Development of a Highly Durable Photocatalytic CO₂ Reduction Using a Mn-Complex Catalyst: Application of Selective Photosplitting of a Mn(0)–Mn(0) Bond

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 10, 2025

fac-[MnI(diimine)(CO)3(L)]0/+ has attracted significant attention as a catalyst for the photocatalytic reduction of CO2. However, in such systems, photoexcitation Mn complexes and reaction intermediates induces their decomposition, which lowers durability these systems. In this study, we clarified primary process whereby complex decomposes during reaction. Based thereupon, successfully constructed highly durable system, turnover number formate (TONHCOO–) exceeded 1700 when fac-[MnI(bpy)(CO)3((OC(O)OC2H5N(C2H5OH)2) (Mn-CO2-TEOA) catalyst, [OsII(4,4′-dimethyl-bpy)(5,5′-dimethyl-bpy)2]2+ (Os) photosensitizer, 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) reductant were used conjunction with irradiation at λex ≥ 620 nm. contrast, same 480 nm lowered TONHCOO– to less than 60. The difference system arises from dependence Mn(0)–Mn(0) dimer [Mn02(bpy)2(CO)6] (Dim-Mn), an intermediate produced reaction, on wavelength irradiated light its photoreactivity. That is, Dim-Mn selectively splitting Mn–Mn bond produce [Mn0(bpy)(CO)3] (Mn•) and, contrary this, Mn(0)–CO bonds further decomposition processes are induced by

Язык: Английский

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Cobalt-Embedded Metal–Covalent Organic Frameworks for CO₂ Photoreduction

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 7, 2025

With the pressing urgency to reduce carbon footprint, photocatalytic dioxide reduction has attracted growing attention as a sustainable mitigating option. Considering important role of catalytic active sites (CASs) in processes, control and design density environment CASs could enhance catalyst performance. Herein, we report novel metal-covalent organic framework (MCOF), MCOF-Co-315, featuring earth-abundant Co cocatalysts conjugation through covalently bonded backbone. MCOF-Co-315 showed CO production rate 1616 μmol g-1 h-1 utilizing Ru(bpy)3Cl2 photosensitizer triethanolamine (TEOA) sacrificial electron donor with 1.5 AM filter, vis mirror module (390-740 nm), irradiation intensity adjusted 1 sun an especially outstanding apparent quantum yield (AQY) 9.13% at 450 nm. The reaction was studied paramagnetic resonance (EPR) spectroscopy, X-ray absorption near-edge structure (XANES), situ synchrotron Fourier Transform Infrared (FT-IR) underlying mechanism is proposed.

Язык: Английский

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Sunlight-driven simultaneous CO2 reduction and water oxidation using indium-organic framework heterostructures

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Март 16, 2025

Abstract Overall artificial photosynthesis, as a promising approach for sunlight-driven CO 2 recycling, requires photocatalysts with efficient light adsorption and separate active sites coupling H O oxidation. Here we show In-based metal–organic framework (MOF) heterostructure, i.e., In-porphyrin (In-TCPP) nanosheets enveloping an In-NH -MIL-68 (M68N) core, via facile one-pot synthesis that utilises competitive nucleation growth of two organic linkers In nodes. The coherent interfaces the core@shell MOFs assure structural stability which will function heterojunctions to facilitate transfer photogenerated charge overall photosynthesis. In-TCPP shell in heterostructure improves capabilities visible absorption enhance photocatalytic reduction. Simultaneously, In-O M68N core efficiently catalyze oxidation, achieving high yields HCOOH (397.5 μmol g −1 h ) (321.2 under focused sunlight irradiation. superior performance this coupled its straightforward synthesis, shows great potential mitigating carbon emissions producing valuable chemicals using solar energy.

Язык: Английский

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Synthesis of flower-like covalent organic frameworks for photocatalytic selective oxidation of sulfide

Journal of the Taiwan Institute of Chemical Engineers, Год журнала: 2024, Номер 164, С. 105680 - 105680

Опубликована: Июль 27, 2024

Язык: Английский

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Molecular catalyst coordinatively bonded to organic semiconductors for selective light-driven CO2 reduction in water

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Ноя. 12, 2024

The selective photoreduction of CO

Язык: Английский

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Simultaneously Tailoring Hydrostability and Photoelectroactivity in Heterocluster Metal–Organic Frameworks for Efficient Photocatalytic Hydrogen Production

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Апрель 3, 2025

The simultaneous enhancement of structural stability and photoelectroactivity in metal-organic frameworks (MOFs) remains a critical challenge for sustainable photocatalytic hydrogen (H2) production. Herein, an atomically-precise heterocluster assembly approach is presented to construct two isostructural 3D MOFs, CuSL-CuX (X = Cl, Br), featuring cds net. CuSL-CuXs integrate hexanuclear copper-sulfur {Cu6S6} cluster dinuclear copper-halogen {Cu2X2} cluster, which not only impart exceptional across broad pH range (1-14) but also enable wide visible-light absorption, tailored redox potentials, efficient charge-carrier dynamics. Notably, halogen substitution markedly boosts activity: CuSL-CuBr achieves H2 evolution rate 50.28 mmol g-1 h-1 without noble metals, doubling that CuSL-CuCl (26.99 h-1) surpassing most reported MOF-based photocatalysts. Both experimental theoretical investigations indicate bromine optimizes electronic structure, refines orbital distribution, accelerates charge separation, ultimately leading promoted efficiency. This research provides insights into the structure-property interplay MOFs establishes paradigm designing robust, high-performance photocatalysts through precise engineering.

Язык: Английский

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Manipulating Charge Dynamics in Carbon Nitride by Carbon Dot Doping for Efficient Photocatalysis

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Апрель 26, 2025

Abstract Graphitic carbon nitride (g‐C 3 N 4 ), a prominent metal‐free semiconductor photocatalyst, faces limitations due to its high exciton binding energy. While significant efforts have been focused on optimizing charge‐carrier processes, the interplay of and free carrier in this system received less attention. Herein, density‐functional theory (DFT) time‐dependent DFT calculations demonstrate that dot‐functionalized g‐C /CD), synthesized via facile thermal polymerization, shifts excited state from localized charge transfer characteristics. The /CD exhibits reduced energy 41.0 24.6 meV, as shown by temperature‐dependent photoluminescence spectroscopy. Particularly, /CD‐10 (10 wt.% CD solution precursors) achieves 3‐fold increase photodegradation rate ( k = 0.020 min⁻¹) an emerging environmental pollutant, levofloxacin (LEV), under 10 W LED light. Enhanced photocatalytic performances correlate with optimized band structure efficient transport, confirmed photophysical photoelectrochemical analyses. Although lifetime is slightly compared pristine , activity remains unaffected, underscoring critical role enhancing efficiency. This work offers insights onto potential manipulating dynamics for improved ‐based photocatalysis applications.

Язык: Английский

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Organic Photocatalyst Utilizing Triplet Excited States for Highly Efficient Visible-Light-Driven Polymerizations

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Май 1, 2025

ConspectusUltraviolet (UV) light has traditionally been used to drive photochemical organic transformations, mainly due the limited visible-light absorption of most molecules. However, high energy associated with UV often causes undesirable side reactions. In late 2000s, MacMillan, Yoon, and Stephenson pioneered use visible in conjunction photocatalysts (PCs) initiate transformations. This innovative approach overcame limitations by utilizing visible-light-absorbing PCs their photoexcited states for electron or transfer, generating reactive radical species promoting photoreactions. Furthermore, while photocatalysis predominantly relied on transition-metal complexes, concerns over potential toxicity, cost, sustainability these metals have driven development PCs. These eliminate need metal removal, offer structural diversity, enable tuning properties, thus paving way creation a tailored library PCs.In recent decades, significant advancements made novel diverse scaffolds, notable example being work Zhang et al. 2016. They demonstrated that cyanoarene analogues, originally developed Adachi thermally activated delayed fluorescence (TADF) light-emitting diodes, could function effectively as Building insights, we PC design platform featuring TADF compounds twisted donor-acceptor structures, which paved new discoveries. We showcased PCs' ability (i) generate long-lived lowest triplet excited (T1) (ii) tune redox potentials independently modifying donor acceptor moieties. Through this platform, discovered varying capability populate T1 states, establishing structure-property relationships within our creating selection criteria targeted Specifically, highly efficient reversible-deactivation polymerizations, including organocatalyzed atom transfer polymerization, photoinduced electron/energy reversible addition-fragmentation chain polymerization dual photoredox/copper catalysis well rapid free polymerizations. also facilitated functionalized, visible-light-cured adhesives advanced display technologies. investigated origins exceptional catalytic performance through comprehensive mechanistic studies, electrochemical photophysical measurements, quantum chemical calculations, kinetics simulations. studied formation degradation key intermediates photocatalytic dehalogenations alkyl aryl halides. Our findings revealed distinctive photodegradation pattern cyanoarene-based PCs, significantly impact efficiency reaction. Additionally, discovery led us introduce concept beneficial first time.Over past based state become central synthesis. Utilizing systems enhance overall various overview contributions visible-light-driven photocatalysis, highlight role broadening applications analysis, enabling more sustainable

Язык: Английский

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Recent Advances in Water-Soluble Photocatalysts-Mediated Aqueous Reactions

Chinese Journal of Organic Chemistry, Год журнала: 2025, Номер 45(4), С. 1097 - 1097

Опубликована: Янв. 1, 2025

Язык: Английский

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Efficient Visible‐Light‐Driven CO₂ Reduction Enabled by a Triazatriangulenium Organic Sensitizer and Iron Molecular Catalyst

ChemCatChem, Год журнала: 2025, Номер unknown

Опубликована: Май 24, 2025

Abstract The development of efficient photocatalytic systems based on earth‐abundant metals for the direct conversion CO 2 into renewable solar fuels is transforming landscape energy conversion. In this study, we present a novel system utilizing triangulenium dye ( N,N′,N′′ ‐tris(2‐hydroxyethyl)‐triazatriangulenium TATH ) hexafluorophosphate) as organic photosensitizer, paired with an iron‐quaterpyridine molecular catalyst and BIH/TEOA sacrificial electron donors. performance significantly enhanced through synergistic electron‐proton relay mechanism between BIH TEOA, which effectively mitigates charge recombination during reduction. Operated in MeCN/NaHCO 3 buffer under visible light, demonstrates exceptional activity selectivity production, achieving turnover number (TON) exceeding 20,000, quantum yield 41.6%, >99% product selectivity. These results surpass benchmark employing noble‐metal photosensitizers such [Ru(bpy) ] 2+ or [Ir(bpy)(ppy) + identical conditions. Remarkably, both photosensitizer maintain operational stability by their high individual TONs. This versatile, noble‐metal‐free holds great potential advancing solar‐to‐fuel reactions.

Язык: Английский

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