This study presents the design and characterization of a triad metal-organic framework (MOF) system composed of pyrene, porphyrin, and phenyl-C-butyric acid (PCBA) for efficient energy and electron transfer processes mimicking natural photosynthesis. The triad MOF, synthesized through a mixed-ligand approach followed by postsynthetic modification, demonstrates sequential energy transfer from pyrene to porphyrin, followed by electron transfer to the PCBA acceptor. Time-resolved photoluminescence (TRPL) spectroscopy was employed to investigate the dynamics of energy and charge transfer, revealing fast interligand energy transfer and subsequent charge separation in the MOF structure. The PCBA-functionalized MOF (PCBA@nMLM) exhibited a significantly enhanced photocatalytic performance compared to the nonfunctionalized counterpart, particularly in the selective aerobic oxidation of sulfides to sulfoxides under visible light irradiation. The enhanced photocatalytic activity is attributed to the prolonged charge separation facilitated by the PCBA moieties, as confirmed by electrochemical impedance spectroscopy (EIS) and transient photocurrent measurements. This work highlights the potential of MOF-based systems in artificial photosynthesis and other photocatalytic applications by effectively harnessing solar energy through optimized energy and charge transfer mechanisms.
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http://dx.doi.org/10.1021/acsami.4c17875 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
City University of Hong Kong, Chemistry, HONG KONG.
Achieving rational control over chemical and energetic properties at the perovskite/electron transport layer (ETL) interface is crucial for realizing highly efficient and stable next-generation inverted perovskite solar cells (PSCs). To address this, we developed multifunctional ferrocene (Fc)-based interlayers engineered to exhibit adjustable passivating and electrochemical characteristics. These interlayers are designed to minimize non-radiative recombination and, to modulate the work function (WF) and uniformity of the perovskite surface, thereby enhancing device performance.
View Article and Find Full Text PDFJ Fluoresc
January 2025
Guangxi Key Laboratory of Electrochemical Energy Materials, School of Chemistry and Chemical Engineering, Guangxi University, No. 100, Daxue East Road, Nanning, Guangxi, 530004, China.
Two dipicolylamine (DPA) derivatives with the pyrene and anthracene groups, 1-(pyren-1-yl)-N, N-bis-(pyridine-2-ylmethyl)benzylamine (L1) and 1-(anthracen-9-yl)-N, N-bis-(pyridine-2-ylmethyl)benzylamine (L2) were synthesized, characterized, and their affinitive properties for metal ions were studied. The mass spectroscopy and Job's plots showed that L1 and L2 reacted with Cu and formed complexes [Cu(L1)(solvent)] (L1-Cu) and [Cu(L2)(solvent)] (L2-Cu), respectively. Both L1 and L2 were fluorescent probes recognizing Cu via the emission quenching and further detecting HS via the emission revival.
View Article and Find Full Text PDFACS Nano
January 2025
School of Information Science and Technology and Department of Optical Science and Engineering and Key Laboratory of Micro and Nano Photonic Structures (MOE), Fudan University, Shanghai 200433, China.
The formation of large polarons resulting from the Fröhlich coupling of photogenerated carriers with the polarized crystal lattice is considered crucial in shaping the outstanding optoelectronic properties in hybrid organic-inorganic perovskite crystals. Until now, the initial polaron dynamics after photoexcitation have remained elusive in the hybrid perovskite system. Here, based on the terahertz time-domain spectroscopy and optical-pump terahertz probe, we access the nature of interplay between photoexcited unbound charge carriers and optical phonons in MAPbBr within the initial 5 ps after excitation and have demonstrated the simultaneous existence of both electron- and hole-polarons, together with the photogenerated carrier dynamic process.
View Article and Find Full Text PDFACS Nano
January 2025
Department of Physics and Astronomy & Nebraska Center for Materials and Nanoscience, University of Nebraska, Lincoln, Nebraska 68588-0299, United States.
A spin valve represents a well-established device concept in magnetic memory technologies, whose functionality is determined by electron transmission, controlled by the relative alignment of magnetic moments of the two ferromagnetic layers. Recently, the advent of valleytronics has conceptualized a valley spin valve (VSV)─a device that utilizes the valley degree of freedom and spin-valley locking to achieve a similar valve effect without relying on magnetism. In this study, we propose a nonvolatile VSV (-VSV) based on a two-dimensional (2D) ferroelectric semiconductor where resistance of -VSV is controlled by a ferroelectric domain wall between two uniformly polarized domains.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, Zhejiang 310014, P. R. China.
Designing advanced catalysts for electrosynthesis of urea is of significance yet remains challenging. Herein, ultrathin two-dimensional Mo-doped PdIn bimetallene nanoribbons were synthesized a one-pot method. Material characterization and electrochemical study revealed that the alloying effect enabled electron transfer from In to Pd and provided dual metal sites with regulated electronic structure for the adsorption and activation of NO and CO, thus facilitating the generation of key active intermediates and promoting the C-N coupling reaction.
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