Directed Electron Delivery from a Pb‐Free Halide Perovskite to a Co(II) Molecular Catalyst Boosts CO₂ Photoreduction Coupled with Water Oxidation

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: Feb. 29, 2024

Abstract The development of high‐performance photocatalytic systems for CO 2 reduction is appealing to address energy and environmental issues, while it challenging avoid using toxic metals organic sacrificial reagents. We here immobilize a family cobalt phthalocyanine catalysts on Pb‐free halide perovskite Cs AgBiBr 6 nanosheets with delicate control the anchors catalysts. Among them, molecular hybrid photocatalyst assembled by carboxyl achieves optimal performance an electron consumption rate 300±13 μmol g −1 h visible‐light‐driven ‐to‐CO conversion coupled water oxidation O , over 8 times unmodified (36±8 ), also far surpassing documented (<150 ). Besides improved intrinsic activity, electrochemical, computational, ex‐/in situ X‐ray photoelectron absorption spectroscopic results indicate that electrons photogenerated at Bi atoms can be directionally transferred catalyst via which strongly bind atoms, substantially facilitating interfacial transfer kinetics thereby photocatalysis.

Language: Английский

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Influence of π–π interactions on organic photocatalytic materials and their performance

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A comprehensive review is provided on the impact, construction strategies and applications of π–π interactions in field photocatalysis.

Language: Английский

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Earth-abundant-metal complexes as photosensitizers in molecular systems for light-driven CO2 reduction

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 500, P. 215529 - 215529

Published: Nov. 6, 2023

Language: Английский

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Precious-Metal-Free CO₂ Photoreduction Boosted by Dynamic Coordinative Interaction between Pyridine-Tethered Cu(I) Sensitizers and a Co(II) Catalyst

JACS Au, Journal Year: 2023, Volume and Issue: 3(7), P. 1984 - 1997

Published: July 14, 2023

Improving the photocatalytic efficiency of a fully noble-metal-free system for CO2 reduction remains fundamental challenge, which can be accomplished by facilitating electron delivery as consequence exploiting intermolecular interactions. Herein, we have designed two Cu(I) photosensitizers with different pyridyl pendants at phenanthroline moiety to enable dynamic coordinative interactions between sensitizers and cobalt macrocyclic catalyst. Compared parent photosensitizer, one pyridine-tethered derivatives boosts apparent quantum yield up 76 ± 6% 425 nm selective (near 99%) CO2-to-CO conversion. This value is nearly twice that no (40 5%) substantially surpasses record (57%) systems reported so far. also realizes maximum turnover number 11 800 1400. In contrast, another in pyridine substituents are directly linked moiety, inactive. The above behavior mechanism systematically elucidated transient fluorescence, absorption, X-ray absorption spectroscopies, chemical calculations. work highlights advantage constructing fine-tune transfer processes within photoreduction.

Language: Английский

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Controlling the Photophysical Properties of a Series of Isostructural d⁶ Complexes Based on Cr⁰, Mn^I, and Fe^II

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(7), P. 4605 - 4619

Published: Feb. 9, 2024

Development of first-row transition metal complexes with similar luminescence and photoredox properties as widely used RuII polypyridines is attractive because metals from the first series are comparatively abundant inexpensive. The weaker ligand field experienced by valence d-electrons challenges installation same types metal-to-ligand charge transfer (MLCT) excited states in precious complexes, due to rapid population energetically lower-lying metal-centered (MC) states. In a family isostructural tris(diisocyanide) 3d6 Cr0, MnI, FeII, increasing effective nuclear strength allow us control energetic order between 3MLCT 3MC states, whereas pyrene decoration isocyanide framework provides over intraligand (ILPyr) chromium(0) complex shows red phosphorescence all other higher energy. manganese(I) complex, microsecond-lived dark 3ILPyr state, reminiscent electronic encountered many polyaromatic hydrocarbon compounds, lowest becomes photoactive. iron(II) MLCT state has shifted so much energy that 1ILPyr fluorescence occurs, parallel excited-state deactivation pathways. Our combined synthetic-spectroscopic-theoretical study unprecedented insights into how charge, strength, π-conjugation affect ligand-based under what circumstances these individual become luminescent exploitable photochemistry. Such key further developments photoredox-active complexes.

Language: Английский

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Rationalizing Photophysics of Co(III) Complexes with Pendant Pyrene Moieties

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

Pendant organic chromophores have been used to improve the photocatalytic performance of many metal-based photosensitizers, particularly in first-row metals, by increasing π conjugation ligands and lowering energy photoactive absorption band. Using a combination spectroscopic studies computational modeling, we rationalize excited state dynamics Co(III) complex containing pendant pyrene moieties, CoL1, where L1 = 1,1′-(4-(pyren-1-yl)pyridine-2,6-diyl)bis(3-methyl-1H-imidazol-3-ium). CoL1 displays higher visible absorptivity, blue luminescence from singlet states compared with CoL0 [L0 1,1′-(pyridine-2,6-diyl)bis(3-methyl-1H-imidazol-3-ium)] which moiety is absent. Emissive properties are highly influenced metal center, reducing fluorescence lifetime 5.9 3.5 ns, shift 43 nm. The lower d orbitals Fe(II) drastically affects character state, resulting mixture intraligand charge-transfer (1ILCT) ligand-to-metal (1LMCT) character. Transient experiments revealed that although dark triplet (3ILPyrene) present, it not efficiently populated possesses short nanosecond-scale lifetime. Instead, metal-centered (3MC) dominate decay path 2.4 ps lifetime, no photoactivity toward oxygen formation or triplet–triplet transfer (TTET). This work shows how various factors can influence excited-state dynamics.

Language: Английский

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Highly efficient electrocatalytic CO ₂ reduction by a Cr ^III quaterpyridine complex

Proceedings of the National Academy of Sciences, Journal Year: 2024, Volume and Issue: 121(14)

Published: March 25, 2024

Design tactics and mechanistic studies both remain as fundamental challenges during the exploitations of earth-abundant molecular electrocatalysts for CO 2 reduction, especially rarely studied Cr-based ones. Herein, a quaterpyridyl Cr III catalyst is found to be highly active electroreduction with 99.8% Faradaic efficiency in DMF/phenol medium. A nearly one order magnitude higher turnover frequency (86.6 s −1 ) over documented catalysts (<10 can achieved at an applied overpotential only 190 mV which generally 300 lower than these precedents. Such high performance this low driving force originates from metal–ligand cooperativity that stabilizes low-valent intermediates serves efficient electron reservoir. Moreover, synergy electrochemistry, spectroelectrochemistry, paramagnetic resonance, quantum chemical calculations allows characterize key II , I 0 CO-bound well verify catalytic mechanism.

Language: Английский

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Self-sensitized Cu(II)-Complex Catalyzed Solar Driven CO₂ Reduction

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Developing a self-sensitized catalyst from earth-abundant elements capable of efficient light harvesting and electron transfer is crucial for enhancing the efficacy CO 2 reduction, environmental cleanup, improving clean energy prospects.

Language: Английский

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New Insight into the Conjugation Effect of Tetranuclear Copper(I) Cluster Catalysts for Efficient Electrocatalytic Reduction of CO₂ into CH₄

ACS Sustainable Chemistry & Engineering, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

Language: Английский

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

ChemSusChem, Journal Year: 2024, Volume and Issue: 17(11)

Published: Jan. 30, 2024

Abstract Mechanistic studies involving characterization of crucial intermediates are desirable for rational optimization molecular catalysts toward CO 2 reduction, while fundamental challenges associated with such studies. Herein we present the systematic mechanistic investigations on a pyrene‐appended Co II macrocyclic catalyst in comparison its pyrene‐free prototype. The comparative results also verify reasons higher catalytic activity pyrene‐tethered noble‐metal‐free photoreduction various photosensitizers, where remarkable apparent quantum yield 36±3 % at 425 nm can be obtained selective production. Electrochemical and spectroelectrochemical conjunction DFT calculations between two have characterized key CO‐bound revealed their different CO‐binding behavior, demonstrating that pyrene group endows corresponding lower potential, stability, greater ease release, all which contribute to better performance.

Language: Английский

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