Porphyrins and phthalocyanines as biomimetic tools for photocatalytic H<sub>2</sub>production and CO<sub>2</sub>reduction

Nikoloudakis, Emmanouil; López‐Duarte, Ismael; Charalambidis, Georgios; Ladomenou, Kalliopi; Ince, Mine; Coutsolelos, Athanassios G.

doi:10.1039/d2cs00183g

Cited by 180 publications

(83 citation statements)

References 339 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Artificial photosynthesis has aspired to combine CO 2 reduction into chemical fuels with efficiency higher than that of natural systems. – Hydrogen molecule produced in PSI models was reported to reduce CO 2 to formic acid (HCO 2 H) under acidic conditions (pH 2.5–5.0) in H 2 O using water-soluble Ru II catalysts [(Cp*)(bpy)Ru II (OH 2 )] 2+ and [(Cp*)((OMe) 2 -bpy)Ru II (OH 2 )] 2+ [(OMe) 2 -bpy = 4,4′-dimethoxy-2,2′-bipyridine) . The HCO 2 H yields, TONs, and TOFs in the CO 2 reduction with water-soluble Ru II catalysts are listed in Table (entries 1 and 2, respectively) .…”

Section: Photosystem I Modelsmentioning

confidence: 99%

Reaction Intermediates in Artificial Photosynthesis with Molecular Catalysts

et al. 2022

View full text Add to dashboard Cite

In nature, water oxidation is catalyzed by Mn4Ca clusters in the oxygen-evolving complex (OEC) of photosystem II (PSII), in which a manganese(V)-oxo species acts as an active reaction intermediate. Electrons and protons taken from water in PSII are used to reduce plastoquinone to plastoquinol via photoinduced charge separation in the photosynthetic reaction center. In photosystem I (PSI), NADP+ coenzyme is reduced by plastoquinol via photoinduced charge separation in the photosynthetic reaction center to produce NADPH, which is used as a reductant to reduce CO2 to carbohydrates in the Calvin cycle. Extensive efforts have so far been made to mimic functions of PSII and PSI for photocatalytic water oxidation and reduction to produce O2 and H2, respectively. Characterization and reactivity of high-valent metal-oxo, -hydroperoxo, -peroxo, and -superoxo intermediates have been investigated to clarify the mechanisms of water oxidation. Metal hydride complexes have also been studied in relation with the catalytic reactivity for water reduction to produce H2 as well as NAD+ reduction to NADH. This Review is intended to provide an overview on the functional model reactions of PSII and PSI for the photocatalytic water oxidation and reduction, respectively. The roles of high-valent metal-oxo, -hydroperoxo, -peroxo, and -superoxo complexes as the reaction intermediates in photocatalytic water oxidation are focused in relation with the catalytic mechanisms of water oxidation. The roles of metal hydride complexes are also discussed in relation with the catalytic mechanisms of hydrogen evolution and NAD+ reduction to NADH. The combination of functional model reactions of PSII and PSI leads to construct molecular artificial photosynthetic systems in which water is split to H2 and O2 in a 2:1 ratio, providing a way to realize artificial photosynthesis in molecular levels.

show abstract

Section: Photosystem I Modelsmentioning

confidence: 99%

Reaction Intermediates in Artificial Photosynthesis with Molecular Catalysts

et al. 2022

View full text Add to dashboard Cite

show abstract

“…Supramolecular systems based on porphyrin derivatives are of great importance, owing to the intrinsic conceptual stimuli and their applications in diverse scientific and technological fields such as organic solar cells [ 1 ], artificial light-harvesting systems [ 2 , 3 ], catalysis [ 4 ] and photocatalysis [ 5 ], photodynamic therapy of tumours [ 6 ] and sensors [ 7 ]. The implementation of elements of chirality [ 8 , 9 , 10 ] infers to these supramolecular architectures unique properties in terms, for example, of chiral recognition and sensing [ 11 , 12 ], asymmetric catalysis and Circularly Polarised Luminescence (CPL) generation [ 13 , 14 , 15 , 16 ].…”

Section: Introductionmentioning

confidence: 99%

Stereospecific Self-Assembly Processes of Porphyrin-Proline Conjugates: From the Effect of Structural Features and Bulk Solvent Properties to the Application in Stereoselective Sensor Systems

Stefanelli

Natale

Paolesse

et al. 2022

IJMS

View full text Add to dashboard Cite

Conjugating the porphyrin ring with an amino acid via amide linkage represents a straightforward way for conferring both amphiphilicity and chirality to the macrocycle. Proline residue is a good choice in this context since its conformational rigidity allows for porphyrin assembling where molecular chirality is efficiently transferred and amplified using properly honed aqueous environments. Herein, we describe the evolution of the studies carried out by our group to achieve chiral systems from some porphyrin-proline derivatives, both in solution and in the solid state. The discussion focuses on some fundamental aspects reflecting on the final molecular architectures obtained, which are related to the nature of the appended group (stereochemistry and charge), the presence of a metal ion coordinated to the porphyrin core and the bulk solvent properties. Indeed, fine-tuning the mentioned parameters enables the achievement of stereospecific structures with distinctive chiroptical and morphological features. Solid films based on these chiral systems were also obtained and their recognition abilities in gaseous and liquid phase are here described.

show abstract

“…Significant effort has been directed towards the development of molecular electrocatalysts for reducing CO2 to CO. [1][2] Product selectivity and the ability to rationally design ligands to improve activity have been key reasons for the extensive effort put into studying the mechanism of molecular electrocatalysts. Key classes of compounds which have been shown to be efficient CO2 reduction catalysts are, among others, metalophthalocyanines, [3][4] metaloporphyrins, [4][5][6] poly-pyridyl rhenium and manganese carbonyls, 7 nickel complexes with azamacrocyclic ligands 8 and polypyridyl complexes of Co/Fe/Ni. 9 Extensive research into the structure-activity relationships of these complexes has led to the development of molecular catalysts that exhibit high rates without compromising overpotential.…”

Section: Introductionmentioning

confidence: 99%

Insights into the Mechanism of CO2 Electroreduction by Molecular Palladium-Pyridinophane Complexes

Chakrabarti

Woods

Mirica

2023

Preprint

View full text Add to dashboard Cite

Herein we report the synthesis, characterization, and electrocatalytic CO2 reduction activity of a series of PdII complexes supported by tetradentate pyridinophane ligands. In particular, we focus on the electrocatalytic CO2 reduction activity of a PdII complex supported by the mixed hard/soft 2,11-dithia[3.3](2,6)pyridinophane (N2S2) ligand . This is one of the few examples of a Pd complexes supported by a mixed hard-soft ligand which selectively produces CO from the electrocatalytic reduction of CO2. Notably, unlike previously reported molecular Pd complexes, selective CO2RR occurs in presence of weak proton sources such as 2, 2, 2 trifluoroethanol (TFE) and phenol, at mild overpotentials (~160 mV) and with high rates (kobs = 4.5 x 103 s-1, with phenol as proton source) and at Faradaic efficiencies of up to 70% for CO, without any H2 being detected. As the catalyst was not stable to long term electrolysis, we analyzed possible decomposition routes for this catalyst and, based on the characterization of its reaction with CO by UV-vis, NMR, and IR spectroscopy, we propose the intermediacy of a binuclear [(N2S2)PdI(η2-CO)]2 species toward the ultimate decomposition of the catalyst into free ligand and Pd0. Overall, these studies offer important insights into Pd catalyst decomposition and may explain the historically poor performance of related Pd molecular catalysts for CO2 reduction. In addition, the structurally-related hard N-donor diazapyridinophane (RN4)Pd complexes are shown to be unstable towards bulk electrolysis at cathodic potentials, suggesting that such compounds are ill-suited for CO2 electroreduction.

show abstract

Porphyrins and phthalocyanines as biomimetic tools for photocatalytic H₂production and CO₂reduction

Abstract: This review summarizes the recent advances in light driven catalytic H2 evolution and CO2 reduction systems towards the production of solar fuels, utilizing porphyrin or phthalocyanine derivatives.

Cited by 180 publications

References 339 publications

Reaction Intermediates in Artificial Photosynthesis with Molecular Catalysts

Reaction Intermediates in Artificial Photosynthesis with Molecular Catalysts

Stereospecific Self-Assembly Processes of Porphyrin-Proline Conjugates: From the Effect of Structural Features and Bulk Solvent Properties to the Application in Stereoselective Sensor Systems

Insights into the Mechanism of CO2 Electroreduction by Molecular Palladium-Pyridinophane Complexes

Contact Info

Product

Resources

About

Porphyrins and phthalocyanines as biomimetic tools for photocatalytic H2production and CO2reduction

Abstract: This review summarizes the recent advances in light driven catalytic H2 evolution and CO2 reduction systems towards the production of solar fuels, utilizing porphyrin or phthalocyanine derivatives.

Cited by 180 publications

References 339 publications

Reaction Intermediates in Artificial Photosynthesis with Molecular Catalysts

Reaction Intermediates in Artificial Photosynthesis with Molecular Catalysts

Stereospecific Self-Assembly Processes of Porphyrin-Proline Conjugates: From the Effect of Structural Features and Bulk Solvent Properties to the Application in Stereoselective Sensor Systems

Insights into the Mechanism of CO2 Electroreduction by Molecular Palladium-Pyridinophane Complexes

Contact Info

Product

Resources

About

Porphyrins and phthalocyanines as biomimetic tools for photocatalytic H₂production and CO₂reduction