Efficient Visible-Light-Driven Carbon Dioxide Reduction using a Bioinspired Nickel Molecular Catalyst: Difference between revisions

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=== Catalysts tested in this study[edit | edit source] ===
=== Catalysts tested in this study[edit | edit source] ===
<chemform smiles="" inchi="" inchikey="" height="200px" width="300px" float="none"></chemform>
<chemform smiles="C1C2CS3[Ni](Cl)(Cl)45S(CC6N4=C(C3)C=CC=6)CC(N=25)=CC=1" inchi="1S/C14H14N2S2.2ClH.Ni/c1-3-11-7-17-9-13-5-2-6-14(16-13)10-18-8-12(4-1)15-11;;;/h1-6H,7-10H2;2*1H;/q;;;+2/p-2" inchikey="XRUWRFIGSFNAGZ-UHFFFAOYSA-L" height="200px" width="300px" float="none">
  -INDIGO-12122410452D


NiN2S2 ([Ni(N2S2)]Cl2): A bioinspired nickel molecular catalyst.
  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 21 26 0 0 0
M  V30 BEGIN ATOM
M  V30 1 C -2.07786 -0.497932 0.0 0
M  V30 2 C -2.07786 -1.32293 0.0 0
M  V30 3 C -1.36339 -1.73543 0.0 0
M  V30 4 C -0.648917 -1.32293 0.0 0
M  V30 5 N -0.648917 -0.497932 0.0 0
M  V30 6 C -1.36339 -0.085432 0.0 0
M  V30 7 C -1.36339 0.739568 0.0 0
M  V30 8 C 0.065554 -1.73543 0.0 0
M  V30 9 S -0.648917 1.15207 0.0 0
M  V30 10 S 0.780025 -1.32293 0.0 0
M  V30 11 C 1.36339 -0.739568 0.0 0
M  V30 12 C 1.36339 0.085432 0.0 0
M  V30 13 C 2.07786 0.497932 0.0 0
M  V30 14 C 2.07786 1.32293 0.0 0
M  V30 15 C 1.36339 1.73543 0.0 0
M  V30 16 C 0.648917 1.32293 0.0 0
M  V30 17 N 0.648917 0.497932 0.0 0
M  V30 18 C 0.065554 1.56457 0.0 0
M  V30 19 Ni 0.072112 -0.019432 0.0 0
M  V30 20 Cl -0.752888 0.327068 0.0 0
M  V30 21 Cl 0.897112 -0.316431 0.0 0
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 2 1 2
M  V30 2 1 2 3
M  V30 3 2 3 4
M  V30 4 1 4 5
M  V30 5 2 5 6
M  V30 6 1 6 1
M  V30 7 1 6 7
M  V30 8 1 4 8
M  V30 9 1 7 9
M  V30 10 1 8 10
M  V30 11 1 10 11
M  V30 12 1 11 12
M  V30 13 2 12 13
M  V30 14 1 13 14
M  V30 15 2 14 15
M  V30 16 1 15 16
M  V30 17 2 16 17
M  V30 18 1 17 12
M  V30 19 1 9 18
M  V30 20 1 18 16
M  V30 21 10 5 19
M  V30 22 10 17 19
M  V30 23 10 9 19
M  V30 24 10 19 10
M  V30 25 1 20 19
M  V30 26 1 19 21
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform>
 
([Ni(N2S2)]Cl2): A bioinspired nickel molecular catalyst.


=== Photosensitizer[edit | edit source] ===
=== Photosensitizer[edit | edit source] ===
<chemform smiles="" inchi="" inchikey="" height="200px" width="300px" float="none"></chemform>
<chemform smiles="N12[Ru](Cl)(Cl)3(N4C=CC=CC=4C4C=CC=CN=43)(N3C=CC=CC=3C=1C=CC=C2)1N2C=CC=CC=2C2C=CC=CN=21" 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-12122410462D
 
  0  0  0  0  0  0  0  0  0  0  0 V3000
M  V30 BEGIN CTAB
M  V30 COUNTS 39 47 0 0 0
M  V30 BEGIN ATOM
M  V30 1 N 1.30208 0.731914 0.0 0
M  V30 2 C 2.02503 0.334465 0.0 0
M  V30 3 C 2.73071 0.761834 0.0 0
M  V30 4 C 2.71343 1.58665 0.0 0
M  V30 5 C 1.99048 1.9841 0.0 0
M  V30 6 C 1.28481 1.55673 0.0 0
M  V30 7 C 2.04231 -0.490355 0.0 0
M  V30 8 N 1.33663 -0.917725 0.0 0
M  V30 9 C 1.3539 -1.74254 0.0 0
M  V30 10 C 2.07685 -2.13999 0.0 0
M  V30 11 C 2.78253 -1.71262 0.0 0
M  V30 12 C 2.76526 -0.887804 0.0 0
M  V30 13 N 0.125472 -1.63593 0.0 0
M  V30 14 C -0.558829 -2.09676 0.0 0
M  V30 15 C -0.501895 -2.91979 0.0 0
M  V30 16 C 0.23934 -3.282 0.0 0
M  V30 17 C 0.92364 -2.82118 0.0 0
M  V30 18 C 0.866706 -1.99814 0.0 0
M  V30 19 C -1.30006 -1.73454 0.0 0
M  V30 20 N -1.357 -0.911512 0.0 0
M  V30 21 C -2.09823 -0.549301 0.0 0
M  V30 22 C -2.78253 -1.01012 0.0 0
M  V30 23 C -2.7256 -1.83316 0.0 0
M  V30 24 C -1.98436 -2.19537 0.0 0
M  V30 25 N -1.22265 0.708208 0.0 0
M  V30 26 C -1.28359 1.53095 0.0 0
M  V30 27 C -2.02658 1.88955 0.0 0
M  V30 28 C -2.70863 1.4254 0.0 0
M  V30 29 C -2.64769 0.602657 0.0 0
M  V30 30 C -1.9047 0.24406 0.0 0
M  V30 31 C -0.601539 1.9951 0.0 0
M  V30 32 N 0.14145 1.63651 0.0 0
M  V30 33 C 0.8235 2.10066 0.0 0
M  V30 34 C 0.762559 2.9234 0.0 0
M  V30 35 C 0.01957 3.282 0.0 0
M  V30 36 C -0.662479 2.81785 0.0 0
M  V30 37 Ru 0.028919 -0.177739 0.0 0
M  V30 38 Cl 1.08492 -0.111739 0.0 0
M  V30 39 Cl -0.961081 -0.210738 0.0 0
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 2 1 2
M  V30 2 1 2 3
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M  V30 6 1 6 1
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M  V30 13 1 12 7
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M  V30 18 2 17 18
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M  V30 20 1 14 19
M  V30 21 2 19 20
M  V30 22 1 20 21
M  V30 23 2 21 22
M  V30 24 1 22 23
M  V30 25 2 23 24
M  V30 26 1 24 19
M  V30 27 2 25 26
M  V30 28 1 26 27
M  V30 29 2 27 28
M  V30 30 1 28 29
M  V30 31 2 29 30
M  V30 32 1 30 25
M  V30 33 1 26 31
M  V30 34 2 31 32
M  V30 35 1 32 33
M  V30 36 2 33 34
M  V30 37 1 34 35
M  V30 38 2 35 36
M  V30 39 1 36 31
M  V30 40 1 37 25 CFG=3
M  V30 41 1 32 37
M  V30 42 1 37 20 CFG=1
M  V30 43 1 37 8 CFG=1
M  V30 44 1 37 13
M  V30 45 1 37 1 CFG=3
M  V30 46 1 39 37
M  V30 47 1 37 38
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform>


=== Investigation[edit | edit source] ===
=== Investigation[edit | edit source] ===
Line 35: Line 192:
* Impact of photosensitizer and electron donor concentrations on performance.
* Impact of photosensitizer and electron donor concentrations on performance.
* Role of acidic co-substrates in improving CO2 reduction rates.
* Role of acidic co-substrates in improving CO2 reduction rates.
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 01|importFile=Template CO2 reduction_v1.0.xlsx|description=Table 01}}


=== Further Information[edit | edit source] ===
=== Further Information[edit | edit source] ===

Revision as of 10:46, 12 December 2024


Abstract[edit | edit source]

The study introduces a bioinspired nickel-based molecular catalyst, [Ni(N2S2)]Cl2 (NiN2S2), for photochemical catalytic reduction of CO2 under visible light. Combining the catalyst with [Ru(bpy)3]Cl2 as a photosensitizer and BIH as a sacrificial electron donor, the system achieved an 89% selectivity towards CO, with a turnover number (TON) of 7991 during 8 hours of irradiation. The process demonstrated high catalytic efficiency with a turnover frequency (TOF) of 1079 h⁻¹ and an apparent quantum yield (AQY) of 1.08%.

Summary[edit | edit source]

Inspired by natural enzymes, this work focuses on the development of a novel nickel catalyst for CO2 photoreduction. NiN2S2, designed with thiol and pyridine ligands, exhibited remarkable activity and selectivity in converting CO2 to CO. Control experiments confirmed the necessity of light, the catalyst, and sacrificial electron donors. Acidic co-substrates such as phenol further enhanced the reaction's efficiency without compromising selectivity. This study establishes NiN2S2 as a promising candidate for sustainable CO2 reduction under visible light.

Additional remarks[edit | edit source]

  • The combination of sulfur and nitrogen ligands in NiN2S2 enhances its stability and catalytic efficiency.
  • Acid additives, particularly phenol, significantly improve reaction rates, indicating a key role in CO2 stabilization and protonation steps.
  • Further research is proposed to optimize ligand coordination and investigate intermediate reaction mechanisms.

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

  • The synthesis and characterization of NiN2S2 using advanced analytical techniques like LC-HRMS and X-ray crystallography.
  • The photocatalytic performance of NiN2S2 in reducing CO2 to CO under visible light, achieving high selectivity and efficiency.
  • Mechanistic insights into the electron transfer process facilitated by the catalyst and photosensitizer.

Catalysts tested in this study[edit | edit source]

100990

([Ni(N2S2)]Cl2): A bioinspired nickel molecular catalyst.

Photosensitizer[edit | edit source]

Ru(bpy)3Cl2

Investigation[edit | edit source]

Key aspects investigated include:

  • Catalyst stability and reusability.
  • Impact of photosensitizer and electron donor concentrations on performance.
  • Role of acidic co-substrates in improving CO2 reduction rates.
Table 01
catcat conc [µM]PSPS conc [mM]e-De-D conc [M]..solvent A...λexc [nm]....
1.

Molecule:100990

1

Ru(bpy)3Cl2

0.7

BIH

0.02

MeCN

420
2.

Molecule:100990

1

Ru(bpy)3Cl2

0.7

TEA

0.02

MeCN

420
3.

Molecule:100990

1

Ru(bpy)3Cl2

0.7

TEOA

0.02

MeCN

420
4.

Molecule:100990

1

Molecule:100991

0.7

BIH

0.02

MeCN

420
5.

Molecule:100990

1

Ru(bpy)3Cl2

0.7

BIH

0.02

MeCN

420
6.

Molecule:100990

1

Ru(bpy)3Cl2

0.7

BIH

0.02

MeCN

420
7.

Molecule:100990

1

Molecule:100992

0.7

BIH

0.02

MeCN

420
8.

Molecule:100990

1

Ru(bpy)3Cl2

0.7

BIH

0.02

MeCN

420
9.

Molecule:100990

1

Ru(bpy)3Cl2

0.7

BIH

0.02

MeCN

420
Investigation-Name: Table 01

Further Information[edit | edit source]

  • Control experiments demonstrated that light, the catalyst, and BIH were essential for activity.
  • The reaction follows a reductive quenching pathway with efficient electron transfer from BIH to the photosensitizer and subsequently to the catalyst.

Sacrificial electron donor[edit | edit source]

In This Study, the Experiments Were Done With the Sacrificial Electron Donor BIH.

Investigations

  • Table 01 (Molecular process, Photocatalytic CO2 conversion experiments)
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