Two new chemically stable metalloporphyrin-bridged metal-catechol frameworks, InTCP-Co and FeTCP-Co, were constructed to achieve artificial photosynthesis without additional sacrificial agents and photosensitizers. The CO photoreduction rate over FeTCP-Co considerably exceeds that obtained over InTCP-Co, and the incorporation of uncoordinated hydroxyl groups, associated with catechol, into the network further promotes the photocatalytic activity. The iron-oxo coordination chain assists energy band alignment and provides a redox-active site, and the uncoordinated hydroxyl group contributes to the visible-light absorptance, charge-carrier transfer, and CO -scaffold affinity. With a formic acid selectivity of 97.8 %, FeTCP-OH-Co affords CO photoconversion with a reaction rate 4.3 and 15.7 times higher than those of FeTCP- Co and InTCP-Co, respectively. These findings are also consistent with the spectroscopic study and DFT calculation.
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http://dx.doi.org/10.1002/anie.202111622 | DOI Listing |
ACS Appl Mater Interfaces
January 2025
Département de chimie, Université de Sherbrooke, Sherbrooke, Québec J1K 2R1, Canada.
Two new nonfused ring nonfullerene electron acceptors, NFAs, (dicarbazolyl)bis(2-(3-oxo-2,3-dihydro-1-inden-1-ylidene)malononitrile) () and -(2-(5,6-fluoro-3-oxo-2,3-dihydro-1-inden-1-ylidene)malononitrile) (), thus exhibiting an A-D-A motif, were synthesized and characterized. As thin films, they exhibit the lowest energy absorption signature near 540 nm, extending down to ∼700 nm. This band is due to an intramolecular charge transfer process from the (nonfused dicarbazoyl; ) moiety to the malononitrile-based units () based on density functional theory calculations (DFT), which are also corroborated by time-dependent DFT (TDDFT) computations.
View Article and Find Full Text PDFNanoscale
January 2025
School of Science, Jiangsu University of Science and Technology, Zhenjiang 212001, China.
Herein, we propose a new GaN/MoSiP van der Waals (vdWs) heterostructure constructed by vertically stacking GaN and MoSiP monolayers. Its electronic, optical, and photocatalytic properties are explored DFT++BSE calculations. The calculated binding energy and phonon spectrum demonstrated the material's high stabilities.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2025
Department of Chemistry, University of Illinois Urbana-Champaign, Urbana, Illinois 61801, United States.
Ammonia has garnered significant attention as a promising hydrogen carrier due to its high volumetric energy density, milder storage conditions, and relatively mature infrastructure. The electrochemical ammonia oxidation reaction (AOR) can facilitate the release of hydrogen from ammonia at the point of use, enabling on-demand hydrogen production without the need for high pressure storage. However, current AOR catalysts exhibit high overpotentials and sluggish kinetics, and they are susceptible to poisoning by AOR byproducts.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Department of Chemistry, College of Science, King Khalid University, Abha 61413, P.O. Box 9004, Saudi Arabia.
Lead-free inorganic halide perovskites, specifically BaPX (X = Cl, F, I, Br) have gained attention in green photovoltaics due to their remarkable mechanical, optical, structural, and electronic properties. Using first-principles calculations, we investigated the mechanical, electronic, and optical characteristics of BaPX, revealing direct band gaps at the -symmetry point, assessed with the PBE and HSE functionals. The charge distribution analysis shows strong ionic bonding between Ba and halides and covalent bonding between P and halides.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2025
College of Chemistry, Chemical Engineering and Environment, Minnan Normal University, Zhangzhou 363000, China.
Two-dimensional (2D) PtSe has attracted significant attention in recent years owing to its exceptional optoelectronic properties. Currently, the contact interface of the PtSe/bulk 2D-three-dimensional (3D) p-n heterojunction exhibits numerous defects. Moreover, the n-type bulk materials serve as a carrier transport layer, resulting in serious recombination losses and deterioration of device stability.
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