胺基化树脂负载Pd(0)对Heck反应催化性能的研究

将氯球用胺化剂、乙二胺、胍进行胺化后负载氯化钯, 在乙醇溶液中用硼氢化钾还原, 制备了含胺功能基树脂负载钯(0)的催化剂; 研究了催化剂对含各种取代基碘代苯与丙烯酸的Heck芳基化反应催化性能. 结果表明, 该类催化剂具有良好的催化活性和重复使用性能, 其中用乙二胺功能化树脂负载的Pd(0)催化剂在90 ℃重复使用17次时能保持良好的催化活性. 催化剂反应前后的SEM形貌图和过滤液的活性试验表明催化剂活性组分Pd(0)在反应中有沥取(leaching)现象.     

四乙烯五胺功能化纤维素负载纳米钯催化剂的制备及其对Suzuki反应催化性能的研究

利用四乙烯五胺对环氧化纤维素进行功能化改性,并以其为载体在95％乙醇溶液中现场还原氯化钯制备出四乙烯五胺功能化纤维素负载的纳米钯催化剂.利用IR,XRD,SEM,TEM等分析方法对其进行了表征并用于催化Suzuki交叉偶联反应.实验表明,该催化剂在温和条件下能有效催化卤代芳烃与芳基硼酸的Suzuki交叉偶联反应,该催化剂经回收重复利用5次后,仍具有较高的催化活性.     

氧化镁负载三聚氰胺缩甲醛高分子钯配合物催化剂催化加氢制备葡辛胺的研究

以氧化镁负载三聚氰胺缩甲醛高分子钯配合物为催化剂, 对葡萄糖与正辛胺催化加氢制备葡辛胺进行了研究. 结果表明在以60 mL乙醇为溶剂, 三乙胺为添加剂(1.0 mL), 于60 ℃的反应温度, 1.5 MPa反应氢压, 0.7 g催化剂用量下反应6 h, 37.2 mmol葡萄糖与31 mmol正辛胺催化加氢可得产率为57.6%的葡辛胺. 相对于雷内镍催化剂, 该催化剂制备简单,制备过程无污染、对环境友好,产物纯度高,并具有适当的可重复使用,因此氧化镁负载三聚氰胺缩甲醛高分子钯配合物是葡辛胺制备的良好催化剂.     

纳米碳纤维负载钯催化剂在Heck反应中的应用——载体相互作用的影响

使用多元醇还原法制备了均匀分散的钯纳米颗粒.将钯纳米颗粒负载于板式、鱼骨式和管式纳米碳纤维,得到稳定、可重复使用的非均相催化剂.实验结果表明,钯纳米胶粒同载体之间的电位差对钯在载体上的负载量、粒子大小以及Heck反应中钯的溶失量有很大的影响.在制备过程中,增加钯纳米胶粒同纳米碳纤维表面的电位差能够大大降低钯在Heck反应中的流失.催化剂的反应活性随钯粒子的增大而降低.     

氨功能化陶瓷膜支撑体担载钯纳米颗粒及其增强的催化性能(英文)

采用双氨基硅烷偶联剂N-β-(氨乙基)-γ-氨丙基三甲氧基硅烷(AAPTS)对陶瓷膜表面接枝功能化并负载钯纳米颗粒,制得一种有效的可重复使用的催化剂.利用X射线衍射、扫描电镜、电子能谱、感应耦合等离子体、X射线光电子能谱和高分辨透射电镜对催化剂进行了物性表征,并将其用于催化对硝基苯酚加氢制对氨基苯酚反应.和单氨基硅烷γ-氨丙基三乙氧基硅烷(3-APTS)功能化改性相比,担载在AAPTS功能化陶瓷膜上的钯纳米颗粒具有更高的催化活性和稳定性.相比于3-APTS,AAPTS分子中含有两个氨基,具有更强的供电子效应,因此钯纳米颗粒可更多更稳定地负载在AAPTS功能化陶瓷膜上,从而具有更高的催化活性和稳定性.     

准均相的铂钯合金纳米催化剂用于芳香族化合物脱卤反应

用一锅法合成的负载于聚酰胺酸盐上的铂钯纳米催化剂,可以通过调节溶液的p H值实现催化剂与反应体系的有效分离和循环利用.准均相的铂钯催化剂应用于水相中卤代芳香族化合物的氢化脱卤反应,转化率达到99%以上,并且在重复使用5次后仍然保持很高的活性.铂钯双金属催化剂拥有比单一金属铂或者钯更高的催化活性,这主要是由于铂钯合金在催化反应时具有协同效应.利用X射线衍射仪(XRD),透射电子显微镜(TEM)等方法对催化剂进行了表征.数据表明铂钯纳米粒子负载于聚酰胺酸上以后可以在水溶液中稳定存在并且处于均匀的分布状态,纳米粒子尺寸约为4 nm.     

聚氯乙烯三乙撑四胺负载钯配合物的制备及对Heck反应的催化性能

以聚氯乙烯为原料, 通过胺化反应制得聚氯乙烯三乙撑四胺, 然后用较简单方法得到聚氯乙烯三乙撑四胺负载钯配合物(PVC-TETA-Pd), 利用XPS, TG, DTA和TEM等手段对其进行了表征. 热分析表明PVC-TETA-Pd在室温至250 ℃范围内有很好的热稳定性; TEM分析证实钯在PVC-TETA-Pd中分布比较均匀, 钯颗粒呈球形, 粒径在2～3 nm. PVC-TETA-Pd不需在惰性气体氛围中就能有效地催化丙烯酸、苯乙烯与芳基碘的Heck芳基化反应, 并且在较低的温度(40 ℃)或较少的催化剂用量(0.02%)下, 对Heck反应仍有较好的催化性能. PVC-TETA-Pd便于回收, 且有很好的重复使用性能, 对于碘苯与丙烯酸的反应, 重复使用十二次, 肉桂酸的产率仍达到80.1%.     

负载型氮杂环卡宾钯络合物催化C—C偶联反应新进展

负载型氮杂环卡宾钯催化的C—C偶联反应由于具有反应活性高,催化剂便于分离和可重复使用等特点,已引起了人们的广泛关注.负载型氮杂环卡宾钯催化剂中的载体材料对催化性能和重复使用性能具有较大的影响.综述了不同类型载体材料制备的负载型氮杂环卡宾钯催化C—C偶联反应的研究进展,载体类型包括聚合物材料、硅材料、碳材料和磁性纳米粒子材料.此外,还对负载型氮杂环卡宾钯催化剂未来的发展前景进行了展望.     

纳米丝负载钯催化剂的制备及催化烯烃加氢性能研究

利用电纺丝技术制备出苯乙烯-丙烯腈共聚物负载钯的纳米丝催化剂.对催化剂进行了SEM、TEM、IR和XPS的测试.所制备的催化剂对α-己烯催化氢化结果表明,该催化剂在常温、氢气常压下具有很高的催化活性和较好的重复使用性,并且催化氢化过程中存在烯烃的异构化反应.实验结果表明,反应时间为150min时纳米催化剂A对α-己烯催化加氢生成正己烷的转化率是传统催化剂PdCl2/-γAl2O3的4.7倍.     

钯纳米颗粒负载在聚苯胺材料上制得催化Suzuki-Miyaura偶联反应的高效催化剂

在最近的几十年里,金属钯催化的Suzuki-Miyaura偶联反应已经得到了越来越多的关注,被广泛应用于药物、天然产物以及新材料的合成.与此同时均相催化剂发展迅速,高效的配体和大量的设计被用于Suzuki-Miyaura偶联反应中,但是钯催化剂的配体通常很昂贵和难以合成,因此钯催化剂系统的回收是非常有价值的,不仅是经济上的原因,同时也避免了产品的污染,所以发展非均相催化剂是必要的.近年来,研究学者们致力于设计非均相的钯催化剂,如将钯纳米颗粒负载到金属有机骨架、介孔分子筛以及活性炭等多种材料上得到的非均相钯催化剂并应用于Suzuki-Miyaura偶联反应中.我们主要介绍了钯纳米颗粒被负载在含磷配体的交联的聚苯胺材料上制得负载的钯催化剂,首先通过钯催化的三(4-碘苯基)胺与金刚烷基膦的C–P偶联,再由钯催化三(4-碘苯基)胺与对苯二胺的C–N偶联,进而得到钯纳米颗粒负载在含金刚烷基膦的聚苯胺材料上的催化剂Pd@PAN-Ad-0.5(钯含量为0.58 wt%),同时我们对催化剂进行了一些表征,如TEM,SEM,XRD,EDX,XPS,FT-IR,ICP等.通过TEM分析,我们发现钯纳米颗粒在聚合物表面分布均匀,并且金属钯的平均粒径为2–3 nm;EDX检测显示催化剂含有C,N,P,Pd,I元素,说明钯负载到含金刚烷基膦的聚苯胺材料上的催化剂Pd@PAN-Ad-0.5已经形成,并被用于Suzuki-Miyaura偶联反应.我们对反应体系中的各种影响因素进行了优化,包括溶剂、碱、反应时间、催化剂加入量以及不同的催化剂的优化,最终确定了最佳反应条件;对于带有不同取代基(如腈基、甲氧基、醛基、酮基以及硝基)的氯代芳烃和溴代芳烃与苯硼酸的Suzuki-Miyaura反应,以较少的催化剂使用量(0.075 mol%Pd)就能获得较高的相应的联苯产物收率.此外,催化剂Pd@PAN-Ad-0.5在偶联反应中具有较高的反应活性的同时,还具有较好的回收使用能力(至少能够回收使用5次),循环使用4次以后还具有较高的催化活性.为了探索催化剂Pd@PAN-Ad-0.5在工业上的应用,由于4'-氯-2-硝基-1,1'-联苯是合成啶酰菌胺药物的重要中间体,因此我们使用催化剂Pd@PAN-Ad-0.5催化2-硝基氯苯与4-氯苯硼酸的偶联反应,目标产物4'-氯-2-硝基-1,1'-联苯的收率高达96%.我们相信这类催化剂应用于实验室或工业上合成联苯化学品具有较大的潜力.     

Copper(I) and palladium nanoparticles supported on ethylenediamine‐functionalized cellulose as an efficient catalyst for the 1,3‐dipolar cycloaddition/direct arylation sequence

Cu(I) and nanoparticles of Pd supported on ethylenediamine‐functionalized cellulose as a novel bio‐supported catalyst was synthesized and characterized. The synthesized catalyst was found to be a highly efficient heterogeneous catalyst for the synthesis of 1,4,5‐trisubstituted 1,2,3‐triazoles through a sustainable 1,3‐dipolar cycloaddition/direct arylation sequence. The catalyst could be easily recovered by simple filtration and reused for at least five cycles without losing its activity. Copyright © 2014 John Wiley & Sons, Ltd.     

络合还原法制备碳载钯纳米粒子及其电催化甲酸氧化

应用柠檬酸钠络合还原法制备了粒径小、分布均匀的碳载Pd纳米粒子(Pd/C).由于柠檬酸钠的络合作用,有效地降低了Pd粒子在形成过程中的团聚.经过简单的热处理调控Pd粒子大小,发现随热处理温度的升高,Pd粒子直径由初始的2.7 nm增大到5.8 nm左右.电化学测试表明Pd/C的Pd粒子尺寸越小,电催化甲酸氧化的质量比活性越高,但如当Pd粒径较大,则催化剂呈现出更高的面积比活性.Pd粒径为3.6 nm的催化剂,其电催化甲酸氧化的稳定性最好.     

EDTA对活性炭的功能化处理及其对炭载Pd催化剂电催化性能的影响

采用乙二胺四乙酸(EDTA)对活性炭进行功能化处理, 研究了其对表面基团、炭载Pd 纳米粒子结构及Pd催化剂电催化性能的影响. 傅里叶变换红外(FTIR)光谱和X射线光电子能谱(XPS)表征表明, EDTA处理在炭表面引入了含氮基团. X射线粉末衍射(XRD)光谱、透射电镜(TEM)和电化学测试结果显示, 活性炭经EDTA处理后, 负载的Pd粒子粒径虽有所增大, 但由于炭载体与Pd粒子相互作用的增强, Pd利用率增加, 催化剂对甲酸氧化的活性和稳定性均显著提高. 电化学阻抗谱(EIS)分析进一步揭示, 甲酸在该催化剂电极上的电氧化反应具有较低的电荷传递电阻.     

配位还原制备膦酸功能化Pd/C催化剂及其应用

采用活性炭为载体,乙二胺四亚甲基膦酸（EDTMPA）作为配位剂和稳定剂,氯化钯（PdCl₂）为前驱体,硼氢化钠（NaBH₄）为还原剂,通过一步还原制备得到膦酸功能化的超细高分散Pd/C催化剂.透射电子显微镜（TEM）及X射线衍射（XRD）分析结果表明,制得的Pd/C催化剂中Pd粒子的平均粒径为2.7 nm,分散度为37.1%,高于同类型商业化催化剂.制得的催化剂对罗丹明（RhB）和对硝基苯酚（4-NP）的催化加氢反应的活化能分别为27.18和16.79 kJ/mol,明显低于商业化Pd/C催化剂（57.12和55.71 kJ/mol）.     

Enhanced oxygen reduction at Pd catalytic nanoparticles dispersed onto heteropolytungstate-assembled poly(diallyldimethylammonium)-functionalized carbon nanotubes

Both Keggin-type phosphotungstic acid (HPW) and Pd are not prominent catalysts towards the oxygen reduction (ORR), but their composite Pd-HPW catalyst produces a significantly higher electrochemical activity for the ORR in acidic media. The novel composite catalyst was synthesized by self-assembly of HPW on multi-walled carbon nanotubes (MWCNTs) via the electrostatic attraction between negatively charged HPW and positively charged poly(diallyldimethylammonium (PDDA)-wrapped MWCNTs, followed by dispersion of Pd nanoparticles onto the HPW-PDDA-MWCNT assembly. The as-prepared catalyst was characterized by transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, thermal gravimetric analysis (TGA), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). TEM images show that Pd nanoparticles were uniformly dispersed on the surface of MWCNTs even when the Pd loading was increased to 60 wt%. Electrochemical activity of the catalysts for the ORR was evaluated by steady state polarization measurements using a rotating disk electrode. Compared with the acid treated MWCNTs, Pd nanoparticles supported on the HPW-assembled MWCNTs show a much higher ORR activity that is comparable to conventional Pt/C catalysts. The high electrocatalytic activities could be related to high dispersion of Pd nanoparticles as well as synergistic effects originating from the high proton conductivity of HPW. The Pd/HPW-PDDA-MWCNTs system as the cathode catalyst in proton exchange membrane fuel cells is demonstrated.     

Synthesis and characterization of Pd catalysts supported on carbon microspheres for formic acid oxidation

A facile preparation of Pd catalyst using carbon microspheres as support was introduced in this paper. The carbon microspheres were prepared with a simple method from dextrose via hydrothermal process and used as catalysts support for formic acid electrooxidation. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) analyses revealed that the as-prepared face-centered cubic crystal Pd nanoparticles were well-dispersed on the surface of the carbon microspheres, and the mean diameter of the nanoparticles was 8.8 nm. The effect of the support on the catalyst performance for formic acid electrooxidation was studied. The as-prepared catalyst showed the enhanced electrochemical surface active area and the higher electrocatalytic activity towards formic acid oxidation compared with Pd/CNTs and Pd/XC-72 catalysts prepared at room temperature. Electrochemical analysis suggested that the carbon microspheres might be good candidates to be used as the supports of catalyst for formic acid electrochemical oxidation.     

Synthesis of highly dispersed Pd/C electro-catalyst with high activity for formic acid oxidation

In this study, we present a simple process to obtain highly dispersed palladium nanoparticles on Vulcan XC-72R carbon support without any protective agent. To obtain high metal loading Pd/C catalyst without any surfactant, we modified the polyol process by employing NH₃ species as a mediation to control the reaction pathway to avoid the precipitation of Pd(OH)₂, and hence the agglomeration of Pd nanoparticles. The obtained Pd/C sample was characterized by X-ray diffraction (XRD) and transmission electron microscope (TEM) techniques. The results show that highly dispersed Pd/C catalyst with an average diameter of 3.0 nm could be obtained in this novel process. The activity of formic acid oxidation on this Pd/C catalyst was examined via cyclic voltammetry technique and it is found that the catalytic activity is greatly enhanced due to the reduced particle size and the improved dispersion of palladium nanoparticles on the carbon surface.     

Immobilized Pd on a NHC functionalized metal–organic framework MIL-101(Cr): an efficient heterogeneous catalyst in Suzuki−Miyaura coupling reaction in water

A novel Pd−NHC functionalized metal–organic framework (MOF) based on MIL-101(Cr) was synthesized and used as an efficient heterogeneous catalyst in the C-C bond formation reactions. Using this heterogeneous Pd catalyst system, the Suzuki−Miyaura coupling reaction was accomplished well in water, and coupling products were obtained in good to excellent yields in short reaction time. The Pd−NHC−MIL-101(Cr) was characterized using some different techniques, including Fourier transform-infrared, X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy, inductively coupled plasma and elemental analysis. The microscopic techniques showed the discrete octahedron structure of MIL-101(Cr), which is also stable after chemical modification process to prepare the catalyst system. The TEM images of the catalyst showed the existence of palladium nanoparticles immobilized in the structure of the catalyst, while no reducing agent was used. It seems that the NHC groups and imidazolium moieties in the structure of the MOF can reduce Pd (II) to Pd (0) species. This modified MOF substrate can also prevent aggregation of Pd nanoparticles, resulting in high stability of them in organic transformation. The Pd−NHC−MIL-101(Cr) catalyst system could be simply extracted from the reaction mixture, providing an efficient synthetic method for the synthesis of biaryls derivatives using the aforementioned coupling reaction. The Pd−NHC−MIL-101(Cr) catalyst could be recycled in this organic reaction with almost consistent catalytic efficiency.     

磷钨酸修饰活性炭载Pd催化剂的制备及对甲酸氧化的电催化性能简

通过水浴浸泡制备了磷钨酸(PWA)修饰的活性炭(PWA/C),再通过液相还原法将Pd沉积于PWA/C复合载体上制备了Pd-PWA/C催化剂. 采用X射线能量色散(EDS)谱、X射线衍射(XRD)谱、透射电子显微镜(TEM)和X射线光电子能谱(XPS)对产物进行表征. 结果表明,磷钨酸修饰活性炭不仅能有效降低Pd纳米粒子的粒径,而且与Pd纳米粒子间发生了强烈作用. 电化学测试结果显示,Pd-PWA/C催化剂对甲酸氧化的电催化活性和稳定性均远优于Pd/C催化剂,这是由于Pd与PWA/C间的强烈作用既能有效降低CO在催化剂上的吸附强度和吸附量,又能降低甲酸分解的速率,从而减弱CO的毒化作用.     

磷钨酸修饰活性炭载Pd催化剂的制备及对甲酸氧化的电催化性能

通过水浴浸泡制备了磷钨酸(PWA)修饰的活性炭(PWA/C), 再通过液相还原法将Pd沉积于PWA/C复合载体上制备了Pd-PWA/C催化剂. 采用X射线能量色散(EDS)谱、 X射线衍射(XRD)谱、 透射电子显微镜(TEM)和X射线光电子能谱(XPS)对产物进行表征. 结果表明, 磷钨酸修饰活性炭不仅能有效降低Pd纳米粒子的粒径, 而且与Pd纳米粒子间发生了强烈作用. 电化学测试结果显示, Pd-PWA/C催化剂对甲酸氧化的电催化活性和稳定性均远优于Pd/C催化剂, 这是由于Pd与PWA/C间的强烈作用既能有效降低CO在催化剂上的吸附强度和吸附量, 又能降低甲酸分解的速率, 从而减弱CO的毒化作用.