丝光沸石的Monte Carla研究：Ⅱ.脱铝丝光沸石的骨架硅,铝分布

以马尔可夫链近似模拟线光沸石脱铝过程，用ＭｏｎｔｅＣａｒｌｏ方法计算脱铝丝光沸石中骨架Ｓｉ－Ａｌ近邻分布｛Ｓｉ（ｎ－Ａｌ）；ｎ＝０－４｝和Ａｌ－Ａｌ次部分布｛Ａｌ（ｍ－Ａｌ）；ｍ＝０－３｝随铝浓度的演化。为使Ｓｉ－Ａｌ近邻分布与对脱铝丝光沸石样品的＾２＾９ＳｉＭＡＳＮＭＲ观测相符，而得到丝光沸石弱酸铝易于解脱的结论，这个结构与八面沸石弱酸铝易于解脱相反。根据计算丝光沸石脱铝的开始阶段，强酸中心...     

丝光沸石的Monte Carlo研究：Ⅲ.酸性与骨架Al—Al次邻分布的关联

基于“酸位效率参量”的定义，对Ｂａｒｔｈｏｍｅｕｆ定义的铝原子酸效率参量αｏ作出诠释。强调αｏ不仅是铝浓度赖而且是样品铝分布状态依赖的。具有相同Ｓｉ／Ａｌ的丝光沸石原粉与经历过脱铝的丝光沸石，二者骨架硅，铝分布有很大区别。根据＾２＾９ＳｉＭＡＳＮＭＲ拟谱我们曾推断丝光沸石的强酸位更易于从骨架解脱，并进一步予言脱铝丝光沸石所进行的氨ＴＰＤ实验所获二者的酸量及酸量／铝原子含量比率的数据。     

脱铝丝光沸石中扭曲四配位铝的27Al 3Q MAS NMR研究

用²⁷Al MAS,3Q MAS NMR研究了脱铝的丝光沸石和无定形硅铝胶中的铝配位态，在丝光沸石中检测到归属于扭曲四配位铝（Distorted Tetrahedrally Coordinated Al, DTA）的信号，通过与无定形硅铝胶的比较，发现扭曲四配位铝的存在是活化和脱铝酸性沸石的典型特征. 从这些结果推断：DTA可能是沸石骨架脱铝形成非骨架铝的中间状态.     

模板剂四乙基氢氧化铵的用量对合成的β沸石结构及脱胺的影响

研究四乙基氢氧化铵（TEA-OH）模板剂用量对合成的β沸石的结构及脱胺行为的影响。合成β沸石的模板剂的较佳用量(TEA+/Al)为2.10～1.68,合成的β沸石的相对结晶度均大于84%;β沸石中的铝含量(Al/Al+Si)及骨架铝含量(TdAl/TdAl+OhAl)随晶化混合液的TEA+/Al而变,存在最佳TEA+/Al点为1.9,此时合成的β沸石非骨架铝量最少,结构硅铝比最高;含TEA的β沸石脱胺过程为Hofmann降解反应,TGA测定的失重量、DSC测定的吸热量与β沸石中TEA含量密切相关.     

Y型沸石脱铝机制和铝状态的NMR研究

对Y型沸石原粉及几种不同脱铝样品进行了几种不同NMR方法的测量,确定了不同处理过程的脱铝机制和骨架内外铝状态的变化,²⁹Si MAS NMR谱给出了骨架Si、Al分布的信息,反映了不同方法处理样品其脱铝机制的差异,据此可以控制Y沸石脱铝过程获得更高的硅铝比,²⁷Al MAS NMR谱、二维章动NMR及¹H-²⁷Al CP/MAS NMR测量表明:水热处理的Y沸石中存在4种不同的铝状态。综合²⁹Si和²⁷Al MAS NMR观测,可相当程度地推断Y型沸石分子筛脱铝改性所发生的内部过程。     

分子筛酸中心与NMR

通过沸石分子筛的固体高分辨核磁共振观测,可以确定骨架硅、铝比,分析硅、铝在骨架上的统计分布特征。基于化学位移或核电四极作用的表征,可识别、分辨铝在沸石中不同结构状态或配位状态;这些微观信息,有助于认识沸石酸性机理,以及对有关其合成、改性的种种研究提供重要依据。     

焙烧对HL沸石结构的影响

运用MAS NMR研究了焙烧对HL沸石结构的影响. 结果表明,高温焙烧将引起HL沸石骨架的脱铝,当焙烧温度高于650 ℃后,沸石骨架脱铝明显;²⁷Al MAS NMR谱表明,从沸石上脱下来的铝,部分形成了NMR不可测的无定形态,且随焙烧温度的升高,NMR不可测铝增多.     

导向剂法合成U沸石的光谱研究

采用导向剂法合成了β沸石。ＸＲＤ光谱测定表明,导向剂的成活以及β沸石的形成被局限于相对较窄的相区范围内。β沸石的２９Ｓｉ和２７Ａｌ－ＮＭＲ 光谱表征进一步说明β沸石骨架硅铝四面体的排列较为规整,其中Ｎａ＋ 离子起着平衡沸石骨架负电荷的作用。     

导向剂法合成β沸石的光谱研究

采用导向剂法合成了β沸石。ＸＲＤ光谱测定表明,导向剂的成活以及β沸石的形成被局限于相对较窄的相区范围内。β沸石的＾２９Ｓｉ和＾２７Ａｌ－ＮＭＲ光谱表征进一步说明β沸石骨架硅铝四面体的排列较为规整,其中Ｎａ＾＋离子起着平衡沸石骨架负电荷的作用。     

菱钾沸石中铝在不等价四面体位上分布的^29SiMASNMR谱研究

根据菱钾沸石＾２９ＳｉＭＡＳＮＭＲ实验讨论了骨架Ｓｉ／Ａｌ比（Ｒ）和Ａｌ在两种不等价四面体位分配比率（ｒ）二者之间必须满足的关系，对于合成原粉，Ａｌ择优占据ＴＢ位；用（ＮＨ４）２ＳｉＦ６同晶取代脱铝，ＴＢ位上的Ａｌ择优解脱。     

Novel Fluorometric Turn On Detection of Aluminum by Chalcone-Based Chemosensor in Aqueous Phase

A novel, 100% water-soluble chalcone based chemosensing receptor {1-[3-(2-Hydroxy-phenyl)-3-oxo-propenyl]-naphthalen-2-yloxy}-acetic acid, L was synthesized and characterized. The receptor L is designed based on the chelation enhanced fluorescence (CHEF) mechanism. The chemosensing properties of L were evaluated by UV–vis and fluorescence spectrometric methods. It exhibits highly selective recognition ability towards aluminum ions in water over other metal ions. The binding stoichiometry of L? Al³⁺ complex is 2:1 by means of Job’s plot and the detection limit is 5.66?×?10^??8 M.     

Warm Gauge-Flation with General Dissipative Coefficient

In this work, we study the effects of generalized dissipative coefficient on the slow-roll inflation driven by non-Abelian gauge field minimally coupled to gravity. The dynamics of warm intermediate and logamediate inflationary models during weak and strong dissipative regimes is analyzed. In both cases, we explore effective scalar potential, slow-roll parameters, scalar and tensor power spectra, scalar spectral index and tensor to scalar ratio under slow-roll conditions. We conclude that our gauge-flationary model with generalized dissipative coefficient remains consistent with the recent data for dissipative parameter m = 3 and m = 1 for weak and strong dissipative eras, respectively.     

Momentum and energy dependence of the anomalous high-energy dispersion in the electronic structure of high temperature superconductors

Using high-resolution angle-resolved photoemission spectroscopy we have studied the momentum and photon energy dependence of the anomalous high-energy dispersion, termed waterfalls, between the Fermi level and 1 eV binding energy in several high-T_{c} superconductors. We observe strong changes of the dispersion between different Brillouin zones and a strong dependence on the photon energy around 75 eV, which we associate with the resonant photoemission at the Cu3p-->3d_{x;{2}-y;{2}} edge. We conclude that the high-energy "waterfall" dispersion results from a strong suppression of the photoemission intensity at the center of the Brillouin zone due to matrix element effects and is, therefore, not an intrinsic feature of the spectral function. This indicates that the new high-energy scale in the electronic structure of cuprates derived from the waterfall-like dispersion may be incorrect.     

Paramagnetic centers in oak and onion extracts

We have used EPR to study oak bark, bulb onion peel, and their aqueous extracts. We have established that their paramagnetic properties are determined by at least four types of paramagnetic centers: semiquinone radicals, Fe³⁺ ions, and two types of Mn²⁺ ions. We have observed that metal ions are extracted by water from the plant raw material without any change in their original coordination environment. The aqueous extracts were subjected to oxidative processes: mild oxidation in the dried state, strong oxidation when stored as solutions. We have shown that when the solutions are stored, the oxidation reaction is catalyzed by the metal ions and is accompanied by formation of semiquinone radicals. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 3, pp. 440–445, May–June, 2009.     

High energy excitations in ion-induced electron emission from AlF3

Measurements of electron emission spectra from surfaces of aluminum fluoride impacted by keV noble gas ions show a high-energy structure, peaking around 7 eV that increases in intensity with ion energy. The shape of this structure, identified by Factor Analysis, is independent of the nature and the energy of the impinging ions. We discuss one electron, two electron and plasmon excitation mechanisms and conclude that the high-energy structure results from the autoionization of F^? 2p⁴nl n′l′ excited by electron promotion in close atomic collisions.     

Stopping of ions and local electron densities at strong coupling

We employ molecular dynamics (MD) computer simulations to investigate ions in electron plasmas at strong coupling. We observed in this regime a stopping power of highly charged ions at low velocities which scales with the charge like Z^1.5. This clearly deviates from the Z² ln(const./Z) scaling of the conventional weak coupling theories and is connected with a strongly enhanced local density of electrons around the ions which is caused by the trapping of electrons in high Rydberg states due to multi-particle collisions occurring at strong coupling. For the parameters corresponding to the less strongly coupled situation in an electron cooler we find a moderate enhancement of the local electron density created under the influence of the external magnetic field. This revised version was published online in August 2006 with corrections to the Cover Date.     

A Pulsed EPR and DFT Investigation of the Stabilization of Coordinated Phenoxyl Radicals in a Series of Cobalt Schiff-Base Complexes

We recently demonstrated how the aerobic addition of acetic acid to N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamino Co^II, [Co(1)], leads to the formation of an unusual coordinated Co^III-phenoxyl radical. In this work, some of the structural aspects associated with the Schiff-base-derived ligand (1) that are crucial for the acid-mediated formation of the phenoxyl radical are investigated. For comparison with [Co(1)], we therefore studied the influence of acetic acid on two complexes: (1) the N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-ethane-diamino Co^II complex, [Co(2)], that lacks the cyclohexyl group of [Co(1)], and (2) the N′-disalicylidene-ethylenediamine Co^II salen complex, [Co(3)], that lacks both the tertiary butyl groups and the cyclohexyl groups. It is shown that the cyclohexyl group of [Co(1)] is not involved in the formation or stabilization of the phenoxyl radical, whereas the tertiary butyl groups of [Co(1)] play a crucial role. In addition, the characteristics of the phenoxyl radical, formed after aerobic addition of acetic acid to [Co(2)], are analyzed in detail by pulsed electron paramagnetic resonance, in combination with isotopic labeling. The experimental data are compared to density functional theory computations and to previous data on the acid-mediated phenoxyl radical of [Co(1)].     

Off-on Fluorescent Sensor from On-off Sensor: Exploiting Silver Nanoparticles Influence on the Organic Fluorophore Fluorescence

Turn-off fluorescence of organic fluorophore, 2-{[4-(2H-Naphtho[1,2-d][1,2,3]triazol-2-yl)-phenyl]carboxylic acid (NTPC), with metal ions (Fe³⁺, Cu²⁺, Pb²⁺) was converted into turn-on fluorescent sensor for biologically important Zn²⁺, Cu²⁺ and Fe³⁺ metal ions in aqueous solution at ppb level by exploiting strong fluorescence quenching phenomena of metal nanoparticles when organic fluorophores assembled in the vicinity of metallic surface. Amino acid attached phenolic ligands (L) were used as reducing as well as functional capping agents in the synthesis of silver nanoparticles (AgNPs). The hydrogen bonding functionality of L facilitated the assembling of NTPC in the vicinity of metallic surfaces that leads to complete quenching of NTPC fluorescence. The strong and selective coordination of L with metal ions (Zn²⁺, Cu²⁺ and Fe³⁺) separates the NTPC from the AgNPs surface that turn-on the NTPC fluorescence. HR-TEM and absorption studies confirm the metal coordination with L and separation of NTPC from the AgNPs surface. Mn²⁺ showed selective red shifting of NTPC fluorescence after 12 h with all sample. Effects of different amino acid attached phenolic ligands were explored in the metal ion sensitivity and selectivity. This approach demonstrates the multifunctional utility of metal NPs in the development of turn-on fluorescence sensor for paramagnetic heavy metal ions in aqueous solution.

Influence of the microstructure on the corrosion behaviour of a shape memory Cu-Al-Be alloy in a marine environment

The influence of the microstructure on the corrosion behaviour of a shape memory Cu-11.40Al-0.55Be (wt.%) polycrystalline alloy in 3.5% NaCl has been studied by microscopical examinations, spectroscopical and X-ray diffraction measurements, and electrochemical tests. Chloride environment can produce a dealuminization attack, and the corrosion behaviour is affected by the alloy microstructural conditions. After long times of immersion, the single β phase microstructure suffers localized corrosion in some regions but dealuminization is generalized on the whole surface. However, in the (β + γ₂) microstructure, preferential dissolution of γ₂ dendritic precipitates occurs, which seems to protect β matrix from dealloying.     

High-order harmonic generations in tilted Weyl semimetals

We investigate high-order harmonic generations (HHGs) under comparison of Weyl cones in two types. Due to the hyperboloidal electron pocket structure, strong noncentrosymmetrical generations in high orders are observed around a single type-II Weyl point, especially at zero frequency. Such a remarkable DC signal is proved to have attributions from the intraband transition after spectral decomposition. Under weak pulse electric field, the linear optical response of a non-tilted Weyl cone is consistent with the Kubo theory. With extensive numerical simulations, we conclude that the non-zero chemical potential can enhance the even-order generations, from the slightly tilted system to the over-tilted systems. In consideration of dynamical symmetries, type-I and type-II Weyl cones also show different selective responses under the circularly polarized light. Finally, using a more realistic model containing two pairs of Weyl points, we demonstrate that paired Weyl points with opposite chirality can suppress the overall even-order generations.