Mn-carbonyl molecular catalysts containing a redox-active phenanthroline-5,6-dione for selective electro- and photoreduction of CO2 to CO or HCOOH: Difference between revisions

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{{#doiinfobox: 10.1016/j.electacta.2017.04.080}}
{{DOI|doi=10.1016/j.electacta.2017.04.080 }}
[[Category:Photocatalytic CO2 conversion to HCOOH]]
[[Category:Photocatalytic CO2 conversion to HCOOH]]
{{BaseTemplate}}
{{BaseTemplate}}


===Abstract===
==== Summary====
A photochemical reduction of CO<sub>2</sub> to CO or formic acid was shown using the manganese complexes {{#moleculelink:|link=KOYXLRUHHLMCRS-UHFFFAOYSA-M|image=false|width=300|height=200}} or {{#moleculelink:|link=JWEFEWAAUDGGIH-UHFFFAOYSA-N|image=false|width=300|height=200}} as catalyst in combination with the ruthenium-based photosensitizer {{#moleculelink:|link=SJFYGUKHUNLZTK-UHFFFAOYSA-L|image=false|width=300|height=200}}, comparing the results to the previously reported catalysts {{#moleculelink:|link=PGQIIBGFONEXSA-UHFFFAOYSA-M|image=false|width=300|height=200}} and {{#moleculelink:|link=ZUZWBGQHMPVNDY-UHFFFAOYSA-M|image=false|width=300|height=200}}. Turnover numbers (TONs) of 58 for formic acid were reached in acetonitrile with complex {{#moleculelink:|link=JWEFEWAAUDGGIH-UHFFFAOYSA-N|image=false|width=300|height=200}}. The experiments were conducted under visible-light irradiation (λ = 480 or 500 nm) using TEOA and BNAH as sacrificial electron donors (see section SEDs below).
====Advances and special progress====
The efficiency of formic acid generation from CO<sub>2</sub> was improved compared to a previously reported manganese complex. The increased water solubility of one of the novel complexes may enable photo- or electrocatalytic CO<sub>2</sub> reduction in aqueous media.
====Additional remarks====
In electrochemical CO<sub>2</sub> reduction experiments, a high selectivity for CO formation was observed, contrary to the preferential formation of formic acid in the photocatalytic CO<sub>2</sub> reduction.
===Content of the published article in detail===
The article contains results for the reduction of CO<sub>2</sub> to formic acid under visible-light catalysis using manganese complexes as catalysts. The catalytic system performs best (referring to the TON of formic acid production) in acetonitrile using catalyst {{#moleculelink:|link=JWEFEWAAUDGGIH-UHFFFAOYSA-N|image=false|width=300|height=200}}.
==== Catalyst====
==== Catalyst====
<chemform smiles="C1C=CN2[Mn+]([Br-])(C#O)(C#O)(C#O)N3=CC=CC4C(=O)C(=O)C=1C=2C=43" inchi="1S/C12H6N2O2.3CHO.BrH.Mn/c15-11-7-3-1-5-13-9(7)10-8(12(11)16)4-2-6-14-10;3*1-2;;/h1-6H;3*1H;1H;/q;;;;;+1/p-1" inchikey="ZMUYZQUZOJZTSM-UHFFFAOYSA-M" height="200px" width="300px" float="none">
<chemform smiles="C1C=CN2[Mn+]([Br-])([C-]#[O+])([C-]#[O+])([C-]#[O+])N3=CC=CC4C(=O)C(=O)C=1C=2C=43" inchikey="KOYXLRUHHLMCRS-UHFFFAOYSA-M" inchi="1S/C12H6N2O2.3CO.BrH.Mn/c15-11-7-3-1-5-13-9(7)10-8(12(11)16)4-2-6-14-10;3*1-2;;/h1-6H;;;;1H;/q;;;;;+1/p-1" float="none" width="200" height="200">
   -INDIGO-02132316042D
   -INDIGO-01102415542D


   0  0  0  0  0  0  0  0  0  0  0 V3000
   0  0  0  0  0  0  0  0  0  0  0 V3000
Line 28: Line 39:
M  V30 16 O 9.39805 -1.2925 0.0 0
M  V30 16 O 9.39805 -1.2925 0.0 0
M  V30 17 Mn 8.375 -5.525 0.0 0 CHG=1
M  V30 17 Mn 8.375 -5.525 0.0 0 CHG=1
M  V30 18 C 7.50897 -6.025 0.0 0
M  V30 18 C 7.50897 -6.025 0.0 0 CHG=-1
M  V30 19 C 9.24102 -6.025 0.0 0
M  V30 19 C 9.24102 -6.025 0.0 0 CHG=-1
M  V30 20 C 8.375 -6.525 0.0 0
M  V30 20 C 8.375 -6.525 0.0 0 CHG=-1
M  V30 21 Br 8.375 -4.525 0.0 0 CHG=-1
M  V30 21 Br 8.375 -4.525 0.0 0 CHG=-1
M  V30 22 O 6.64295 -6.525 0.0 0
M  V30 22 O 6.64295 -6.525 0.0 0 CHG=1
M  V30 23 O 8.375 -7.525 0.0 0
M  V30 23 O 8.375 -7.525 0.0 0 CHG=1
M  V30 24 O 10.1071 -6.525 0.0 0
M  V30 24 O 10.1071 -6.525 0.0 0 CHG=1
M  V30 END ATOM
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 BEGIN BOND
Line 67: Line 78:
M  V30 END CTAB
M  V30 END CTAB
M  END
M  END
</chemform><chemform smiles="C12N3[Mn+](C#O)(C#O)(C#O)(N#CC)N4=CC=CC(C(=O)C(=O)C=1C=CC=3)=C24" inchi="1S/C12H6N2O2.C2H3N.3CHO.Mn/c15-11-7-3-1-5-13-9(7)10-8(12(11)16)4-2-6-14-10;1-2-3;3*1-2;/h1-6H;1H3;3*1H;/q;;;;;+1" inchikey="YEWOWPOKKZXMQA-UHFFFAOYSA-N" height="200px" width="300px" float="none">
</chemform><chemform smiles="C12N3[Mn+]([C-]#[O+])([C-]#[O+])([C-]#[O+])(N#CC)N4=CC=CC(C(=O)C(=O)C=1C=CC=3)=C24.F[P-](F)(F)(F)(F)F" inchikey="JWEFEWAAUDGGIH-UHFFFAOYSA-N" inchi="1S/C12H6N2O2.C2H3N.3CO.F6P.Mn/c15-11-7-3-1-5-13-9(7)10-8(12(11)16)4-2-6-14-10;1-2-3;3*1-2;1-7(2,3,4,5)6;/h1-6H;1H3;;;;;/q;;;;;-1;+1" float="none" width="200" height="200">
   -INDIGO-02132316072D
   -INDIGO-01102415522D


   0  0  0  0  0  0  0  0  0  0  0 V3000
   0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 BEGIN CTAB
M  V30 COUNTS 26 29 0 0 0
M  V30 COUNTS 33 35 0 0 0
M  V30 BEGIN ATOM
M  V30 BEGIN ATOM
M  V30 1 C 8.22511 -3.34193 0.0 0
M  V30 1 C 8.22511 -3.34193 0.0 0
Line 92: Line 103:
M  V30 17 Mn 8.75 -4.975 0.0 0 CHG=1
M  V30 17 Mn 8.75 -4.975 0.0 0 CHG=1
M  V30 18 N 10.8 -4.975 0.0 0
M  V30 18 N 10.8 -4.975 0.0 0
M  V30 19 C 7.76789 -5.55711 0.0 0
M  V30 19 C 7.76789 -5.55711 0.0 0 CHG=-1
M  V30 20 C 9.78211 -5.53211 0.0 0
M  V30 20 C 9.78211 -5.53211 0.0 0 CHG=-1
M  V30 21 C 8.75 -5.975 0.0 0
M  V30 21 C 8.75 -5.975 0.0 0 CHG=-1
M  V30 22 O 6.90187 -6.05711 0.0 0
M  V30 22 O 6.90187 -6.05711 0.0 0 CHG=1
M  V30 23 O 8.75 -6.975 0.0 0
M  V30 23 O 8.75 -6.975 0.0 0 CHG=1
M  V30 24 O 10.6481 -6.03211 0.0 0
M  V30 24 O 10.6481 -6.03211 0.0 0 CHG=1
M  V30 25 C 11.5909 -4.96618 0.0 0
M  V30 25 C 11.5909 -4.96618 0.0 0
M  V30 26 C 12.3319 -4.95736 0.0 0
M  V30 26 C 12.3319 -4.95736 0.0 0
M  V30 27 F 12.617 -2.25 0.0 0
M  V30 28 P 13.483 -1.75 0.0 0 CHG=-1
M  V30 29 F 14.349 -2.25 0.0 0
M  V30 30 F 13.483 -0.75 0.0 0
M  V30 31 F 14.349 -1.25 0.0 0
M  V30 32 F 12.617 -1.25 0.0 0
M  V30 33 F 13.483 -2.75 0.0 0
M  V30 END ATOM
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 BEGIN BOND
Line 131: Line 149:
M  V30 28 3 18 25
M  V30 28 3 18 25
M  V30 29 1 25 26
M  V30 29 1 25 26
M  V30 30 1 27 28
M  V30 31 1 28 29
M  V30 32 1 28 30
M  V30 33 1 28 31
M  V30 34 1 28 32
M  V30 35 1 28 33
M  V30 END BOND
M  V30 END BOND
M  V30 END CTAB
M  V30 END CTAB
Line 193: Line 217:
M  V30 END CTAB
M  V30 END CTAB
M  END
M  END
</chemform>{{#moleculelink:|link=NUEMFRBQUXRMAE-UHFFFAOYSA-M|image=true}}
</chemform>{{#moleculelink:|link=ZUZWBGQHMPVNDY-UHFFFAOYSA-M|image=true}}


====Photosensitizer ====
====Photosensitizer ====
{{#moleculelink:|link=HNVRWFFXWFXICS-UHFFFAOYSA-N|image=true}}
<chemform smiles="" inchi="" inchikey="SJFYGUKHUNLZTK-UHFFFAOYSA-L" height="200px" width="300px" float="none"></chemform>


====Investigation====
====Investigation====
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}}
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}}


==== Sacrificial electron donor====
====Sacrificial electron donor====
{{#moleculelink:|link=CMNUYDSETOTBDE-UHFFFAOYSA-N|image=true}}{{#moleculelink:|link=GSEJCLTVZPLZKY-UHFFFAOYSA-N|image=true}}
In this study, the experiments were done with the sacrificial electron donors TEOA ([[Molecule:100507|100507]]) and BNAH ({{#moleculelink:|link=CMNUYDSETOTBDE-UHFFFAOYSA-N|image=false|width=300|height=200}}).
====Additives====
In this study, ascorbic acid was tested as an additive and control experiments under argon atmosphere were performed.[[Category:Publication]]

Latest revision as of 13:48, 23 May 2024


Abstract[edit | edit source]

Summary[edit | edit source]

A photochemical reduction of CO2 to CO or formic acid was shown using the manganese complexes Mn(phdk)(CO)3Br or Mn(phdk)(CO)3(MeCN) as catalyst in combination with the ruthenium-based photosensitizer Ru(bpy)3Cl2, comparing the results to the previously reported catalysts Mn(phen)(CO)3Br and Mn(bpy)(CO)3Br. Turnover numbers (TONs) of 58 for formic acid were reached in acetonitrile with complex Mn(phdk)(CO)3(MeCN). The experiments were conducted under visible-light irradiation (λ = 480 or 500 nm) using TEOA and BNAH as sacrificial electron donors (see section SEDs below).

Advances and special progress[edit | edit source]

The efficiency of formic acid generation from CO2 was improved compared to a previously reported manganese complex. The increased water solubility of one of the novel complexes may enable photo- or electrocatalytic CO2 reduction in aqueous media.

Additional remarks[edit | edit source]

In electrochemical CO2 reduction experiments, a high selectivity for CO formation was observed, contrary to the preferential formation of formic acid in the photocatalytic CO2 reduction.

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

The article contains results for the reduction of CO2 to formic acid under visible-light catalysis using manganese complexes as catalysts. The catalytic system performs best (referring to the TON of formic acid production) in acetonitrile using catalyst Mn(phdk)(CO)3(MeCN).

Catalyst[edit | edit source]

Mn(phdk)(CO)3Br Mn(phdk)(CO)3(MeCN) Mn(phen)(CO)3Br Mn(bpy)(CO)3Br

Photosensitizer[edit | edit source]

Ru(bpy)3Cl2

Investigation[edit | edit source]

catcat conc [µM]PSPS conc [mM]e-De-D conc [M]solvent A...additivesλexc [nm].TON COTON HCOOH.
1.

Mn(phdk)(CO)3Br

Ru(bpy)3Cl2

100

BNAH

0.1

MeCN

480852
2.

Mn(phdk)(CO)3(MeCN)

Ru(bpy)3Cl2

100

BNAH

0.1

MeCN

4801558
3.

Mn(phdk)(CO)3(MeCN)

Ru(bpy)3Cl2

100

BNAH

0.1

MeCN

480948
4.

Mn(bpy)(CO)3Br

Ru(bpy)3Cl2

100

BNAH

0.1

MeCN

4804715
5.

Mn(phdk)(CO)3(MeCN)

Ru(bpy)3Cl2

100

BNAH

0.1

MeCN

500740
6.

Mn(phdk)(CO)3(MeCN)

Ru(bpy)3Cl2

100

BNAH

0.1

MeCN

457734
7.

Mn(phdk)(CO)3(MeCN)

2

Ru(bpy)3Cl2

100

BNAH

0.1

MeCN

480518
8.

Mn(phdk)(CO)3(MeCN)

Ru(bpy)3Cl2

200

BNAH

0.1

MeCN

480852
9.

Mn(phdk)(CO)3(MeCN)

Ru(bpy)3Cl2

100

BNAH

0.1

MeCN

480
10.

Mn(phdk)(CO)3(MeCN)

Ru(bpy)3Cl2

100

BNAH

0.1

MeCN

500
11.

Mn(phdk)(CO)3(MeCN)

Ru(bpy)3Cl2

100


MeCN

4803
12.

Mn(phdk)(CO)3(MeCN)


BNAH

0.1

MeCN

500
13.

Mn(phdk)(CO)3Br

Ru(bpy)3Cl2

100

BNAH

0.1

MeCN

Argon gas480
14.


Ru(bpy)3Cl2

100

BNAH

0.1

MeCN

480
15.


Ru(bpy)3Cl2

100

BNAH

0.1

MeCN

480
16.

Mn(phdk)(CO)3Br

Ru(bpy)3Cl2

100

BNAH

0.1

DMF

4802122
17.

Mn(phdk)(CO)3Br

Ru(bpy)3Cl2

100

BNAH

0.1

DMF

4802
18.

Mn(phdk)(CO)3Br

Ru(bpy)3Cl2

100


DMF

480913
19.

Mn(phen)(CO)3Br

Ru(bpy)3Cl2

100

BNAH

0.1

DMF

480174
20.

Mn(bpy)(CO)3Br

Ru(bpy)3Cl2

100

BNAH

0.1

DMF

480639
21.

Mn(phdk)(CO)3(MeCN)

Ru(bpy)3Cl2

100


H2O

ascorbic acid/NaA480
22.

Mn(phdk)(CO)3(MeCN)

Ru(bpy)3Cl2

100


H2O

ascorbic acid/NaA500
Investigation-Name: Table 1

Sacrificial electron donor[edit | edit source]

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

Additives[edit | edit source]

In this study, ascorbic acid was tested as an additive and control experiments under argon atmosphere were performed.

Investigations

  • Table 1 (Molecular process, Photocatalytic CO2 conversion experiments)
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