Ag/N-TiO2/SBA-15光催化剂的制备及其可见光催化还原CO2

以钛酸四正丁酯(TB),羧基改性的SBA-15 (COOH/SBA-15),尿素和AgNO3为原料,利用溶剂热及焙烧处理制得Ag/N-TiO₂/SBA-15催化剂. 采用X 射线衍射(XRD),低温N2吸脱附,X 射线光电子能谱(XPS),紫外-可见漫反射光谱(UV-vis DRS),荧光(PL)光谱,电感耦合等离子体原子发射光谱(ICP)和元素分析(EA)等表征. 结果显示：Ag/N-TiO₂/SBA-15样品具有介孔结构,TiO₂以单一的锐钛矿晶型均匀的分散在载体表面,Ag以单质形态沉积在TiO₂表面,N则掺入到TiO₂晶格中,并以取代N(O-Ti-N)和间隙N(Ti-O-N)两种方式共存. Ag/N-TiO₂/SBA-15催化剂中单质Ag既可以捕获光生电子提高量子效率,又促进了TiO₂对可见光的吸收. N掺杂拓宽了TiO₂吸收光谱的吸收范围,并且适量的N掺杂有助于光生电荷的分离,提高了光催化效率. 以光催化还原CO₂为探针反应,考察了催化剂在可见光下的催化活性. 结果表明：Ag/N-TiO₂/SBA-15系列催化剂均表现出了可见光催化还原CO₂性能,发现当Ag的质量分数为2%,N与Ti的物质的量比为3时,催化剂光催化活性最佳,产物甲醇产量高达45.7 μmol·g^-1·h^-1.     

原位还原法制备SBA-15介孔分子筛负载纳米银颗粒

利用一种温和的还原剂六亚甲基四胺(HMT)通过一步合成的方法制备了介孔Ag/SBA-15分子筛, 采用粉末X射线衍射(XRD)、透射电镜(TEM)和氮气吸附/脱附等手段对样品进行了表征. 样品的比表面积为525 m²/g, 平均孔径为5.4 nm. 用XPS、广角XRD和高分辨TEM等手段证实样品中的银为金属态的纳米颗粒. 研究结果表明, 以六亚甲基四胺为还原剂通过原位还原的方法能使银纳米颗粒较好地分散到介孔材料的孔道中.     

一种新的高活性CO氧化催化剂Ag/SBA-1

 以SBA-15为载体,采用后修饰法制备了Ag/SBA-15催化剂. XRD和TEM结果表明,金属Ag粒子均匀分散于SBA-15的纳米孔道中,粒子平均大小为4～5 nm. 同时,负载金属Ag纳米粒子后,载体的介孔结构仍然能很好地保持. CO催化氧化测试结果表明,Ag/SBA-15具有很高的催化活性,120 ℃时就能使CO完全氧化. 而在富H2气氛下,80 ℃时CO的转化率达到最大值(48%),此时O2的选择性为28%. 高温H2还原是活化Ag/SBA-15的必要步骤.     

Au/SBA-15 的制备及其催化 CO 氧化反应性能

 以 SBA-15 为载体, 采用沉积沉淀法制备了纳米 Au 催化剂, 研究了不同预处理条件对 Au 在载体表面状态的影响, 考察了催化剂样品催化 CO 氧化性能. 以高分辨率透射电子显微镜、N2 吸附、X 射线衍射、紫外-可见漫反射吸收谱、X 射线光电子能谱和电感耦合等离子体发射光谱等手段对催化剂的结构和表面性质进行了表征. 结果表明, 经还原焙烧处理后的 Au/SBA-15 催化剂热稳定性较好, Au 在 SBA-15 孔道表面呈高分散状态, 样品在 CO 氧化反应中表现出优异的低温催化活性和高温稳定性, 同时具有优异的抗烧结性能和良好的循环稳定性.     

Ag/SBA-15低温气相选择性催化氧化苯甲醇合成苯甲醛

以SBA-15为载体,采用浸渍法制备了不同Ag含量的Ag/SBA-15,通过N₂吸附-脱附、X射线衍射、扫描电子显微镜、高分辨透射电子显微镜、X射线光电子能谱和电感耦合等离子体质谱对催化剂进行了表征。将Ag/SBA-15用于苯甲醇气相选择性催化氧化合成苯甲醛,研究了反应条件对转化率和选择性的影响。结果表明,Ag/SBA-15具有均一的一维孔道结构、较厚的孔壁（3-5 nm）及较大的比表面积（411-541 m²/g）,其规整纳米空间的限域作用使一定负载量的Ag以纳米尺寸均匀分散于介孔SBA-15孔道内,增加了活性组分的比表面积。亲核性氧物种从Ag到SBA-15表面的氧溢流,提高了低温下Ag/SBA-15对苯甲醇气相选择性氧化合成苯甲醛的催化性能。5.3% Ag/SBA-15中的Ag粒径为5-6 nm,且均匀分散于载体孔道中,反应温度为220℃时,苯甲醇转化率为87%,苯甲醛选择性为95%;240℃时,苯甲醇转化率和苯甲醛选择性分别高达94%和97%;并在240-300℃范围内,其催化活性和选择性保持不变,表现出了良好的温度耐受能力。催化剂经活化再生可以连续使用40 h,选择性基本保持不变。     

嫁接法制备Ni/SBA-15催化剂的催化氯苯加氢脱氯

SBA-15表面经嫁接方式引入氨基官能团,与Ni络合制备了SBA-15负载的Ni催化剂(Ni/SBA-15N)。同时,采用传统的浸渍法制备了具有相似Ni负载量的催化剂(Ni/SBA-15)。在负载量相近条件下,Ni/SBA-15N的Ni颗粒分散性均高于Ni/SBA-15。XRD和TPR结果表明,催化剂焙烧后,在氨化SBA-15表面,Ni以硅酸镍形式存在,而在SBA-15表面,Ni以NiO形式存在。Ni/SBA-15对氯苯催化加氢脱氯活性不随Ni负载量的变化而变化;而在Ni/SBA-15N中,Ni负载量增加,催化剂活性增加。     

Ag/SBA-15表面催化过程的现场SERS研究

以三嵌段共聚物P₁₂₃为模板剂, 正硅酸乙酯为硅源, 水热合成了介孔分子筛SBA-15, 通过对SBA-15内外表面修饰, 使用银氨溶液和硝酸银溶液作为金属源合成Ag/SBA-15, 透射电镜(TEM)研究表明在SBA-15孔道内较好地分散了颗粒状和棒状的Ag纳米粒子. 以苯硫酚作为探针分子, 研究了负载Ag纳米粒子的SBA-15的SERS效应, 结果表明Ag/SBA-15具有良好的SERS活性. 另外, 该材料对催化硼氢化钠还原对硝基苯酚具有良好的催化效果, 通过结合现场SERS技术, 研究了该催化过程的机理.     

VOx/SBA-15催化剂上甲苯气相部分氧化

采用等体积浸渍法制备了不同负载量的VOx/SBA-15催化剂。UV-Vis和H2-TPR等表征结果表明,在较低钒负载量下,钒物种的分散程度较高,主要以孤立的VO4 3－以及少量聚合体V－O－V形式存在;钒负载量较高时会有大量的聚合体V－O－V甚至晶相V2O5出现,而且,催化剂的酸性随着钒物种的高度分散而降低。甲苯气相部分氧化反应结果表明,随着钒负载量的提高,苯甲醛的选择性先升后降,CO、CO2等选择性逐渐提高。这是由于催化剂存在大量的聚合体V－O－V和晶相V2O5时,聚集态钒物种表面较多的酸量促使苯甲醛深度氧化。在相同钒负载量下,催化剂VOx/SBA-15的钒物种分散状态优于VOx/MCM-41和VOx/SiO2,从而使得催化剂VOx/SBA-15呈现较高的苯甲醛选择性。     

BiVO_4/SBA-15催化剂的制备及其光催化氧化脱硫性能

采用水热后合成法制备了BiVO_4/SBA-15催化剂,利用XRD、SEM-EDS和N2吸附-脱附等手段对其进行表征分析,并在自制的光催化反应装置中对其静态光催化氧化脱硫性能进行了研究。结果表明,BiVO_4/SBA-15催化剂具有SBA-15分子筛的介孔孔道结构,BiVO_4均匀分布在SBA-15分子筛表面。BiVO_4/SBA-15催化剂具有良好的催化氧化脱硫性能,在BiVO_4负载量为15%、水热合成时间为18 h、530℃下焙烧3 h制备的BiVO_4/SBA-15催化剂,对模拟柴油的脱硫率可达95.6%。     

CO oxidation catalyzed by Ag/SBA-15 catalysts: Influence of the hydrothermal treatment

Four types of SBA-15 were prepared with different times and temperatures of treatment in order to obtain a range of micropore sizes. CO oxidation was used as a probe reaction in order to evaluate the nature of the active species when SBA-15s were doped with ca 10% Ag deposited from an AgNO₃ solution and calcined or reduced at 350 °C. The texture (TEM, nitrogen physisorption), structure (XRD) and reducibility (TPR) of the various catalysts (Ag/SBA-15) were studied and compared to those of a catalyst prepared by deposition of silver on fumed silica as a reference. These catalysts differ initially by the nature of silica and by pore sizes. In CO oxidation, pre-reduced catalysts are more active than pre-oxidised ones. This has to do with two phenomena, i.e. sintering, which produces large inactive silver particles, and formation of active silver species in the form of small Ag₂O particles.     

还原气氛对CoFe/SBA-15催化剂F-T反应性能的影响

考察了不同还原气氛处理CoFe/SBA-15催化剂对F-T反应性能的影响。结果表明,H2气氛下有利于六方钴的生成;催化剂的活性取决于钴含量,随着钴含量的增加,F-T反应中CO转化率增加,C5+选择性增加。随着铁含量的增加,催化剂表现了较高的CO2选择性。CO还原有利于立方钴的生成,导致催化活性相比H2还原的催化剂活性要低。同时CO还原容易产生积炭使催化剂的钴活性位被覆盖,导致甲烷选择性随着钴含量增加而升高。但碳化铁的生成有利于提高20Fe/SBA-15催化剂的活性,有利于低碳烃生成及C2~4烃烯烷比增加。     

Investigation of CO and formaldehyde oxidation over mesoporous Ag/Co3O4 catalysts

CO and formaldehyde (HCHO) oxidation reactions were investigated over mesoporous Ag/Co₃O₄ catalysts prepared by one-pot (OP) and impregnation (IM) methods. It was found that the one-pot method was superior to the impregnation method for synthesizing Ag/Co₃O₄ catalysts with high activity for both reactions. It was also found that the catalytic behavior of mesoporous Co₃O₄ and Ag/Co₃O₄ catalysts for the both reactions was different. And the addition of silver on mesoporous Co₃O₄ did not always enhance the catalytic activity of final catalyst for CO oxidation at room temperature (20 °C), but could significantly improve the catalytic activity of final catalyst for HCHO oxidation at low temperature (90 °C). The high surface area, uniform pore structure and the pretty good dispersion degree of the silver particle should be responsible for the excellent low-temperature CO oxidation activity. However, for HCHO oxidation, the addition of silver played an important role in the activity enhancement. And the silver particle size and the reducibility of Co₃O₄ should be indispensable for the high activity of HCHO oxidation at low temperature.     

Electrocatalytic oxidation of carbon monoxide and methanol at Pt nanoparticles confined in SBA-15: voltammetric and in situ infrared spectroscopic studies

Electrocatalytic oxidation of carbon monoxide and methanol at Pt nanoparticles confined in mesoporous molecular sieve SBA-15 was studied by using cyclic voltammetry and in situ FTIR spectroscopy. Cyclic voltammetric studies revealed that the Pt nanoparticles confined in SBA-15 exhibit a high activity in the presence of hydrated phase consisting of SiO₂ in the SBA-15. In situ FTIR spectroscopy results discovered that IR absorption of CO adsorbed on Pt nanoparticles confined in SBA-15 has been enhanced 11-fold, and the full-width at half-maximum of the CO band is significantly increased, in comparison with IR feature of CO adsorbed on a bulk Pt electrode. The linearly adsorbed CO species is the only intermediate derived from dissociative adsorption of methanol, which is more readily oxidized to form CO₂ in the aid of the active oxide in SBA-15.This paper is dedicated to Professor G. Horanyi on the occasion of his 70th birthday and in recognition of his outstanding contribution to electrochemistry