蜂窝陶瓷骨架微结构修饰调控制备Pd/CNTs@CHC催化剂用于PS加氢

通过高温焙烧和氢氟酸瞬间蚀刻修饰堇青石蜂窝陶瓷骨架和孔壁表面结构,采用XRD、SEM、TEM表征修饰前后结构和形貌变化,探究陶瓷结构对机械强度、碳纳米管形貌结构及复合载体性质的影响,考察Pd/CNTs@CHC-HFn催化剂催化聚苯乙烯(PS)加氢性能及催化剂用量与加氢度的关系。结果表明,高温焙烧消除了骨架内部孔道,陶瓷表面变得平整密实;瞬间蚀刻增大了表面粗糙度,易于CNTs在表面生长,但蚀刻次数增加,导致蚀刻由表面向骨架内部侵入、CNTs在骨架内部生长,降低载体的机械强度。CNTs@CHC-HFn载体表面的CNTs可显著提高复合催化剂的加氢性能,其中加氢活性位Pd分布均匀,平均粒径为3.6 nm,当催化剂用量为3.0 g cat·(g PS)~(-1)时,其中含0.378 g CNTs和0.054 g Pd,反应6 h加氢度可达100%。     

碳纳米管-氧化铝复合载钯催化剂制备及性能研究

固定床选择性加氢反应一般要求催化剂具有良好的机械强度、较适宜的比表面积和孔容、活性组分高度分散等。为克服钯/碳纳米管（Pd/CNTs）催化剂成型性和强度不足的问题,将自产CNTs提纯后与氧化铝制成复合载体（CNTs-Al₂O₃）。表征结果显示,复合载体中CNTs与氧化铝混合均匀,CNTs保留了原有的管状结构,碳管的端口呈打开状态。对比实验结果表明,添加5%~10%CNTs（以质量分数计）的复合载体比单纯氧化铝载体负载乙酸钯后制成的催化剂活性更强。与盐酸和乙酸相比,以有机酸柠檬酸和乙二胺四乙酸作为钯的酸性络合剂时,更能减少载体比表面积和孔容的损失,活性组分在载体表面的分散性更好。在优选出的催化剂体系下,当反应温度取90~110 ℃、氢气压力取1.2~1.6 MPa条件时,可以获得更高的目标产物选择性和收率。     

精C_5饱和加氢Pd/Al_2O_3催化剂的制备

研究负载在Al2O3载体上的Pd催化剂对精C5饱和加氢反应的性能。以工厂精C5为原料,考察载体焙烧温度、Pd负载量和催化剂制备工艺对催化剂性能的影响。结果表明,载体最佳焙烧温度为700℃,Pd最佳负载质量分数为0.3%,Pd最佳负载时间为4 h,催化剂最佳焙烧温度为500℃,催化剂最佳焙烧时间为4 h,以此条件制备的催化剂进行C5饱和加氢评价,加氢效率不低于94%。     

添加ZrO2的Pd/Al2O3催化剂及其催化蒽醌加氢性能

以四氯合钯（II）酸（H2PdCl4）为前体,活性氧化铝（Al2O3）为载体,硝酸锆（Zr（NO3）4）为添加组分,采用不同方式的分步浸渍法制备了添加ZrO2的Pd/Al2O3催化剂。考察了制备方法和反应条件对催化剂蒽醌加氢催化性能的影响,发现催化剂活性与制备方法有关。当对添加锆的载体进行适当焙烧,控制Pd负载量为0.3%,还原温度低于300℃时,催化剂的蒽醌加氢活性较高,与未添加ZrO2的催化剂相比提高了约20%。X射线衍射（XRD）、氮气物理吸附（BET）、透射电镜（TEM）、X光电子能谱（XPS）和程序升温还原（TPR）等表征对催化剂物相结构、比表面积、表面形貌及组分间相互作用的分析表明,ZrO2的掺杂提高了载体Al2O3的高温稳定性,改善了催化剂中活性组分Pd与载体间的相互作用,促进了Pd在载体表面的分散,从而提高了催化活性。     

Pd/C催化聚苯乙烯加氢制聚环己烷基乙烯的研究

研究了不同载体负载的Pd催化剂Pd/MCM-41、Pd/Al₂O₃、Pd/MC和Pd/C在聚苯乙烯（PS）加氢制聚环己烷基乙烯（PCHE）中的性能。考察了催化剂质量、搅拌速度、反应温度、反应时间及反应压力等对PS加氢反应的影响。结果表明，具有较高分散度的Pd/C催化剂表现出优异的催化活性和稳定性。在催化剂质量为0.1 g和较低的反应温度（160℃）下，Pd/C催化PS加氢的转化率>99%,且产物PCHE具有较高的玻璃化转变温度、较低的密度和吸水性及较高的抗拉强度。     

蒽醌加氢钯催化剂载体改性研究

针对Pd/Al2O3催化剂载体的改性进行研究,将1 000℃焙烧后的氧化铝粉末与未焙烧的活性氧化铝粉末按不同比例混合和焙烧制备载体,采用等体积浸渍法制得负载Pd的Pd/Al2O3催化剂。采用XRD、BET、NH3-TPD和HOT对载体以及催化剂进行表征,并考察催化剂的蒽醌加氢性能。结果表明,提高载体中焙烧后氧化铝粉末的比例,导致载体中γ-Al2O3减少和δ-Al2O3增多,载体酸性降低,Pd分散度变大,从而提高了催化剂氢化效率。当焙烧后氧化铝质量分数为40%时,分散度和活性表面积达到最大,晶粒度最小,氢化效率最高,催化活性最佳。     

过氧化氢蒽醌加氢流化床Pd/Al_2O_3催化剂载体性质与催化性能的关系

以氯化钯为前驱体,活性氧化铝为载体,采用等体积浸渍法制备蒽醌加氢流化床Pd/Al_2O_3催化剂。考察载体比表面积、孔容、孔径、粒度分布及表面形貌与催化剂催化性能的关系,结果表明,载体比表面积较高,小孔径且孔径分布不均匀,粒度较大且粒度分布均匀,载体表面光滑且成球性好的载体对应的催化剂性能较好。采用优化后活性氧化铝载体制备的Pd/Al_2O_3催化剂的氢化效率和选择性分别为9.98 g·L-1和80.3%。     

焙烧温度对氧化铝-活性炭复合载体性能的影响

采用混捏法制备氧化铝-活性炭(AAC,质量比为4∶1)复合载体,考察焙烧温度对复合载体性能的影响,采用FT-IR、XRD、颗粒强度测定仪以及N2吸附等表征复合载体。结果表明,焙烧与否对载体的比表面积、径向抗压碎力及表面酸度等均有一定影响,焙烧温度不同,对复合载体表面物相的影响程度不同。随着焙烧温度升高,浸渍法制备的Ni Mo/AAC催化剂对二苯并噻吩的加氢脱硫活性先降低后升高。     

单分散氮掺杂的碳纳米球负载钯催化氯代硝基苯加氢反应

高效钯炭催化剂的研制是卤代硝基苯选择性加氢还原制备卤代苯胺工艺取得突破的关键。以单分散氮掺杂的碳纳米球为载体、钯为活性组分,采用浸渍法制备出负载型的Pd/CN-x(x代表碳基载体的焙烧温度),并对其催化氯代硝基苯加氢制备氯代苯胺反应的性能进行了研究。分别采用傅里叶变换红外光谱(FT-IR)、X射线衍射光谱(XRD)、透射电子显微镜(TEM)、场发射扫描电镜(SEM)以及X射线光电子能谱(XPS)技术对Pd/CN-x催化剂的形貌、结构及表面化学性质进行了表征分析。考察了不同温度下制备出的碳氮材料负载钯催化剂对氯代硝基苯选择性加氢还原反应活性和选择性的影响。研究结果表明,以单分散氮掺杂的碳纳米球为载体能够实现金属Pd颗粒的均匀分散,因而催化剂表现出优异的催化加氢性能。其中,Pd/CN-600催化剂表现出100%的3-氯硝基苯转化率,同时对3-氯苯胺的选择性高达76.9%。此外,载体表面含氮官能团影响活性Pd组分的有效分散,进而影响3-氯苯胺的选择性。     

Pd/CNTs金属纳米催化剂的制备及其催化对氯硝基苯加氢性能

通过硝酸浸渍法对碳纳米管(CNTs)进行预处理改性,并采用乙二醇液相还原法制备Pd/CNTs纳米催化剂,通过XRD、TEM、BET、拉曼光谱、ICP等手段对其进行表征。结果表明,Pd/CNTs催化剂中Pd的负载量为0.9 wt%,Pd纳米颗粒均匀地分散在CNTs表面,粒径平均大小为5 nm。该催化剂用于对氯硝基苯的选择加氢反应,在常压、60℃下反应2 h,转化率为94.7%,选择性为89.2%。     

催化剂制备与研究 预处理对钯炭催化剂及其在肉桂醛加氢中性能的影响

采用不同预处理方式对活性炭表面进行改性,并制备钯炭催化剂。对活性炭的比表面积、孔结构等物理性质和含氧官能团种类以及钯炭催化剂进行表征,探究预处理对活性炭表面物化性能产生的变化和对钯炭催化剂在肉桂醛加氢反应中催化活性的影响。结果表明,氧化预处理使活性炭的比表面积和孔容下降,使钯炭催化剂上的钯粒子尺寸相对更小;碱预处理有一定的扩孔作用,使钯炭催化剂上的钯粒子尺寸更大。在肉桂醛加氢反应中,钯粒子尺寸越小的催化剂催化活性更高,而钯粒子尺寸更大的催化剂上肉桂醇选择性更高。     

Pd/Al2O3催化剂用于连续重整汽油全馏分加氢的失活分析

研究了负载在氧化铝载体上的贵金属Pd基催化剂在重整生成油选择性加氢脱烯烃反应中的性能。结果表明,在连续重整生成油全馏分的选择性加氢实验中，采用现有工业常用的工艺条件，单使用Pd作活性组分的Pd/Al₂O₃催化剂不能满足产品质量要求。探讨了切割馏分油加氢反应中催化剂失活原因，并对失活前后的催化剂采用XRD、SEM和FTIR等手段进行分析表征。结果表明，造成催化剂失活原因是催化剂表面油品中重组分等热敏类物质强吸附或聚合作用的结果。改进后的双金属Pd基催化剂UDO-01可用于重整生成油全馏分的选择性加氢脱烯烃反应，加氢后产品的溴价小于200 mg Br·(100 g-油)^-1,芳烃损失小于0.5%，且表现出好的稳定性。     

Synthesis of palladium nanoparticles on carbon nanotubes and graphene for the chemoselective hydrogenation of para-chloronitrobenzene

We have studied the synthesis of palladium nanoparticles over carbon nanotubes (Pd/CNT) and graphene (Pd/G) and we have tested their catalytic performance in the liquid phase chemoselective hydrogenation of para-chloronitrobenzene at room temperature. The catalysts were characterized by N₂ adsorption/desorption isotherms, TEM, X-ray diffraction, infrared and X-ray photoelectron spectroscopy and ICP-OES. The palladium particle size on Pd/G (3.4 nm) and Pd/CNT (2.8 nm) was similar though the deposition was higher on Pd/G. Pd/CNT was more active which can be ascribed to the different surface area and electronic properties of the Pd nanoparticles over CNT, while the selectivity was 100% to the corresponding haloaniline over both catalysts and they were quite stable upon recycling.     

Selection of the optimum composition of an alumina support of Pd/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts for pyrolysis gasoline hydrogenation

To optimize the chemical composition of catalysts for the selective hydrogenation of diene and vinyl aromatic hydrocarbons in pyrolysis gasoline, we study the effect of the acid-base and textural characteristics of a support modified with additives of sodium compounds on the activity and stability of the catalysts in reactions of hydrogenation and oligomerization of unsaturated compounds. It is shown that the rate of formation of oligomeric compounds depends on the number of Lewis (Q _CO > 34 kJ/mol) and Brönsted sites (ν_OH = 3688 cm^?1). An increase in their total amount on the catalyst surface leads to an increase in the rate of formation of oligomeric hydrocarbons. The amount of surface condensation products is determined by the concentration of strong aprotic sites with Q _CO > 35 kJ/mol. Alumina support samples with a high surface concentration of medium-strong Lewis sites, wedge-shaped or conical pores, and the preferential distribution of porometric volume in pores with a diameter of 5–15 nm are characterized by a significant ability to oligomerize unsaturated compounds. Catalysts that contain 0.5 wt % Na exhibit the lowest oligomerization ability and a high stabile activity in reactions of hydrogenation of diene and vinyl aromatic hydrocarbons in pyrolysis gasoline. For the selective hydrogenation of diene and vinyl aromatic hydrocarbons in pyrolysis gasoline, we recommend a catalyst with 0.5 wt % Pd supported from palladium acetylacetonate on δ-Al₂O₃ modified with 0.5 wt % sodium; it is characterized by the absence of wedge-shaped or conical pores, the preferential (60.7%) distribution of porometric volume in a range of d _p > 15 nm, and a low aprotic acidity (L = 3.1 μmol/g), which contributes to the decrease in the amount of resulting condensation products (V = 3.6 μg/(gcat h)) and a high stable activity (DN = 0.68 g J₂/100 g) in reactions of hydrogenation of unsaturated compounds.     

氮杂碳包铁负载钯催化苯甲醇无溶剂氧化

以氮杂碳包铁(Fe@NC)为载体、聚乙烯吡咯烷酮为稳定剂,通过液相还原H_2PdCl_4和后续焙烧法制备新型的磁可分离Pd/Fe@NC催化剂,并进行AAS、TEM、XRD和XPS表征,将制备的催化剂用于苯甲醇无溶剂需氧氧化反应,考察焙烧温度、反应温度、催化剂用量和碱性助剂对其催化性能的影响,研究催化剂的循环使用性能。结果表明,Pd负载质量分数为4.86%,Pd有效负载比例为97.2%;Pd颗粒在载体上分散均匀,平均粒径为5 nm;催化剂活性物种组成包括Pd~0和含量较低的络合Pd(Ⅱ)及PdO。在无溶剂、无碱性助剂、O_2分压101.325 kPa(O_2流量为20 m L·min~(-1))和低催化剂用量[n(Pd)∶n(苯甲醇)=1∶2 000]条件下,Pd/Fe@NC可高效催化苯甲醇的氧化反应,100℃反应24 h,苯甲醇转化率达86%,苯甲醛选择性为87%,反应过程中无任何有毒物质产生与排放。催化剂循环使用7次后,催化活性略有提高,催化过程中络合的Pd(Ⅱ)向Pd0的转化是其活性提高的主要原因。     

An optimized process for in situ formation of multi-walled carbon nanotubes in templated pores of polymer-derived silicon oxycarbide

A reliable and optimized process to grow carbon nanotubes (CNTs) in templated pores of polymer derived ceramic (PDC) matrix was developed. It is realized through the pyrolysis of a preceramic polymer, i.e., poly (methyl-phenyl-silsesquioxane) (denoted as PMPS), in argon atmosphere at 1000 °C together with nickel-catalyst-coated poly-methyl-methacrylate (PMMA) microbeads (denoted as PMMA-Ni). PMPS served as both a precursor for the ceramic matrix and a carbon source for the CNT growth. PMMA microbeads were used as sacrificial pore formers and coated with nickel via an electroless plating method, which provides an improved control of particle size of the catalyst and its distribution in the material. The influence of PMMA-Ni loading on the in situ growth of CNTs and the properties of CNTs/SiOC nanocomposites were studied through thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, and density/porosity measurements. Under optimized conditions, uniform distribution of in situ grown CNTs was observed within the templated pores of the SiOC matrix. The optimized process leads to reproducible high yield of CNTs in the pores. The development of such novel CNT/cellular ceramic nanocomposite materials is of significant interest for a variety of sensor applications.     

Phenol hydrogenation to cyclohexanone over palladium nanoparticles loaded on charming activated carbon adjusted by facile heat treatment

Selective phenol hydrogenation is a green approach to produce cyclohexanone. It still remains a big challenge to prepare efficient supports of the catalysts for the phenol hydrogenation via a simple and cost-effective approach. Herein, a facile approach was developed, i.e., direct calcination of activated carbon (AC) under argon at high temperature, to improve its structure and surface properties. The modified AC materials were supported with Pd nanoparticles (NPs) to fabricate the Pd/C catalysts. The as-prepared Pd/C600 catalyst exhibits superior catalytic performance in the phenol hydrogenation, and its turnover frequency (TOF) value is 199.2 h^-1, 1.31 times to that of Pd/C-raw. The Pd/C600 catalyst presents both better hydrophobicity and more structural defects, contributing to the improved dispersibility in the reaction solution (phenol-cyclohexane), the better Pd dispersion and the smaller Pd size, which result in the enhancement of the catalytic performance. Furthermore, the as-prepared Pd/C600 catalyst shows a good recyclability.     

Carbon nanotubes based on anodic aluminum oxide nano-template

The effect of reaction gas and catalyst on the growth of carbon nanotubes (CNTs) in the anodic aluminum oxide (AAO) nano-template was investigated. A mechanism of CNT growth was proposed, which involves the competitive catalytic carbon deposition between on the Co catalyst particles electrodeposited at the bottom of the pores and on the AAO template itself. Presence of H₂ in the reacting gas mixture significantly affected the morphology and the wall structure of synthesized CNTs: CNTs of high crystallinity grew out of pores with H₂ while no CNTs overgrew in the absence of H₂. CNT synthesis by CO disproportionation showed a lower growth rate and a higher degree of ordering than those grown by C₂H₂ pyrolysis. The unified mechanism of CNT growth on AAO template is also proposed.