Perovskite–Molecular Photocatalyst Synergy and Surface Engineering for Superior Photocatalytic Performance

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 15, 2025

Metal halide perovskite nanocrystals (NCs), known for their strong visible-light absorption and tunable optoelectronic properties, show significant promise photocatalytic applications. However, efficiency is often hindered by rapid charge recombination insufficient exciton dissociation, limiting effective catalysis. Excited-state interactions at the NC interface are critical in determining performance, underscoring need strategies that enhance separation minimize recombination. To address these challenges, we developed a composite material combining cesium lead bromide (CsPbBr3) with ferrocene carboxylic acid (FcA), hole-extracting moiety. This integration enhances dissociation through energy level alignment suppression, resulting 3-fold increase oxidation yield of benzylamine to N-benzylidenebenzylamine (35 ± 5% versus 12 2% pristine CsPbBr3). Additionally, thionyl (SOBr2) surface modification strips off ligands introduces ions onto CsPbBr3 NCs, further improving transfer substrate accessibility, 27 within 3 h. While SOBr2 treatment initial catalytic its acidic nature may reversible reactions side products over extended reaction times. study highlights impact molecular engineering on optimizing interfacial dynamics, providing pathway toward robust, high-efficiency photocatalysts sustainable chemical transformations.

Language: Английский

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Photo‐Induced Bandgap Engineering of Metal Halide Perovskite Quantum Dots In Flow

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 11, 2025

Abstract Over the past decade, lead halide perovskite (LHP) nanocrystals (NCs) have attracted significant attention due to their tunable optoelectronic properties for next‐generation printed photonic and electronic devices. High‐energy photons in presence of haloalkanes provide a scalable sustainable pathway precise bandgap engineering LHP NCs via photo‐induced anion exchange reaction (PIAER) facilitated by situ generated anions. However, mechanisms driving remain not fully understood. This study elucidates underlying PIAER through an advanced microfluidic platform. Additionally, first instance PIAER, transforming CsPbBr 3 into high‐performing CsPbI NCs, with assistance thiol‐based additive is reported. Utilizing intensified photo‐flow microreactor accelerates rate 3.5‐fold, reducing material consumption 100‐fold compared conventional batch processes. It demonstrated that act as photocatalysts, oxidative bond cleavage dichloromethane promoting photodissociation 1‐iodopropane using high‐energy photons. Furthermore, it plays dual role: surface passivation, which enhances photoluminescence quantum yield, facilitates PIAER. These findings pave way tailored design perovskite‐based materials.

Language: Английский

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Application of Lead-Free Metal Halide Perovskite Heterojunctions for the Carbohalogenation of C–C Multiple Bonds

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

A graphitic carbon nitride/lead-free double perovskite heterojunction (g-C3N4/Cs2AgBiCl6) has been adopted as a heterogeneous photocatalyst under visible light irradiation. The employed material enabled the atom transfer radical addition-type carbohalogenation of multiple C-C bonds, including (internal) alkenes and alkynes, with alkyl halides. protocol showed remarkable functional group tolerance, compatible late-stage functionalization natural pharmaceutical derivatives, could be easily scaled up, delivering >1 g desired products.

Language: Английский

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Long‐Lived Charge Separation Enabled by Molecular Engineering of Phenazine‐Based Hole Transport Materials

Small, Journal Year: 2025, Volume and Issue: unknown

Published: April 18, 2025

Abstract Achieving long‐lived charge‐separated states is paramount for advancing perovskite solar cells technology, enhancing efficiency, and enabling kinetically slow processes like photocatalysis. While hole transport materials (HTMs) are essential efficient charge extraction, conventional suffer from high defect densities at the perovskite/HTM interface, leading to severe nonradiative recombination losses. Previous strategies surface passivation often rely on external treatments, which pose scalability challenges. This work overcomes these limitations by integrating functionality directly into HTMs through targeted molecular engineering of phenazine derivatives. By leveraging anchoring capability 1,10‐phenanthroline (Phen) skeleton strategically incorporating electron‐donating (─NH 2 , ─OCH 3 ) electron‐withdrawing (─NO ─Br) groups, electron density systematically modulated control transfer dynamics. Electron‐donating groups (EDGs) increase core, suppressing trap‐assisted stabilizing states. In contrast, (EWGs) promote dipole formation sites, prolonged separation, as confirmed observed sustained bleaching in transient absorption spectroscopy. study reveals profound impact substituent electronic effects interfacial interactions, offering a design strategy optimizing mitigation optoelectronics. These findings provide scalable approach perovskite‐based photovoltaics photocatalytic applications.

Language: Английский

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Unlocking Enhanced Light Harvesting in Perovskites: A Light‐Mediated Ligand Management Approach

Advanced Optical Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 23, 2024

Abstract Interfaces between nanocrystals and their stabilizing ligands in light‐harvesting devices are crucial for mediating energy transfer, essential efficient solar conversion. In metal halide perovskites, a promising material these devices, Förster resonance transfer (FRET) within perovskite/acceptor‐molecule complexes offers pathway optimized transfer. However, traditional methods optimizing FRET perovskite‐chromophore hybrids based on static modifications. This study presents an innovative approach light‐driven dynamic control of FRET, achieving ≈14% enhancement efficiency CsPbBr 3 (CPB NCs) rhodamine B isothiocyanate (RITC) dye. UV light is utilized to reversibly regulate NC‐ligand binding thus the coupling CPB NCs RITC at interface. critically relies strong NC–ligand interactions, such as Pb ─ S bond RITC. Light exposure weakens surface ligands, allowing RITC, with its bond, attach more effectively promote enhanced light‐activated absent Rhodamine (RhB) lacking NCS group, motif. The findings reveal importance interactions dynamically manipulating light. pioneering method nanoscale paves way devices.

Language: Английский

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Enhancing the Photocatalytic Performance of CsPbBr₃ Nanocrystals through Ferrocene-Assisted Exciton Dissociation and Halide Vacancies

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 27, 2024

Excited-state interactions at the interfaces of nanocrystals play a crucial role in determining photocatalytic efficiency. CsPbBr

Language: Английский

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