絮凝法制备TiO2/MCM-41复合光催化剂及其性能的研究

以MCM-41分子筛为介孔材料,采用絮凝法制备复合光催化剂,通过XRD对复合光催化剂的晶型结构和形貌进行了表征,以人工合成染料罗丹明B为降解对象,考察絮凝pH、煅烧时间、煅烧温度、光照时间、催化剂投加量对复合光催化剂活性的影响。实验结果表明：在絮凝pH值为4时所得絮凝污泥,经700℃煅烧2h后的复合光催化剂具有最佳的光催化活性,在紫外光下照射浓度为20mg/L的罗丹明B 40min可获得98%以上的降解效果。     

聚硅硫酸钛制备复合光催化剂及降解甲基橙的研究

以无机钛盐、硅酸盐为原料,制备了聚硅硫酸钛絮凝剂,然后利用其水溶液水解产物制备复合光催化剂,考察了钛与硅摩尔比、水解pH值、调节pH值所用碱的种类、煅烧温度和煅烧时间对该复合光催化剂降解甲基橙时活性的影响,并利用扫描电镜（SEM）和X射线衍射（XRD）对其进行了物性测试分析。结果表明：n（Ti）：n（Si）=12：1的聚硅酸硫酸钛,以NH3.H2O调节pH值,在pH值为6时水解,产物在650℃煅烧1.5h后制得的复合光催化剂活性最高,当其投加量为0.5g.L-1时,光催化反应30min后,甲基橙的脱色率可达100%。物性分析表明,聚硅钛制备的复合光催化剂是一种以锐钛矿为主、分散均匀的纳米级球形颗粒。     

煅烧阶段对分子筛负载型TiO2催化剂活性影响研究

以介孔硅基分子筛(MCM-41)为载体,采用溶胶-凝胶法制备分子筛负载型TiO2催化剂。针对催化剂在负载前后及煅烧阶段对其晶型、晶粒及催化活性的影响,从煅烧成型工艺和XRD、TEM表征的角度进行研究;以酸性红B为模拟降解物,通过对分子筛负载型TiO2催化剂的活性评价,从煅烧温度、煅烧时间及碳化效应3个方面考察对催化剂活性的影响。结果表明,在600℃下煅烧2 h制备的负载型催化剂的活性最高,催化剂投加量0.5 g/L,光催化反应2 h对50 mg/L的酸性红B的降解率达93%。分子筛负载TiO2在高温煅烧阶段能够有效抑制锐钛相晶型的转变及TiO2纳米晶粒的尺寸,增加单位质量活性位的个数,提高催化性能。煅烧成型阶段空气通入量和升温速度对催化剂活性影响显著,缺氧、无氧及过快的升温速度都会导致碳化效应的产生,严重降低催化剂光催化性能。     

无机钛硅源、液相水解-水热法制备TiO2/SiO2复合光催化剂

以无机物硫酸钛为钛源、聚硅酸为硅源,采用液相水解-水热法制备了TiO2/SiO2复合光催化剂,考察了水热温度和水热时间对TiO2/SiO2光催化活性的影响,并利用SEM、XRD和BET等手段对光催化剂的形貌、晶相和比表面积等进行了表征。结果表明,在最佳条件下制备的光催化剂在对25 mg/L的甲基橙光催化氧化30 min后,甲基橙的脱色率可达86.7%。物性分析表明,TiO2/SiO2复合光催化剂是一种分散均匀的纳米级球形颗粒,具有较大的比表面积,形成了以锐钛矿相为主的TiO2;硅的加入有效地抑制了TiO2晶粒的生长。     

铈离子掺杂MCM-41分子筛的合成及其性能研究

以硅酸钠为硅源,十六烷基三甲基溴化铵(CTAB)为模板剂,通过碱性介质中的水热反应制备了全硅MCM-41分子筛以及掺杂铈的Cex-MCM-41(x=0. 5%,1. 0%,2. 0%)分子筛,考察了分子筛焙烧温度和铈离子掺杂量对MCM-41分子筛结构和性质的影响。研究表明,在550℃下焙烧制备的分子筛具备六方有序规则介孔结构和狭缝状介孔结构,结晶度较好,比表面积较大,其中全硅MCM-41分子筛的比表面积达到1 032. 04 m2/g;铈掺杂量1. 0%的Ce1-MCM-41的比表面积达到824. 61 m2/g;焙烧温度过高,或掺杂铈量过大时,不易获得六方有序规则介孔。掺杂的铈离子,可进入分子筛晶格取代硅离子构成分子筛骨架。     

铈离子掺杂MCM-41分子筛的合成及其性能研究

以硅酸钠为硅源,十六烷基三甲基溴化铵(CTAB)为模板剂,通过碱性介质中的水热反应制备了全硅MCM-41分子筛以及掺杂铈的Cex-MCM-41(x=0. 5%,1. 0%,2. 0%)分子筛,考察了分子筛焙烧温度和铈离子掺杂量对MCM-41分子筛结构和性质的影响。研究表明,在550℃下焙烧制备的分子筛具备六方有序规则介孔结构和狭缝状介孔结构,结晶度较好,比表面积较大,其中全硅MCM-41分子筛的比表面积达到1 032. 04 m2/g;铈掺杂量1. 0%的Ce1-MCM-41的比表面积达到824. 61 m2/g;焙烧温度过高,或掺杂铈量过大时,不易获得六方有序规则介孔。掺杂的铈离子,可进入分子筛晶格取代硅离子构成分子筛骨架。     

环己烷催化氧化制环己酮的MCM-41催化剂研究

以十六烷基三甲基溴化铵为模板剂,正硅酸乙酯为硅源,采用水热合成法制备纯MCM-41分子筛和掺杂不同金属离子的MCM-41分子筛,并采用等体积浸渍法将一定量的金属离子负载在纯MCM-41分子筛内表面上,制备了负载型和掺杂型2类不同的MCM-41分子筛催化剂.分别考察了负载和掺杂的金属种类、金属Cr负载和掺杂量等对环己烷氧化制环己酮中的催化活性和选择性的影响.研究表明:采用掺杂制备的MCM-41分子筛催化剂活性明显高于负载型MCM-41分子筛催化剂;Cr掺杂量增加,虽然环己烷氧化转化率增加,但产物选择性下降;掺杂Cr的MCM-41分子筛催化剂,用于环己烷氧化制环己酮,在Si与Cr摩尔比为50以下、反应温度75℃、H2O2与环己烷摩尔比为1.2的条件下,环己烷的转化率可达60%左右,环己酮和环己醇的总选择性可达94%以上.     

微乳液法制备纳米SiO2/TiO2及其光催化性能

以无机物聚合硅酸为硅源、硫酸钛为钛源,采用微乳液法制备了SiO2/TiO2复合光催化剂,考察了制备条件对SiO2/TiO2光催化活性的影响,并利用SEM、FTIR、XRD和BET等技术手段对光催化剂进行了表征。结果证明,SiO2和TiO2颗粒之间存在着强的相互作用,形成了Ti-O-Si键,从而抑制了TiO2粒径的增大,延缓了TiO2由锐钛矿相向金红石相的转变。对甲基橙等染料的光催化降解实验结果表明,SiO2/TiO2的光催化活性并非随着TiO2的含量增加而提高,当硅与钛物质的量比为1∶1并在160℃的温度下水热合成2.5 h时,SiO2/TiO2光催化剂在紫外光照15 min后对甲基橙的脱色率为85.5%,与同等条件下制备的TiO2相比具有更好的光催化活性和更大的比表面积。     

自组装复合模板法制备Fe3+掺杂TiO2光催化材料

以聚乙烯醇和聚乙二醇为复合模板剂,硫酸氧钛为前驱体,制备了Fe3+掺杂有序介孔TiO2光催化材料。结果表明,当Fe3+掺杂浓度为0.25%,煅烧温度为400℃时,孔径可达到6.5 nm,且结构有序,稳定性高。光催化降解丙酮的活性评价表明,上述条件下Fe3+掺杂能够明显提高TiO2的光催化活性。     

Fe/TiO2/MCM-41复合光催化材料的制备及表征

采用溶胶-凝胶法制备了掺杂与负载相结合的光催化剂Fe/TiO2/MCM-41,通过考察掺杂金属种类和掺杂量,探讨了制备条件对复合材料性能的影响,并用XRD、BET、TEM和XPS对其进行表征。结果表明,Fe3+掺杂量为0.05%时,光降解初始浓度为25 mg/L的甲基橙溶液30 min后脱色率达到95%以上。Fe/TiO2/MCM-41是一种比表面积达349.77 m2/g的介孔材料,具有锐钛矿和金红石相的混晶结构;光催化剂中铁以+3价形式存在,表面羟基氧所占比例为37%,掺杂铁抑制了TiO2粒子的生长。将Fe/TiO2/MCM-41用于光催化氧化水中的对硝基苯甲酸,当催化剂投加量为0.5 g/L、对硝基苯甲酸初始pH为5、浓度为2×10-4mol/L时,紫外光照30 min后,对硝基苯甲酸降解率达到58%以上。     

WO3-ZSM-5/MCM-41催化剂的合成 及其催化氧化脱硫研究

以氢氧化钠溶液处理微孔沸石ZSM-5来提供硅铝源,合成了ZSM-5/MCM-41复合结构型分子筛。采用XRD、N2吸附脱附、TEM等方法对其进行了表征,考察了其水热稳定性。实验结果表明,碱处理合成的ZSM-5/MCM-41同时具有微孔孔道和介孔孔道结构,并具有优于介孔MCM-41分子筛的水热稳定性。以ZSM-5/MCM-41为载体负载三氧化钨后应用于噻吩/正辛烷模拟油体系,双氧水为氧化剂,催化氧化脱硫,WO3-ZSM-5/MCM-41（三氧化钨质量分数为10%）表现出良好的催化性能,脱硫率可达到93.6%。     

Y-Beta/MCM-41复合分子筛的合成和性能

在酸性水热条件下,通过附晶生长法合成Y-Beta/MCM-41复合分子筛,并对其结构、形貌、水热稳定性及催化性能进行研究。结果表明,合成的Y-Beta/MCM-41复合分子筛比表面积高和水热稳定性好,对α-甲基萘的催化裂解性能明显优于机械混合物,表现出良好的催化性能。     

Pd-β/MCM-41复合分子筛加氢裂解废食用油性能研究

以碱处理β沸石作为硅铝源,以CTAB为模板剂,合成了β/MCM-41介孔-微孔复合分子筛,以其为载体制备Pd-β/MCM-41复合分子筛催化剂,利用XRD、N₂吸附-脱附、NH₃-TPD和XRF等技术对其进行了表征,并与γ-Al₂O₃、USY、ZSM-5等载体制备的催化剂比较了废食用油加氢裂解活性。结果表明：β/MCM-41复合分子筛同时具备β沸石和MCM-41分子筛的结构,β/MCM-41为载体时,Pd-β/MCM-41催化剂具有适宜的中强酸性中心,适宜的孔道分布结构,催化剂加氢裂解废食用油的活性最高。此外还考察了催化剂制备条件对废食用油加氢裂解反应的影响,结果表明：采用离子交换法制备负载量2%的Pd-β/MCM-41复合分子筛催化剂、焙烧温度为500 ℃时,催化剂对废食用油加氢裂解的效果最好。此时,原料油的转化率可以达到85.9%,生物汽油的收率可以达到16.4%,生物柴油的收率达到17.8%,且此催化剂水热稳定性较好,再生性能良好,工业化应用前景较好。     

微波条件下钴掺杂对MCM-41分子筛结构性能的影响

以十六烷基三甲基溴化铵为模板剂,通过微波辐射方法合成钴掺杂MCM-41介孔分子筛。采用X射线粉末衍射、红外光谱、透射电子显微镜、等离子发射光谱和N2吸附-脱附等技术对样品进行表征。结果表明：样品经550℃焙烧后,模板剂被有效去除。微波辐射条件下,成功合成出钴掺杂介孔分子筛样品。与纯硅的分子筛样品相比,钴掺杂的介孔分子筛比表面积增大,孔径分布均匀。     

Synthesis, Characterization of Ag/MCM-41 and the Catalytic Performance for Liquid-phase Oxidation of Cyclohexane

Nano-scale silver supported mesoporous molecular sieve Ag/MCM-41 was directly prepared by one-pot synthesis method. The prepared sample was characterized by XRD, TEM, and N₂ sorption. The results showed that the sample of Ag/MCM-41 had no appreciable incorporation of silver into the mesoporous matrix of MCM-41 with good crystallinity, and silver nanoparticles were dispersed inside or outside of the channels in the mesoporous host. The catalytic performance of the sample for the cyclohexane liquid-phase oxidation into cyclohexanone and cyclohexanol by oxygen in the absence of solvents without inducing agents was investigated. The 83.4% selectivity to cyclohexanol and cyclohexanone at 10.7% conversion of cyclohexane was obtained over Ag/MCM-41 catalyst at 428 K for 3 h. The turn over numbers (TONs) of Ag/MCM-41 was up to 2946. The catalytic activity of Ag/MCM-41 was also compared with Ag/TS-1 as well as Ag/Al₂O₃. The results indicated that Ag/MCM-41 showed superior activity to both Ag/TS-1 and Ag/Al₂O₃. A calcined Ag/MCM-41 was found to be an efficient catalyst for the cyclohexane oxidation into cyclohexanol and cyclohexanone using oxygen as oxidant.     

新型高水热稳定性MOR/MCM-41复合分子筛的合成

以丝光沸石分子筛为硅铝源,通过碱液处理和表面活性剂的自组装作用,水热条件下合成了MOR/MCM-41复合分子筛。通过XRD、SEM、TEM、N2吸附/脱附和水热稳定性处理等手段对合成的复合材料进行了表征。结果表明,复合材料不仅保留了原丝光沸石晶体的规则形貌,同时兼具微孔分子筛MOR和介孔分子筛MCM-41的特征,且介孔(20~30 nm)在微孔分子筛中较均匀地分布。水热处理测试结果表明,MOR/MCM-41复合分子筛具有较高的水热稳定性,水热处理100 h后介孔结构依然存在。     

Characterisation and catalytic properties of MCM-41 and Pd/MCM-41 materials

Pure silica MCM-41 mesoporous molecular sieve material was synthesised and characterised by in situ synchrotron XRD, TEM, TGA/DTA and DRIFTS techniques. In situ energy dispersive XRD (EDXRD) confirmed the exact nature of the pore diameter of MCM-41 and the change in crystal structure on calcination. The IR band at 1057 cm^-1 of as-synthesised MCM-41 was shifted by 14 cm^-1 on heating to 673 K due to increased condensation of silanol groups to form Si-O-Si bridges. Calcined MCM-41 materials were used to support Pd, and the catalytic activities for 1-hexene and benzene selective hydrogenation were investigated. The Pd/MCM-41 catalyst showed high activity in hydrogenation of 1-hexene at an inlet reaction temperature of 298 K, but did not show any activity in hydrogenation for benzene. TEM results for the reduced Pd/MCM-41 catalysts revealed that the average Pd particle size was around 2-2.5 nm and these particles were located in the pores of MCM-41 and showed good distribution. TPR measurements showed that about 70% of palladium oxide (PdO) loading in the calcined catalysts was reduced at sub-ambient temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ag-BiVO4／MCM-41制备表征及光催化性能研究

采用浸渍法将Ag-BiVO4固载于MCM-41介孔分子筛上,制备了Ag-BiVOdMCM-41新型复合可见光催化荆,用IR、XRD、SEM等分析测试手段对其进行了结构和性能表征。分析表明：Ag-BiVO4光催化剂为单斜耜结构,复合光催化剂具有较大的比表面积。在λ〉400nm的可见光照射下,以降解亚甲基蓝溶液进行了光催化剂的光催化性能评价。实验结果表明,Ag—BiVO4/MCM-41具有高的可见光催化活性,且具备良好的吸附性能和高的光催化效率。     

Utilization of ZSM-5/MCM-41 composite as FCC catalyst additive for enhancing propylene yield from VGO cracking

A micro-mesoporous ZSM-5/MCM-41 composite molecular sieve (ZM13) was synthesized and tested as an FCC catalyst additive to enhance the yield of propylene from catalytic cracking of vacuum gas oil (VGO). The catalytic performance of the additive was assessed using a commercial equilibrium USY FCC catalyst (E-Cat) in a fixed-bed micro-activity test unit (MAT) at 520?°C and various catalyst/oil ratios. MCM-41, ZSM-5 and two ZSM-5/MCM-41 composites were systematically characterized by complementary techniques such as XRD, BET, FTIR and SEM. The characterization results showed that the composites contained secondary building unit with different textural properties compared to pure ZSM-5 and MCM-41. MAT results showed that the VGO cracking activity of E-Cat did not decrease by using these additives. The highest propylene yield of 12.2 wt% was achieved over steamed ZSM-5/MCM-41 composite additive (ZM13) compared with 8.6 wt% over conventional ZSM-5 additive at similar gasoline yield penalty. The enhanced production of propylene over composite additive was attributed to its mesopores that suppressed secondary and hydrogen transfer reactions and offered easier transport and accessibility to active sites. Gasoline quality was improved by the use of all additives except MCM-41, as octane rating increased by 6?C12 numbers.