2-1(3,4)5;/h2*(H,2,3,4,5);/q;;+2/p-2" inchikey="BSUSEPIPTZNHMN-UHFFFAOYSA-L" height="200px" width="300px" float="none">
+  -INDIGO-08112313202D
+  0  0  0  0  0  0  0  0  0  0 V3000
+M  V30 BEGIN CTAB
+M  V30 COUNTS 11 8 0 0 0
+M  V30 BEGIN ATOM
+M  V30 1 Cl 5.85991 -4.47939 0.0 0
+M  V30 2 O 5.02832 -4.47939 0.0 0
+M  V30 3 O 5.86723 -3.65532 0.0 0
+M  V30 4 O 6.74625 -4.48672 0.0 0
+M  V30 5 O 5.85991 -5.31088 0.0 0 CHG=-1
+M  V30 6 Cl 10.3764 -4.54882 0.0 0
+M  V30 7 O 9.53063 -4.54882 0.0 0
+M  V30 8 O 10.3839 -3.71065 0.0 0
+M  V30 9 O 11.1931 -4.55661 0.0 0
+M  V30 10 O 10.3764 -5.39468 0.0 0 CHG=-1
+M  V30 11 Co 7.8 -4.45 0.0 0 CHG=2
+M  V30 END ATOM
+M  V30 BEGIN BOND
+M  V30 1 2 1 2
+M  V30 2 2 1 3
+M  V30 3 2 1 4
+M  V30 4 1 1 5
+M  V30 5 2 6 7
+M  V30 6 2 6 8
+M  V30 7 2 6 9
+M  V30 8 1 6 10
 M  V30 END BOND
 M  V30 END CTAB
@@ Line 338: / Line 379: @@
 ==== Investigations ====
+{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Optimizations of conditions for Co(qpy)(H2O)2(ClO4)2 and Ru(bpy)3Cl2}}
+{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Optimizations of conditions for Fe(qpy)(H2O)2(ClO4)2 and Ru(bpy)3Cl2}}
+{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Optimizations of conditions for Co(qpy)(H2O)2(ClO4)2 and purpurin}}
+{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Optimizations of conditions for Fe(qpy)(H2O)2(ClO4)2}}
-{{#experimentlist:|form=Cyclic_Voltammetry_experiments|name=Fe(qpy)(H2O)2(ClO4)2 and Ru(bpy)3Cl2}}
+==== Sacrificial electron donor ====
+In this study, the experiments were done with the sacrificial reductant BIH ([[Molecule:100508|100508]]).
+==== Additives====
+In this study, control experiments were conducted under an argon atmosphere.[[Category:Publication]]

Highly Efficient and Selective Photocatalytic CO2 Reduction by Iron and Cobalt Quaterpyridine Complexes: Difference between revisions

Latest revision as of 09:55, 22 May 2024

Contents

Abstract[edit | edit source]

Summary[edit | edit source]

Advances and special progress[edit | edit source]

Additional remarks[edit | edit source]

Content of the published article in detail[edit | edit source]

Catalysts[edit | edit source]

Photosensitizers[edit | edit source]

Investigations[edit | edit source]

Sacrificial electron donor[edit | edit source]

Additives[edit | edit source]

Investigations

Topics

Highly Efficient and Selective Photocatalytic CO2 Reduction by Iron and Cobalt Quaterpyridine Complexes: Difference between revisions

Latest revision as of 09:55, 22 May 2024

Abstract[edit | edit source]

Summary[edit | edit source]

Advances and special progress[edit | edit source]

Additional remarks[edit | edit source]

Content of the published article in detail[edit | edit source]

Catalysts[edit | edit source]

Photosensitizers[edit | edit source]

Investigations[edit | edit source]

Sacrificial electron donor[edit | edit source]

Additives[edit | edit source]

Investigations

Current site

Topics