Efficient Visible-Light-Driven Carbon Dioxide Reduction using a Bioinspired Nickel Molecular Catalyst: Difference between revisions
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=== Abstract | === Abstract === | ||
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%. | 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 | ==== Summary ==== | ||
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. | 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 | ==== Additional remarks ==== | ||
* The combination of sulfur and nitrogen ligands in NiN2S2 enhances its stability and catalytic efficiency. | * The combination of sulfur and nitrogen ligands in NiN2S2 enhances its stability and catalytic efficiency. | ||
| Line 15: | Line 15: | ||
* Further research is proposed to optimize ligand coordination and investigate intermediate reaction mechanisms. | * Further research is proposed to optimize ligand coordination and investigate intermediate reaction mechanisms. | ||
=== Content of the published article in detail | === Content of the published article in detail === | ||
* The synthesis and characterization of NiN2S2 using advanced analytical techniques like LC-HRMS and X-ray crystallography. | * The synthesis and characterization of NiN2S2 using advanced analytical techniques like LC-HRMS and X-ray crystallography. | ||
| Line 21: | Line 21: | ||
* Mechanistic insights into the electron transfer process facilitated by the catalyst and photosensitizer. | * Mechanistic insights into the electron transfer process facilitated by the catalyst and photosensitizer. | ||
=== Catalysts tested in this study | === Catalysts tested in this study === | ||
<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="100px" width="150px" float="none"> | <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="100px" width="150px" float="none"> | ||
-INDIGO-12122410452D | -INDIGO-12122410452D | ||
| Line 85: | Line 85: | ||
([Ni(N2S2)]Cl2): A bioinspired nickel molecular catalyst. | ([Ni(N2S2)]Cl2): A bioinspired nickel molecular catalyst. | ||
=== Photosensitizer | === Photosensitizer === | ||
<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"> | <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 | -INDIGO-12122410462D | ||
| Line 184: | Line 184: | ||
M V30 END CTAB | M V30 END CTAB | ||
M END | M END | ||
</chemform><chemform smiles="C1C=C2P(~[Cu+ | </chemform><chemform smiles="C1C=C2P(~[Cu+](~P(C3C=CC=CC=3)(C3C=CC=CC=3)C3C4OC2=C(C(C)(C)C=4C=CC=3)C=1)1~N2=C(C)C=C(C3C=CC=CC=3)C3C=CC4C(C5C=CC=CC=5)=CC(C)=N~1C=4C=32)(C1C=CC=CC=1)C1C=CC=CC=1.[P-](F)(F)(F)(F)(F)F" inchikey="CSSGIEBQRQRBLV-UHFFFAOYSA-P" inchi="1S/C39H32OP2.C26H20N2.Cu.F6P/c1-39(2)33-25-15-27-35(41(29-17-7-3-8-18-29)30-19-9-4-10-20-30)37(33)40-38-34(39)26-16-28-36(38)42(31-21-11-5-12-22-31)32-23-13-6-14-24-32;1-17-15-23(19-9-5-3-6-10-19)21-13-14-22-24(20-11-7-4-8-12-20)16-18(2)28-26(22)25(21)27-17;;1-7(2,3,4,5)6/h3-28H,1-2H3;3-16H,1-2H3;;/q;;2*-1/p+2" float="none" width="200" height="200"> | ||
-INDIGO- | -INDIGO-12162417082D | ||
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 | M V30 COUNTS 78 90 0 0 0 | ||
M V30 BEGIN ATOM | M V30 BEGIN ATOM | ||
M V30 1 C -3.79376 2.14341 0.0 0 | M V30 1 C -3.79376 2.14341 0.0 0 | ||
| Line 207: | Line 207: | ||
M V30 15 C -4.78962 0.583363 0.0 0 | M V30 15 C -4.78962 0.583363 0.0 0 | ||
M V30 16 C -4.78962 -0.583363 0.0 0 | M V30 16 C -4.78962 -0.583363 0.0 0 | ||
M V30 17 Cu | M V30 17 Cu 0.68774 -0.185058 0.0 0 CHG=1 | ||
M V30 18 C 2.74227 1.50444 0.0 0 | M V30 18 C 2.74227 1.50444 0.0 0 | ||
M V30 19 N 2.74227 0.679442 0.0 0 | M V30 19 N 2.74227 0.679442 0.0 0 | ||
| Line 262: | Line 262: | ||
M V30 70 C 0.18041 1.42705 0.0 0 | M V30 70 C 0.18041 1.42705 0.0 0 | ||
M V30 71 C 1.04325 1.93268 0.0 0 | M V30 71 C 1.04325 1.93268 0.0 0 | ||
M V30 72 P | M V30 72 P 7.55 0.2 0.0 0 CHG=-1 | ||
M V30 73 F 8. | M V30 73 F 8.08382 1.01593 0.0 0 | ||
M V30 74 F 8. | M V30 74 F 8.51593 -0.058819 0.0 0 | ||
M V30 75 F | M V30 75 F 7.80882 -0.765926 0.0 0 | ||
M V30 76 F | M V30 76 F 6.84289 -0.507107 0.0 0 | ||
M V30 77 F | M V30 77 F 6.55 0.2 0.0 0 | ||
M V30 78 F 7.05 1.06603 0.0 0 | |||
M V30 | |||
M V30 END ATOM | M V30 END ATOM | ||
M V30 BEGIN BOND | M V30 BEGIN BOND | ||
| Line 328: | Line 321: | ||
M V30 49 1 18 44 | M V30 49 1 18 44 | ||
M V30 50 1 29 45 | M V30 50 1 29 45 | ||
M V30 51 | M V30 51 8 17 19 | ||
M V30 52 | M V30 52 8 17 28 | ||
M V30 53 1 5 46 | M V30 53 1 5 46 | ||
M V30 54 1 14 47 | M V30 54 1 14 47 | ||
| Line 368: | Line 361: | ||
M V30 89 1 72 77 | M V30 89 1 72 77 | ||
M V30 90 1 72 78 | M V30 90 1 72 78 | ||
M V30 END BOND | M V30 END BOND | ||
M V30 END CTAB | M V30 END CTAB | ||
| Line 545: | Line 532: | ||
</chemform> | </chemform> | ||
=== Investigation | === Investigation === | ||
Key aspects investigated include: | Key aspects investigated include: | ||
| Line 553: | Line 540: | ||
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 01|importFile=Template CO2 reduction_v1.0.xlsx|description=Table 01}} | {{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 01|importFile=Template CO2 reduction_v1.0.xlsx|description=Table 01}} | ||
=== Further Information | === Further Information === | ||
* Control experiments demonstrated that light, the catalyst, and BIH were essential for activity. | * 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. | * The reaction follows a reductive quenching pathway with efficient electron transfer from BIH to the photosensitizer and subsequently to the catalyst. | ||
==== Sacrificial electron donor | ==== Sacrificial electron donor ==== | ||
In this Study, the experiments were done with the sacrificial electron donor [[Molecule:100508|BIH]]. | In this Study, the experiments were done with the sacrificial electron donor [[Molecule:100508|BIH]]. | ||
[[Category:Photocatalytic CO2 conversion to CO]] | [[Category:Photocatalytic CO2 conversion to CO]] | ||
{{Tags|tags=CO2 photoreduction, photocatalysis, visible-light catalysis, nickel catalyst, bioinspired catalyst, molecular catalyst, [Ni(N2S2)]Cl2, Ru(bpy)3Cl2, BIH, sacrificial electron donor, homogeneous catalysis, artificial photosynthesis, CO production, high turnover number, quantum yield, ligand design, sulfur-nitrogen ligands, proton source, reductive quenching pathway, earth-abundant metals}} | |||
Latest revision as of 11:40, 21 November 2025
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]
([Ni(N2S2)]Cl2): A bioinspired nickel molecular catalyst.
Photosensitizer[edit | edit source]
Ru(bpy)3Cl2
100991
2,4,5,6-Tetrakis(diphenylamino)isophthalonitrile
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
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | e-D conc [M] | . | . | solvent A | . | . | . | λexc [nm] | . | . | . | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 1 | 0.7 | 0.02 | 420 | |||||||||||||
| 2. | 1 | 0.7 | 0.02 | 420 | |||||||||||||
| 3. | 1 | 0.7 | 0.02 | 420 | |||||||||||||
| 4. | 1 | 0.7 | 0.02 | 420 | |||||||||||||
| 5. | 1 | 0.7 | 0.02 | 420 | |||||||||||||
| 6. | 1 | 0.7 | 0.02 | 420 | |||||||||||||
| 7. | 1 | 0.7 | 0.02 | 420 | |||||||||||||
| 8. | 1 | 0.7 | 0.02 | 420 | |||||||||||||
| 9. | 1 | 0.7 | 0.02 | 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.
Tags: CO2 photoreduction, photocatalysis, visible-light catalysis, nickel catalyst, bioinspired catalyst, molecular catalyst, [Ni(N2S2)]Cl2, Ru(bpy)3Cl2, BIH, sacrificial electron donor, homogeneous catalysis, artificial photosynthesis, CO production, high turnover number, quantum yield, ligand design, sulfur-nitrogen ligands, proton source, reductive quenching pathway, earth-abundant metals |
[[Tag::[Ni(N2S2)]Cl2| ]]
Investigations
- Table 01 (Molecular process, Photocatalytic CO2 conversion experiments)
