醋酸乙烯Pd—Au／SiO2催化剂的老化研究

比较了乙烯气相法合成醋酸乙烯Pd—Au／SiO2催化剂不同反应时期的结构变化情况，指出催化剂的失活主要是由于稠环有机物的不可逆吸附而不是活性组分Pd晶粒增长造成的，由此提出了催化剂的多种老化方法促使Pd晶粒增长以降低初活性，从而达到缩短催化剂驯化期的目的。以XRD作为主要表征手段，研究了制备过程中各种气氛下的高温老化方法对Pd—Au／SiO2体系的影响。结果表明，高温焙烧不影响Pd，Au的合金结构，但会促使金属微粒的凝聚生长，从而降低了催化剂初活性，缩短了工业运行的驯化期，尤其是醋酸气氛老化的催化剂具有更好的活性稳定性和更高的反应选择性。     

Pd/Fe3O4催化剂的制备及在Suzuki偶联反应中的应用

利用浸渍法制备Pd/Fe3O4负载型磁性纳米催化剂。通过透射电镜(TEM)、X射线衍射(XRD)、电感耦合等离子体-发射光谱(ICP)及振动样品磁强计(VSM)等物理化学手段对其进行了表征。将Pd/Fe3O4催化剂应用于卤代芳烃与芳基硼酸的Suzuki偶联反应中。研究结果表明:Pd/Fe3O4催化剂具有一定的磁性,利用外磁场可方便快速地分离出催化剂。负载Pd的质量分数为12.01%时,催化活性最高;在空气中,无需在惰性气体的保护下能有效地催化芳基硼酸与卤代芳烃的Suzuki偶联反应,催化剂重复使用5次后,催化活性没有明显的降低。     

碱洗对Pd／C催化剂性能的影响研究

碱洗能恢复被污染物覆盖的pd／C的活性,但同时对催化剂也有不利的影响。碱洗方式的不同对催化剂造成不利的影响程度也不同。实验室的实验结果表明,高温在线碱洗会减少Pd组分的溶解。不管怎样进行再生,多次碱洗均会降低催化剂强度,故应尽量减少碱洗次数。     

烷基苯酚加氢用Pd/C催化剂性能研究

采用浸渍法制备不同助剂改性的Pd/C催化剂,并与未添加助剂的Pd/C催化剂对比,考察不同助剂对苯酚加氢制备环己酮用Pd/C催化剂性能影响。结果表明,助剂Zn对催化剂活性和选择性影响较小,助剂Mg、Fe、Co使烷基苯酚加氢用Pd/C催化剂活性和选择性均有所提升,且以CoCl2为Co源,质量含量为2.0%Co修饰的Pd/C催化剂效果较优,催化剂重复使用性能良好。     

Pd-M(Ce、Ca、Fe)/γ-Al_2O_3催化2,5-二氢呋喃加氢性能

通过分步浸渍法制备了Pd含量为0.3%,M含量为3.0%的Pd-M(M=Ce、Ca、Fe)/γ-Al_2O_3催化剂,采用XRD、N_2物理吸附-脱附、H_2-TPR、H_2-TPD和Py-IR等对催化剂进行表征,并研究了助剂对Pd/γ-Al_2O_3催化剂催化2,5-二氢呋喃加氢性能的影响。结果表明,在Pd/γ-Al_2O_3催化剂中引入助剂,降低了Pd与金属相互作用,同时减少了表面暴露L酸位点;促进了2,5-二氢呋喃加氢转化为四氢呋喃,抑制了异构化产物2,3-二氢呋喃的产生。特别是Fe的引入,与Pd之间的协同作用,使CC双键在Pd表面吸附增强,2,5-二氢呋喃转化率大幅提高。该催化剂在反应温度30℃,氢压0.5 MPa和反应时间1 h的加氢条件下,2,5-二氢呋喃转化率达到94.25%,目标产物四氢呋喃选择性达到99.97%。     

金催化剂催化氧化葡萄糖研究

采用固定化凝胶法制备1％ Au／C催化剂。对Au／C催化剂的寿命进行了测试,结果显示：经过9次重复使用,每次3h,Au／C催化剂的活性下降．同时比较了制备的Au／C和商业Pd／C催化剂对葡萄糖的液相催化氧化反应,证明Au／C催化剂明显优于Pd／C催化剂．     

延长Pd/C催化剂使用寿命

本文围绕延缓Pd/C催化剂中Pd晶粒的烧结及减少Cu、Fe等离子对催化剂的污染的原理方面进行了工艺实验 ,提出了在使用初期 ,采取比原来值高的H2 供应量 ;中期控制在设计范围内 ;在使用后期 ,特别是超过设计寿命时 ,采取强化工艺 ,提高H2 分压 ,有效地保护Pd晶粒的活性中心 ,以延缓Pd/C催化剂中的Pd烧结及减少杂质离子的污染。并对受到污染而活性下降的Pd/C催化剂用碱洗恢复活性的方法进行了有关实验 ,常温下先用 2 0 %NaOH溶液浸泡 4h ,再用 5 %NaOH溶液浸泡 4h ,即能够有效地去除污染物 ,恢复催化剂的活性。延缓Pd/C催化剂中的Pd烧结和碱洗均能延长Pd/C催化剂使用寿命     

Pd／CNFs催化剂在Heck反应中的应用

文章考查了纳米碳纤维（CNFs）作为催化剂戴体负载贵金属钯所制备的催化剂用于Heck反应的催化性能；比较了不同制备方法所制备的Pd／CNFs催化剂的催化性能，Pd／CNFs的热稳定性及其重复使用性能。结果表明，Pd／cNFs催化剂是一类催化性能好、热稳定性高、适用面广且有很好重复使用性能的Heck反应非均相催化剂。     

改性Cu-Mn-Ce-O三效催化剂的制备及其性能研究

在制备Cu-Mn-Ce-O三效催化剂的基础上制备出搀杂K、Fe、TiO2和Pd的三效催化剂；用脉冲－－火焰装置产生出适合评价催化剂三效活性的模拟汽车尾气，通过实验研究了所制备各种催化剂的空燃比特性和温度特性，结果表明：搀杂非贵金属K、Fe和TiO2只能提高某些组分的转化率，但缩小了催化剂的操作窗口；贵金属Pd的加入提高了催化剂的三效活性，加宽了催化剂的操作窗口，但催化剂的起燃温度并没有明显降低。     

低活性钯炭催化剂的工艺控制方法

分析了Pd/C催化剂活性降低的原因,介绍了天津PTA装置在Pd/C催化剂活性降低时采取的工艺控制手段。经过工艺调整,延长了催化剂的使用寿命。Pd/C催化剂的最长使用寿命达到6.13万倍,超过设计寿命1倍多。     

Pd/Fe双金属对1,2,4-三氯苯的催化脱氯

采用Pd/Fe双金属体系对1,2,4-三氯苯（1,2,4-TCB）进行了快速催化还原脱氯的研究.结果表明,在钯的催化作用下,零价铁对1,2,4-TCB有较好的还原脱氯效率.当Pd/Fe双金属的钯化氯为0.06%时,催化剂用量为1g/40mL,反应1h后TCB的脱氯率可达99%.反应速率随钯化氯的提高而增加.反应在Pd/Fe表面进行,符合准一级反应,反应速率常数为0.0837min-1.TCB在催化脱氯的过程中先脱氯成为DCB,再依次脱氯为氯苯和苯.     

Pd/Fe双金属对水中m-二氯苯的催化脱氯

引　言氯代芳烃及其衍生物化学性质稳定 ,易在生物体内累积 ,大多被列为美国EPA环境优先控制污染物 ,一旦进入环境将对人类及其生态环境造成长期威胁 .因此 ,氯代芳烃的治理技术日益引起全球的关注[1] .自 2 0世纪 80年代末提出金属铁屑用于地下水的原位修复以来[2 ,3] ,用Fe0 还原脱氯已成为一个非常活跃的研究领域 ,特别是应用于地下水修复方面的研究 .Fernando等[4～ 7] 将双金属催化剂用于有机氯的催化还原脱氯 ,Fe0 表面的Pd或Ni等金属加速了还原脱氯反应 ,脱氯速率比Fe0 体系快得多 .本研究利用Pd/Fe双金属对m DCB进行了催化还…     

The Mechanism of N2O Decomposition on Fe-ZSM-5: An Isotope Labeling Study

The role of Fe promoters has been investigated on Pd/ceria, Pt/ceria and Rh/ceria catalysts for the water–gas shift (WGS) reaction in 25 torr of CO and H₂O under differential reaction conditions. While no enhancement was observed with Pt and Rh, the activity of Pd/ceria increased by as much as an order of magnitude upon the addition of an optimal amount of Fe. Similarly, the addition of 1 wt% Pd to an Fe₂O₃ catalyst increased the WGS rate at 453 K by a factor of 10 over that measured on Fe₂O₃ alone, while the addition of Pt or Rh to Fe₂O₃ had no effect on rates. The amount of Fe that was necessary to optimize the rates increased with Pd loading but was independent of the order in which Fe and Pd were added to the ceria. Increased WGS activity was also observed upon the addition of Fe to Pd supported on Ce_0.5Zr_0.5O₂. XRD measurements, performed after running the catalyst under WGS conditions, show the formation of a Fe–Pd alloy, even though similar measurements on an Fe/ceria catalyst showed that Fe₃O₄ was the stable phase for Fe in the absence of Pd. Possible implications of these results on the development of new WGS catalysts are discussed.     

Pd/Fe对-二氯苯的催化脱氯及其动力学

o-Dichlorobenzene (o-DCB) was dechlorinated by Pd/Fe powder in water through catalytic reduction. The dechlorination reaction is believed to take place on the surface site of the catalyst via a pseudo-first-order reaction. The final reduction product of o-DCB is benzene. The dechlorination rate increases with the increase of bulk loading of palladium due to the increase of both the surface loading of palladium and the total surface area. Dechlorination efficiency accounts for 90% at Pd/Fe mass ratio 0.02% and metal to solution ratio about 53.3g-L-1 in 120 minutes. Dechlorination is affected by the reaction temperature, pH, Pd/Fe ratio and the addition of Pd/Fe. Ea is found to be 102.5kJ.mol-1 in the temperature ra,nge of 287-313K.     

Effect of Palladium on Iron Fischer–Tropsch Synthesis Catalysts

Studies were conducted to investigate the effect of Pd on the Fischer–Tropsch Synthesis (FTS) selectivity, activity and kinetics as well as on the water–gas shift activity of an iron catalyst. Two palladium promoted catalysts (Pd0.002/Fe100 and Pd0.005/Fe100) were prepared from a base Fe100/Si5.1 (atomic ratio) catalyst. Results of FTS over the two palladium promoted catalysts were compared to those obtained from the K/Fe/Si base catalyst and a Cu/K/Fe/Si catalyst. The results indicate that Pd enhanced the FT activity while the selectivity for CO₂ and CH₄ changed little compared to the results for the base catalyst and the Cu promoted catalyst. Palladium promotion had a negative effect on the C₂—C₄ olefin to paraffin ratio. Pd promotion led to a higher WGS rate than the other two catalysts at high syngas conversions. A higher WGS rate compared to the FTS rate was obtained only for the Pd promoted catalysts. The FTS rate constant for the Pd promoted catalyst is higher than the base catalyst but lower than for the Cu promoted catalyst.     

Hydrodechlorination of 2,4,6-trichlorophenol for a permeable reactive barrier using zero-valent iron and catalyzed iron

Dehalogenation of toxic organic compounds has been intensively studied during the last decade by using zero-valent iron (ZVI). However, the reactivity of iron is compound specific and very low reactivities were reported for aromatic compounds including chlorophenols. In this study, hydrodechlorination of 2,4,6-trichlorophenol (2,4,6-TCP) was conducted in a batch system by using ZVI and catalyzed iron. No degradation was observed with ZVI over the 40 days experiments. Catalyzed ZVIs removed 2,4,6-TCP and palladium-coated iron (Pd/Fe) and nickel-coated iron (Ni/Fe) showed relatively enhanced reactivity while copper-coated iron (Cu/Fe) and platinum-coated iron (Pt/Fe) showed lower reactivities. The surface area normalized kinetic constants (k _SA ) of Pd/Fe, Ni/Fe, Cu/Fe, Pt/Fe are 2.54×10⁻⁴, 1.01 × 10⁻⁴, 2.24×10⁻⁵, 2.56×10⁻⁵ L m⁻² h⁻¹, respectively. The identification of less chlorinated phenols and phenol confirmed that the removal is dechlorination. Pd/Fe system exerts relatively low pH compared with the ZVI system, and the low pH is favorable for the dechlorination. The reactivity enhancement of catalyzed iron was discussed in terms of catalytic effects and the corrosion potential by the bimetal coupling. Variable Pd content on the Pd/Fe was tested, and the degradation rate of 2,4,6-TCP increased in proportion to the increase of Pd content.     

Treatment of chlorinated organic contaminants with nanoscale bimetallic particles

Nanoscale bimetallic particles (Pd/Fe, Pd/Zn, Pt/Fe, Ni/Fe) have been synthesized in the laboratory for treatment of chlorinated organic pollutants. Specific surface areas of the nanoscale particles are tens of times larger than those of commercially available microscale metal particles. Rapid and complete dechlorination of several chlorinated organic solvents and chlorinated aromatic compounds was achieved by using the nanoscale bimetallic particles. Evidence observed suggests that within the bimetallic complex, one metal (Fe, Zn) serves primarily as electron donor while the other as catalyst (Pd, Pt). Surface-area-normalized reactivity constants are about 100 times higher than those of microscale iron particles. Production of chlorinated byproducts, frequently reported in studies with iron particles, is notably reduced due to the presence of catalyst. The nano-particle technology offers great opportunities for both fundamental research and technological applications in environmental engineering and science.