掺杂Fe^(3+)与La^(3+)离子的TiO_2薄膜光反应活性的研究(英文)

利用溶胶-凝胶技术在载玻片衬底上制备了透明的TiO2薄膜。为了增强TiO2薄膜的光反应活性,对TiO2薄膜分别进行了不同浓度的Fe3+和La3+离子掺杂。离子掺杂的TiO2薄膜在可见光区有良好的透光性,通过降解罗丹明B染料溶液,评估了掺杂Fe3+和La3+离子的TiO2薄膜的光反应活性。结果表明,当Fe和La的原子分数比为0.5at%时增强了TiO2薄膜的光反应活性。

巯基丙烯酸酯树脂的合成及自引发光聚合反应

以4,4'-二巯基苯硫醚和1,6-己二醇二丙烯酸酯通过"巯基-双键"反应合成了4,4'-二巯基苯硫醚己酯二丙烯酸酯(TBHDA)及苯硫酚改性双三羟甲基丙烷四丙烯酸酯(TP-DiTMP4A)和超支化丙烯酸酯预聚物(TP-P1000As).采用1H NMR和FTIR谱对产物结构进行了表征.采用Photo-DSC方法对产物的自引发光聚合反应活性进行了研究,结果表明,TBHDA本体及与EB605的混合体系均显示出较高的自引发光聚合反应活性,而TP-DiTMP4A和TP-P1000As的自引发光聚合反应活性较低;相对TP-P1000As而言,TP-DiTMP4A具有较高的光聚合反应活性是由于其较高的硫醚键和丙烯酸酯双键浓度所致.

Photocatalytic activity of Fe-doped diopside

UV-visible light induced photocatalytic degradation of methylene blue (MB) over Fe-doped diopside was investigated. The structure, composition, morphology and absorption property of UV-visible light of as-prepared samples were characterized using XRD, SEM, FTIR and UV-vis DRS. The experimental results show that doping Fe3+ induced the formation of some new species in diopside, and promoted light adsorption property of diopside in UV-visible region. Photochemical reactivity of Fe-doped diopside obviously depended on the content of doping Fe3+. The diopside with 1.848% Fe3+ exhibited the superior photocatalytic activity with 95% degradation of MB under UV-visible light for 3 h. The photocatalytic degradation kinetics of MB over all samples showed the first-order reaction nature.

Growth and Physiological Features of Cyanobacterium Anabaena sp. Strain PCC 7120 in a Glucose-Mixotrophic Culture

Mixotrophic growth is one potential mode for mass culture of microalgae and cyanobacteria particularly suitable for the production of high value bioactive compounds and fine chemicals.The typical heterocystous cyanobacterium Anabaena sp.PCC 7120 was grown in the presence of exogenous glucose in light.Glucose improved the cell growth evidently,the maximal specific growth rate under mixotrophic condition（0.38 d 1）being 1.6-fold of that of photoautotrophic growth.Mixotrophy caused a variation in cellular pigment composition,increasing the content of chlorophyll a and decreasing the contents of carotenoid and phycobiliprotein relative to chlorophyll a.Fluorescence emission from photosystem II（PSII）relative to photosystem I was enhanced in mixotrophic cells,implying an increased energy distribution in PSII.Glucokinase（EC 2.7.1.2）activity was further induced in the presence of glucose.The mixotrophic culture was scaled up in a 15 L airlift photobioreactor equipped with an inner and an outer light source.A modified Monod model incorporating the specific growth rate and the average light intensity in the reactor was developed to describe cell growth appropriately.The understanding of mixotrophic growth and relevant physiological features of Anabaena sp.PCC 7120 would be meaningful for cultivation and exploitation of this important cyanobacterial strain.

Identification of active sites for hydrogenation over Ru/SBA-15 using in situ Fourier-transform infrared spectroscopy

The active sites for hydrogenation over Ru/SBA‐15catalysts were identified using in situ Fourier‐transform infrared spectroscopy.The amount of active sites was proportional to the interfacial circumference of the Ru particles.In contrast,the rate of hydrogen spillover from Ru to the support was inversely proportional to the size of the Ru metal particles.Consequently,a catalyst with small Ru metal particles has a high rate of hydrogen spillover but a low density of active sites,whereas one with large Ru particles has a low rate of hydrogen spillover but a high density of active sites.The formation of these active sites is probably an intermediate step in hydrogen spillover.

A Mechanism Study of a Novel Acid-Activatable Michael-Type Fluorescent Probe for Thiols

A Michael addition is usually taken as a base-catalysed reaction. However, our synthesized 2-（quinolin-2-ylmethylene） malonic acid （QMA） as a Michael-type thiol fluorescent probe is acid-active in its sensing reaction. In this work, based on theoretic calculation and experimental study on 7-hydroxy-2-（quinolin-2-ylmethylene） malonic acid, we demonstrated that QMA as a Michael acceptor is acid-activatable, i.e., it works only in solutions at pH〈7, and the lower the pH of solutions is, the higher reactivity QMA has. In alkaline solution, the malonate QMA[-2H＋]2- cannot react with both RSand RSH. In contrast, 2-（quinolin-2- ylmethylene） malonic ester （QME）, the ester of QMA, reveal a contrary pH effect on its sensing reaction, that is, it can sense thiols in alkaline solutions but not in acidic solutions, like a normal base-catalysed Michael addition. The values of activation enthalpies from theoretic calculation support the above sensing behavior of two probes under different pH conditions. In acidic solutions, the protonated QMA is more highly reactive towards electrophilic attack over its other ionized states in neutral and alkaline solutions, and so can react with lowly reactive RSH. In contrast, there is a big energy barrier in the interaction of QME with RSH （acidic solutions）, and the reaction of QME with the highly reactive nucleophile RS- is a low activation energy process （in alkaline solutions）. Theoretic calculation reveals that the sensing reaction of QMA undergoes a 1,4-addition process with neutral thiols （RSH）, and a 1,2-addition pathway for the sensing reaction of QME with RS-. Therefore, the sensing reaction of QMA is an acid-catalysed Michael addition via a 1,4-addition, and a normal base-catalysed Michael addition via a 1,2-addition.

Preparation of Cu-BiVO_4 and Its Photocatalytic Properties for Desulfurization of Model Oil

A photocatalyst Cu-BiVO4 was synthesized by the hydrothermal method and was characterized by XRD, UV-vis DRS, and N2 adsorption-desorption measurement. The catalytic activity of the Cu-BiVO4 samples was studied on desulfurization of thiophene dissolved in n-octane, which was used as a model light oil, via photocatalytic oxidation reaction under illumination by visible light. The catalyst characterization results indicated that the loading of Cu on the catalyst did not change the crystal phase of BiVO4, and the crystallinity of the Cu-BiVO4 sample was found to be better at pH=7. The Cu-BiVO4 samples presented a significant bathochromic shift of the absorption band in the visible region, and the absorption intensity increased for the composite catalyst. The desulfurization experiments showed that the Cu-BiVO4 sample prepared at a pH value of 7 had a better catalytic activity. Under proper operating conditions, the desulfurization rate of the model compound achieved by Cu-BiVO4 sample prepared at pH=7 could reach as high as 90%.

Oxygen Transfer and Hydrodynamics in a Flexible Fibre Biofilm Reactor for Wastewater Treatment

A flexible fibre biofilm reactor was developed for treatment of organic wastewaters.The hydrodynamic characteristics and mass transfer coefficients of oxygen were studied and compared with those of the conventional activated sludge processes.Tracer experiments were performed to obtain the residence time distributions of the reactors.The results indicated that both reactors could be treated as mixed flow reactors.The effects of flow rates of water and air on the overall mass transfer coefficient of oxygen were investigated,and the correlations between the mass transfer coefficient and the ratio of flow rates were obtained.Compared to the conventional activated sludge reactor,the mass transfer coefficients in the flexible fibre reactor were similar to but slightly lower,and less sensitive to the variation in the ratio of flow rates.It indicated that the fibre packing in the reactor hindered the oxygen transfer to some extent.

Completely Autotrophic Nitrogen-removal over Nitrite in Two Types of Reactors

Two lab-scale reactors, suspended-sludge and fluidized.bed, were conducted with the feed of ammonium-rich synthetic wastewater devoid of COD. Completely autotrophic nitrogen-removal process was fulfilled in both reactors and the maximum efficiencies of nitrogen removal were achieved, 65% in the suspended-sludge reactor and 73% in the fluidized-bed reactor respectively. Different from the steady performance of the fluldized-bed reactor, the suspended-sludge reactor came to deteriorate constantly after a period of stable operation, resulting in almost complete loss of the N-removal ability in the suspending system. Molecular methods such as PCR and FISH were employed for describing the microbial characteristics in two systems. This study suggests that a biofllm system is a suitable configuration for completely autotrophic N-removal with more feasibility and stability than a suspending system.

Observation of mitochondrial activity based on temporal and spatial pH variations measured by near-field fluorescent ratiometry

A novel method combining dual wavelength fluorescent ratiometry with scanning near-field optical microscopy (SNOM) is proposed and developed to measure the concentration and distribution of protons in the vicinity of biological samples. This method involves immersing mitochondria in a pH-sensitive fluorescent dye solution instead of injecting the dye into the surface of the mitochondrial membrane. It uses a dual emission pH-sensitive dye and SNOM with a thermally pulled and metal-coated optical fiber probe to improve the spatial resolution. The time dependence of the fluorescence intensity ratio (FIR) under acid addition and the response of mitochondria to nutritional supplementation were studied by using this method. Activation of mitochondria and a distance-dependent delay in the FIR response were observed. The results confirmed that mitochondrial activity could be observed by using this method.

Function-switchable metal/semiconductor junction enables efficient photocatalytic overall water splitting with selective water oxidation products

A novel metal/semiconductor photocatalyst,Cu nanoparticles(NPs)modified TiO2 hollow spheres(Cu/TiO2),was designed for efficient photocatalytic overall water splitting(POWS)under both ultraviolet(UV)and visible(Vis)light.This Cu/TiO2 photocatalyst possesses excellent POWS performance under Vis light at the highest level among the reported TiO2-based photocatalysts.Interestingly,the metal/semiconductor junction formed between Cu and TiO2 enables controlled water-oxidation product selectivity(H2O2 or O2)via different reaction pathways regulated by irradiation wavelengths.Under UV light,the electrons excited in TiO2 are captured by Cu NPs through the Cu/TiO2 Schottky interface for H2 production,with the photoholes in TiO2 producing H2O2 through a two-electron process;whilst under Vis light,Cu NPs act as plasmon to inject hot electrons to TiO2 for H2 production,while O2 is produced by hot holes on Cu NPs via a four-electron process.This rational design of function-switchable metal/semiconductor junction may be helpful to understand the mechanisms for POWS with desired gas/liquid water-oxidation products.

Synergetic enhancement of surface reactions and charge separation over holey C_(3)N_(4)/TiO_(2)2D heterojunctions

Efficient charge separation and rapid interfacial reaction kinetics are crucial factors that determine the efficiency of photocatalytic hydrogen evolution.Herein,a fascinating 2D heterojunction photocatalyst with superior photocatalytic hydrogen evolution performance–holey C_(3)N_(4)nanosheets nested with TiO_(2)nanocrystals(denoted as HCN/TiO_(2))–is designed and fabricated via an in situ exfoliation and conversion strategy.The HCN/TiO_(2)is found to exhibit an ultrathin 2D heteroarchitecture with intimate interfacial contact,highly porous structures and ultrasmall TiO_(2)nanocrystals,leading to drastically improved charge carrier separation,maximized active sites and the promotion of mass transport for photocatalysis.Consequently,the HCN/TiO_(2)delivers an impressive hydrogen production rate of 282.3 lmol h^(-1)per10 mg under AM 1.5 illumination and an apparent quantum efficiency of 13.4%at a wavelength of 420 nm due to the synergetic enhancement of surface reactions and charge separation.The present work provides a promising strategy for developing high-performance 2D heterojunctions for clean energy applications.

An efficient and facile synthesis of N-Cbz-β-aminoalkanesulfonamides

An efficient method for the synthesis of N-Cbz-β-aminoalkanesulfonamides was described.N-Cbz-β-aminoalkanesulfonamides were readily prepared in good yields from a variety of amino alcohols,including optically active ones,via N-Cbz protection with benzyl chloroformate,Mitsunobu esterification reaction with thiolacetic acid,N-chlorosuccinimide oxidation,and ammonolysis process.