Design of Frustrated Lewis Pair in Defective TiO2 for Photocatalytic Non-Oxidative Methane Coupling

The efficient C-H polarization is the prerequisite for the low-temperature photocatalytic CH4 conversion, which however is restricted by the poor stretching ability of short-distanced lattice atoms. Herein, frustrated Lewis pair (FLP) composed of doped ion in TiO2 as Lewis acid (LA) and neighboring Ti-OH as Lewis base (LB) with a long distance (0.31-0.37 nm) were designed through DFT calculation and fabricated by hydrogenation treatment of metal-doped TiO2-SiO2 with macroporous-mesoporous structure. Benefitting from the long LA-LB distance and matched acid-base intensity, hydrogenated Ga-doped composite achieves superior C-H stretching with a high CH4 conversion rate (139 µmol g−1 h−1) to ethane. The photo-irradiation causes the electron excitation from Ga to Ti-OH according to the time-dependent DFT calculation and in situ EPR analysis, which promotes the formation and coupling of ·CH3. This work provides a key underpinning for regulating the characteristics of FLP for C-H activation and C-C coupling via light irradiation.

Вероятность ионизации атомов, распыленных при бомбардировке поверхности металлов одно- и многозарядными ионами

The processes of ionization of atoms sputtered under bombardment of clean metal surface by singly and multiply charged ions with kinetic energy of several keV were studied. Within the framework of simple phenomenological model of ion formation, the relaxation of local electron excitation in metal was taking into account. Analytical expressions for estimation of ionization probability of sputtered atoms was obtain. It was shown, that in comparison with singly charged ions, bombardment of metals with multiply charged ions results to significant increase of ionization probability of sputtered atoms due to more efficient excitation of electrons and increase of relaxation time of this excitation.

Axial uniformity diagnosis of coaxial surface wave linear plasma by optical emission spectroscopy

The coaxial surface wave linear plasma with preeminent axial uniformity is developed with the 2.45 GHz microwave generator. By optical emission spectroscopy, parameters of the argon linear plasma with a length over 600 mm are diagnosed under gas pressure of 30 Pa and 50 Pa and different microwave powers. The spectral lines of argon and Hβ (486.1 nm) atoms in excited state are observed for estimating electron excitation temperature and electron density. Spectrum bands in 305–310 nm of diatomic OH (A2 Σ+-X2 Πi) radicals are used to determine the molecule rotational temperature. Finally, the axial uniformity of electron density and electron excitation temperature are analyzed emphatically under various conditions. The results prove the distinct optimization of compensation from dual powers input, which can narrow the uniform coefficient of electron density and electron excitation temperature by around 40% and 22% respectively. With the microwave power increasing, the axial uniformity of both electron density and electron excitation temperature performs better. Nevertheless, the fluctuation of electron density along the axial direction appeared with higher gas pressure. The axial uniformity of coaxial surface wave linear plasma could be controlled by pressure and power for a better utilization in material processing.

Improvement of the Efficiency of TiO2 Photocatalysts with Natural Dye Sensitizers Anthocyanin for the Degradation of Methylene Blue: Review

One of the potential methods utilized for dye degradation is photocatalitic, due to its low cost, highly effective, and environmentally friendly. Effectivenes of TiO2 photocatalysts can be enhanced by adding a dye sensitizer. Dye-sensitizer material absorbs visible light to facilitate electron excitation process. Addition of dye-sensitizer on TiO2 photocatalyst promotes it to be more responsive to visible light. Natural anthocyanin dyes are often used as sensitizers of TiO2 semiconductors. Anthocyanins are, usually in the purple to the red color range, a group of natural dyes found in the flowers, leaves, and fruit of plants. The essential principles of dye sensitization to TiO2 have been explored in this review. It is feasible to reduce the band gap energy in the TiO2 photocatalyst by modifying it using a natural dye sensitized modification. Dye sensitizers on TiO2 nanotubes plate have the potential to be employed in a dye degradation photocatalytic system

Tumor Cell Distinguishable Nanomedicine Integrating Chemotherapeutic Sensitization and Protection

Theoretically, with a high enough drug dosage, cancer cells could be eliminated. However, the dosages that can be administered are limited by the therapeutic efficacy and side effects of the given drug. Herein, a nanomedicine integrating chemotherapeutic sensitization and protection was developed to relieve the limitation of administration dosage and to improve the efficacy of chemotherapy. The nanomedicine was endowed with the function of synergistically controlled release of CO and drugs under near-infrared (NIR) light irradiation. CO photo-induced release system (COPIRS) was synthesized by constructing an electron excitation–electron transfer group–electron-induced CO release structure and was used as the hydrophobic part, and then hydrophilic polymer (polyethylene glycol; PEG) was introduced by a thermal-responsive groups (DA group), forming a near-infrared-induced burst-release nanocarrier. In vitro and in vivo experiments showed that the nanomedicine can distinguish between tumor and normal cells and regulates the resistance of these different cells through the controlled release of carbonic oxide (CO), simultaneously enhancing the efficacy of chemotherapy drugs on tumor cells and chemotherapeutic protection on normal cells. This strategy could solve the current limitations on dosages due to toxicity and provide a solution for tumor cure by chemotherapy.

Understanding the Electronic Interactions, Vertical Excitation Analysis, and the Photovoltaic Properties of 5-(2-ethylhexyl)-1,3-di(furan-2-yl)-4H-thieno[3,4-c]pyrrole-4,6-dione

Organic photovoltaic (OPV) are a promising new class of photovoltaic as they offer several advantageous features including large surface area to volume ratio, low cost, lightweight properties, and durability. The limitation of OPV that prevented their adoption for use in the past was their low power conversion efficiency (PCE) but that drawback has been solved by the development of the donor-acceptor-donor (D-A-D) system with high conversion efficiencies. Herein, 5-(2-ethylhexyl)-1,3-di (furan-2-yl)-4H-thieno [3,4-c]pyrrole-4,6(5H)-dione (FTPF), a donor-acceptor-donor monomer was investigated for its optoelectronic, excited state, and photovoltaic properties using a density functional theory (DFT) and time-dependent density function theory (TD-DFT) at the B3LYP/6-31+G(d,p) theoretical method. The spectral analysis (FT-IR, UV-vis, and NMR), electronic molecular properties, natural bonding orbitals (MOs and NBOs) analyses, and excitation were studied at this level in gas, hexane, DMF, and THF. The UV-Vis spectrum showed that FTPF exhibited mono-absorption in non-polar gas and hexane, but dual absorptions in polar solvents (DMF and THF) having maximum wavelength (λmax) at 351, 359, 371 and 373 nm in gas, hexane, THF, and DMF respectively, showing a major red shift as solvent became polar. The hole-electron excitation studies of the first five singlet states: S0→S1/S2/S3/S4/S5 in gas and DMF phases showed that S0→S1 is a delocalized π→π* Rydberg excitations originating from the D-A-D C=C π bonds, S0→S2 is π→π* local excitation, while S0→S3 in water occurred as an n→π* from the carbonyl and azolide groups of the acceptor unit, but n→π* charge transfer (CT) in DMF. The S0→S5 in water and S0→S4 are n→π* LE type excitations, while S0→S5 in DMF conformed to a delocalized π→π* excitation extended over the D-A-D conjugated backbone. FTPF provided efficient electron injection in all studied solvent; showing that FTPF is a sure-bet for opto-electronic application.

Multi-electron excitation contributions towards primary and satellite states in the photoelectron spectrum

The computation of Dyson orbitals and corresponding ionization energies has been implemented within the Equation of Motion Coupled Cluster Singles, Doubles, and Perturbative Triples (EOMCC3) method. Coupled to an accurate description of the electronic continuum via a time-dependent density functional approach using a multicentric B-spline basis, this yields highly accurate photoionization dynamical parameters (cross-sections, branching ratios, asymmetry parameters, and dichroic coefficients) for primary states (1h) as well as satellite states of (2h-1p) character. Illustrative results are presented for the molecular systems H2O, H2S, CS, CS2 and (S)-propylene oxide (a.k.a. methyloxirane).

Probing Electron Excitation Characters of Carboline-Based Bis-Tridentate Ir(III) Complexes

In this work, we report a series of bis-tridentate Ir(III) metal complexes, comprising a dianionic pyrazole-pyridine-phenyl tridentate chelate and a monoanionic chelate bearing a peripheral carbene and carboline coordination fragment that is linked to the central phenyl group. All these Ir(III) complexes were synthesized with an efficient one-pot and two-step method, and their emission hue was fine-tuned by variation of the substituent at the central coordination entity (i.e., pyridinyl and phenyl group) of each of the tridentate chelates. Their photophysical and electrochemical properties, thermal stabilities and electroluminescence performances are examined and discussed comprehensively. The doped devices based on [Ir(cbF)(phyz1)] (Cb1) and [Ir(cbB)(phyz1)] (Cb4) give a maximum external quantum efficiency (current efficiency) of 16.6% (55.2 cd/A) and 13.9% (43.8 cd/A), respectively. The relatively high electroluminescence efficiencies indicate that bis-tridentate Ir(III) complexes are promising candidates for OLED applications.

Fluorescent Probe for Simultaneous Detection of Human Serum Albumin and Sulfur Dioxide: A Theoretical Analysis

A small molecule probe for simultaneous detection of HSA and SO2 via their distinct fluorescent signals was designed recently. This effective tool provided a significant boost in understand underlying mechanism of synergistic action between SO2 and HSA in disease. The structure and fluorescent character of this probe molecule were studied under density functional theory in this work. The different stable conformations of probe C23 were found through theoretical method which explained the no experimental fluorescent character of the probe itself. The electron excitation analysis indicated the charge transfer process in the restricted C23 (binding to the hydrophobic cavity of HSA) and CS (C23 reaction with SO2) when the molecules were under optical excitation. The theoretical results could be helpful for understanding the electronical properties in the probe and providing the insights for designing new probe molecules.