制备条件对Pd/TiO_2催化剂上对羧基苯甲醛加氢性能的影响

采用浸渍法以TiO2成型载体制备了Pd/TiO2催化剂,考察了浸渍液pH值、Pd负载量、焙烧温度以及还原温度等因素对粗对苯二甲酸(CTA)中的主要杂质对羧基苯甲醛(4-CBA)的加氢精制性能的影响,并采用BET、XPS、XRD、H2-TPR等手段对催化剂进行了表征。结果表明,浸渍液pH值的升高会造成催化剂表面Pd原子富集,导致催化剂比表面积降低。Pd负载量0.5%时,催化剂所提供的活性中心数目足以满足4-CBA加氢所需。适当提高催化剂焙烧温度,有利于含钯前驱体的分解,催化剂还原温度过高时,会造成Pd/TiO2催化剂活性的迅速降低。Pd/TiO2催化剂的适宜制备条件为:浸渍液pH=2.0、Pd负载量0.5%、催化剂焙烧温度400℃、还原温度低于200℃。     

糠醛液相脱羰用Pd/γ-Al2O3催化剂制备新工艺研究及活性评价

采用浸渍沉淀法制备了糠醛液相脱羰用Pd/Υ-Al2O3催化剂,讨论了浸渍初始液pH、加入载体后浸渍液pH、还原时pH、浸渍时间对催化剂活性的影响,确定了最佳的制备条件为:浸渍初始液pH=1;加入载体后浸渍液pH =7;还原时pH =8;浸渍时间=60 min.X射线衍射表征结果显示,催化剂中的钯以零价态存在,透射电镜分...     

还原制备时的pH值对Pd/C催化剂性能的影响

采用液相还原法,以甲酸为还原剂制备了负载量为5%的Pd/C催化剂。考察了还原过程中p H值对Pd/C上硝基苯液相催化加氢性能的影响,并用XRD、SEM、TEM等手段对催化剂的结构进行了表征。结果表明,制备过程中随着p H的增大,催化剂活性先增大后减小;适宜的p H值能加快Pd还原反应的速率,有利于粒子快速成核,降低生成大粒径Pd粒子的几率,减少团聚,使Pd粒子均匀分散在活性炭载体上,获得较高的催化活性。p H=9时制得的催化剂上Pd晶粒分布均匀,平均粒径为3.63 nm;在50℃、H2压力0.8 MPa、搅拌速率100 r/min,反应45 min的条件下,这一催化剂对硝基苯加氢液相催化为苯胺的转化频率(TOF)达到8758 h-1。     

用乙酰丙酮钯作前驱物制备Pd/C催化剂的研究

分别采用乙酰丙酮钯、氯化钯和硝酸钯作前驱物,用浸渍-还原法制备了一系列Pd/C催化剂,以松香歧化反应评价其活性,研究了活性炭类型、载体预处理、溶剂、还原方法及温度等因素对Pd/C催化剂活性的影响.结果表明,采用具有较大比表面积和孔容的活性炭作载体有利于钯在其表面的均匀分布和催化剂活性的提高;以Pd(acac)2作前驱体,以及使用极性较强的溶剂与用无机配合物前驱体相比,制备的Pd/C催化剂活性较高;TG-DTA分析表明Pd(acac)2在350℃下完全分解,基于此结果,作者在350℃条件下采用氢气干法还原,制备出活性略高于从日本进口的Pd/C催化剂.     

La助剂对Pd-AL2O3催化C3H8氧化性能的研究

采用不同稀土La前驱体浸渍掺杂改性Pd/γ-Al2O3催化剂,利用多功能催化性能评价装置测试不同催化剂的C3H8催化氧化性能,并通过H2-TPR、XRD、XPS等手段对催化材料进行结构表征,结果表明：La能促进贵金属钯分散,增强钯与载体相互作用,稳定高活性Pd2+物种,从而提高了催化剂的C3H8催化氧化性能。在选用不同La前驱体改性的Pd/γ-Al2O3催化剂中,硝酸镧改性效果最佳,能更好地促进活性金属钯的分散和Pd2+高活性物种的稳定。相比Pd/γ-Al2O3,La改性催化剂均降低了C3H8和NO的反应转化温度。选用不同La前驱体对催化活性影响存在差异的主要原因是La前驱体添加而引起的金属-载体相互作用和活性贵金属钯的分散状态变化。     

超声浸渍法制备Pd/Al_2O_3催化剂及其催化硝基苯加氢性能

以粉状γ-Al2O3为载体,分别采用超声浸渍和普通浸渍方法制备了Pd含量为5%的负载型催化剂,并将其用于硝基苯加氢反应。采用XPS和扫描电镜等手段对催化剂的理化性质进行了分析,考察了浸渍方法对催化剂活性金属分散度的影响。结果表明,与普通浸渍法相比,超声浸渍法制备的负载型Pd催化剂金属分散度明显提高,因而对硝基苯加氢反应表现出较高的催化活性。以KBH4为还原剂,通过超声浸渍制备的负载型Pd催化剂具有较高的钯分散度,在硝基苯加氢反应中表现出更高的催化活性。     

负载型纳米Pd/C的尺寸可控制备及其2,3,6-三氯吡啶加氢性能

在催化剂制备过程中引入氨羧络合剂(氨三乙酸三钠,NTA),通过配位作用稳定并保护Pd粒子,得到纳米Pd/C催化剂,研究了氨三乙酸三钠引入量对Pd/C催化剂结构的影响。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电镜(TEM)及化学吸附(H_2-TPR)表征发现,与常规浸渍法制备的Pd/C催化剂相比,氨三乙酸三钠的引入能够有效减小Pd的平均粒径,并且通过调变氨三乙酸三钠的量可以获得Pd粒子不同大小的负载型Pd/C催化剂,随着氨三乙酸三钠引入量的增多(Pd摩尔含量的0.5、1、2倍),Pd粒径由5.7 nm减小至2.1 nm,但是继续增加氨三乙酸三钠的量(Pd摩尔含量的4倍),Pd粒径不再继续减小。当氨三乙酸三钠:Pd=1:1时,即Pd粒子大小约为4 nm时,催化剂获得了最佳催化反应性能,反应6 h原料全部转化,2,3-二氯吡啶的选择性可达76.86%。     

茚虫威中间体合成用钯炭催化剂的载体研究

通过催化加氢合成茚虫威(indoxacarb)中间体反应用钯炭催化剂的性能对比,考察了钯炭催化剂的载体和载体预处理对催化剂性能的影响。实验结果表明:硝酸超声回流处理活性炭可以有效地去除活性炭中的杂质灰分,减小杂质对催化剂性能的影响;选择平均孔径大和比表面积高的活性炭为Pd/C催化剂载体可以获得较好的催化反应活性和选择性。     

氧化锡锑负载纳米Pd催化H2O2电还原反应的催化性能

分别以氧化锡锑(ATO)与活性炭(Vulcan XC-72)为载体,采用化学还原法制备了Pd/ATO及Pd/C催化剂,使用X射线衍射法及循环伏安曲线对催化剂进行了表征,通过线性伏安曲线及计时电流曲线考察了2种催化剂对H2O2电还原反应的催化性能。研究结果表明:Pd/ATO与Pd/C催化剂中Pd粒子的平均粒径分别为2.94 nm和8.27 nm,Pd/ATO催化剂的电化学比表面积更高,E=0.25 V时,Pd/ATO催化剂上H2O2还原反应的电流密度较Pd/C催化剂高约350 mA/mgPd,ATO提Pd     

Pd含量对催化剂加氢脱氧性能的影响

采用浸渍法制备了系列不同Pd含量的催化剂,通过XRD、H_2-TPR、BET等分析表征技术和以油酸甲酯为模型化合物的加氢反应体系,考察了Pd含量对催化剂催化加氢脱氧性能和催化加氢饱和性能的影响。结果表明,适量的Pd有助于提高Pd在载体上的分散度,减小其与载体的相互作用强度,从而可提高催化剂的加氢脱氧性能和加氢饱和性能,也可使油酸甲脂的加氢脱氧方式越容易按加氢脱羧或脱羰的方式进行;2%Pd/γ-Al_2O_3催化剂的催化加氢脱氧转化率和加氢饱和转化率均为100%,且加氢脱氧方式完全按加氢脱羧或脱羰方式进行。     

碳载纳米钯催化剂半工业级制备工艺研究

对浸渍方法，活性碳载体，还原方法进行了筛选试验。结果表明：浸渍方法决定Pd/C催化剂中钯粒子粒度的大小，在载体上的分布均匀性及催化活性；还原方法是决定催化活性大小的又一决定性因素，活性碳载体的性质也影响催化剂的性能，根据试验结果，选择了较佳的浸渍方法S-6，C-8活性碳，还原方法R-4，建立了半工业级的生产工艺，用此工艺可生产出钯粒度3-10nm，催化活性等于或优于日本同类产品的催化剂。     

沉淀剂对Ru-Zn催化剂催化苯选择加氢性能的影响

采用共沉淀法制备Ru-Zn催化剂,考察了沉淀剂种类、沉淀pH值对其催化苯选择性加氢性能的影响,并采用N2物理吸附、XRD、SEM、H2-TPR对催化剂进行了表征。结果表明,以NaOH为沉淀剂,沉淀pH=7时制备的Ru-Zn-f催化剂性能较好,苯转化率为40%时,环己烯选择性为82.70%,且该催化剂重复使用5次后,环己烯选择性仍维持在81%以上,稳定性好,具有较好的工业应用前景。     

Characterization and catalytic properties of nano-sized Pt metal catalyst on TiO2-SiO2 synthesized by photo-assisted deposition and impregnation methods

The photo-assisted deposition (PAD) and impregnation (img) syntheses of nano-sized Pt metal on TiO₂-SiO₂ are reported. The prepared catalysts were characterized by different techniques such as XRD, XAFS, TEM and nitrogen adsorption analysis. Photocatalytic reactivity using Pt-TiO₂-SiO₂ catalysts under visible-light condition for the oxidation of 2-propanol was evaluated. The results showed a notable photocatalytic activity of PAD-Pt-TiO₂-SiO₂ which was 1.5 and 4.7 times higher than that of imp-Pt-TiO₂-SiO₂ and TiO₂-SiO₂, respectively. Furthermore, PAD-Pt-TiO₂-SiO₂ catalysts exhibit a better catalytic property for hydrogenation of nitrobenzene, compared to the catalysts prepared by impregnation method.     

Pdx-Co/C催化甲酸的电氧化性能研究

以活性碳(Vulcan XC-72)为载体,用化学还原法制备了不同Pd/Co摩尔比的Pdx-Co/C催化剂。用透射电镜(TEM)、X射线衍射(XRD)及X射线光电子能谱(XPS)对催化剂进行了表征,采用循环伏安法考察了催化剂对甲酸电氧化反应的催化性能。结果表明,Pdx-Co复合催化剂粒子均匀分散在碳载体表面;催化剂中掺入的少量Co元素部分进入Pd晶格,形成了Pd-Co合金;随着Pd/Co摩尔比的增加,Pd颗粒粒径先增大后减小,催化活性也表现出相同的变化趋势;当Pd:Co=8:1时,所得Pd8-Co/C对甲酸氧化的催化活性最高,峰电流密度可达到15.907 mA/cm²。     

The activation of supported Au catalysts prepared by impregnation

In this study, Au/TiO₂, Au/γ-Al₂O₃, and Au/C catalysts were prepared by an incipient-wetness impregnation method. The CO oxidation activity after different pretreatment was analyzed. Two pretreatments are found possible to activate these catalysts for CO oxidation: (i) high-temperature hydrogen reduction and (ii) aqueous base treatment using NH3(aq). The high-temperature hydrogen reduction is effective for Au/TiO₂ and Au/C, but not Au/Al₂O₃. The base treatment is effective for Au/Al₂O₃ and Au/TiO₂, but not Au/C. Small Au particles of ca. 2 nm size were observed in activated Au catalysts from both pretreatments; however, the high-temperature H₂ reduction procedure also resulted in large Au particles of ca. 25 nm size which makes it a less efficient pretreatment than the base treatment. The activated Au/TiO₂ catalysts show comparable turnover frequency as the Au/TiO₂ catalyst prepared by a deposition precipitation method. The effective pretreatments were found to be accompanied by a reduced acidity, which is measured by the pH of aqueous catalyst suspension. Reasons for such activation are discussed.     

Preparation of platinum-iridium nanoparticles on titania nanotubes by MOCVD and their catalytic evaluation

Pt based catalysts are commonly used in several industrial processes involving hydrogenation and dehydrogenation reactions. New deposition methods as well as support materials are being investigated to generate new catalysts with superior catalytic activity. In this work, platinum-iridium (Pt-Ir) nanoparticles of about 5 nm in size were supported on titania (TiO₂) nanotubes by metal organic chemical vapor deposition (MOCVD). The TiO₂ nanotubes were prepared by an alkali hydrothermal method using sodium hydroxide solution at 100 °C, during 64.8 ks. Pt-Ir nanoparticles were obtained by controlling the MOCVD conditions at 400 °C and 66.6 kPa.Textural properties and particle size were investigated by nitrogen physisorption (BET method), X-ray diffraction, Raman spectroscopy and high resolution transmission electron microscopy. Catalytic activity was measured in cyclohexene disproportion as the test molecule for hydrogenation/dehydrogenation reactions. The TiO₂ nanotubes exhibit a considerable high surface area of about 425,000 m²/kg, however, after calcination at 400 °C their nanotubular morphology was partially transformed. In spite of this change, the 5 nm Pt-Ir nanoparticles supported on TiO₂ nanotubes were more active in the cyclohexene disproportion reaction than conventional Pt-Ir/alumina catalysts in the whole range of temperatures investigated (50–250 °C). Hydrogenation reactions (high selectivity to cyclohexane) predominate at temperatures below 150 °C.     

SnO_2纳米棒负载Pd-Sb催化甲酸电氧化

采用溶剂热法制备了SnO_2纳米棒载体,用溶剂热还原法制备了Pd/SnO_2催化剂和不同Pd/Sb原子数比的系列PdSb/SnO_2复合催化剂。用XRD、SEM、TEM、EDS等手段对样品进行分析表征,并以循环伏安法对比评价催化剂对甲酸的电催化氧化性能。表征结果表明,制备所得SnO_2纳米棒载体为针状,大小均匀,平均直径为100 nm;负载所得催化剂中活性粒子大小约为13.5 nm,掺杂Sb后,粒径约为9.5 nm。电催化氧化性能对比结果表明,Pd/Sb原子数比为4:1的Pd_4Sb/SnO_2复合催化剂对甲酸的氧化具有较好的催化能力,当E=0.25 V(vs SCE)时,Pd_4Sb/SnO_2上甲酸氧化的峰电流密度达到25 mA/cm~2,远远高于Pd/SnO_2催化剂。