沉积贵金属Pt的Pt/TiO2膜利用可见光催化降解苯酚

采用溶胶-凝胶法制备锐钛矿纳米TiO2光催化材料,并用化学还原法还原氯铂酸溶液(H2PtCl6·4H2O)制备Pt胶体,然后滴涂在制备好的锐钛矿纳米TiO2基片上即对其进行贵金属修饰,从而得到纳米光催化材料Pt/TiO2膜.采用XRD、XPS、UV-Vis和SEM等手段对其表面理化特性进行了表征.以苯酚溶液为光催化降解...     

TiO2,ZnO光催化降解庚烷的活性研究

采用XRD，SPS，XPS，BET技术对TiO2和ZnO超细粉进行了结构、性能测试、考察了不同粒径的超细粉和普通商品（体相）TiO2、ZnO对庚烷的气相光催化反应，结果表明，TiO2（锐钛矿型）光催化活性大于ZnO，锐钛矿型TiO2光催化活性较金红石型TiO2好，对于同一结构的粒子来说，粒径愈小，表面羟基含量愈高，光催化活性愈高，通过反应产物的分析，探讨了反应机理。     

染料化合物在改性介孔TiO_2上的吸附

以聚乙烯醇-碘复合物修饰的介孔TiO2纳米材料为吸附剂,研究了介孔TiO2对亚甲基蓝、甲基橙、茜素红和二甲酚橙染料化合物的吸附作用.考察了4种染料初始浓度和初始pH值对吸附的影响.实验结果表明,染料化合物的结构和性质影响介孔TiO2对它们的吸附平衡时间和吸附量.二甲酚橙、甲基橙、茜素红和亚甲基蓝有最佳吸附去除率的初始pH值分别为2.0、2.0、3.0和8.0;平衡吸附时间分别为100 min、10 min、100 min和60 min.介孔TiO2对亚甲基蓝、茜素红、二甲酚橙的饱和吸附量分别为80.32 mg·g-1、78.72 mg·g-1、71.64 mg·g-1,甲基橙的饱和吸附量超过200 mg·g-1.改性介孔TiO2对亚甲基蓝、茜素红、二甲酚橙的吸附符合二级动力学方程.     

纳米TiO2混合晶体的制备及其光催化降解活性

以乙酸为水解抑制剂，采用sol-gel法制备纳米TiO2混合晶体催化剂，考察了抑制剂用量、煅烧温度、粒径等对催化性能的影响．结果表明，乙酸的用量影响催化剂的活性，当CH3COOH：Ti(OBu)4=0．8—1．0：1时效果较好；煅烧温度直接影响混合晶体的组成，580℃时锐钛矿／金红石=20．62，650℃时锐钛型／金红石=2．46，混合晶体具有较高的催化性能，粒径大小对TiO2的催化性能影响很大，粒子尺寸愈小，则比表面积愈大，电子．空穴愈难复合，有利于对活性艳红X-3B的降解．     

P掺杂TiO_2纳米管的制备及其对光催化甘油水溶液制氢性能的影响

以P掺杂的TiO2纳米颗粒为前驱体,采用水热合成法制备了系列P掺杂的TiO2纳米管.用N2吸附-脱附、透射电子显微镜(TEM)、X射线衍射(XRD)、激光拉曼光谱(Raman)、紫外可见漫反射(UV-Vis DRS)等方法对光催化材料的表面形貌、颗粒尺寸、孔结构、表面构造、吸光性能进行了分析.研究结果表明,所制备的各样品均为两端开口的纳米管形貌,管长为几十纳米到几百纳米,管外径约10 nm,内径约4 nm,管壁为多层;P掺杂后的系列TiO2纳米管仍保持锐钛矿晶型;掺杂的P可以进入到TiO2的骨架中,并形成P—O—Ti键,在TiO2禁带内引入杂质能级,降低了禁带能量,提高了TiO2的吸光性能及光生电子和空穴的分离性能.光催化甘油水溶液制氢活性评价表明,P掺杂的TiO2纳米管表现出了远高于纯TiO2管以及相同掺杂量的纳米颗粒的光催化制氢性能,2%P掺杂的样品在紫外灯和氙灯辐射下,其最高产氢速率可分别达1850μmol·(h·g)-1和335μmol·(h·g)-1.P掺杂TiO2样品光催化活性的提高与其禁带能量降低以及光生电子和空穴的分离性能增加有关.     

绢云母负载N掺杂纳米二氧化钛的制备及性能研究

以绢云母为载体,采用水解-沉淀法制备出了绢云母负载纳米TiO2粉体(TiO2/M),以尿素为氮源,采用后掺杂法制得具有可见光响应的N掺杂TiO2/M.采用XRD,XPS,SEM,DUV等手段对样品进行了性能表征;并以日光色镝灯为光源,甲基橙为模拟污染物检测其光催化活性.研究了N的掺杂对粉体中TiO2晶相结构,粒度和光催化性能的影响.结果表明,绢云母与TiO2通过桥氧相连形成包覆层,N的掺杂抑制了TiO2晶粒的长大,减缓锐钛矿向金红石相的转变,同时N的掺杂形成Ti—O—N键,形成新的能级结构,使样品对光的吸收边红移至440—550 nm,具有明显的可见光响应,对甲基橙的光催化降解率与没有掺N的样品相比,最高可达1.6倍.     

铂掺杂二氧化钛的制备及光催化乳酸制氢的研究

采用溶胶-凝胶法和甲醛还原法制备了Pt/TiO2光催化剂,并采用XRD对其结构进行了表征.当焙烧温度为500℃时,制备的纳米二氧化钛为纯锐钛矿相;在二氧化钛表面沉积少量的铂对二氧化钛的晶相和粒径几乎没有影响,但可以使二氧化钛光催化的产氢性能提高近10倍.以乳酸为电子供体,对影响其光催化产氢的因素进行了详细地考察.研究结果表明,光催化分解乳酸产氢的最佳条件为焙烧温度500℃、焙烧时间2 h、载铂量0.8%、催化剂用量0.14 g·L-1和pH 1-2.     

载钛活性炭纤维的制备及其对水中罗丹明B的光催化降解

通过溶胶凝胶法制备载钛活性炭纤维(TiO2-ACF)复合材料,采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、紫外-可见吸收(UV-Vis)、傅里叶红外分光光度计(FT-IR)、X射线光电子能谱(XPS)对TiO2-ACF进行了表征,并研究了TiO2-ACF对水中罗丹明B的光催化性能.结果表明,煅烧温度为400—600℃时,负载在ACF上的TiO2为锐钛矿型,当煅烧温度上升到700℃时,TiO2开始出现金红石型,600℃时煅烧制备的TiO2-ACF对水中罗丹明B的降解效果最佳;TiO2-ACF对罗丹明B的吸附能力比ACF低;但是在紫外光条件下,60 min后TiO2-ACF对罗丹明B的降解率比ACF、TiO2对罗丹明B的降解率分别高8.6%和16.2%,TiO2-ACF表现出较高的光催化活性.     

TiO2纳米棒对四环素的光催化降解

采用一步水热法合成了钛酸纳米材料,并以此为前驱体,通过二次水热处理制备了新型材料.使用XRD,TEM,N2吸附等温线等手段对催化剂进行了表征.结果表明,两种材料都为棒状纳米催化剂,其中二次水热材料为锐钛矿.光催化降解四环素结果表明两种催化剂都具有较高活性,二次水热纳米棒反应速率常数为一次水热材料的7倍;动力学实验表明TiO2纳米棒对四环素的光催化反应符合Langmuire-Hin-shelwood模型.     

碘铈共掺杂纳米TiO_2的制备及可见光光催化性能

采用溶胶凝胶法制备了不同原料比例碘铈共掺杂纳米TiO2催化剂,运用X射线光电子能谱（XPS）,X射线衍射（XRD）,透射电镜（TEM）等检测手段对催化剂进行了初步表征.结果表明,经过450℃煅烧处理得到的TiO2、铈掺杂TiO2以及碘铈共掺杂TiO2催化剂均为锐钛矿相,掺杂的Ce和I原子可能以I—Ce—O及O—Ti—I等键合方式进入TiO2晶格内部,此外,I-Ce离子共掺杂能有效降低TiO2表面的电子-空穴对的复合.以染料罗丹明B（Rhodamine B,RhB）和无色小分子水杨酸（Salicylic acid,SA）为降解的目标化合物,发现碘铈共掺杂的最佳物质的量之比为nCe∶nI∶nTi=0.04∶0.05∶1,即I0.05Ce0.04TiO2催化剂在可见光照射下（λ〉420 nm）降解目标化合物其光化学活性明显优于单掺铈的TiO2催化剂和未掺杂的TiO2.该催化反应涉及到空穴氧化,并伴有羟基自由基（.OH）、超氧自由基（O2.-）及H2O2等氧化物种的产生.     

La~(3+)和Fe~(3+)共掺杂TiO_2/浮石的制备及光催化矿化二级出水的效果

采用溶胶-凝胶法和浸涂法制备了以浮石为载体、La~(3+)和Fe~(3+)为共掺杂离子的TiO_2光催化剂,并用其光催化矿化城市污水处理厂二级出水.La~(3+)、Fe~(3+)改性TiO_2/浮石催化剂用X射线衍射、电镜扫描进行了表征和分析,探讨了La~(3+)、Fe~(3+)掺杂量对TiO_2光催化性能的影响,以及浮石粒径、涂膜层数、催化剂投加量对TiO_2/浮石光催化矿化二级出水效果的影响.结果显示,所制备的TiO_2以混晶形式存在,锐钛矿的含量为78.1%,平均粒径为36nm;TiO_2薄膜在浮石上负载良好,当La~(3+)、Fe~(3+)掺杂量分别为0.5%和0.05%、浮石粒径为20-40目、涂膜层数为4层、催化剂投加量为15 g·L~(-1),光催化反应时间为200min时,二级出水中TOC的去除率为51.6%,La~(3+)、Fe~(3+)改性TiO_2/浮石光催化是一种有效的污水深度处理方法.     

纳米TiO2催化声化学降解酸性红B的研究

以经过高温活化处理的锐钛型纳米TiO2为催化剂,考察了各种因素对酸性红B溶液超声降解反应的影响。结果表明:锐钛型纳米TiO2对酸性红B溶液超声降解反应具有明显的催化作用,其降解效果明显好于单纯使用超声波降解。超声频率40 kHz,输出功率50 W,催化剂用量0.5 g/L,pH=3.0,酸性红B溶液的初始浓度20 mg/L的条件下,60 min降解率即可达80%左右,120 min基本降解完全。因此,纳米锐钛型TiO2催化超声降解偶氮染料的方法切实可行,而且具有良好的应用前景。     

Mechanism of dichloromethane disproportionation over mesoporous TiO2 under low temperature

• Mechanism of DCM disproportionation over mesoporous TiO₂ was studied. • DCM was completely eliminated at 350℃ under 1 vol.% humidity. • Anatase (001) was the key for disproportionation. • A competitive oxidation route co-existed with disproportionation. • Disproportionation was favored at low temperature. Mesoporous TiO₂ was synthesized via nonhydrolytic template-mediated sol-gel route. Catalytic degradation performance upon dichloromethane over as-prepared mesoporous TiO₂, pure anatase and rutile were investigated respectively. Disproportionation took place over as-made mesoporous TiO₂ and pure anatase under the presence of water. The mechanism of disproportionation was studied by in situ FTIR. The interaction between chloromethoxy species and bridge coordinated methylenes was the key step of disproportionation. Formate species and methoxy groups would be formed and further turned into carbon monoxide and methyl chloride. Anatase (001) played an important role for disproportionation in that water could be dissociated into surface hydroxyl groups on such structure. As a result, the consumed hydroxyl groups would be replenished. In addition, there was another competitive oxidation route governed by free hydroxyl radicals. In this route, chloromethoxy groups would be oxidized into formate species by hydroxyl radicals transfering from the surface of TiO₂. The latter route would be more favorable at higher temperature.     

吸附模式对有机物光催化降解的影响3.MEA-Langmuir-Hinshelwood光催化降解动力学方程

传统的Langmuir-Hinshelwood方程式不能定性、定量地解释H-酸在TiO2表面的吸附平衡常数KL与其在TiO2悬浮液中的光催化降解速率r之间的关系.这是因为在实际测定中,吸附平衡常数KL一般是通过给定有机物的平衡吸附量和平衡浓度而求得的.这样的KL不能表达给定有机物不同吸附模式吸附力的差别.因而以往的理论方法不能描述吸附力对光催化降解动力学的影响,而只能描述吸附量对r的影响.亚稳平衡态吸附(MEA)理论认为,同一吸附质在相同的热力学条件下可以不同的MEA态(包括同一溶质的不同吸附构型/模式)达到实际的吸附终态.从MEA的概念对Langmuir-Hinshelwood模型进行半经验性修正,可以较好地描述吸附量和吸附力(吸附模式)共同对H-酸在TiO2悬浮液中光催化降解动力学的影响.     

TiO2/活性炭催化剂对4-CP的吸附和光催化活性

采用常压金属有机物化学气相沉积技术在活性炭表面沉积构成纳米TiO2催化剂,XRD分析表明,沉积在活性炭表面的TiO2为锐钛矿晶型.TEM分析表明负载量为8%(wt)时,TiO2颗粒的粒径为10-20nm;载体负载前后BET面积仅改变了6%,表明负载TiO2后对活性炭的结构影响不大.利用Langmuir-Hinshelwood动力学模型探讨了TiO2/活性炭催化剂对4-CP的吸附行为和光催化活性之间的关系,求出4-CP降解反应速率常数Kr,在紫外光照条件下催化剂对4-CP的吸附明显增强.     

载体特性对Pd-Cu/TiO2催化剂催化脱氮性能的影响

以Pd-Cu／TiO2为催化剂，采用催化加氢技术进行脱氮研究．结果表明：TiO2载体的特性对催化活性及N2选择性有显著影响，与773K和973K温度下焙烧得到的载体相比，以573K温度下焙烧得到的TiO2为载体制备的Pd（5wt％）-Cu（1．25wt％）／TiO2催化剂可显著提高催化效率及N2选择性．     

MoO3/TiO2催化剂对NH3选择性催化还原NOx的研究

通过共混法制备MoO3／TiO2催化剂,还原脱除NOx的研究．对于100目的催化剂,并在固定床反应器中进行了NH3选择性催化在较低温度下(≤583K),升高温度和降低空速,NOx脱除率提高;在反应温度较高时,NH3氧化的副反应的影响加强,此时过度延长反应时间和提高反应温度反而会使NOx脱除率降低．在583K和空速为12kh“时,NOx转化率可达92％．FT-IR光谱和XRD分析结果表明,MoO3形成分散相,均匀分布在TiO2颗粒表面并形成稳定的Mo=0基,它的加入没有影响TiO2(锐态矿型)的结构和形貌．     

Green epoxidation on Ti-mesoporous catalysts

New mesoporous catalysts with a mean pore size of 65 Å have been synthesised by grafting titanium on a mesoporous silica SBA15 (Santa BArbara) by means of titanium tetrachloride in the gas phase. These catalysts have been tested for the green epoxidation of cyclooctene, cyclohexene, (R)-limonene and -pinene by hydrogen peroxide, tert-butyl hydroperoxide or cumyl hydroperoxide. The selectivity is 100% and epoxide yields can reach almost 100% in the case of organic hydroperoxides without any leaching of titanium species. Here we show that cyclohexene epoxidation could be used as the first step of a greener synthesis of adipic acid.     

Crystalline mesoporous transition metal oxides: hard-templating synthesis and application in environmental catalysis

Mesoporous silicas such as MCM-41 and SBA-15 possess high surface areas, ordered nanopores, and excellent thermal stability, and have been often used as catalyst supports. Although mesoporous metal oxides have lower surface areas compared to mesoporous silicas, they generally have more diversified functionalities. Mesoporous metal oxides can be synthesized via a soft-templating or hard-templating approach, and these materials have recently found some applications in environmental catalysis, such as CO oxidation, N₂O decomposition, and elimination of organic pollutants. In this review, we summarize the synthesis of mesoporous transition metal oxides using mesoporous silicas as hard templates, highlight the application of these materials in environmental catalysis, and furnish some prospects for future development.     

Preparation of nZVI embedded modified mesoporous carbon for catalytic persulfate to degradation of reactive black 5

• The MCNZVI is prepared as an interesting material for PS activation. • Graphitized carbon shells facilitate electron transfer from Fe⁰. • The MCNZVI exhibits excellent performance to degrade RB5 by ¹O₂. • The MCNZVI has high stability and reusability in the oxidation system. High-efficiency and cost-effective catalysts with available strategies for persulfate (PS) activation are critical for the complete mineralization of organic contaminants in the environmental remediation and protection fields. A nanoscale zero-valent iron-embedded modified mesoporous carbon (MCNZVI) with a core-shell structure is synthesized using the hydrothermal synthesis method and high-temperature pyrolysis. The results showed that nZVI could be impregnated within mesoporous carbon frameworks with a comparatively high graphitization degree, rich nitrogen doping content, and a large surface area and pore volume. This material was used as a persulfate activator for the oxidation removal of Reactive Black 5 (RB5). The effects of the material dosage, PS concentration, pH, and some inorganic anions (i.e., Cl⁻, SO₄²⁻) on RB5 degradation were then investigated. The highest degradation efficiency (97.3%) of RB5 was achieved via PS (20 mmol/L) activation by the MCNZVI (0.5 g/L). The pseudo-first-order kinetics (k = 2.11 × 10⁻² min⁻¹) in the MCNZVI/PS (0.5 g/L, 20 mmol/L) was greater than 100 times than that in the MCNZVI and PS. The reactive oxygen species (ROS), including ¹O₂, SO₄^·−, HO^·, and ·O₂⁻, were generated by PS activation with the MCNZVI. Singlet oxygen was demonstrated to be the primary ROS responsible for the RB5 degradation. The MCNZVI could be reused and regenerated for recycling. This work provides new insights into PS activation to remove organic contamination.