BiPO4/石墨烯光电极的制备及其光电催化性能（英文）

光电催化(PEC)氧化法是一种使用半导体电极材料在光和电的共同作用下处理水中有机污染的有效方法.在PEC工艺中,施加偏压不仅可以利用电催化对有机污染物进行降解,而且在偏压作用下,光生电子-空穴对能够得到有效的分离和传输,从而大大提高了机物污染物的去除速率.尽管PEC技术已经取得了许多重要的突破,但是能量转换效率仍然无法满足实际应用.因此,开发具有优异性能,良好稳定性和低成本的光电极材料是一项具有挑战性的研究工作.本文采用两步电沉积法制备了BiPO4纳米棒/还原氧化石墨烯/FTO复合光电极(BiPO4/r GO/FTO).电镜结果表明,电沉积制得的纳米棒状磷酸铋均匀负载在石墨烯纳米片层表面.采用甲基橙为模型体系,考察了复合光电极的光电催化活性.BiPO4/r GO/FTO复合电极的光电催化降解速率是BiPO4/FTO光电极的2.8倍,显示出优良的光电催化活性.实验进一步研究了工作电压和BiPO4沉积时间对甲基橙光电降解性能的影响.最佳的BiPO4沉积时间为45 min,最佳工作电压为1.2 V.捕获实验和ESR实验表明羟基自由基(·OH)和超氧化物自由基(·O2-)是该电极的主要活性物种.BiPO4/r GO/FTO复合电极经过四次循环实验后其降解甲基橙效率保持不变,显示出高稳定性,采用光电流,交流阻抗及其荧光测试对其光催化机理进行推测.结果表明该复合光电极具有高PEC活性的主要原因是:石墨烯的引入加快了BiPO4的电子空穴的分离,拓宽了石墨烯的可见光吸收范围;同时,石墨烯诱导产生的BiPO4混合相也进一步促进了光生电子空穴的分离,提高了光电降解活性.     

Intelligence Way from Eco-friendly Synthesis Strategy of New Heterocyclic Pyrazolic Carboxylic α-Amino Esters

The α-amino acid derivatives constitute a class of compounds of particular medicinal and synthetic attention and considerable interest has been devoted to their synthesis in recent years. In the present work, we develop the computational study of the synthesis reaction of new pyrazolyl α-amino esters derivatives using the Gaussian 09 based on the DFT/B3LYP density functional theory method, with the base 6-31G(d, p) to ensure the possibility of carrying out these reactions within the laboratory of synthesis. Indeed, this research has encouraged us to establish an economical synthesis strategy of these products in overall yields of 73.5% to 87% to have access to new active biomolecule through the O-alkylation reaction between methyl α-azidoglycinate N-benzoylated and primary pyrazole alcohols[(3,5-dimethyl-1H-pyrazol-1-yl)methanol, (1H-pyrazol-1-yl)methanol and (3-ethoxy-5-methyl-1H-pyrazol-1-yl)methanol] under different operating conditions. The structure of the prepared heterocyclic systems was characterized by conventional spectroscopic techniques, like ¹H NMR, ¹³C NMR, and MS. The results revealed that the experimental study is in good correlation with the computational one.     

Temperature-dependent infrared absorption cross sections of methyl cyanide (acetonitrile)

Pressure broadened (1 atm. N₂) absorption cross sections and integrated band intensities have been derived from laboratory spectra of CH₃CN, recorded at 276, 298, and 323 K, covering 600-. The spectra were recorded at a resolution of using a commercial Fourier transform spectrometer and a custom flowing sample delivery system. We report integrated absorption cross sections for intervals corresponding to the most prominent bands, compare the results with previously reported values, and discuss error sources, which are estimated as ∼7% with systematic error the largest error source.     

Thermosensitive poly(methyl methacrylate) emulsion prepared in the presence of poly(vinyl alcohol) with a cloud point as a protective colloid

An emulsion of poly(methyl methacrylate) (PMMA) was prepared using poly(vinyl alcohol) (PVA) of low degree of hydrolysis with a cloud point as a protective colloid. The behaviour of an aqueous solution of PVA with 80% degree of hydrolysis was first investigated in terms of the Huggins constant in viscometry. MMA was polymerized using the PVA at 20 °C, where no abnormality in the aqueous PVA was observed. The change in transmittance of the emulsion observed with a UV–vis photometer revealed that in the case of UV light of wavelength 370 nm, the transmittance decreased markedly at around 30 °C with an increase in temperature, and then increased with a decrease in temperature. The thermosensitive property resulted from PVA with a low degree of hydrolysis with a cloud point, at a higher temperature of which the PVA loses solubility in water owing to weakening of the hydrogen bond between PVA molecules and water.     

A theoretical study of CH4 dissociation on Pt(1 0 0) surface

Density functional theory calculations have been performed on the adsorption of H and CH₃, and the dissociation of CH₄ on Pt(1 0 0) surface. It was found that H was adsorbed on the top and bridge sites, while CH₃ was adsorbed only on the top site. The coadsorption of methyl and hydrogen which has also been investigated shows that the interaction between the two adsorbates is stabilising. In addition, two distinct pathways were explored, differing by the initial adsorbed state of CH₄. They converge readily to the same transition state corresponding to an activation energy value of 0.53 eV. These results compare favourably with existing data in the literature for Pt(1 1 1) and Pt(1 1 0).     

Thermal degradation and flame retardance in copolymers of methyl methacrylate with diethyl(methacryloyloxymethyl)phosphonate

Methyl methacrylate (MMA) has been free radically copolymerized, both in bulk and in solution, with diethyl(methacryloyloxymethyl)phosphonate (DEMMP), to give polymers which are significantly flame retarded when compared with PMMA, as indicated by the results of limiting oxygen index (LOI) measurements, UL 94 tests, and the results of cone calorimetric experiments. The physical and mechanical properties of the copolymers are similar to those of PMMA, except that the bulk copolymers are slightly crosslinked, and are better than those of PMMA flame retarded to a similar extent by some phosphate and phosphonate additives. Examination of the some of the gaseous products of pyrolysis and combustion, and of chars produced on burning, show that flame retardation occurs in the copolymers by both a condensed-phase and a vapour-phase mechanism. The condensed-phase mechanism is shown to involve generation of phosphorus acid species followed by reaction of these with MMA units giving rise to methacrylic acid units. The methacrylic acid units subsequently form anhydride links, which probably impede depolymerization of the remaining MMA sequences, resulting in evolution of less MMA (the major fuel when MMA-based polymers burn). By undergoing decarboxylation, leading to interchain cyclisation and, eventually, to aromaticisation, the anhydride units are probably also the principal precursors to char.     

S0 and S1 spectroscopy of jet cooled 9-cyano-10-methylanthracene: The methyl group as a molecular rotor

Jet-cooled fluorescence excitation and dispersed fluorescence spectra of 9-methylanthracene (MA), 9-cyanoanthracene (CA) and 9-cyano-10-methylanthracene (CMA) have been measured. The spectra of MA and CMA near the S₀-S₁ origin reveal a prominent torsional progression due to the hindered methyl group rotation and its torsional vibration against the aromatic ring frame. Additionally, the laser induced fluorescence LIF excitation spectrum of CMA shows the splitting of many vibrational modes.Observed positions and relative intensities of the methyl internal rotational bands were interpreted in terms of transitions calculated based on the quantum mechanical one-dimensional rotor. The low-frequency vibrational bands were interpreted also with the all electron quantum mechanical calculations within the RHF/6-31G(d,p), CIS/3-21G and CIS/6-31G(d,p) approximations. It is predicted that in the case of MA the eclipsed geometry (one C-H in the plane of the ring) is most stable in both S₀ and S₁ states. Conformation of the methyl group in CMA is suggested to change upon S₁ ← S₀ excitation (π/12 phase shift of the methyl group). The predicted energy barrier for methyl group rotation in the S₀ state of CMA is considerably higher (72 cm⁻¹) than that in the S₁ state (22 cm⁻¹). Following the present quantum mechanical calculations, the carbon atom of the methyl group belongs to the aromatic plane in the S₀ ground state but it deviates from this plane in the S₁ excited state. These in turn suggest that the calculated barrier for methyl group rotation in CMA has a 6-fold symmetry in the S₀ ground state and roughly a 4-fold symmetry in the S₁ state.     

In situ monitoring of the H concentration change near an electrode surface through electrolysis using slab optical waveguide pH sensor

The H⁺ concentration change was monitored near an electrode surface through an electrolysis using a slab optical waveguide technique. Indium tin oxide transparent electrode modified by porous insulating polymer to which methyl red was covalently immobilized was used as a guiding layer, and the absorbance change of the polymer film was monitored. H⁺ generation at the vicinity of the electrode through the oxidation of ascorbic acid could be monitored by this technique.