Photocatalytic Reduction of CO2 by Highly Efficient Homogeneous FeII Catalyst based on 2,6-Bis(1’,2’,3’-triazolyl-methyl)pyridine. Comparison with Analogues.: Difference between revisions

Latest revision as of 16:12, 10 January 2025

A photochemical reduction of CO₂ to CO was shown using the iron complex 100941 as catalyst in combination with the copper photosensitizer 100940. Turnover numbers (TONs) of 576 and a selectivity of 67% for CO were reached in MeCN/TEOA. The experiments were conducted under visible-light irradiation (λ = 420 nm) using BIH as sacrificial electron donor (see section SEDs below). The homoleptic iron complex 100942 and the cobalt complexes 100944 and 100945 were tested for CO₂ reduction as well, but did not show substantial conversion of CO₂ to CO.

Advances and special progress[edit | edit source]

The authors reported a iron complex with one of the highest activities for CO₂ reduction among earth-abundant systems with monometallic iron catalysts.

Additional remarks[edit | edit source]

In addition to the production of CO, a substantial amount of H₂ (TON of 287) was formed in the reduction process with complex 100941.

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 the iron complex 100941 as a catalyst. The catalytic system performs best (referring to the TON of CO production) in MeCN/TEOA.

Catalyst[edit | edit source]

100941 100942 100944 100945

Photosensitizer[edit | edit source]

100940

Investigation[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 CH4	TON H2
1.	Molecule:100941	10	Molecule:100940	1.0	BIH	0.02	MeCN		420	107		43
2.	Molecule:100941	10	Molecule:100940	1.0	BIH	0.02	MeCN		420	109		54
3.	Molecule:100941	33	Molecule:100940	0.33	BIH	0.00666	MeCN		420	238		137
4.	Molecule:100941	33	Molecule:100940	1.0	BIH	0.02	MeCN		420	314		151
5.	Molecule:100941	10	Molecule:100940	1.0	BIH	0.02	MeCN		420	576		287
6.	Molecule:100941	10	Molecule:100940	1.0	BIH	0.1	MeCN		420	80		33
7.	Molecule:100941	10	Molecule:100940	1.0	BIH	0.02	MeCN	water	420	7.4		6.4
8.	Molecule:100941	10	Molecule:100940	1.0	BIH	0.02	MeCN		420	3.2		1.6
9.	Molecule:100941	10	Molecule:100940	1.0	BIH	0.02	MeCN		420	80		34
10.	Molecule:100941	10	Molecule:100940	1.0	BIH	0.02	MeCN		420	100		43
11.			Molecule:100940	1.0	BIH	0.02	MeCN		420	0		1
12.	Molecule:100941	10			BIH	0.02	MeCN		420	0		0
13.	Molecule:100941	10	Molecule:100940	1.0	BIH	0.02	MeCN			0		0
14.	Molecule:100941	10	Molecule:100940	1.0	BIH	0.02	MeCN		420	0		0
15.	Molecule:100941	10	Molecule:100940	1.0	BIH	0.02	MeCN	Hg	420	93		50
16.	Molecule:100941	10	Molecule:100940	1.0	BIH	0.02	MeCN		solar simulator	450		348
17.	Molecule:100941	10	Molecule:100940	1.0			MeCN		420	6.8	0	0
18.	Molecule:100941	10	Molecule:100940	1.0	BIH	0.02	MeCN		420	44	1.16	0
19.	Molecule:100941	10	Molecule:100940	1.0			MeCN		420	0	0	0
20.	Molecule:100941	10	Molecule:100940	1.0	BIH	0.02	MeCN		420	0	0	0

Investigation-Name: Optimization of CO2 reduction conditions

	cat	cat conc [µM]	PS	PS conc [mM]	e-D	e-D conc [M]	solvent A	λexc [nm]	TON CO	TON H2
1.	Molecule:100942	100	Molecule:100940	1.0	BIH	0.02	MeCN	420	7.8	2
2.	Molecule:100944	100	Molecule:100940	1.0	BIH	0.02	MeCN	420	1.1	7.4
3.	Molecule:100945	100	Molecule:100940	1.0	BIH	0.02	MeCN	420	0.7	4.9

Investigation-Name: CO2 reduction experiments testing different catalysts

Sacrificial electron donor[edit | edit source]

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

Additives[edit | edit source]

In this study, control experiments with Hg and without CO₂ were conducted.

Investigations

CO2 reduction experiments testing different catalysts (Molecular process, Photocatalytic CO2 conversion experiments)
Optimization of CO2 reduction conditions (Molecular process, Photocatalytic CO2 conversion experiments)

DOI	10.1002/cctc.202201163
Authors	Lisa‐Lou Gracia, Elham Barani, Jonas Braun, Anthony B. Carter, Olaf Fuhr, Annie K. Powell, Karin Fink, Claudia Bizzarri,
Submitted	07.10.2022
Published online	28.10.2022
Licenses	http://creativecommons.org/licenses/by-nc/4.0/,
Subjects	-
Go to literature page

@@ Line 4: / Line 4: @@
 ===Abstract===
 ====Summary====
-A photochemical reduction of CO<sub>2</sub> to CO was shown using the iron complex {{#moleculelink:|link=ZCGUPOIZKSBSCM-UHFFFAOYSA-N|image=false|width=300|height=200}} as catalyst in combination with the copper photosensitizer {{#moleculelink:|link=SVWABAAUBHILMW-UHFFFAOYSA-P|image=false|width=300|height=200}}. Turnover numbers (TONs) of 576 and a selectivity of 67% for CO were reached in MeCN/TEOA. The experiments were conducted under visible-light irradiation (λ = 420 nm) using BIH as sacrificial electron donor (see section SEDs below). The homoleptic iron complex {{#moleculelink:|link=SIMPDUKIPFZEDX-UHFFFAOYSA-N|image=false|width=300|height=200}} and the cobalt complexes {{#moleculelink:|link=JDMNOCVBLMVSON-UHFFFAOYSA-N|image=false|width=300|height=200}} and {{#moleculelink:|link=QMZVNZOKJUBNLZ-UHFFFAOYSA-N|image=false|width=300|height=200}} were tested for CO<sub>2</sub> reduction as well, but did not show substantial conversion of CO<sub>2</sub> to CO.
+A photochemical reduction of CO<sub>2</sub> to CO was shown using the iron complex {{#moleculelink:|link=ZCGUPOIZKSBSCM-UHFFFAOYSA-N|image=false|width=300|height=200}} as catalyst in combination with the copper photosensitizer {{#moleculelink: |link=QVCHJOOPCKCUBW-UHFFFAOYSA-P|image=false|width=300|height=200}}. Turnover numbers (TONs) of 576 and a selectivity of 67% for CO were reached in MeCN/TEOA. The experiments were conducted under visible-light irradiation (λ = 420 nm) using BIH as sacrificial electron donor (see section SEDs below). The homoleptic iron complex {{#moleculelink: |link=MDOYJUSGWSBHCN-UHFFFAOYSA-L|image=false|width=300|height=200}} and the cobalt complexes {{#moleculelink:|link=JDMNOCVBLMVSON-UHFFFAOYSA-N|image=false|width=300|height=200}} and {{#moleculelink: |link=BIZSTNKZWFMLKY-UHFFFAOYSA-L|image=false|width=300|height=200}} were tested for CO<sub>2</sub> reduction as well, but did not show substantial conversion of CO<sub>2</sub> to CO.
 ====Advances and special progress====
 The authors reported a iron complex with one of the highest activities for CO<sub>2</sub> reduction among earth-abundant systems with monometallic iron catalysts.
@@ Line 119: / Line 119: @@
 M  V30 END CTAB
 M  END
-</chemform><chemform smiles="[Fe]12(~N3N(C=C(C4C=CC=CC=4)N=3)CC3C=CC=C(CN4C=C(C5C=CC=CC=5)N=N4~1)N=3~2)12~N3=NC(C4C=CC=CC=4)=CN3CC3N~1=C(CN1N~2=NC(C2C=CC=CC=2)=C1)C=CC=3" inchi="1S/2C23H19N7.Fe/c2*1-3-8-18(9-4-1)22-16-29(27-25-22)14-20-12-7-13-21(24-20)15-30-17-23(26-28-30)19-10-5-2-6-11-19;/h2*1-13,16-17H,14-15H2;" inchikey="SIMPDUKIPFZEDX-UHFFFAOYSA-N" height="200px" width="300px" float="none">
+</chemform><chemform smiles="[Fe+2]12(~N3N(C=C(C4C=CC=CC=4)N=3)CC3C=CC=C(CN4C=C(C5C=CC=CC=5)N=N4~1)N=3~2)12~N3=NC(C4C=CC=CC=4)=CN3CC3N~1=C(CN1N~2=NC(C2C=CC=CC=2)=C1)C=CC=3.Cl([O-])(=O)(=O)=O.Cl([O-])(=O)(=O)=O" inchikey="MDOYJUSGWSBHCN-UHFFFAOYSA-L" inchi="1S/2C23H19N7.2ClHO4.Fe/c2*1-3-8-18(9-4-1)22-16-29(27-25-22)14-20-12-7-13-21(24-20)15-30-17-23(26-28-30)19-10-5-2-6-11-19;2*2-1(3,4)5;/h2*1-13,16-17H,14-15H2;2*(H,2,3,4,5);/q;;;;+2/p-2" float="none" width="200" height="200">
-   -INDIGO-05142414142D
+   -INDIGO-01102515082D
   0  0  0  0  0  0  0  0  0  0 V3000
 M  V30 BEGIN CTAB
-M  V30 COUNTS 61 74 0 0 0
+M  V30 COUNTS 71 82 0 0 0
 M  V30 BEGIN ATOM
-M  V30 1 Fe 8.525 -6.2 0.0 0
+M  V30 1 Fe 8.525 -6.2 0.0 0 CHG=2
 M  V30 2 C 8.52537 -0.950795 0.0 0
 M  V30 3 C 9.39094 -2.44904 0.0 0
@@ Line 187: / Line 187: @@
 M  V30 60 C 14.0517 -8.40364 0.0 0
 M  V30 61 C 15.016 -8.13856 0.0 0
+M  V30 62 Cl 15.9 -2.475 0.0 0
+M  V30 63 O 15.9 -1.475 0.0 0
+M  V30 64 O 14.9341 -2.73382 0.0 0
+M  V30 65 O 16.6934 -3.08376 0.0 0
+M  V30 66 O 16.7969 -2.03271 0.0 0 CHG=-1
+M  V30 67 Cl 16.8845 -4.79562 0.0 0
+M  V30 68 O 16.8845 -3.79562 0.0 0
+M  V30 69 O 15.9186 -5.05444 0.0 0
+M  V30 70 O 17.6779 -5.40438 0.0 0
+M  V30 71 O 17.7814 -4.35333 0.0 0 CHG=-1
 M  V30 END ATOM
 M  V30 BEGIN BOND
@@ Line 263: / Line 273: @@
 M  V30 73 8 1 46
 M  V30 74 8 1 15
+M  V30 75 2 62 63
+M  V30 76 2 62 64
+M  V30 77 2 62 65
+M  V30 78 1 62 66
+M  V30 79 2 67 68
+M  V30 80 2 67 69
+M  V30 81 2 67 70
+M  V30 82 1 67 71
 M  V30 END BOND
 M  V30 END CTAB
@@ Line 371: / Line 389: @@
 M  V30 END CTAB
 M  END
-</chemform><chemform smiles="[Co]12(~N3C(CN4C=C(C5C=CC=CC=5)N=N4~1)=CC=CC=3CN1N~2=NC(C2C=CC=CC=2)=C1)12~N3N(C=C(C4C=CC=CC=4)N=3)CC3C=CC=C(CN4C=C(C5C=CC=CC=5)N=N4~1)N=3~2" inchi="1S/2C23H19N7.Co/c2*1-3-8-18(9-4-1)22-16-29(27-25-22)14-20-12-7-13-21(24-20)15-30-17-23(26-28-30)19-10-5-2-6-11-19;/h2*1-13,16-17H,14-15H2;" inchikey="QMZVNZOKJUBNLZ-UHFFFAOYSA-N" height="200px" width="300px" float="none">
+</chemform><chemform smiles="[Co+2]12(~N3C(CN4C=C(C5C=CC=CC=5)N=N4~1)=CC=CC=3CN1N~2=NC(C2C=CC=CC=2)=C1)12~N3N(C=C(C4C=CC=CC=4)N=3)CC3C=CC=C(CN4C=C(C5C=CC=CC=5)N=N4~1)N=3~2.Cl(=O)([O-])(=O)=O.Cl(=O)([O-])(=O)=O" inchikey="BIZSTNKZWFMLKY-UHFFFAOYSA-L" inchi="1S/2C23H19N7.2ClHO4.Co/c2*1-3-8-18(9-4-1)22-16-29(27-25-22)14-20-12-7-13-21(24-20)15-30-17-23(26-28-30)19-10-5-2-6-11-19;2*2-1(3,4)5;/h2*1-13,16-17H,14-15H2;2*(H,2,3,4,5);/q;;;;+2/p-2" float="none" width="200" height="200">
-   -INDIGO-05142414222D
+   -INDIGO-01102515112D
   0  0  0  0  0  0  0  0  0  0 V3000
 M  V30 BEGIN CTAB
-M  V30 COUNTS 61 74 0 0 0
+M  V30 COUNTS 71 82 0 0 0
 M  V30 BEGIN ATOM
-M  V30 1 Co 10.25 -5.675 0.0 0
+M  V30 1 Co 10.25 -5.675 0.0 0 CHG=2
 M  V30 2 C 9.38485 -10.4751 0.0 0
 M  V30 3 C 11.0902 -10.4746 0.0 0
@@ Line 439: / Line 457: @@
 M  V30 60 C 4.96306 -5.45448 0.0 0
 M  V30 61 C 4.0933 -3.95891 0.0 0
+M  V30 62 Cl 17.95 -1.975 0.0 0
+M  V30 63 O 17.95 -0.975 0.0 0
+M  V30 64 O 18.9159 -2.23382 0.0 0
+M  V30 65 O 17.6912 -2.94093 0.0 0 CHG=-1
+M  V30 66 O 16.9841 -2.23382 0.0 0
+M  V30 67 Cl 18.125 -4.51704 0.0 0
+M  V30 68 O 18.125 -3.51704 0.0 0
+M  V30 69 O 19.0909 -4.77586 0.0 0
+M  V30 70 O 17.8662 -5.48296 0.0 0 CHG=-1
+M  V30 71 O 17.1591 -4.77586 0.0 0
 M  V30 END ATOM
 M  V30 BEGIN BOND
@@ Line 515: / Line 543: @@
 M  V30 73 8 1 16
 M  V30 74 8 1 4
+M  V30 75 2 62 63
+M  V30 76 2 62 64
+M  V30 77 1 62 65
+M  V30 78 2 62 66
+M  V30 79 2 67 68
+M  V30 80 2 67 69
+M  V30 81 1 67 70
+M  V30 82 2 67 71
 M  V30 END BOND
 M  V30 END CTAB
@@ Line 521: / Line 557: @@
 ====Photosensitizer====
-<chemform smiles="CC1C=CC2C3=C4C(=CC=2)C=CC(C)=N4~[Cu]2(~P(C4C=CC=CC=4)(C4C=CC=CC=4)C4=CC=CC=C4OC4C=CC=CC=4P~2(C2C=CC=CC=2)C2C=CC=CC=2)~N=13" inchi="1S/C36H28OP2.C14H12N2.Cu/c1-5-17-29(18-6-1)38(30-19-7-2-8-20-30)35-27-15-13-25-33(35)37-34-26-14-16-28-36(34)39(31-21-9-3-10-22-31)32-23-11-4-12-24-32;1-9-3-5-11-7-8-12-6-4-10(2)16-14(12)13(11)15-9;/h1-28H;3-8H,1-2H3;/q;;-2/p+2" inchikey="SVWABAAUBHILMW-UHFFFAOYSA-P" height="200px" width="300px" float="none">
+<chemform smiles="CC1C=CC2C3=C4C(=CC=2)C=CC(C)=N4~[Cu+]2(~P(C4C=CC=CC=4)(C4C=CC=CC=4)C4=CC=CC=C4OC4C=CC=CC=4P~2(C2C=CC=CC=2)C2C=CC=CC=2)~N=13.[B-](F)(F)(F)F" inchikey="QVCHJOOPCKCUBW-UHFFFAOYSA-P" inchi="1S/C36H28OP2.C14H12N2.BF4.Cu/c1-5-17-29(18-6-1)38(30-19-7-2-8-20-30)35-27-15-13-25-33(35)37-34-26-14-16-28-36(34)39(31-21-9-3-10-22-31)32-23-11-4-12-24-32;1-9-3-5-11-7-8-12-6-4-10(2)16-14(12)13(11)15-9;2-1(3,4)5;/h1-28H;3-8H,1-2H3;;/q;;2*-1/p+2" float="none" width="200" height="200">
-   -INDIGO-05142413492D
+   -INDIGO-01102515052D
   0  0  0  0  0  0  0  0  0  0 V3000
 M  V30 BEGIN CTAB
-M  V30 COUNTS 56 66 0 0 0
+M  V30 COUNTS 61 70 0 0 0
 M  V30 BEGIN ATOM
 M  V30 1 C 12.15 -4.31795 0.0 0
@@ Line 544: / Line 580: @@
 M  V30 15 C 11.65 -6.91603 0.0 0
 M  V30 16 C 12.15 -6.05 0.0 0
-M  V30 17 Cu 9.575 -4.05 0.0 0
+M  V30 17 Cu 9.575 -4.05 0.0 0 CHG=1
 M  V30 18 C 7.81136 1.15012 0.0 0
 M  V30 19 C 8.67693 -0.348124 0.0 0
@@ Line 584: / Line 620: @@
 M  V30 55 C 12.9808 -4.7288 0.0 0
 M  V30 56 C 13.6926 -5.43137 0.0 0
+M  V30 57 B 15.5 0.25 0.0 0 CHG=-1
+M  V30 58 F 15.5 1.25 0.0 0
+M  V30 59 F 14.659 0.125 0.0 0
+M  V30 60 F 16.366 -0.25 0.0 0
+M  V30 61 F 15.5 -0.75 0.0 0
 M  V30 END ATOM
 M  V30 BEGIN BOND
@@ Line 652: / Line 693: @@
 M  V30 65 8 17 31
 M  V30 66 8 17 32
+M  V30 67 1 57 58
+M  V30 68 1 57 59
+M  V30 69 1 57 60
+M  V30 70 1 57 61
 M  V30 END BOND
 M  V30 END CTAB

Photocatalytic Reduction of CO2 by Highly Efficient Homogeneous FeII Catalyst based on 2,6-Bis(1’,2’,3’-triazolyl-methyl)pyridine. Comparison with Analogues.: Difference between revisions

Latest revision as of 16:12, 10 January 2025

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]

Catalyst[edit | edit source]

Photosensitizer[edit | edit source]

Investigation[edit | edit source]

Sacrificial electron donor[edit | edit source]

Additives[edit | edit source]

Investigations

Topics

Photocatalytic Reduction of CO2 by Highly Efficient Homogeneous FeII Catalyst based on 2,6-Bis(1’,2’,3’-triazolyl-methyl)pyridine. Comparison with Analogues.: Difference between revisions

Latest revision as of 16:12, 10 January 2025

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]

Catalyst[edit | edit source]

Photosensitizer[edit | edit source]

Investigation[edit | edit source]

Sacrificial electron donor[edit | edit source]

Additives[edit | edit source]

Investigations

Current site

Topics