Hydrogenation catalysis of nanosized palladium supported by polymer/silica disupporter. II. Effects of the characteristics of the catalyst on hydrogenation

A series of nanosized palladium catalysts supported by silica and polymers, prepared by the complex transformation method, were used for catalytic hydrogenation of nitrobenzene. It was found that both the thickness of the polymer layer and the size of the palladium particles would affect the catalysis. The results indicated that the reaction rate would be optimal when a polymer supporter formed a single layer on the silica surface. The catalytic activity of the catalyst would not simply increase with the decrease of the size of palladium particles. The effects of other conditions on the catalytic properties, such as the order during preparation of the catalyst, solvent, and the pH values, were also discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3661–3665, 2003     

壳聚糖的降解动力学研究

用亚硝酸钠降解壳聚糖,研究了降解温度、降解时间对壳聚糖降解过程的影响.结果表明,在20 min内,壳聚糖分子量迅速减小,30 min后,壳聚糖分子量减小的趋势变缓;随着温度的升高,壳聚糖分子量减小的速度加快,但对脱乙酰度影响不大.壳聚糖的降解符合无规降解过程,其降解表观速率常数随温度升高而增大,降解活化能为63.3 kJ·mol-1.用亚硝酸钠降解壳聚糖是一种制备低分子量壳聚糖的快速且分子量可控的方法.     

冷冻干燥法制备壳聚糖/粘土多孔微球负载钯催化剂的性能研究

利用冷冻干燥法制备得到了具有多孔结构的壳聚糖/粘土(蒙脱土)微球负载钯催化剂,催化剂孔径尺寸较大(100μm)。该催化剂应用于典型丙烯酸丁酯与芳基碘系物的Heck反应时,有较高的催化活性。加入适量粘土使壳聚糖分子链能有效地插入到蒙脱土的片层间,良好的插层结构有助于提升催化材料的耐热性和机械性能。相应地,壳聚糖/粘土多孔微球负载钯催化剂比纯壳聚糖负载钯多孔微球催化剂有更高的重复使用性能。     

Coke deposition on supported palladium catalysts

Palladium/silica catalysts of varying dispersities were submitted to the coking reaction with cyclopentane at 500°C. Temperature programmed oxidation curves reveal the presence of two peaks for carbon deposition on the metallic function: the first one near 250°C would correspond to coke deposited on palladium atoms of high coordination and the second one near 400°C would involve palladium atoms of low coordination.     

Oxidation of benzyl alcohol using supported gold–palladium nanoparticles

A key discovery in the last two decades has been the realisation that gold, when prepared as supported nanoparticles, is exceptionally effective as an oxidation catalyst, particularly for the oxidation of alcohols. The catalytic efficacy is enhanced further by the alloying of gold with palladium. In this paper we study the effect of the method preparation of gold–palladium alloy nanoparticles supported on titania and investigate the activity of the materials for the selective oxidation of benzyl alcohol. We contrast impregnation and deposition–precipitation methods and demonstrate that the most active catalysts are prepared using the deposition–precipitation method.     

芳胺化PVDC负载钯化合物在微波促进下催化Suzuki偶联反应

聚偏二氯乙烯(PVDC)被二苯胺(DPA)修饰后可以有效负载氯化钯,从而制得催化剂PVDC-DPA-Pd。利用TG,DTA,IR等测试手段对其表征。热分析表明,催化剂在室温至150℃有很好的热稳定性。该催化剂在微波促进条件下在较短时间内就可以有效地催化芳基溴化合物(甚至活化的芳基氯化物)与四苯硼钠间的Suzuki偶联反应,并且在较短的时间(10 min)或较少的催化剂用量(0.01%)下,仍有很好的产率。并且催化剂回收再利用3次后,产率仍能达到75%。     

Kinetics of acid catalysed degradation of cellulose triacetate in chloroalkane solvents: 1. Dichloromethane

The kinetics of degradation of cellulose triacetate in a dichloromethane-acetic anhydride mixture with perchloric or sulphuric acid catalyst was studied. Decrease in molecular weight with time was followed viscometrically using limiting viscosity numbers, calculated by a single-point method, and Mark-Houwink constants for the solvent mixture. Dependence of first-order rate constants on catalyst concentration and temperature was investigated and Arrhenius parameters, activation entropies and catalytic coefficients were obtained. A suggested reaction mechanism for degradation based on H⁺ and Ac⁺ (acetylium ion) acting as catalytic species is proposed.     

钯触媒在蒽醌法生产双氧水的应用

根据国内双氧水生产装置上钯催化剂的使用情况,阐述了蒽醌法生产过氧化氢中所用钯催化剂的装填、活化、应用和再生等过程的优化控制和注意事项。提出了改善操作条件的办法,如温度、压力、工作液流量及循环氢化液流量等。提出了用蒸汽或有机溶剂使催化剂再生的方法。     

交联腐植酸负载钯催化剂对Heck反应催化性能研究

通过简单的方法制得了环氧氯丙烷交联腐植酸负载钯配合物催化剂,并通过IR、TG进行表征。该催化剂能够成功地催化芳基卤和不同取代芳基卤与丙烯酸、苯乙烯和丙烯酰胺的Heck反应。进一步研究显示:环氧氯丙烷交联腐植酸负载钯催化剂还能够催化溴苯与丙烯酸、苯乙烯和丙烯酰胺的反应,产率都达到95%以上;在62℃及催化剂钯含量为0.038%的条件下也能很好地催化碘苯与丙烯酸的反应。催化剂经过简单的分离处理重复使用7次仍然可以得到75.6%的产率。     

Studies on the thermal stability and degradation kinetics of Pd/PC nanocomposites

Effect of heating rate, Pd content, and synthesis method on the thermal stability of the ex situ and in situ Palladium/polycarbonate (Pd/PC) nanocomposites was investigated. TEM images revealed discrete Pd nanoclusters of about 5 and 15 nm sizes for 1 and 2 vol % ex situ nanocomposites, respectively. However, agglomerated Pd nanoclusters were noticed in the in situ samples, irrespective of the Pd content. The ex situ Pd/PC nanocomposites showed high onset temperature (Ti) for thermal degradation of PC than the in situ and pure PC samples. Pd content and heating rates were found to have a positive influence on the Ti and Tm (temperature at the maximum degradation rate occurs) of the Pd/PC nanocomposites. Thermal degradation of the PC was found to follow the first‐order kinetics in the Pd/PC nanocomposites. The activation energies associated with the degradation were determined by using the Kissinger method. These activation energies are used to construct the Master decomposition curve (MDC) and weight–time–temperature (α–t–T) plots that describe the time‐temperature dependence of the PC pyrolysis in the Pd/PC nanocomposites. These constructed α–t–T plots were validated with the data from isothermal measurements. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of alkyl nitrite decomposition on catalytic performance of CO coupling reaction over supported palladium catalyst

The syntheses of dimethyl oxalate (DMO) and diethyl oxalate (DEO) by CO coupling reaction in gaseous phase were investigated in a fixed bed reactor over Pd-Fe/Al₂O₃ catalyst. The catalytic performance was characterized by CO conversion, space-time yield (STY) and selectivity of DMO (or DEO). The results showed that over Pd-Fe/Al₂O₃ catalyst, the STY of DMO was higher than that of DEO under the same reaction conditions. The optimum reaction temperatures for synthesizing DMO and DEO were 403 K and 393 K, respectively, at the molar ratio 1 ∶ 1 of alkyl nitrite to CO. The difference in synthesizing DMO and DEO on the same catalyst was attributed to the decomposition performances of methyl nitrite (MN) and ethyl nitrite (EN), as density functional theory (DFT) calculation showed that EN decomposed more easily than MN.     

SiO_2-TiO_2负载钯催化剂的制备及其催化Suzuki反应研究

以正硅酸乙酯和钛酸正丁酯作前体,通过均匀沉淀法制备了SiO2-TiO2复合氧化物,并采用X射线粉末衍射(XRD)对复合氧化物进行了表征。采用浸渍制备了复合氧化物负载的钯催化剂Pd/SiO2-TiO2,并考察了负载催化剂在Suzuki反应中的催化性能。当投料摩尔比n(Pd)∶n(PhBr)∶n[PhB(OH)2]∶n(K2CO3)为1∶70∶105∶140,Ti/Si摩尔比和钯质量分数分别为0.5和2.0%时,回流反应10 h,联苯产率达92.8%。负载催化剂通过简单过滤即可回收利用,在5次循环使用过程中,催化活性除第1次有明显降低外,其后基本保持不变。     

Reprint of: Oxidative dehydrogenation of cyclohexane and cyclohexene over supported gold, –palladium catalysts

Supported gold, palladium and gold–palladium catalysts have been used to oxidatively dehydrogenate cyclohexane and cyclohexenes to their aromatic counterpart. The supported metal nanoparticles decreased the activation temperature of the dehydrogenation reaction. We found that the order of reactivity was Pd ≥ Au–Pd > Au supported on TiO₂. Attempts were made to lower the reaction temperature whilst retaining high selectivity. The space-time yield of benzene from cyclohexane at 473 K was determined to be 53.7 mol/kg_cat/h rising to 87.3 mol/kg_cat/h at 673 K for the Pd catalyst. Increasing the temperature in this case improved conversion at a detriment to the benzene selectivity. Oxidative dehydrogenation of cyclohexene over AuPd/TiO₂ or Pd/TiO₂ catalysts was found to be very effective (conversion >99% at 423 K). These results indicate that the first step in the reaction sequence of cyclohexane to cyclohexene is the slowest step. These initial results suggest that in a fixed-bed reactor the oxidative dehydrogenation in the presence of oxygen, palladium and gold–palladium catalysts are readily able to surpass current literature examples and with further modification should yield even higher performance.     

Chitosan application on wool before enzymatic treatment

The influence of a chitosan application on wool fabric before a treatment with a proteolytic enzyme has been investigated. The enzymatic treatment enhances whiteness and confers shrink resistance to wool, but an increase in the enzyme concentration leads to a detrimental effect on the physicomechanical properties. A chitosan treatment before the enzymatic treatment additionally improves the shrink resistance and increases the weight loss. To better investigate the role played by the chitosan, surface‐related properties, such as the friction coefficient, the compressional behavior (compressibility, linearity of compression, and thickness), the wearing resistance (weight loss after abrasion), the bursting resistance (bursting strength and deformation), and surface topography, have been studied. The results suggest that the chitosan pretreatment reduces the damage caused by the subsequent enzymatic treatment. They also imply a protective effect of the bursting and wearing resistance, which prevent excessive weight loss due to abrasion. A significant influence of the wool fiber cell membrane complex on the surface‐related properties has been demonstrated through regression analysis and scanning electron microscopy observations. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1938–1946, 2005     

用于汽车尾气净化的单钯催化剂催化行为的研究

研究了Pd-Ce-Ba催化剂活性和热稳定性。结果表明,该催化剂具有低温活性好。高效和热稳定性好的性能特点。对CO。HC的起燃温度和半转化温度分别为120℃。160℃和140℃。190℃,经原料气预处理或经原料气多次评价后的氧化反应结果明显优于催化剂未经受任何预处理的结果。稀土元素Ce及碱土金属Ba的氧化物在催化剂表面的富聚和在活性氧化铝涂层中的存在,对Pd组分起到分散。隔离和稳定结构的作用,保证了催化剂良好的热稳定性。     

Cysteine-Functionalized Chitosan Magnetic Nano-Based Particles for the Recovery of Uranium(VI): Uptake Kinetics and Sorption Isotherms

Magnetic-chitosan nanoparticles, functionalized with cysteine, were synthesized and characterized by element analysis, FT-IR, XRD, TEM, and vibrating sample magnetometry. The sorbent was tested for U(VI) recovery, considering:

• a. pH effect,

• b. sorption isotherms (fitted by Langmuir equation), and

• c. uptake kinetics (modeled using the PSORE).

Maximum sorption capacity approached 100 mg U g^?1. The nanometric size of sorbent reduces the impact of resistance to intraparticle diffusion; this may explain the fast kinetics (equilibrium within 50 min). The reaction is exothermic, spontaneous. The metal could be desorbed using acidified urea solution and the sorbent could be recycled for 5 cycles.     

聚苯乙烯负载二环己胺钯催化Heck反应的研究

以聚苯乙烯树脂为载体、二环己胺为配体制备聚苯乙烯负载胺钯催化剂。采用XPS、XRD、TG、DTA和SEM等方法对其进行表征,针对不同催化体系探讨丙烯酸、苯乙烯与芳基碘的Heck反应的催化性能。结果表明,高分子胺配体与钯之间形成配位作用,制备的催化剂在室温～200 ℃有较好的热稳定性。该负载型催化剂在N₂氛围只需少量的催化剂就能较好地催化丙烯酸、苯乙烯与芳基碘的Heck反应,较高收率地生成取代的反式肉桂酸和1,2-二苯基乙烯。     

硼杂碳包镍负载钯催化芳香醇需氧氧化

以硼杂碳包镍(Ni@BC)为载体,采用乙醇还原前驱体H_2PdCl_4法制备了一种新型磁可分离Pd/Ni@BC催化剂,并对其进行AAS、TEM、XRD和XPS表征,选取苯甲醇需氧氧化为探针反应,考察催化剂用量、反应温度和反应时间对催化性能的影响,研究催化剂对其他芳香醇的催化性能和循环使用性能。AAS结果表明,Pd负载质量分数为9.1%,与理论负载量一致。TEM结果显示,Pd纳米颗粒均匀分散在载体表面,平均粒径为4 nm。XRD和XPS结果均表明,催化剂的活性物种为Pd0。在反应温度80℃、O2_压力101.325 k Pa(流速20 m L·min~(-1))、CH_3CN为溶剂和K_2CO_3为碱性助剂条件下,Pd/Ni@BC对多种芳香醇的氧化反应表现出很高的催化活性和选择性,能将苯甲醇、对甲基苯甲醇、对乙基苯甲醇、对异丙基苯甲醇、肉桂醇、安息香、二苯甲醇以及邻甲基苯甲醇等定量转化为相应的醛或酮。催化剂重复使用5次,苯甲醇转化率由97.3%降至78.9%,Pd的少量脱落和部分氧化是催化剂活性降低的主要原因。     

The influence of sulfur dioxide on propane oxidation activity over supported platinum and palladium

Earlier studies have shown that sulfur dioxide and metal-support interaction can strongly influence propane oxidation over platinum. In particular, oxidation activity is enhanced when platinum is supported on sulfated -alumina or zirconia compared to -alumina. Therefore, it is of interest to compare the performance of palladium under the same experimental conditions. Four model catalysts were examined: Pt/-alumina, Pt/zirconia, Pd/-alumina and Pd/zirconia. The metal loading was kept at or below 0.05 wt% to emphasize changes in activity attributable to metal-support interaction. Reaction rates were measured with and without sulfur dioxide. Surface sulfation was analyzed by measuring acid strength and evaluating spectra obtained by Fourier-transform infrared spectroscopy. In contrast to platinum, sulfation does not promote propane oxidation on Pd/-alumina, and Pd/zirconia is less active than Pd/-alumina.