Visible-Light-Driven Photocatalytic CO2 Reduction by a Ni(II) Complex Bearing a Bioinspired Tetradentate Ligand for Selective CO Production: Difference between revisions

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DOI 10.1021/jacs.7b01956
Authors Dachao Hong, Yuto Tsukakoshi, Hiroaki Kotani, Tomoya Ishizuka, Takahiko Kojima,
Submitted 28.04.2017
Published online 04.05.2017
Licenses -
Subjects Colloid and Surface Chemistry, Biochemistry, General Chemistry, Catalysis
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{{#doiinfobox: 10.1021/jacs.7b01956}}
{{BaseTemplate}}
[[Category:Photocatalytic CO2 conversion to CO]]
{{DOI|doi=10.1021/jacs.7b01956}}
 
=== Abstract ===
 
==== Summary ====
A photochemical reduction of CO<sub>2</sub> to CO was shown using the nickel complex {{#moleculelink:|link=SOBXSEUOEROXNJ-UHFFFAOYSA-L|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}}. Turnover numbers (TONs) over 700 and a selectivity of >99% for CO were reached in dimethylacetamide/water. The experiments were conducted under visible-light irradiation (λ = 450 nm) using BIH as sacrificial reductants (see section SEDs below).
 
==== Advances and special progress ====
A nickel catalyst inspired by the CODH enzyme (carbon monoxide dehydrogenase) was employed for the photocatalytic reduction of CO<sub>2</sub> with the back then highest reported TON values among nickel complexes in systems with [Ru(bpy)<sub>3</sub>]<sup>2+</sup>.
 
==== Additional remarks ====
The binding of CO<sub>2</sub> to the nickel(0) species was identified as the potential rate-determining step of the reduction.
 
=== 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 a nickel complex as a catalyst. The catalytic system performs best (referring to the TON of CO production) in dimethylacetamide/water.
 
==== Catalyst====
{{#moleculelink:|link=SOBXSEUOEROXNJ-UHFFFAOYSA-L|image=true}}
 
====Photosensitizer====
<chemform smiles="C1C=N2[Ru+2]3(N4C(C5N3=CC=CC=5)=CC=CC=4)3(N4=CC=CC=C4C4=CC=CC=N43)N3=CC=CC=C3C2=CC=1.[Cl-].[Cl-]" inchi="1S/3C10H8N2.2ClH.Ru/c3*1-3-7-11-9(5-1)10-6-2-4-8-12-10;;;/h3*1-8H;2*1H;/q;;;;;+2/p-2" inchikey="SJFYGUKHUNLZTK-UHFFFAOYSA-L" height="200px" width="300px" float="none">
  -INDIGO-11272316582D
 
  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 39 45 0 0 0
M  V30 BEGIN ATOM
M  V30 1 C 8.38485 -1.67507 0.0 0
M  V30 2 C 10.1152 -1.67459 0.0 0
M  V30 3 C 9.25164 -1.17497 0.0 0
M  V30 4 C 10.1152 -2.67553 0.0 0
M  V30 5 C 8.38485 -2.68002 0.0 0
M  V30 6 N 9.25382 -3.17503 0.0 0
M  V30 7 C 10.9812 -3.17553 0.0 0
M  V30 8 C 12.7115 -3.17389 0.0 0
M  V30 9 C 11.8476 -2.67484 0.0 0
M  V30 10 C 12.7121 -4.17483 0.0 0
M  V30 11 N 10.9818 -4.18048 0.0 0
M  V30 12 C 11.8512 -4.67491 0.0 0
M  V30 13 N 10.9848 -6.20007 0.0 0
M  V30 14 C 12.7152 -6.19959 0.0 0
M  V30 15 C 11.8516 -5.69997 0.0 0
M  V30 16 C 12.7152 -7.20053 0.0 0
M  V30 17 C 10.9848 -7.20502 0.0 0
M  V30 18 C 11.8538 -7.70003 0.0 0
M  V30 19 C 10.1188 -7.70502 0.0 0
M  V30 20 C 9.2551 -9.20433 0.0 0
M  V30 21 C 10.1192 -8.70573 0.0 0
M  V30 22 C 8.38792 -8.70444 0.0 0
M  V30 23 N 9.24818 -7.20313 0.0 0
M  V30 24 C 8.38534 -7.70875 0.0 0
M  V30 25 C 5.70985 -6.27507 0.0 0
M  V30 26 N 7.44015 -6.27459 0.0 0
M  V30 27 C 6.57664 -5.77497 0.0 0
M  V30 28 C 7.44015 -7.27553 0.0 0
M  V30 29 C 5.70985 -7.28002 0.0 0
M  V30 30 C 6.57882 -7.77503 0.0 0
M  V30 31 C 6.57664 -4.77497 0.0 0
M  V30 32 C 5.71006 -3.2773 0.0 0
M  V30 33 C 5.7098 -4.27494 0.0 0
M  V30 34 C 6.57657 -2.77625 0.0 0
M  V30 35 N 7.44661 -4.27191 0.0 0
M  V30 36 C 7.44015 -3.27186 0.0 0
M  V30 37 Ru 9.21263 -5.19691 0.0 0 CHG=2
M  V30 38 Cl 14.05 -1.95 0.0 0 CHG=-1
M  V30 39 Cl 14.1 -3.225 0.0 0 CHG=-1
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 2 3 1
M  V30 2 2 4 2
M  V30 3 1 1 5
M  V30 4 1 2 3
M  V30 5 2 5 6
M  V30 6 1 6 4
M  V30 7 1 4 7
M  V30 8 2 9 7
M  V30 9 2 10 8
M  V30 10 1 7 11
M  V30 11 1 8 9
M  V30 12 2 11 12
M  V30 13 1 12 10
M  V30 14 2 15 13
M  V30 15 2 16 14
M  V30 16 1 13 17
M  V30 17 1 14 15
M  V30 18 2 17 18
M  V30 19 1 18 16
M  V30 20 1 17 19
M  V30 21 2 21 19
M  V30 22 2 22 20
M  V30 23 1 19 23
M  V30 24 1 20 21
M  V30 25 2 23 24
M  V30 26 1 24 22
M  V30 27 2 27 25
M  V30 28 2 28 26
M  V30 29 1 25 29
M  V30 30 1 26 27
M  V30 31 2 29 30
M  V30 32 1 30 28
M  V30 33 1 27 31
M  V30 34 2 33 31
M  V30 35 2 34 32
M  V30 36 1 31 35
M  V30 37 1 32 33
M  V30 38 2 35 36
M  V30 39 1 36 34
M  V30 40 10 35 37
M  V30 41 10 6 37
M  V30 42 10 37 11
M  V30 43 10 13 37
M  V30 44 10 37 23
M  V30 45 10 26 37
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform>
 
====Investigation====
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}}
 
==== Sacrificial electron donor ====
In this study, the experiments were done with the sacrificial electron donors TEOA ([[Molecule:100507|100507]]), BIH ([[Molecule:100508|100508]]), and TEA ([[Molecule:100505|100505]]).
 
==== Additives ====
In this study, no additives were tested.
[[Category:Photocatalytic CO2 conversion to CO]][[Category:Publication]]

Latest revision as of 10:37, 11 April 2024


Abstract[edit | edit source]

Summary[edit | edit source]

A photochemical reduction of CO2 to CO was shown using the nickel complex [Ni(bpet)(MeCN)2][ClO4]2 as catalyst in combination with the ruthenium-based photosensitizer Ru(bpy)3Cl2. Turnover numbers (TONs) over 700 and a selectivity of >99% for CO were reached in dimethylacetamide/water. The experiments were conducted under visible-light irradiation (λ = 450 nm) using BIH as sacrificial reductants (see section SEDs below).

Advances and special progress[edit | edit source]

A nickel catalyst inspired by the CODH enzyme (carbon monoxide dehydrogenase) was employed for the photocatalytic reduction of CO2 with the back then highest reported TON values among nickel complexes in systems with [Ru(bpy)3]2+.

Additional remarks[edit | edit source]

The binding of CO2 to the nickel(0) species was identified as the potential rate-determining step of the reduction.

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 a nickel complex as a catalyst. The catalytic system performs best (referring to the TON of CO production) in dimethylacetamide/water.

Catalyst[edit | edit source]

[Ni(bpet)(MeCN)2][ClO4]2

Photosensitizer[edit | edit source]

Ru(bpy)3Cl2

Investigation[edit | edit source]

catcat conc [µM]PSPS conc [mM]e-De-D conc [M]solvent A...λexc [nm].TON CO.TON H2..
1.

[Ni(bpet)(MeCN)2][ClO4]2

0.03

Ru(bpy)3Cl2

0.5

BIH

0.1

DMA

4507136.9
2.

[Ni(bpet)(MeCN)2][ClO4]2

0.03

Ru(bpy)3Cl2

0.5

BIH

0.1

DMF

45015911
3.

[Ni(bpet)(MeCN)2][ClO4]2

0.03

Ru(bpy)3Cl2

0.5

BIH

0.1

DMA

450673.4
4.

[Ni(bpet)(MeCN)2][ClO4]2

0.03

Ru(bpy)3Cl2

0.5

BIH

0.1

MeCN

450
5.

[Ni(bpet)(MeCN)2][ClO4]2

0.03

Ru(bpy)3Cl2

0.5

TEA

0.1

DMA

450
6.

[Ni(bpet)(MeCN)2][ClO4]2

0.03

Ru(bpy)3Cl2

0.5

TEOA

0.1

DMA

4502.625.5
Investigation-Name: Table 1

Sacrificial electron donor[edit | edit source]

In this study, the experiments were done with the sacrificial electron donors TEOA (100507), BIH (100508), and TEA (100505).

Additives[edit | edit source]

In this study, no additives were tested.

Investigations

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