CdS／ZnO复合光催化剂催化分解硫化氢制氢研究

采用溶胶-凝胶-沉淀的方法,制备出CdS／ZnO复合光催化剂,并通过XRD和UV—Vis漫反射光谱对催化剂进行了表征。考察了ZnO制备过程中胶溶剂种类、CdS物质的量百分含量（X）和焙烧温度（T）对CdS／ZnO复合光催化剂的性质与光催化分解硫化氢制氢性能的影响。实验结果表明：CdS／ZnO复合催化剂中,ZnO和CdS为六方晶系,UV—Vis吸收边有不同程度的红移。当以氨水为胶溶剂,T为400℃,x为50时,制备出的CdS／ZnO复合催化剂,其光催化分解硫化氢制氢速率最大,可达35mmol／g·h。     

SO4^2-／TiO2-SnO2固体超强酸的制备与光催化性能研究

为了提高TiO2的光催化性能,本文制备了SO4^2-／TiO2-SnO2固体超强酸（STS）,采用1R对STS的结构进行了表征,采用UV—Vis对光催化产物进行了分析,研究了STS光催化甲基橙降解的性能,结果表明适宜的制备条件为：n（TiO2）：n（SnO2）=12,焙烧温度为450℃,焙烧时间为4h,硫酸浓度为0．5mol／L,催化剂用量为0．3g／200mL,甲基橙降解率可达93％。IR分析表明在STS中形成了超强酸活性中心,UV-Vis分析表明甲基橙降解较为完全。     

紫外光催化分解硫化氢制氢的研究

以纳米TiO2（P25）作为光催化剂,10W低压汞灯作为光源（简称UVC,特征波长为253．7nm）,进行光催化分解硫化氢制氢反应的研究。考察了UVC分解硫化氢和TiO2光催化分解硫化氢的协同作用以及UVC催化分解硫化氢制氢的实验条件,包括光催化剂的用量,反应溶液溶氧,硫化氢的连续通入等对产氢结果的影响。实验结果表明,TiO2可以促进UVC分解硫化氢制氢反应;反应溶液溶氧量的降低和硫化氢的连续通入可以提高反应的产氢量。当以250mL 0．1mol／L硫化钠水溶液为反应介质,TiO2加入量为0．05g,并以40mL／h速率连续通入硫化氢时,UVC催化分解硫化氢的产氢速率可达4．04mL／W·h。     

F—TiO2光催化剂的制备及性能

TiO2具有化学稳定性好、成本低、耐腐蚀、无毒以及独特的光学、电学性质,纳米TiO2是目前最具应用前景的光催化剂。采用溶胶一凝胶法制备了F掺杂的TiO2光催化剂,用X-射线衍射（XRD）和紫外一可见光谱（UV—Vis）对其进行了表征,并通过降解甲基橙溶液来检测其光催化性能,研究了不同掺杂量、煅烧温度、煅烧时间等制备条件对F—TiO2光催化剂光催化性能的影响。结果表明,制备出的F-TiO2比未掺杂的TiO2具有较好的可见光响应,紫外光区响应并未受到影响。合成F—TiO2催化剂的最佳条件为F掺杂量为1．4％,煅烧温度600℃,煅烧时间2h。     

微波助离子液体中氮掺杂TiO2催化剂的制备及其微波强化光催化活性

在室温离子液体介质中,采用溶胶-凝胶法以及微波干燥的方法制备了氯掺杂的光催化剂TiO2-N。在室温条件下,以甲基橙为模拟污染物,在微波超声波组合催化合成仪中,分别利用微波辐射（MW）、紫外光照（UV）和微波辐射一紫外光照（MW—UV）三种降解方式,主要考察了N掺杂量、微波干燥功率、微波干燥时间、煅烧温度和煅烧时间等因素对TiO2-N光催化活性的影响。结果表明,在离子液体用量为5．6mL、N掺杂量n（N）／n（Ti）=3：1、微波干燥功率210W、微波干燥时间20min、煅烧温度600℃、煅烧时间2h的条件下所制得的TiO2-N光催化剂具有较高的光催化活性;TiO2-N光催化剂在三种降解方式下对甲基橙的降解效果为：MW—UV〉UV〉MW,这表明微波与紫外光照有较好的协同作用,即微波一紫外光照具有强化TiO2-N催化剂降解甲基橙的效果。     

纳米CdS/TiO2对亚甲基蓝废水溶液的光催化降解研究

利用纳米TiO2光催化氧化技术对亚甲基蓝废水溶液进行了光催化净化研究，考察了CdS催化剂复合量、光催化剂焙烧温度对亚甲基蓝废水溶液光催化氧化的影响。研究表明：染料浓度在7．5mg，L，3％CdS／TiO2复合半导体光催化剂2．5g／L，三支8W主波长为365nm紫外灯作光源，配以适量的氧气，可达到较好的光催化降解率。适量CdS改性增强了复合半导体材料的电子和空穴分离效率，有效地提高了CdS／TiO2光催化剂的光催化活性。     

JCdS／ZnO复合半导体光催化剂的制备、表征及分解水制氢

在超声条件下,采用溶胶凝胶法制备Zn（OH）2溶胶,然后在其上沉积沉淀CdS,制备CdS／Zn（OH）2催化剂前驱体。前驱体分别在空气和氮气下焙烧,制得两种CdS／ZnO复合光催化剂。催化剂表征和分解水制氢实验结果表明,两种CdS／ZnO复合光催化剂在可见光区均有强吸收。空气条件下焙烧制得的光催化剂中有CdO存在,经XRF测量其组成为29.3％CdS-18.6％CdO／ZnO（物质的量分数）,其光催化分解水制氢效果明显高于氮气下焙烧制得的光催化剂,平均产氢速率达5.2mmol（h·gcat）^-1。     

碳化树脂/CdS复合催化剂的制备及其光催化产氢性能研究

以光水解制氢中的优势材料硫化镉（CdS）作为光催化剂,借助碳化树脂（CPR）材料的导电性质,制备碳化树脂/硫化镉（CPR/CdS）复合催化剂,对CPR/CdS催化剂的理化性质和催化机理进行分析。与纯CdS相比,CPR/CdS具有更高的比表面积。通过光催化降解水产氢确定CPR的最佳用量和产氢性能。结果表明：0.5-CPR/CdS催化剂用量为0.15 g,体系pH值为5时,光催化产氢速率最高,为403.24μmol/h,循环5次实验光催化产氢速率均可以达到370μmol/h左右,稳定性良好。在复合材料中引入CPR后,CPR的掺入不仅能够提供活性位点,还能够作为电子捕获剂和电子传输剂有效分离光生电子和空穴,从而大幅度延长光生载流子的寿命,达到提高光催化反应活性的效果。     

CdS／TiO2光催化去除水体中氨氮的研究

利用溶胶-凝胶法制备了不同比率的CdS掺杂TiO2复合纳米颗粒催化剂，并用其进行了紫外光、日光灯和太阳光全波长光催化去除水中氨氮和其它形式无机氮的对比实验研究．考察了添加催化剂的量、CdS复合比率、有氧化态氮亚硝酸根或硝酸根与氨氮共存时光催化脱氮的耦合效果、外加光源等对脱除氨氮效率的影响，并研究了后3个因素对CdS光腐蚀程度的影响．对于氨氮初始质量浓度为50mg／L的模拟废水，在通空气搅拌条件下，n（CAS）：n／（TiO2）=0．17的CdS／TiO2催化剂脱氮效果最佳，此时经紫外光照2h后脱除氨氮效率达41．5％．实验结果表明：复合催化剂中CdS的含量是影响光催化活性和光腐蚀程度的重要因素．     

Eu3＋掺杂TiO2光催化剂的制备及废水处理性能研究

以钛酸四正丁酯、氯化铕为原料,采用溶胶-凝胶法合成了Eu3＋掺杂纳米TiO2光催化剂,借助X-射线粉末衍射（XRD）及UV-Vis测试手段对样品进行了表征,并以罗丹明B为模型污染物考察了Eu3＋掺杂量对样品光催化活性的影响规律。XRD分析表明,所得粉体均为锐钛矿相纳米TiO2,且Eu3＋掺杂后随着掺杂量的增加,纳米TiO2特征衍射峰宽化,强度降低;UV—Vis光谱分析表明,适量铕掺杂使得催化剂在400～600Bin的可见光区对光的吸收显著增强,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,当Eu3＋掺杂量为0．5％时其光催化活性最好,并将该光催化剂用于炼油厂废水的处理,对其实际应用进行了探索。     

Synthesis, characterization, and catalytic properties of a hydrothermally stable Beta/MCM-41 composite from well-crystallized zeolite Beta

A Beta/MCM-41 composite has been synthesized with a new method by using well-crystallized zeolite Beta as silica and aluminum source. The prepared composite was characterized by XRD, FTIR, N₂ adsorption/desorption at 77 K, FE-SEM, DTG, ²⁹Si MAS NMR spectral techniques. It was shown that the composite consisted of a highly ordered mesoporous MCM-41 phase and a zeolite Beta phase. Its hexagonal mesoporous structure was still retained after statically treated for 120 h in boiling water. In contrast, the structure of generally synthesized Al-MCM-41 nearly completely collapsed. This might be attributed to the assembly of the dissolved fragments such as the first and/or secondary structural units of zeolite Beta into the mesoporous structure around surfactant micelles. This is supported by the catalytic result that the prepared composite showed higher activity and selectivity for medium fraction in hydrocracking of Daqing vacuum residue than the parent zeolite Beta, the Al-MCM-41 as well as the mechanical mixture of these two materials.     

Self-Bonded Zeolite Beta/MCM-41 Composite Spheres

Self-bonded zeolite Beta/MCM-41 composite spheres were prepared using a two-step synthesis procedure. In the first step, mesoporous zeolite Beta spheres were obtained using anion exchange resin as macrotemplate. In the second step, the MCM-41 or Al-MCM-41 was grown both on sphere surfaces and in the pore structure of the pre-formed zeolite Beta spheres. Finally, the templating agents used in the synthesis of mesophase were removed by calcination leaving behind self-bonded Beta/MCM-41 composite spheres. Beta/MCM-41 composites were characterized by XRD, SEM and nitrogen adsorption measurements. Materials with controlled macroshape, composition and complex porosity were prepared by the approach.     

Al-MCM-41介孔分子筛吸附喹啉的性能

在碱性条件下,采用水热晶化法,以偏硅酸钠为硅源,铝酸钠为铝源,CTAB为结构模板剂,成功合成出了含铝介孔分子筛Al-MCM-41。采用XRD、BET等手段对合成的Al-MCM-41进行表征,对柴油中的氮化物喹啉进行了吸附实验,考察了Al-MCM-41介孔分子筛对氮化物喹啉的吸附能力,探究了硅铝比为60的Al-MCM-41分子筛对喹啉溶液吸附的热力学和动力学行为,测得353.15～393.15 K 温度范围内的吸附等温线数据,用Langmuir、Freundlich方程对此进行拟合,并根据热力学原理计算得到吸附过程中的ΔH、ΔG、ΔS值和吸附表观活化能。结果表明, 硅铝比为60的Al-MCM-41具有较大的孔容、比表面积和较窄的孔径分布,结晶度和有序性高。等温吸附平衡符合Freundlich 等温线模型,其ΔH -0.7682 kJ·mol^-1,ΔG -28.1215 kJ·mol^-1, ΔS 73.2434 J·mol^-1·K^-1,吸附动力学符合Pseudo拟二级方程,E_a为2.8575 kJ·mol^-1。     

SO2-4/TiO2-Al-MCM-41制备及其催化合成戊酸丁酯

选择硅酸四乙酯为硅源,在室温和pH=3.5条件下合成具有较低硅铝比的MCM-41型分子筛。以其为基础载体,采用浸渍和焙烧法制备含钛分子筛型固体超强酸。低温N₂吸附、IR、SEM和XRD分析表明,铝已进入分子筛的骨架中;Hammett指示剂测定表明,酸强度H₀<－14.52。以戊酸丁酯合成为探针反应,考察了催化剂的催化性能。结果表明,反应温度为138 ℃、催化剂用量为反应物总质量的1%、丁醇和戊酸的物质的量比为3∶1条件下,产品转化率达98.5%。     

Synthesis of dypnone using SO4/Al-MCM-41 mesoporous molecular sieves

The mesoporous molecular sieves Al-MCM-41 with Si/Al ratio equal to 16, was synthesized under hydrothermal conditions using cetyltrimethylammonium bromide (CTMA⁺Br⁻) as surfactant. The same ratio of Al-MCM-41 materials was impregnated using sulfuric acid, the materials as sulfated Al-MCM-41 (SO₄²⁻/Al-MCM-41). The mesoporous materials viz Al-MCM-41 and SO₄²⁻/Al-MCM-41 were characterized using several techniques e.g. ICP-AES, Nephelometer, XRD, FT-IR, TG/DTA, N₂-adsorption, solid-state-NMR, SEM and TPD-pyridine. ICP-AES studies indicated the presence of Al in the mesoporous materials. Nephelometer studies indicated the SO₄²⁻ presence of the SO₄²⁻/Al-MCM-41. XRD studies indicated that the calcined materials of Al-MCM-41 and SO₄²⁻/Al-MCM-41 had the standard MCM-41 structure. The surface area, pore diameter, pore volume and wall thickness of the mesoporous materials were calculated by BET and BJH equations, respectively. Crystallinity, surface area, pore diameter and pore volume of SO₄²⁻/Al-MCM-41 decreased except wall thickness and the expelling aluminum from the Al-MCM-41 framework increased the Lewis acidity. FT-IR studies indicated that Al-ions were incorporated in the hexagonal mesoporous structure of Al-MCM-41 and sulfuric acid was impregnated into hexagonal Al-MCM-41 materials. The thermal stability of as-synthesized Al-MCM-41 materials and SO₄²⁻/Al-MCM-41 materials were studied using TG/DTA. The environments of the Al-ions coordinated in the silica matrix were determined by ²⁷Al-MAS-NMR. The morphology of Al-MCM-41 and SO₄²⁻/Al-MCM-41 was determined by SEM. The total acidity of Al-MCM-41 and SO₄²⁻/Al-MCM-41 materials was determined by TPD-pyridine. The catalytic results were compared with those obtained by using sulfuric acid, amorphous silica–alumina, H-β, USY and H-ZSM-5 zeolites. The SO₄²⁻/Al-MCM-41 catalyst exclusively forms the product of dypnone from self-condensation of acetophenone molecules due to higher number of Lewis acid sites and has much higher yields than other catalysts except USY.     

High activity in catalytic cracking of large molecules over a novel micro-micro/mesoporous silicoaluminophosphate

Abstract  

A novel micro-micro/mesoporous silicoaluminophosphate ZSM-5-SAPO-5/MCM-41 (define as MZS-5) composite material with regular spherical morphology was synthesized through a novel process of the self-assembly of CTAB surfactant micelles with silica-alumina source which originated from the alkaline treatment of ZSM-5 zeolite. The physical properties of the MZS-5 composite material were characterized by XRD, FT-IR, Nitrogen adsorption–desorption, SEM and Py-FTIR techniques. Catalytic tests showed that the MZS-5 composite catalyst exhibited higher catalytic activity compared with the conventional microporous ZSM-5, SAPO-5 zeolite and mesoporous Al-MCM-41 molecular sieve for catalytic cracking of 1,3,5-triisopropylbenzene (TIPB). The remarkable catalytic reactivity of TIPB molecules was mainly attributed to the presence of the hierarchical zeolite structure. In the MZS-5 structure, the mesopores provided pathways for transportation of larger molecules and the microporous ZSM-5 and SAPO-5 zeolite provided acidic sites for catalytic activity.     

H2SO4和Al2（SO4）3改性中孔分子筛Al-MCM-41及其催化性能

用SO24-物质的量相同的H2SO4和Al2(SO4)3分别对Al-MCM-41进行改性,得到样品SO42-/Al-MCM-41和Al/SO24-/Al-MCM-41。采用X射线多晶衍射(XRD)、红外光谱(FTIR)、N2吸附-脱附和NH3程序升温脱附(NH3-TPD)等测试技术对样品进行表征。分别用H2SO4、MCM-41、Al-MCM-41、SO42-/Al-MCM-41和Al/SO24-/Al-MCM-41催化合成丙酸香叶酯,比较了它们的催化性能。结果表明,H2SO4和Al2(SO4)3改性对Al-MCM-41中孔分子筛结构影响不明显,都可提高其酸性,改性后中孔分子筛的骨架仍保持着六方介孔结构,孔径、孔容和比表面积有所降低,但用Al2(SO4)3改性的分子筛酸性和催化性能更强;SO42-/Al-MCM-41的酸催化活性主要源于SO42-与分子筛表面硅羟基作用形成的双齿螯合配位结构,而Al/SO42-/Al-MCM-41的酸催化活性一方面来自SO24-与分子筛表面硅羟基作用形成的双齿螯合配位结构,另一方面,也来自与分子筛骨架接枝的铝,使其产生了更多的Brnsted酸中心。     

Al-MCM-41分子筛对多环烃的催化异构化性能

采用室温法合成了Al-MCM-41分子筛,采用XRD、FT-IR和表面测定仪等方法表征了Al-MCM-41分子筛的结构。以多环烃endo-TCD（桥式四氢双环戊二烯）异构化反应为例考察了不同铝硅物质的量比的Al-MCM-41分子筛催化异构化性能,在此基础上研究了表面负载无机酸及贵金属Pt的促进作用。结果表明,Al-MCM-41分子筛对endo-TCD具有良好的催化异构化作用,无机酸的负载对催化剂活性和提高金刚烷收率具有一定促进作用,而采用化学还原法负载Pt则未达到预期目的。     

Effect of lanthanum addition on the thiophene hydrodesulfurization activity over Al-MCM-41 supported molybdenum catalysts

A series of Al-MCM-41 modified with 1–7% lanthanum were used as supports to prepare the Mo/La–Al-MCM-41 catalysts containing 10 wt.% molybdenum. The supports and catalysts were characterized with XRD, BET, XPS, TPD, TEM and SEM, and their catalytic activities were tested for thiophene hydrodesulfurization. The La addition did not cause any significant collapse of the structure and morphology of Al-MCM-41 samples, and increased the acidity of Al-MCM-41 samples. The Mo/La–Al-MCM-41 catalysts showed higher thiophene HDS activity than non-modified catalysts. The La-modified catalysts showed an enhanced butene selectivity but a decreased tetrahydrothiophene selectivity, indicating that the La–Al-MCM-41 supports contained a larger amount of acid sites.