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6 result(s) for "LMCT"
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Pt-Chitosan-TiO2 for Efficient Photocatalytic Hydrogen Evolution via Ligand-to-Metal Charge Transfer Mechanism under Visible Light
The Pt-chitosan-TiO2 charge transfer (CT) complex was synthesized via the sol-gel and impregnation method. The synthesized photocatalysts were thoroughly characterized, and their photocatalytic activity were evaluated toward H2 production through water reduction under visible-light irradiation. The effect of the preparation conditions of the photocatalysts (the degree of deacetylation of chitosan, addition amount of chitosan, and calcination temperature) on the photocatalytic activity was discussed. The optimal Pt-10%DD75-T200 showed a H2 generation rate of 280.4 μmol within 3 h. The remarkable visible-light photocatalytic activity of Pt-chitosan-TiO2 was due to the CT complex formation between chitosan and TiO2, which extended the visible-light absorption and induced the ligand-to-metal charge transfer (LMCT). The photocatalytic mechanism of Pt-chitosan-TiO2 was also investigated. This paper outlines a new and facile pathway for designing novel visible-light-driven photocatalysts that are based on TiO2 modified by polysaccharide biomass wastes that are widely found in nature.
Titanium-Dioxide-Based Visible-Light-Sensitive Photocatalysis: Mechanistic Insight and Applications
Titanium dioxide (TiO2) is one of the most practical and prevalent photo-functional materials. Many researchers have endeavored to design several types of visible-light-responsive photocatalysts. In particular, TiO2-based photocatalysts operating under visible light should be urgently designed and developed, in order to take advantage of the unlimited solar light available. Herein, we review recent advances of TiO2-based visible-light-sensitive photocatalysts, classified by the origins of charge separation photo-induced in (1) bulk impurity (N-doping), (2) hetero-junction of metal (Au NPs), and (3) interfacial surface complexes (ISC) and their related photocatalysts. These photocatalysts have demonstrated useful applications, such as photocatalytic mineralization of toxic agents in the polluted atmosphere and water, photocatalytic organic synthesis, and artificial photosynthesis. We wish to provide comprehension and enlightenment of modification strategies and mechanistic insight, and to inspire future work.
Self-Assembly of a Two-Dimensional Coordination Polymer Based on Silver and Lanthanide Tetrakis-Acylpyrazolonates: An Efficient New Strategy for Suppressing Ligand-to-Metal Charge Transfer Quenching of Europium Luminescence
A new strategy for the easy polymerization of anionic [Ln(Qcy)4]− (HQcy-4-(cyclohexanecarbonyl)-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one) into two-dimensional layers of [AgLn(Qcy)4]n (Ln = Sm, Eu, Gd, Tb and Dy) is proposed by binding the single molecular anions [Ln(Qcy)4]− to silver cations through the coordination of the pyridinic nitrogen atoms of the pyrazolonate rings. The luminescent properties of [AgLn(Qcy)4]n have been studied in detail, and it was shown that the previously described low photoluminescence quantum yield (PLQY) of [Eu(Qcy)4]− is due to Ligand-To-Metal Charge Transfer (LMCT) quenching, which is effectively suppressed in the heterometallic [AgEu(Qcy)4]n polymer. Sensibilization coefficients for H3O[Eu(Qcy)4], [AgEu(Qcy)4]n, and H3O[Sm(Qcy)4] complexes (n ≈ 1) were estimated via theoretical analysis (also by using Judd-Ofelt theory for Sm3+) and PLQY measurements.
Enhancing Photocatalytic Performance of NH2-UIO66 by Defective Structural Engineering
NH 2 -UIO66 (NU) is a promising photocatalyst for the reduction of Cr(VI) to low-toxic Cr(III) driven by visible light under ambient conditions. However, the main limitation in this process is the inefficient ligand to metal charge transfer (LMCT) of photo-excited electrons, which is caused by inherent energy gap (Δ E LMCT ). This study synthesized the defective NU (NUX-H, where X is the molar equivalent of the modulator) with reduced Δ E LMCT through linkers removal via acid treatment. The electronic structure of NUX-H was systematically investigated, and the results indicated that the structural defects in NUX-H strongly altered the environment of the Zr atoms. Furthermore, they substantially lowered the energy of the unoccupied d orbitals (LUMO), which was beneficial to efficient LMCT, resulting in an improved photocatalytic activity of NUX-H toward high-concentration (100 mg/L) Cr(VI) reduction. Compared to NU with defect-free structure, the reducing rate of Cr(VI) was increased by 47 times. This work introduced an alternative strategy in terms of designing efficient photocatalysts for reducing Cr(VI) under ambient conditions.
Ligand-to-Metal Charge Transfer Resulting in Metalloaromaticity of R,R-Cyclohexyl-1,2-bis(2-Oxidonaphthylideneiminato-N,N′,O,O′)Cu(II): A Scrutinized Structural Investigation
Molecular and crystal structure analysis of a tetradentate ligand-to-metal charge transfer (LMCT) complex, [ R,R -cyclohexyl-1,2-bis(2-oxidonaphthylideneiminato- N,N′,O,O′ )]Cu(II), are described and characterized by X-ray crystallography and FTIR spectroscopy. The Cu(II) centers are coordinated by four atoms of the donor set [N 2 O 2 ] in a distorted square-planar fashion, which can be attributed to an active electronic delocalization within metallacycles and polychelating property of the pro-ligand. Bond valences of copper centers in four crystallographically independent monomers are slightly distinguished from each other, which is associated with differences in charge delocalization levels of the pro-ligands. Total valence of the copper center is increased with increasing π-electron donation from naphthalene fragments to metallacycles. This charge transfer leads to π···π interactions between metallacycles including imine bridges. In addition, decreases in the centroid–centroid distances of π···π interactions are associated with increased aromatic character of metallacycles. Molecules of the complex are stacked as dimers in the crystal structure formed by π···π interactions and aggregations of these dimeric formations along a -axis are strengthened by C–H···O type H-bonds and C–H···π interactions.
Metallation of Seaweed Fucus vesiculosus Metallothionein: As3+ and Cd2+ binding
This chapter contains sections titled: Introduction Characterization of the rfMT Equilibrium metallation studies of rfMT studied using ESI‐MS and UV‐visible absorption techniques Dynamic metallation studies of rfMT studied using ESI‐MS techniques Conclusions Acknowledgments References