Cobalt-based tripodal complexes as molecular catalysts for photocatalytic CO<sub>2</sub> reduction

Liu, Dong-Cheng; Luo, Zhi-Mei; Aramburu-Trošelj, Bruno M.; Ma, Fan; Wang, Jia-Wei

doi:10.1039/d3cc04759h

Cited by 6 publications

(4 citation statements)

References 66 publications

(50 reference statements)

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“…[4][5] The molecular catalysts based on earth-abundant metals are relatively appealing for their merits in lowering the expense for large-scale applications. [6][7][8] Researchers have devoted to tailoring the earth-abundant molecular catalysts for CO 2 reduction with diverse strategies, such as electronic modification, [9][10][11][12] extension of conjugation, [10,13] introduction of pendant proton relays, [14][15] Coulombic interaction, [16][17] dinuclear synergy, [18][19] etc. However, the current mechanistic understanding of these effects is challenging and insufficient, especially if experimental and theoretical studies are not well combined, which should be essential in further catalyst optimization.…”

Section: Introductionmentioning

confidence: 99%

Unveiling the Activity and Mechanism Alterations by Pyrene Decoration on a Co(II) Macrocyclic Catalyst for CO₂ Reduction

Zhang,

Huang,

Luo

et al. 2024

ChemSusChem

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Mechanistic studies involving characterization of crucial intermediates are desirable for rational optimization of molecular catalysts toward CO2 reduction, while fundamental challenges are associated with such studies. Herein we present the systematic mechanistic investigations on a pyrene‐appended CoII macrocyclic catalyst in comparison with its pyrene‐free prototype. The comparative results also verify the reasons of the higher catalytic activity of the pyrene‐tethered catalyst in noble‐metal‐free CO2 photoreduction with various photosensitizers, where a remarkable apparent quantum yield of 36±3% at 425 nm can be obtained for selective CO production. Electrochemical and spectroelectrochemical studies in conjunction with DFT calculations between the two catalysts have characterized the key CO‐bound intermediates and revealed their different CO‐binding behavior, demonstrating that the pyrene group endows the corresponding CoII catalyst a lower catalytic potential, a higher stability, and a greater ease in CO release, all of which contribute to its better performance.

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Section: Introductionmentioning

confidence: 99%

Unveiling the Activity and Mechanism Alterations by Pyrene Decoration on a Co(II) Macrocyclic Catalyst for CO₂ Reduction

Zhang,

Huang,

Luo

et al. 2024

ChemSusChem

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“…Indeed, many Co complexes based on poly-aromatic aza ligands were reported to display good to excellent activity in reductive catalytic processes. [8][9][10][11][12][13][14][15] With TMPA ligands specifically, Co II complexes were described as active for electro-and photocatalytic reduction of small molecules such as CO 2 [16][17][18][19] and O 2 [20] along with H 2 evolution. [21][22][23][24][25][26] Most of the reported Co II complexes coordinated to a TMPA unit, devoid of cavitary control, are mono-cationic species due to their propensity to bind anions: some are 5-coordinate with an anion (such as I À , Cl À , Br À , TfO À , SCN À or carboxylates) bound at the apical site of the trigonal pyramid or 6-coordinate with anionic donors.…”

Section: Introductionmentioning

confidence: 99%

TMPA‐based Cavitary Cobalt (II) Funnel Complexes

Nyssen,

Abudayyeh,

Zhurkin

et al. 2024

Eur J Inorg Chem

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The synthesis of a series of mononuclear, dicationic CoII funnel complexes is reported herein. Three ligands Calix‐TMPAX present a calix[6]arene cone closed at its small rim by a tris(2‐pyridylmethyl)amine (TMPA) unit and differ by the nature of three cavity walls, anisole, phenol or quinone. The X‐ray diffraction structure of [CoII(MeCN)Calix‐TMPAOMe](ClO4)2 displays a trigonal bipyramidal geometry, with Co bound to all 4 nitrogen atoms of the TMPA cap, and to one MeCN guest molecule buried inside the calixarene cavity. All complexes were fully characterized in solution as high spin 5‐coordinate species using various techniques, including 1H NMR spectroscopy. For comparison purpose, an analogous CoII complex based on the TMPACH2OH ligand, devoid of a calixarene core, was synthetized. Its X‐ray structure shows a dicationic 7‐coordinate cobalt(II) center in the N4O3 environment provided by the ligand, leaving no space for exogenous ligand binding. This contrasts with the 5‐coordinate complexes obtained with the calix‐ligands that allow guest‐ligand binding and exchange. A brief overview of the coordination properties of the calix‐complexes, compared to those obtained with TMPA ligands, devoid of a cavity, highlights major differences in terms of complexation kinetics, geometry, coordination to the labile site, anion affinity, nuclearity, and stability.

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“…Homogeneous, molecular photocatalytic systems are appealing in this term for the highly optimizable structures of the main molecular components, i.e., catalyst and photosensitizer (PS), in which their optimizations can be oriented by their well-defined structure–activity relationship and photocatalytic mechanisms. ,− Although selective molecular catalysts for photocatalytic CO 2 reduction in fully aqueous media have been developed, as exemplified by those earth-abundant ones like cobalt porphyrins, ,− Ni cyclam, ,− etc., the design of a versatile PS remains as one of the major bottlenecks to further improve the photocatalytic performance. As shown in Figure , one of the representative PSs in aqueous solutions is Ru(bpy) 3 2+ (bpy = 2,2′-bipyridine; denoted as RuBPY ; Figure ), ,,,− which still relies on the use of precious metal, restricting the large-scale applications.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient, Noble-Metal-Free, Fully Aqueous CO₂ Photoreduction Sensitized by a Robust Organic Dye

Ma,

Luo,

Wang

et al. 2024

J. Am. Chem. Soc.

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The development of efficient, selective, and durable CO 2 photoreduction systems presents a long-standing challenge in full aqueous solutions owing to the presence of scarce CO 2 and the fierce competition against H 2 evolution, which is even more challenging when noble metals are not utilized. Herein, we present the facile decorations of four phosphonic acid groups on a donor− acceptor-type organic dye to obtain a water-soluble photosensitizer (4P-DPAIPN), which succeeds the excellent photophysical and photoredox properties of its prototype, exhibiting long-lived delayed fluorescence (>10 μs) in aqueous solutions. Combining 4P-DPAIPN with a cationic cobalt porphyrin catalyst has accomplished record-high apparent quantum yields of 9.4−17.4% at 450 nm for CO 2 -to-CO photoconversion among the precedented systems (maximum 13%) in fully aqueous solutions. Remarkable selectivity of 82−93% and turnover number of 2700 for CO production can also be achieved with this noble-metal-free system, outperforming a benchmarking ruthenium photosensitizer and a commercial organic dye under parallel conditions. Such high performances of 4P-DPAIPN can be well maintained under real sunlight. More impressively, no significant decomposition of 4P-DPAIPN was detected during the long-term photocatalysis. Eventually, the photoinduced electron transfer pathways were proposed.

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Cobalt-based tripodal complexes as molecular catalysts for photocatalytic CO₂ reduction

Abstract: The progress in cobalt tripodal complexes as molecular catalysts for CO2 photoreduction is summarized.

Cited by 6 publications

References 66 publications

Unveiling the Activity and Mechanism Alterations by Pyrene Decoration on a Co(II) Macrocyclic Catalyst for CO₂ Reduction

Unveiling the Activity and Mechanism Alterations by Pyrene Decoration on a Co(II) Macrocyclic Catalyst for CO₂ Reduction

TMPA‐based Cavitary Cobalt (II) Funnel Complexes

Highly Efficient, Noble-Metal-Free, Fully Aqueous CO₂ Photoreduction Sensitized by a Robust Organic Dye

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Cobalt-based tripodal complexes as molecular catalysts for photocatalytic CO2 reduction

Abstract: The progress in cobalt tripodal complexes as molecular catalysts for CO2 photoreduction is summarized.

Cited by 6 publications

References 66 publications

Unveiling the Activity and Mechanism Alterations by Pyrene Decoration on a Co(II) Macrocyclic Catalyst for CO2 Reduction

Unveiling the Activity and Mechanism Alterations by Pyrene Decoration on a Co(II) Macrocyclic Catalyst for CO2 Reduction

TMPA‐based Cavitary Cobalt (II) Funnel Complexes

Highly Efficient, Noble-Metal-Free, Fully Aqueous CO2 Photoreduction Sensitized by a Robust Organic Dye

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Resources

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Cobalt-based tripodal complexes as molecular catalysts for photocatalytic CO₂ reduction

Unveiling the Activity and Mechanism Alterations by Pyrene Decoration on a Co(II) Macrocyclic Catalyst for CO₂ Reduction

Unveiling the Activity and Mechanism Alterations by Pyrene Decoration on a Co(II) Macrocyclic Catalyst for CO₂ Reduction

Highly Efficient, Noble-Metal-Free, Fully Aqueous CO₂ Photoreduction Sensitized by a Robust Organic Dye