强悬浮性纳米TiO2的制备、表征及光催化活性研究(Ⅰ)制备与表征

以热分解方法制备纳米TiO2,后续处理采用甲基硅油淬火改性和自然冷却,对改性前后的产物进行了XRD,TEM,FTIR等表征。结果表明,两种后续处理方法对所制备的纳米TiO2的物相、晶粒度、结晶度影响不大;但经硅油改性后的纳米TiO2的团聚程度降低。进一步的研究表明,经硅油改性后的纳米TiO2可长期悬浮于水的表面及浅层,这可能有利于直接用阳光有效光催化降解污水和光催化剂的回收再利用。     

强悬浮性纳米TiO2的制备、表征及光催化活性研究（I）制备与表征

以热分解方法制备纳米TiO2，后续处理采用甲基硅油淬火改性和自然冷却，对改性前后的产物进行了XRD，TEM，FTIR等表征。结果表明，两种后续处理方法对所制备的纳米TiO2的物相、晶粒度、结晶度影响不大；但经硅油改性后的纳米TiO2的团聚程度降低。进一步的研究表明，经硅油改性后的纳米TiO2可长期悬浮于水的表面及浅层，这可能有利于直接用阳光有效光催化降解污水和光催化剂的回收再利用。     

Ag-TiO_2/KIT-6复合纳米光催化剂的研究

以有序介孔SiO2(简称KIT-6)为载体,采用钛酸丁酯水解法将纳米TiO2与KIT-6复合,并通过沉积沉淀法将纳米Ag粒子负载于其上,首次制得Ag-TiO2/KIT-6复合光催化剂,并采用相同的方法制备了一系列相关的催化剂.以光催化降解甲基橙来评价其催化性能,光催化活性顺序为Ag-TiO2/KIT-6＞Ag/TiO2＞TiO2/KIT-6＞TiO2＞Ag/KIT-6.利用XRD、N2物理吸附、XPS、UV-Vis DRS和TEM对系列催化剂进行表征,结果表明Ag-TiO2之间形成的异质结和催化剂的大比表面积是Ag-TiO2/KIT-6具有最高光催化活性的重要原因.其中Ag-TiO2之间的异质结结构,有效抑制了光生电子和光生空穴在TiO2表面和体相内部的复合,提高了光催化活性;此外Ag-TiO2/KIT-6的大比表面积大大提高了催化剂的吸附能力,增加了催化剂与污染物的接触,达到快速光催化降解污染物的目的.     

Ag负载WO3/TiO2光催化剂的合成及其催化性能

以钛酸丁酯、无水乙醇、钨酸铵为原料,采用溶胶-凝胶法合成了WO3/TiO2复合光催化剂;采用光还原技术制备了Ag负载WO3/TiO2光催化剂,借助X射线粉末衍射(XRD)和UV-Vis光谱等技术对样品的组成和光吸收性能进行了表征,并以罗丹明B为模型污染物考察样品的光催化活性。XRD分析表明,所得粉体均为锐钛矿型纳米TiO2,且与WO3复合后,纳米TiO2特征衍射峰宽化,强度降低;UV-Vis光谱分析表明,载银使得催化剂在400—700nm的可见光区域对光响应,且在紫外光区吸收显著增强,对光具有更高的利用率;以罗丹明B为降解物的光催化实验表明,WO3复合对纳米TiO2光催化活性有显著的影响,而载Ag后其光催化活性进一步提高,将该光催化剂用于炼油厂废水的处理,效果较好。     

CdSe纳米粒子负载的TiO2纳米带复合材料制备及其可见光催化性能

采用水热法制备了CdSe 纳米粒子负载的锐钛矿型TiO2纳米带复合材料,并对产物的晶体结构、形貌尺寸、CdSe负载量及其可见光催化性能进行了测试.结果表明,产物中CdSe纳米粒子以闪锌矿型面心立方结构负载在TiO2纳米带表面,负载量可控;虽然CdSe纳米粒子的负载降低了TiO2纳米带比表面积,但是显著增强了产物可见光吸...     

Ag/TiO2纳米材料的制备和光致变色性能研究

 采用光催化还原法在不同温度热处理的TiO2薄膜表面沉积Ag纳米颗粒,制备了Ag/TiO2纳米薄膜材料。通过UV-Vis吸收光谱表征对比了不同温度热处理的TiO2对Ag粒子光催化沉积的影响,发现500℃退火处理TiO2薄膜较利于Ag纳米粒子的光催化沉积;在650 nm红色激光照射下,500℃退火处理的Ag/TiO2样品具有明显的光致变色现象,对此变色过程中涉及的机理进行了讨论,且发现随着Ag纳米颗粒光催化沉积时间的增长,Ag/TiO2薄膜光致变色的响应速率提高,但Ag纳米颗粒过多会抑制Ag/TiO2薄膜的变色响应速率。     

不同干燥法制备纳米TiO2光催化剂的光谱研究

本文分别用常态、超临界乙醇和超临界CO2干燥法干燥钛酸正丁酯的醇凝胶，制备纳米TiO2光催化剂。应用XRD，FTIR，FT－Raman和Fluorescent spectrum(FS)等光谱技术对催化剂进行了表征。以光催化降解罗丹明B为模型反应，比较所得样品光催化活性。实验结果表明，不同干燥方法对催化剂的晶相结构、半导体能带结构、光吸收性能、表面性质及光催化活性均产生显著的影响，用超临界CO2干燥法制备的TiO2光催化剂具有较好的光催化活性。     

Pt／TiO2粉末的结构和性能

TiO2半导体光催化技术是一种新型的环境污染物净化技术。传统的TiO2光催化剂太阳能利用率和光量子利用率低，限制了光催化技术的工业化应用。因此缩短催化剂的禁带宽度使吸收光谱向可见光谱扩展和抑制TiO2光生电子与空穴的复合是提高太阳能利用率的技术关键。掺杂可在半导体表面引入缺陷位置或改变结晶度，影响电子与空穴的复合或拓展光的吸收波段，从而影响TiO2的光催化活性。由于金属元素掺杂TiO2的催化活性强烈地依赖于TiO2的价态、结构以及金属元素与TiO2之间的细微作用，文中采用溶胶凝胶法制备纳米Pt/TiO2粉末，     

纳米TiO2的表面能态及光生电子-空穴对复合过程的研究

以液相法制备了水溶态纳米TiO2,并通过X射线衍射(XRD)、X射线光电子能谱(XPS)和傅里叶红外光谱仪(FTIR)对纳米TiO2的结构和组成作了细致分析.并对其紫外-可见光谱(UY-Vis spectrum)和荧光发光光谱(PL spectrum)进行了分析.结果发现纳米TiO2呈现较好的锐钛矿型,平均粒径为5 nm.水溶态纳米TiO2由于吸附而在表面形成了Ti-OH和Ti-H2O的表面态,其能级位于其价带以上约0.6和0.54eV;500℃热处理后样品的表面吸附水基本消失,但OH-仍然存在,同时在纳米TiO2晶格中出现了氧空位,其能级位于价带以上3.13 eV.对于水溶态纳米TiO2,表面复合是电子-空穴对的主要复合过程;热处理后的样品,由于表面态遭到破坏,粒子半径变大,直接复合成为电子-空穴对的主要复合过程,同时还伴随有通过氧空位的间接复合和通过Ti-OH的表面复合.     

光电变色器件用纳米晶氧化钛薄膜的微结构与特性

纳米晶TiO2薄膜在光电变色器件中具有很重要的作用。它的微结构直接影响染料的吸附、光的散射以及电荷输运的特性。因此，探索TiO2薄膜的微结构(如粒径、表面形貌和厚度等)及光电性能是非常有意义的。采用电子束蒸发工艺制备了光电变色器件用纳晶TiO2薄膜，利用原子力显微镜、X射线衍射、俄歇电子能谱等手段对纳米晶TiO2薄膜的表面形貌、结晶状态及组分进行了分析。从理论上研究和讨论了纳米晶TiO2薄膜晶粒尺寸对光电性能的影响，并用量子限制效应解释了吸收光谱峰值波长随粒径减小而发生蓝移的现象。     

Isotopic catalysis and isotopic analysis

Isotopes with magnetic nuclei accelerate the biochemical reactions of adenosine triphosphate synthesis by a factor of two to three. An isotope effect in which isotopes are preserved in the reaction system is known as isotopic catalysis. It has been revealed in enzymatic reactions catalyzed by magnesium, zinc, and calcium ions. Isotopic catalysis is sensitive to paramagnetic impurities, which inhibit it. It is shown that the presence of paramagnetic iron ions eliminates isotope effect and suppresses the isotopic catalysis of adenosine triphosphate synthesis.     

紫外拉曼光谱及其在催化研究中的应用

本文介绍了紫外拉曼光谱及其在催化研究中的应用。研究内容包括积炭 ,担载型过渡金属氧化物 ,分子筛 ,杂原子分子筛中骨架杂原子的识别和有机物的单层分散等。由于避开荧光干扰和使用较短波长的激发线提高了拉曼光谱的灵敏度和信噪比 ,特别是利用拉曼共振效应 ,不但灵敏度大幅度提高 ,而且与紫外吸收相关的局部结构被选择地鉴别。紫外拉曼光谱拓宽了拉曼光谱在催化 ,生物化学和材料科学等领域的应用。     

Homogeneous catalysis on the gas-phase dehydration reaction of tertiary alcohols by hydrogen bromide. Density functional theory calculation

The gas-phase thermal dehydration mechanism of tert-butanol, 2-methyl-2-butanol, 2-methyl-2-pentanol and 2,3-dimethyl-2-butanol by homogeneous catalysis of hydrogen bromide was examined by density functional theory calculations with the hybrid functionals: M062X, CAMB3LYP and WB97XD. Reasonable agreements were found between theoretical and experimental enthalpy values at the WB97XD/6-311++G(d,p) level. The dehydration mechanism of tert-butanol with and without catalysis was evaluated in order to examine the catalyst effect on the mechanism. The elimination reaction without catalysis involves a four-membered transition state (TS), while the reaction with catalysis involves a six-membered TS. The mechanism without catalysis has enthalpy activation over 150 kJ mol^–1 greater than the catalysed reaction. In all these reactions, the elongation of the C–O bond is significant in the TS. The un-catalysed reaction is controlled by breaking of C–O bond, and it was found to be more synchronous (Sy ≈ 0.91) than the hydrogen bromide catalysed reactions (Sy ≈ 0.75–0.78); the latter reactions are dominated by the three reaction coordinates associated with water formation. No significant effect on the enthalpies of activation was observed when the size of the alkyl chain was increased.     

Paraelectricity in magnetized massless QED

We show that the chiral-symmetry-broken phase of massless QED in the presence of a magnetic field exhibits strong paraelectricity. A large anisotropic electric susceptibility develops in the infrared region, where most of the fermions are confined to their lowest Landau level, and dynamical mass and anomalous magnetic moment are generated via the magnetic catalysis mechanism. The nonperturbative nature of this effect is reflected in the dependence of the electric susceptibility on the fine-structure constant. The strong paraelectricity is linked to the electric dipole moments of the particle-antiparticle pairs that form the chiral condensate. The significant electric susceptibility can be used as a probe to detect the realization of the magnetic catalysis of chiral symmetry breaking in physical systems.     

基于量子催化的离散调制连续变量量子密钥分发

相比于离散变量量子密钥分发,连续变量量子密钥分发虽然具备更高的安全码率等优势,但是在安全传输距离上却略有不足.尽管量子催化的运用对高斯调制连续变量量子密钥分发协议的性能,尤其在安全传输距离方面有着显著的提升,然而能否用来改善离散调制协议的性能却仍然未知.鉴于上述分析,本文提出了一种基于量子催化的离散调制协议的方案,试图在安全密钥率、安全传输距离和最大可容忍过噪声方面进一步提升协议性能.研究结果表明,在相同参数下,当优化量子催化引入的透射率T,相比于原始四态调制协议,所提方案能够有效地提升量子密钥分发的性能.特别是,对于可容忍过噪声为0.002,量子催化可将安全通信距离突破300 km,密钥率为10^-8bits/pulse,而过大的可容忍噪声会抑制量子催化对协议性能的改善效果.此外,为了彰显量子催化的优势,本文给出了点对点量子通信的最终极限Pirandola-Laurenza-Ottaviani-Banchi边界,仿真结果表明,虽然原始方案与所提方案都未能突破这种边界,但是相比于前者,后者能够在远距离通信上逼近于这种边界,这为实现全球量子安全通信的最终目标提供理论依据.     

On charge conservation and baryon-number violation in the monopole-fermion system

Around the 't Hooft-Polyakov monopole, charged fermion fields satisfy a peculiar boundary condition which mixes different U(1)-charge states at the monopole core. In a perturbative semi-classical treatment, this seems to imply violation of the charge superselection rule. It is explicitly demonstrated how this difficulty is resolved when higher order corrections are taken into account. We also show that the charge mixing boundary condition is essential for the monopole catalysis of baryon decay and that the chiral anomaly is not directly responsible for this effect. All non-trivial local fermion condensates are derived for an arbitrary number of fermion flavours.     

Morphology and microstructure of patterned nickel incorporated amorphous carbon films by simple pyrolysis

A simple but novel pyrolysis technique for the fabrication of nickel incorporated diamond-like carbon films with ring-like pattern was presented. Without using any template under ambient atmospheric pressure, nickel incorporated diamond-like carbon films exhibited some regular ring-like patterns on the films surface dependent on the nickel content to some extent, characterized by scanning electron microscopy. Compared with pure carbon films, nickel incorporation greatly enhanced carbon films graphitization. Besides the influence of the treatment temperature, the formation of the as-deposited films with ring-like patterns was also closely related to the synergy of the catalysis effect of nickel particles and the induction to reduce surface tension.     

铁电材料光催化活性的研究进展

光催化技术被认为是最有前景的环境污染处理技术,这就使得光催化剂材料备受瞩目.近年来,铁电材料作为新型光催化剂材料受到人们越来越多的关注,其原因在于铁电材料特有的自发极化有望解决催化反应过程中的电子-空穴对复合问题,进而提高光催化活性.本文从两个方面对铁电极化如何影响光催化进行综述:一方面,从铁电极化入手归纳总结其对电子-空穴对分离的影响,进而更深入地从极化引发的退极化场和能带弯曲两个部分来阐述具体的影响机理;另一方面,为了消除静电屏蔽,分别从温度、应力(应变)、电场三个外场因素调控极化入手,归纳总结外场调控极化对电子-空穴对分离的影响,进而影响光催化活性.最后对该领域今后的发展前景进行了展望.     

Transesterification of an RNA model in buffer solutions in H2O and D2O

Transesterification of a phosphodiester bond of RNA models has been studied in various buffer solutions, under neutral and slightly alkaline conditions in H₂O and D₂O. The results show that imidazole is the only buffer system where a clear buffer catalysis on the cleavage of a phosphodiester bond is observed. The rate enhancement in sulphonic acid buffers is smaller, and a sulphonate base, particularly, is inactive as a catalyst. The rate‐enhancing effect of imidazole is, however, catalytic, and the catalytic inactivity of sulphonate buffers can be attributed to their structure and/or charge. The catalysis by imidazole is a complex system which, in addition to first‐order reactions, involves a process that shows a second‐order dependence in imidazole concentration. The latter reaction becomes significant in acidic imidazole buffers (pH < pK_a), as the buffer concentration increases. The kinetic solvent deuterium isotope effect k_H/k_D, referring to first‐order catalysis by imidazole base, is 2.3 ± 0.3. That referring to second‐order catalysis is most probably much larger, but an accurate value could not be obtained. Copyright © 2007 John Wiley & Sons, Ltd.     

Radiative corrections in monopole catalysis of baryon number violation

We propose an improved framework for discussing the monopole catalysis of proton decay. Instead of discarding higher partial waves from the outset we integrate over them and obtain the s-wave effective action. We present a detailed calculation to confirm that the effects of higher partial waves through one-loop radiative corrections neither spoil nor modify the conventional treatment of monopole catalysis of proton decay.