Texture and catalytic properties of palladium supported on thermally expanded natural graphite

Data about preparation and properties of palladium catalysts on porous supports prepared by intercalation and subsequent thermal expansion of natural graphite are presented. Some relations between the structure of the graphite support, the state of supported palladium and its catalytic properties in the model reaction of cyclohexene liquid-phase hydrogenation were established. This revised version was published online in June 2006 with corrections to the Cover Date.     

Self-regeneration of activated carbon modified with palladium catalyst for electrochemical dechlorination

Catalyst regeneration and the retention of high catalytic activity are still the critical issues in environmental application.A novel fluidized gas-liquid-solid electrochemical reactor was developed to simultaneously remove chlorinated pollutants and in situ regenerate the spent catalyst.Activated carbon modified with palladium catalyst (AC-Pd) was prepared for electrochemical dechlorination.For the 4-chloropbenol wastewater of initial concentration 200 mg L~(-1),the removal efficiency could nearly reach 100% in less than 30 min.Catalytic activity of AC-Pd catalyst was preserved effectively even in consecutive cycling run without special regeneration.OH radicals,generated by electrochemical reaction,played a critical role in self-regeneration of AC-Pd.High catalytic activity of spent AC-Pd catalyst provided an attractive alternative in wastewater treatment.     

利用石墨烯-炭黑组成的二元碳载体增强甲酸在钯催化剂上电化学氧化的活性

本文采用"一锅法"将氧化石墨烯(GO)、炭黑(C)和钯离子用NaBH4共还原,制备了石墨烯-炭黑二元载体(Gr-C)负载的钯催化剂(20%Pd/Gr-C),用于催化甲酸的电氧化反应.电化学测试结果表明,前驱体GO和C的质量比为3:7的Pd/Gr0.3C0.7催化剂催化活性最好,它的峰电流密度(102.14 mA mgPd-1)约为Pd/C催化剂(34.40 mA mgPd-1)的3倍,为钯/石墨烯催化剂(Pd/Gr,38.50 mA mgPd-1)的2.6倍.甲酸在Pd/Gr0.3C0.7催化剂电极直接氧化时的峰电位比Pd/C催化剂的峰电位负移约120 mV,比Pd/Gr催化剂的峰电位负移约70 mV.采用透射电子显微镜(TEM)、扫描电子显微镜(SEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)、拉曼光谱、电感耦合等离子发射光谱(ICP-AES)等手段对催化剂进行了表征.从SEM图像可以观察到,球形的炭黑团簇聚集在具有褶皱的石墨烯面上,形成了炭黑团簇/石墨烯三维立体结构,有效地抑制了相邻石墨烯层在范德华力作用下的吸引聚集和堆叠造成的石墨烯表面积减小,减小了单层石墨烯叠合成为多层石墨所造成的导电性损失,避免了相邻石墨烯片叠合形成封闭空间,有助于反应物和产物分子的运动.载体的三维结构使反应物分子更容易到达钯纳米粒子,有利于催化性能的提高.XPS结果也证实了二元Gr-C载体对Pd催化的促进作用.Pd/Gr0.3C0.7催化剂的Pd 3d5/2峰发生了右移,表明Pd 3d电子结合能正移,Pd 3d电子云密度降低.具有较低的3d电子云密度的Pd不易与甲酸氧化过程中吸附的中间体(COOH)ads结合,钯催化剂上(COOH)ads表面覆盖率降低,从而使甲酸更容易直接脱氢氧化生成CO2,有利于甲酸通过直接途径进行电化学氧化.与Pd/C,Pd/Gr相比,Pd/Gr0.3C0.7催化剂对甲酸电氧化有最好的催化活性.Pd/Gr0.3C0.7催化剂优异的催化活性可归因于其内在的三维纳米结构:炭黑团簇有效地抑制了石墨烯纳米片的聚集,保持了其大的比表面积和高导电性,促进了反应物和产物分子的运动.此外,Pd纳米粒子与二元载体之间的强相互作用降低了Pd的3d电子云密度,使甲酸氧化主要经直接途径进行.本文证实了钯金属和石墨烯-炭黑二元载体之间的强相互作用,提供了简单和高性价比的方法以提高钯基催化剂的活性,有利于工业化的应用.     

Hydrogenation of carbon monoxide over technetium catalysts

Supported Tc catalysts are active in CO hydrogenation, their activity depending on the nature of the support. The reaction proceeds predominantly toward methane formation. All catalysts studied yielded very little C₂ and C₃ hydrocarbons. The thermal desorption data indicate that the CO strongly bound to the substrate is responsible for CH₄ formation.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1507–1511, July, 1992.     

Lactose oxidation over palladium catalysts supported on active carbons and on carbon nanofibres

Liquid-phase lactose oxidation was investigated over supported Pd/C and Pd-carbon nanofibre catalysts, which were characterized by several methods. A complex relationship between catalyst activity and catalyst acidity was established, i.e. optimum catalyst acidity resulted in the highest activity in lactose oxidation. In-situ catalyst potential measurements during lactose oxidation gave information about the extent of accumulation of oxygen on the metal surface. These results could be correlated with catalyst deactivation, which was extensive over the most acidic catalysts at low reaction temperatures. Selectivity for the desired product, lactobionic acid, was a maximum of approximately 83% at 93% conversion. The main side-product was lactulose formed via isomerisation of lactose. Lower selectivity toward lactobionic acid was obtained when the rate of oxidation of lactose was low.     

不同MgO载体对合成低碳烯烃用铁锰基催化剂的影响

采用共沉淀法、硝酸盐热分解法制备的MgO和商品MgO为载体,使用共浸渍法制备了系列FeMn/MgO催化剂,以CO加氢合成低碳烯烃为模型反应,对不同催化剂的反应性能进行了考察,采用X射线光电子能谱、N2物理吸附、X射线物相分析、程序升温还原等表征技术对催化剂的结构和性能进行了表征。结果表明,采用共沉淀法制备的MgO载体比表面积最大,达到203.5m²/g,以此为载体制备的催化剂取得了最优的CO加氢合成低碳烯烃性能。在340℃、2.0MPa、1600h^-1的反应条件下,CO转化率达到91.36%,C₂⁼～C₄⁼选择性为58.48%。催化剂的比表面积大,活性组分分布均匀且在表面含量高及低温还原性能的明显改善是其具有优异的催化性能的重要原因。     

Adsorption of methyl mercaptan on surface modified activated carbon

The influence of surface modification of activated carbon on the adsorption of methyl mercaptan in N(2) was investigated. The modification of the activated carbon was carried out by treatment with HNO(3)/H(2)SO(4) solutions, heat-treatment in Ar, and adsorption of cetylamine. Acid-treatment increased the adsorption of methyl mercaptan compared with the original activated carbon, and the adsorbed amounts increased with ratio of H(2)SO(4) in HNO(3)/H(2)SO(4) solutions. This result suggests that hydrogen bonding between acidic groups formed by acid-treatment and thiol groups of methyl mercaptan plays a role in adsorption of methyl mercaptan on activated carbon.     

Copolymerization of carbon monoxide and norbornadiene with a palladium catalyst

Carbon monoxide (CO) and norbornadiene (NBD) with Pd(CH₃CN)₄(BF₄)₂ were copolymerized under various conditions at 50°C. Elemental analysis, infrared spectra, UV, Raman, and NMR spectra showed that the copolymers contained both ketone and unsaturated ring structures. Bidentate nitrogen ligands and phosphorus ligands proved to be more effective at stabilizing catalytic activity than monodentate arsenic ligands or phosphorus ligands. Methanol, protic acid, and an oxidant served as the coinitiator and chain transfer agent, respectively. X-ray diffraction analysis showed the copolymer to be partially crystalline. Thermogravimetric analysis showed that the TG curve for the NBD/CO copolymer has two stages with two maxima peaks at 251 and 470°C. This phenomenon was probably due to increased instability of the copolymers as CO content is increased. Hydrogenation of norbornadiene/CO copolymer with LiAlH₄ and Pd/C in THF yields a hydroxyl-containing polymer and norbornene/CO copolymer, respectively. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1157–1166, 1997     

Palladium-ceria catalysts: Metal-support interactions and reactivity of palladium in selective hydrogenation of but-1-yne

The influence of palladium-ceria interactions on the reactivity of palladium in but-1-yne hydrogenation has been investigated and compared with previous results obtained on alumina. The main differences from Pd-alumina catalysts are (i) the enhancement of the turnover frequency ascribed to electron transfer from ceria to Pd, (ii) the diminution of the selectivity to but-1-ene, attributed to hydrogen spillover.     

Catalytic activity of palladium supported on single wall carbon nanotubes compared to palladium supported on activated carbon Study of the Heck and Suzuki couplings, aerobic alcohol oxidation and selective hydrogenation

Nanoparticles (2–10 nm) of palladium have been deposited on single wall carbon nanotubes (SWNT) by spontaneous reduction from Pd(OAc)₂ or from oxime carbapalladacycle. These catalysts exhibit higher catalytic activity than palladium over activated carbon (Pd/C) for the Heck reaction of styrene and iodobenzene and for the Suzuki coupling of phenylboronic and iodobenzene. This fact has been attributed as reflecting the dramatic influence of the size particle on the activity of the palladium catalyst for CC bond forming reactions as compared to other reaction types less demanding from the point of view of the particle size. Thus, in contrast to the Heck and Suzuki reactions, Pd/C is more active than palladium nanoparticles deposited on SWNT for the catalytic oxidation by molecular oxygen of cinnamyl alcohol to cinnamaldehyde and for the hydrogenation of cinnamaldehyde to 3-phenylpropionaldehyde.     

Synthesis of carbon nanostructures on the Fe-Mo catalysts supported on modified SiO2

Carbon nanostructures were synthesized by the pyrolysis of an CH₄-H₂ mixture. The synthesis was carried out on the Fe-Mo catalysts supported on the SiO₂ surface by high-frequency diode sputtering or chemical deposition from a solution of a heterometallic carbonylchalcogenide complex. Structure features of the formed carbon nanostructures affected by the size of catalytic particles, temperature of the process, and composition of the gas mixture were revealed. The presence of sulfur in the catalyst composition results in the formation of nanofibers with the bamboo-like structure. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1372–1376, August, 2006.     

助剂Fe和反应修饰剂修饰的Ru催化剂上苯选择加氢制环己烯

共沉淀法制备了Ru-Fe(x)催化剂,并利用X射线衍射(XRD)、X射线荧光光谱(XRF)、N2物理吸附和透射电镜等手段对催化剂进行了表征.结果表明,Ru-Fe(x)催化剂中助剂Fe以Fe3O4形式存在.单独Fe3O4并不能提高Ru催化剂的环己烯选择性.但在加氢过程中Fe3O4可与反应修饰剂ZnSO4反应生成(Zn(OH)2)3(ZnSO4)(H2O)x(x=1 or 3).化学吸附的(Zn(OH)2)3(ZnSO4)(H2O)x(x=1 or 3)在提高Ru催化剂环己烯选择性中起着关键作用.此外,Ru-Fe(x)催化剂的性能还与浆液中的Zn2+浓度和pH值有关.在0.61 mol/L ZnSO4溶液中Ru-Fe(0.47)催化剂不但给出了56.7%的环己烯收率,而且具有良好的稳定性和重复使用性能.化学吸附在Ru表面的Fe2+同样能提高Ru催化剂的环己烯选择性.在0.29 mol/L和0.61 mol/L FeSO4溶液中Ru-Fe(0.47)催化剂上化学吸附Fe2+量近似,性能近似.因为Fe2+和Zn2+性质的差异,在0.29 mol/L和0.61 mol/L FeSO4溶液中Ru-Fe(0.47)催化剂的环己烯选择性分别低于在同浓度的ZnSO4溶液中的.     

Surface structural characterization of highly porous activated carbon prepared from corn grain

A novel corn grain precursor was used for the preparation of activated carbon by chemical activation. The detailed investigation of the porosity development in the prepared activated carbon was done by altering the various activation conditions such as the activation temperature, activation time and ratio between the powdered form of carbonized corn grain char and KOH. The surface characteristics including the surface roughness of all the activated carbon samples were evaluated from the analysis of nitrogen (N₂) adsorption isotherm data. At the maximum of 2978 m²/g, a super surface area having the corn grain‐based activated carbon (CG‐AC) was synthesized by using the following conditions: 1/4 ratio of powdered form of carbonized corn grain char/KOH; 800 °C; and 4 h. The possibility of preparing highly porous activated carbons with controlled porosity by varying different activation conditions was found from the pore size distribution results. In particular, the domination of the ratio between the powdered form of carbonized corn grain char and KOH on the porosity development was high compared to the activation temperature and activation time. In addition, the surface roughness calculated from the surface fractal dimension indicates the decrease of surface roughness with increasing activation conditions. Copyright © 2009 John Wiley & Sons, Ltd.     

Activity of palladium on charcoal catalysts in cross-coupling reactions

Comparison of the activity of several commercially available Pd/C catalysts in C-C, C-N, and C-S bond forming cross-coupling reactions has demonstrated the importance of the choice of the catalyst source. Investigations showed marked difference in activity between the catalysts. Moreover, the catalytic activity of each catalyst varies with respect to the coupling. The first Pd/C catalyzed Hiyama coupling is reported.     

聚苯胺-改性木质素磺酸钠复合材料基活性炭负载Pd催化剂对甲酸氧化的催化性能

将聚苯胺/改性木质素磺酸钠复合材料在不同炭化温度下进行处理得到活性炭材料,利用红外光谱、拉曼光谱、比表面积分析和扫描电镜等手段对其结构和表面性质进行了表征。通过液相还原方法将Pd纳米颗粒负载在所制备的活性炭材料上,获得Pd/C催化剂用于甲酸氧化,并采用X射线衍射、透射电镜和电化学测试等方法对该Pd/C催化剂进行表征。结果表明,以800℃下炭化得到的活性炭材料为载体所制备的Pd-AC800催化剂其催化性能最优;Pd粒径为5.4 nm,电化学活性面积为53.78 m²/g。由于在该催化剂上甲酸氧化通过直接途径进行,Pd-AC800可用作直接甲酸燃料电池的催化剂。     

Effects of a chemically modified multiwall carbon nanotubes on electro-optical properties of PDLC films

Polymer dispersed liquid crystal (PDLC) films are fabricated by well-known polymerization-induced phase separation method. In this paper, the dispersion of multi-walled carbon nanotubes (MWCNT) in liquid crystals has been enhanced by chemical modification and we have investigated their effects on the morphology, electro-optical properties and conductivity of the PDLC films. Results indicated that the threshold voltage and the saturation voltage of PDLC films decreased with the increase of the doping concentration of MWCNT or chemically modified MWCNT, because carbon nanotubes can enhance the electric field by reducing the resistivity of the medium and increasing the capacitance of the cells. It can be viewed obviously that the contrast ratio of the PDLC films doped with the chemically modified MWCNT is higher than that of the MWCNT.     

Synthesis and characterization of nickel catalysts supported on different carbon materials

Nickel catalysts supported on various carbon materials such as multiwall carbon nanotubes, shortened length carbon nanotubes, graphite and amorphous carbon were synthesized, characterized and tested in cyclohexene hydrogenation reaction. We have found that carbon nanotube supports are superior to graphite and amorphous carbon both in terms of catalytic activity and stability.     

PVC-丁二酮肟膜修饰玻碳电极及其在钯的分析中的应用

制备了 PVC-丁二酮肟修饰电极 ,研究了膜电极的响应过程和钯在此电极表面的伏安特性。用微分脉冲伏安法测定 ,钯在 4.76× 1 0 -9mol/ L～ 9.53×1 0 -8mol/ L 的浓度范围内 ,电流与浓度的对数成线性关系 ,检出限为 1 .52×1 0 -9mol/ L。此法可用于矿样中钯的测定。     

Preconcentration of traces of gold, silver and palladium on activated carbon and its determination in geological samples by flame AAS after wet ashing

A simple, rapid and cost effective preconcentration method is described for the determination of traces of gold (Au), silver (Ag) and palladium (Pd) in geological samples by flame atomic absorption spectrophotometry (AAS). The method is based on sorption of analytes (Au, Ag and Pd) on powdered activated carbon (AC) at pH 1 in hydrochloric acid (HCl) medium. The samples are decomposed by aqua regia — HCl treatment. The quantitative sorption (better than 92%) of analytes is obtained on AC (in absence of complexing agent), by simply manipulating optimal conditions. The unique feature of the method is, the analytes are recovered quantitatively from AC by oxidizing and completely solubilising the carbon using concentrated nitric acid (HNO₃) and perchloric acid (HClO₄) i.e. by wet ashing. The method of wet ashing has several advantages over conventional dry ashing. The accuracy of the method is evaluated by analysing, five Canada centre for mineral and energy technology (CANMET) standards; MA-3, MA-1b, FER-1, SU-1A, and CPB-1. In addition, ASK-3 and one inhouse standard, kolar gold field (KGF) samples was also analysed. As no standard for Pd is available, its accuracy was evaluated by standard addition method. The method was applied on numerous geological samples for the determination of Au, Ag and Pd down to 0.1 ppm (based on 10 g sample) within ±10% R.S.D. (n=5). The method could easily be adopted by any laboratory as the inputs are minimal (AC), inexpensive and easily available.     

Carbon nanofiber supported palladium catalyst for liquid-phase reactions: An active and selective catalyst for hydrogenation of cinnamaldehyde into hydrocinnamaldehyde

Carbon nanofibers (CNFs) prepared by decomposition of ethane over a Ni/alumina catalyst, are used as support for palladium clusters. The carbon support displays a mean diameter of 40–50 nm, lengths up to several tens of micrometers, as highlighted by transmission electron microscopy (TEM) observations and a specific surface area of about 50 m²/g. The spheroidal palladium particles have a relatively homogeneous and sharp size distribution, centered at around 4 nm. This novel Pd/carbon nanofiber catalyst displays unusual catalytic properties and is successfully used in the selective hydrogenation of the C=C bond in cinnamaldehyde at a reaction temperature of around 80°C, under continuous hydrogen flowing at atmospheric pressure. The high performances of this novel catalyst in terms of efficiency and selectivity are, respectively, related to the inhibition of the mass-transfer processes over this non-porous material and to peculiar palladium–carbon interactions. It is concluded that the absence of microporosity in the carbon nanofibers favours both the high activity and selectivity which is confirmed by comparison with the commercially available high surface area charcoal supported palladium catalyst.