Li+掺杂纳米TiO2的制备及其光催化性能研究

采用溶胶-凝胶法和浸渍法制备了Li⁺掺杂纳米TiO₂光催化剂,并用XRD和TEM等技术进行了表征;用pH值漂移法测量了催化剂的零电位pH值(pHpzc).结果表明,500℃煅烧制得的催化剂均为锐钛矿相;Li⁺的掺杂抑制了TiO₂粒子的生长,提高了催化剂的分散性;催化剂的零电位pH值为6.6—8.1,其值取决于Li⁺的浓度和掺杂方式.分别以紫外光和太阳光为光源,孔雀石绿和甲基橙为降解物评价了催化剂的光催化活性;并用气相色谱测试了污染物降解产生的CO₂的含量.结果显示,对孔雀石绿的降解,浸渍法和溶胶-凝胶法掺Li⁺都能有效提高TiO₂的光催化活性,但浸渍法比溶胶-凝胶法效果更好,催化活性最高的为浸渍法制备的5%(摩尔分数)Li⁺掺杂TiO₂,其在紫外光和太阳光下的光催化活性分别比纯TiO₂提高了6—8倍和9—10倍;对甲基橙的降解,除溶胶-凝胶法制备的3%(摩尔分数)Li⁺掺杂TiO₂能稍提高光催化活性外,其它Li⁺的掺杂都不同程度降低了TiO₂的光催化活性;随污染物降解率的增加,最终降解产物CO₂的含量增加.实验结果表明,Li⁺掺杂改变了催化剂表面的电荷状态从而改变了催化剂的零电位pH值是造成催化剂降解不同污染物具有不同催化活性的主要原因.     

碳纳米管的表面修饰及TiO2-CNTs复合催化剂的光催化性能

运用酸氧化和聚乙烯醇表面修饰碳纳米管, 修饰的碳纳米管的水分散性能显著改善. 进一步地运用低温水热法合成表面修饰的碳纳米管复合TiO₂, 观察到了复合催化剂紫外及可见光激发下的光催化性能的明显提升. 红外光谱、X光电子能谱、差热-热重分析、X光衍射、Brunauer-Emmett-Teller低温氮吸附、透射电镜及紫外-可见漫反射光谱等表征表明, 复合催化剂光催化性能改善与碳纳米管良好水溶液分散性能导致的TiO₂在修饰的碳纳米管表面的均匀、致密分散和密切键合, 从而充分利用碳纳米管的功能密切关联.     

模拟太阳光下稀土Gd掺杂TiO2纳米晶的光催化性能研究

以甲基橙的光催化降解为探针反应,采用氙灯模拟自然条件下的太阳光,评价了通过酸催化的溶胶-凝胶法制备的稀土Gd掺杂改性TiO₂纳米晶的光催化活性及对甲基橙水溶液TOC的去除效果.运用XRD和UV-Vis DRS表征技术考察了Gd掺杂对纳米TiO₂的微晶尺寸、晶体结构与光学性能的影响.结果表明,Gd掺杂可以抑制TiO₂由锐钛矿相向金红石相的转变,阻碍TiO₂晶粒增长,使TiO₂的光吸收带边发生蓝移且有利于对可见光的吸收,从而使Gd掺杂TiO₂在模拟太阳光下光催化降解甲基橙的能力得到明显提高,但样品对甲基橙水溶液TOC的去除效果要滞后于其对色度的去除.     

锰离子控制掺杂二氧化钛薄膜光催化活性增强的机理探讨

采用溶胶-凝胶法通过工艺控制制备了锰离子以不同形式掺杂TiO₂的光催化剂薄膜,并通过XPS和SEM对薄膜的结构进行表征.通过UV-Vis分光光度计及电化学工作站表征了薄膜的光吸收性能和光电化学性能,通过甲基橙溶液的光催化降解脱色率来表征催化剂薄膜的光催化活性.结果表明,以锰离子MT掺杂方式制备的TiO₂薄膜可明显增强TiO₂的光催化活性,而以MM掺杂方式制备的TiO₂薄膜反而降低了TiO₂的光催化活性;锰离子MT掺杂方式的最佳掺杂质量分数为0.8%.催化剂薄膜的电化学行为显示,薄膜具有p-n结的电容-电压特性,锰离子MT掺杂TiO₂薄膜的开路电位和瞬时光电流信号较强,说明其光生载流子易于生成并且分离效果较好.依据半导体的p-n结原理探讨了锰离子控制掺杂TiO₂的光催化活性机理.     

花状CeO2/TiO2异质结的构筑及光催化性能

采用溶剂热法制备了三维花状CeO₂/TiO₂异质结光催化剂,然后以甲基橙(MO)为模拟有机污染物,在氙灯照射下考察了其光催化活性。结果表明,花状结构由纳米片和纳米颗粒复合而成,纳米片上均匀地附着CeO₂颗粒。Ce/Ti的物质的量之比(n_Ce/n_Ti)和溶剂热时间影响异质结的光催化性能,当n_Ce/n_Ti=0.1、溶剂热时间为6 h时,CeO₂/TiO₂的光催化活性达到最佳,氙灯照射50 min的降解率达95%,光催化活性优于纯TiO₂,这主要是CeO₂和TiO₂形成了异质结,有利于光生电子和空穴的分离。     

明胶对纳米二氧化钛相变和光催化活性的影响

以明胶为分散剂采用溶胶-凝胶法制备了纳米晶TiO₂粉末.通过XRD、TG-DTA、AFM、N₂吸附-解吸等手段,考察了明胶对TiO₂煅烧过程中相变和平均粒径的影响;用光催化降解甲基橙检测了明胶用量对样品光催化活性的影响.结果表明:明胶的存在抑制了TiO₂由无定形向锐钛矿的相变,降低了锐钛矿向金红石的相变温度;同时,TiO₂纳米晶的平均粒径也随明胶用量的增加而减小.600℃煅烧样品的光催化活性随明胶用量的增加而提高;800℃煅烧样品在m_G:m_TBOT(明胶与钛酸四丁酯的质量比)=1:8时,具有最高的光催化活性.     

TiO2与碳纳米管的复合及光催化协同作用*

TiO₂与碳纳米管均是近15年来最受关注的功能材料。将TiO₂与碳纳米管复合构建的TiO₂/碳纳米管兼有两种材料的特点及优点,在许多领域得到广泛研究。本文基于国内外最新研究进展,系统综述了近年来逐步建立起来的制备TiO₂/碳纳米管的方法,着重介绍了混合法、化学气相沉积法、静电纺丝法、溶胶-凝胶法、水热溶剂热法等几种比较主要的方法。并且以TiO₂ /碳纳米管在光催化领域的应用研究为侧重点,详细分析了碳纳米管在促进TiO₂光生电子-空穴分离、增强可见光吸收等方面的协同作用。文章最后指出相关研究中有待解决的问题,并对此类材料的发展趋势做了展望。     

掺杂WO3的SiO2/TiO2的溶胶热液合成及光催化性能

采用溶胶-热液合成法制备了掺杂WO₃的SiO₂/TiO₂复合光催化剂,用X射线衍射、红外光谱、Zeta电位分析、BET和透射电镜对样品进行了表征,并以甲基橙降解评价了其光催化性能.结果表明:改性后的光催化剂表现出较高的光催化性能,WO₃和SiO₂不仅增加了锐钛矿TiO₂的稳定性,并阻止了TiO₂晶粒的聚集生长.     

Nd2O3/TiO2光催化剂的光生羟基自由基和光活性

以硝酸钕和钛酸四正丁酯作为前驱体,采用溶胶-凝胶法制备了Nd₂O₃/TiO₂纳米光催化剂,并通过XRD和BET等手段进行了表征.以对苯二甲酸作为探针分子,结合化学荧光技术研究了光催化剂表面羟基自由基的生成;并以甲基橙为光催化降解反应模型化合物,考察了光催化剂的活性.测定了甲基橙在TiO₂和Nd₂O₃/TiO₂(1.0%)光催化剂上的吸附常数.结果表明:Nd₂O₃掺杂使TiO₂的粒径减小,比表面积增大;羟基自由基的生成速率越大,催化剂的催化活性越高.Nd₂O₃掺杂有利于反应底物在催化剂表面的吸附,Nd₂O₃的最佳掺入量为Nd/Ti(摩尔比)=1.0%.     

耐高温核/壳结构TiO2/SiO2复合气凝胶的制备及其光催化性能

以钛酸四丁酯为源, 采用苯胺-丙酮原位生成水溶胶-凝胶法, 在乙醇超临界干燥过程中用部分水解的钛醇盐和硅醇盐对TiO₂凝胶进行超临界修饰制备了具有核/壳纳米结构的块体TiO₂/SiO₂复合气凝胶. 制备的复合气凝胶具有优异的机械性能, 其杨氏模量可达4.5 MPa. 复合气凝胶同时具有极好的高温热稳定性. 经过1000 ℃热处理后, 线性收缩由纯TiO₂气凝胶的31%降至复合气凝胶的10%, 且比表面积由纯TiO₂气凝胶的31 m²·g^-1提升至复合气凝胶的143 m²·g^-1. 此外, 该复合气凝胶经1000 ℃热处理后具有优异的光催化降解亚甲基蓝的性能. 其优异的光催化性能得益于TiO₂/SiO₂复合气凝胶1000 ℃处理后高的比表面积和小的颗粒尺寸. 优良的耐热性能、力学性能和光催化性能使获得的具有核/壳纳米结构的TiO₂/SiO₂复合气凝胶在光催化领域具有良好的应用前景.     

一维新型碳的同素异形体:碳链

碳链是一种完全一维的、具有电子轨道sp杂化结构的新型碳的同素异形体.正是由于碳链的独特的一维结构,使其拥有区别于富勒烯、石墨烯和碳纳米管的化学键,从而表现出更加优异的性能,如:理论预言碳链的机械强度是石墨烯的几倍;碳链的导热也类似于石墨烯和碳纳米管;碳链是具有直接带隙的半导体材料,且带隙的大小可以通过其长度来调控,其长...     

The Colloidal Stabilization of Carbon with Carbon: Carbon Nanobubbles as both Dispersant and Glue for Carbon Nanotubes

The superior physical properties of carbon nanotubes (CNTs) have led to their broad application. Intrinsically, CNTs tend to agglomerate from hydrophobic interactions, which is highly undesirable for solution processing and device fabrication. Commonly, a stabilizer consisting of organic surfactants or polymers is used to disperse CNTs. Recently, we synthesized nitrogen‐doped carbon hollow nanospheres (25–90 nm), termed carbon “nanobubbles”. They bear superior dispersability in water and distinctive graphitic order. Herein, we describe the nanobubble‐assisted dispersion of CNTs in aqueous solution upon sonication. This process relies on the π–π interaction between the two aromatic carbon nanostructures, which can process their carbon mixture in water into conductive filter membranes, ink, and discs. This stabilization can be extended to other aromatic carbons. In addition, the π–π interaction may create a new type of carbon p–n junction that can be used to improve charge separation.     

Adsorption of Carbon Dioxide on Activated Carbon

The adsorption of CO2 on a raw activated carbon A and three modified activated carbon samples B, C, and D at temperatures ranging from 303 to 333 K and the thermodynamics of adsorption have been investigated using a vacuum adsorption apparatus in order to obtain more information about the effect of CO2 on removal of organic sulfur-containing compounds in industrial gases. The active ingredients impregnated in the carbon samples show significant influence on the adsorption for CO2 and its volumes adsorbed on modified carbon samples B, C, and D are all larger than that on the raw carbon sample A. On the other hand, the physical parameters such as surface area, pore volume, and micropore volume of carbon samples show no influence on the adsorbed amount of CO2. The Dubinin-Radushkevich (D-R) equation was the best model for fitting the adsorption data on carbon samples A and B, while the Preundlich equation was the best fit for the adsorption on carbon samples C and D. The isosteric heats of adsorption on carbon samples A, B, C, and D derived from the adsorption isotherms using the Clapeyron equation decreased slightly increasing surface loading. The heat of adsorption lay between 10.5 and 28.4 kJ/mol, with the carbon sample D having the highest value at all surface coverages that were studied. The observed entropy change associated with the adsorption for the carbon samples A, B, and C (above the surface coverage of 7 ml/g) was lower than the theoretical value for mobile adsorption. However, it was higher than the theoretical value for mobile adsorption but lower than the theoretical value for localized adsorption for carbon sample D.     

Growth of Single-walled Carbon Nanotubes on Substrates Using Carbon Monoxide as Carbon Source

The growth of single-walled carbon nanotubes(SWCNTs) on substrates has attracted great interests because of the potential applications in various fields. Carbon monoxide(CO) was used as the carbon source for the growth of SWCNTs on silicon substrates. Random or oriented SWCNTs can be produced by varying the CO flow rate. When the flow rate of CO was as low as 20 sccm(sccm:standard cubic centimeter per minute), dense SWCNT networks with clean surface were produced. When the flow rate was above 50 sccm, vertically aligned SWCNT(VA-SWCNT) arrays were grown. Well-aligned VA-SWCNT arrays were obtained in the temperature range of 650-800℃ and the content of large-diameter(above 1.7 nm) tubes in the array increased with the temperature. The height of the array was affected by the growth temperature, the CO flow rate, and the growth time. These findings indicate CO can be used as an efficient carbon source for the growth of SWCNTs on substrates under low flow rates.     

埃洛石纳米管模板法一步法制备一维碳纳米管/碳纳米棒混合纳米碳材料

利用埃洛石纳米管(HNTs)特有的中空纳米结构,以及丰富的界面化学性质,以聚乙烯醇(PVA)为碳源,采用浸渍填充纳米孔方法实现了一步制备一维碳纳米管(CNTs)/碳纳米棒(CNRs)混合纳米碳材料。考察模板剂(HNTs)和碳源(PVA)之间的比例关系对混合纳米碳材料的结构影响,利用XRD、FTIR、Raman、N2吸附-脱附测试、TEM、SEM以及电阻率和分散性等表征手段分析混合纳米碳材料的结构变化。结果发现,PVA填充含量的增加将导致产物中CNRs的质量分数增加;当PVA和HNTs质量之比为1∶1时,所制备的CNTs/CNRs的孔体积达到最大值2.142 cm~3·g-1,比表面积达到583 m~2·g-1,并且表现出较好的电导率和分散性,表明低的PVA填充比例制备的混合碳材料中CNTs含量较高。     

Carbon clusters

Some of the most significant discoveries and achievements concerning the mass spectra and gas phase ion chemistry of carbon clusters are reviewed. These include (1) nanosecond and femtosecond laser ionizations; (2) ion structures through ion/molecule reactions, ion chromatography, and computational methods; (3) carbon cluster cooling through radiative decay, dissociative decay, and thermionic emission; (4) mechanisms and energetics of fragmentation reactions; (5) endohedral fullerenes including recent data on ion beam implantation, and (6) ion chemistry as a function of the fullerene charge state.     

二氧化碳与低碳经济发展

由于二氧化碳无色无味,又存在于大气中,因此它在植物生长中的重要性被人类忽略了。其实二氧化碳是光合作用的反应物,是植物生长的重要原料;又是一种新型绿色肥料。人类应该着力开发以二氧化碳为原料的新型肥料发展低碳经济。     

Ni/γ-Al2O3催化剂上CH4-CO2重整体系中积碳-消碳的研究

用动态热重技术和色谱技术联用以及XRD和TEM等表征手段,研究了Ni/γ-Al     

Palladium-Catalyzed Addition of Carbon Monoxide and Carbon Tetrachloride to 1-Octene in Supercritical Carbon Dioxide

The Pd-catalyzed addition of carbon monoxide and carbon tetrachloride to 1-octene gave coadduct [alkyl 2-( 2, 2, 2-trichloroethyl)octanoate] as the major product in supercritical carbon dioxide by using pyridine as the base. It was found that the selectivity and the yield of coadduct were greatly affected by the pressure of carbon dioxide, the reaction temperature and the amounts of alcohol and base used.     

碳纳米管含量对炭炭复合材料组织及力学性能的影响

炭纤维上原位合成了均匀生长且具有伸张形貌的碳纳米管,借助化学气相渗透制备了碳纳米管增强的炭炭复合材料,研究了不同含量的碳纳米管对炭炭复合材料组织和力学性能的影响。结果表明：炭纤维上生长碳纳米管改变了热解炭的沉积行为,诱导了各向同性热解炭的生成,且随着碳纳米管含量的增加,各向同性热解炭的厚度增加,但是复合材料的d002值却明显降低。微量的碳纳米管即可显著提高复合材料的力学强度,随着其含量的增加,复合材料的力学强度和模量迅速提高,但材料的断裂行为却急剧恶化,断裂模式由最初的假塑性断裂转变为脆性断裂。