PEDOT-supported Pd nanoparticles as a catalyst for hydrazine oxidation

Composite poly-3,4-ethylenedioxythiophene (PEDOT)/palladium (Pd) films were obtained by chemical deposition of dispersed palladium nanoparticles into PEDOT conducting polymer matrix. The amounts of palladium particles incorporated into PEDOT films were estimated by electrochemical quartz crystal microbalance measurements. It was shown that palladium loading depends on the time a PEDOT film is exposed in the solution, containing Pd(II)-ions, on the concentration of Pd(II) ions and the film thickness. X-ray photoelectron spectroscopy data have confirmed the presence of metallic palladium in the polymer. The morphology of pristine and composite films as well as the size of Pd nanoparticles and their distribution were characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). From SEM images, it was found that Pd particles decorated PEDOT globular structures as quasi-spherical particles, and their mean size was dependent on synthesis conditions. The nanoparticles were non-uniformly dispersed on the polymer surface. The comparison of TEM images of composite PEDOT/Pd films obtained for different times of metal loading was made. The remarkable effect of loading time on the size of particles has been established: the mean size of dominating palladium particles was close to 6–10 nm for 30 s of metal deposition, and it was getting larger with the increase of deposition time (close to 15–30 nm for 120 s). It is most likely that with prolongation of synthesis time, the deposition of palladium predominantly proceeds on the already deposited palladium clusters, resulting in the extension growth of their size. Catalytic properties of PEDOT/Pd composite films were studied in respect to hydrazine oxidation by cyclic voltammetry and voltammetry on rotating disk electrode. The obtained data allow to conclude that the process of hydrazine oxidation on PEDOT/Pd composites takes place predominantly on palladium particles, located on the surface or in the near-surface layers of the polymer. The diffusion nature of the limiting current of hydrazine oxidation on composite PEDOT/Pd film in phosphate buffer solution рН = 6.86 was confirmed, and hydrazine diffusion coefficient was calculated. The increase of the limiting currents of hydrazine oxidation with the increase of Pd deposition time was observed, resulting from the increase of the active surface area of palladium particles, acting as microelectrodes. The electroanalytical applications of these nanocomposite materials for the determination of hydrazine were demonstrated.     

Sensitive and selective determination of hydrazine using glassy carbon electrode modified with Pd nanoparticles decorated multiwalled carbon nanotubes

A glassy carbon electrode modified with palladium nanoparticles decorated multiwalled carbon nanotubes (GCE/nanoPd-MWCNTs) was fabricated. Incorporation of palladium nanoparticles onto the carbon nantube surface by thermal decomposition of palladium acetate led to the fabrication of a sensor with a significant decrease in hydrazine electrooxidation potential. The sensor exhibited low detection limits, high sensitivity and selectivity, rapid response, and good stability toward hydrazine detection.     

弱磁性Co0.85Se纳米片负载碳纳米管作为电催化析氢催化剂

氢气是一种环境友好可再生的清洁能源,电解水无疑是一种很好的制氢方法.然而,电催化分解水析氢受到其缓慢的动力学过程、较低的催化性能和较差的稳定性的限制.为了使整个过程更节能,具有高电流密度和低的过电势的高效电催化剂被广泛研究.非化学计量相硒化钴(Co0.85Se)作为一种重要的金属硫属化合物具有优异的催化性能而广受关注.但是低维的Co0.85Se活性位点少,分散性差,电子传递能力低,导致其电催化剂活性差.多壁碳纳米管(MWCNTs)具有多种电性能,包括金属导电性和电子存储能力等.因此,MWCNTs的特殊结构和高导电性可以有效地促进电子从电催化剂向碳纳米管的转移,实现高效电分解水制氢性能.本文在不使用表面活性剂和模板的情况下,通过一步水热溶剂热法合成弱磁性Co0.85Se纳米片负载碳纳米管电催化剂.采用磁滞回线研究Co0.85Se和MWCNTs/Co0.85Se的磁性能,结果表明其有弱顺磁性,Co0.85Se纳米片之间的空间距离增强导致粒子间偶极相互作用减弱,从而使MWCNTs/Co0.85Se纳米复合材料的矫顽力值增加到158 Oe.随着微晶尺寸的减小和纳米颗粒间距的增大,MWCNTs/Co0.85Se催化剂的比表面积增大,有利于提高其电催化活性.扫描电镜和透射电镜展示出Co0.85Se纳米片分散性较差,且团聚现象严重,而MWCNTs/Co0.85Se纳米复合催化剂显示Co0.85Se纳米片均匀分散在MWCNTs表面,且纳米片尺寸明显减小,有利于Co0.85Se纳米片暴露更多的活性位点.线性扫描伏安曲线测量表明,在酸性溶液中Co0.85Se纳米片在电流密度为10 mA cm?2时,其过电势为319 mV(vs.RHE),30 wt%MWCNTs/Co0.85Se的过电势为266 mV(vs.RHE).Co0.85Se和MWCNTs/Co0.85Se的Tafel斜率分别为92.6和60.5 mV dec?1.此外,MWCNTs/Co0.85Se的电流交换密度(j0)为0.07 mA cm?2.较小的Tafel斜率和高的电流交换密度表明,MWCNTs/Co0.85Se具有良好的反应动力学和快速的质子分离速率.交流阻抗谱表明MWCNTs/Co0.85Se比Co0.85Se电阻更小,电子传输速率更快.电化学活性表面积与双电层在固液界面处的电容测量值成正比.结果显示,30 wt%MWCNTs/Co0.85Se的双电层电容为0.22 mF cm^-2,高于Co0.85Se和15 wt%的rGO/Co0.85Se(0.04 mF cm^-2,0.17 mF cm^-2),这表明较大的电化学活性表面积有利于析氢反应进行.30 wt%MWCNTs/Co0.85Se的循环稳定测试表明其具有较好的稳定性.综上,本文介绍了通过一步水热法合成具有弱磁性的Co0.85Se和MWCNTs/Co0.85Se电催化剂,碳纳米管作为一种高导电性材料被引入Co0.85Se纳米片中以减少Co0.85Se的团聚,使Co0.85Se的活性位点增加,进而提高电催化制氢性能.     

Nanosizing low-loading Pd on phosphorus-doped carbon nanotubes for enhanced HCOOH oxidation performance

Pd possesses higher activities than Pt for HCOOH oxidation as anode catalysts. However, because of the ease of Pd oxidation, the electrocatalytic stability of Pd is not satisfactory. Herein, low-loading Pd with high dispersions and narrow size distributions is nanosized on phosphorus-doped carbon nanotubes and applied as efficient anode catalysts for HCOOH oxidation. Surface analyses reveal that the decreased Pd3d electron density caused by electron transfer from Pd to P-doped CNTs enhances the HCOOH oxidation performance.     

Efficient anchorage of Pt clusters on N-doped carbon nanotubes and their catalytic activity

We report an efficient method for anchoring Pt clusters (e.g., 6 nm in size) on the surfaces of N-doped multi-walled carbon nanotubes (MWNTs-CN_x) using a relatively simple method consisting of a hydrothermal treatment of Na₂[PtCl₆] · 6H₂O and N-doped nanotubes dispersed in acetic acid. The catalytic properties of this material were evaluated finding that the conversion of cinnamaldehyde using Pt-coated MWNTs-CN_x could increase up to 6 times with respect to that obtained for uncoated MWNTs-CN_x and pure carbon CNTs. Therefore, we envisage this material could be either used as an efficient catalyst or as a sensor.     

氮掺杂碳纳米管包覆碳化硅作为不含金属的催化剂(英文)

A hierarchical metal-free catalyst consisting of nitrogen-doped carbon nanotubes decorated onto a silicon carbide (N-CNTs/SiC) macroscopic host structure was prepared. The influence of N-CNTs incorporation on the physical properties of the support was evaluated using different characterization techniques. The catalyst was tested as a metal-free catalyst in the selective oxidation of H2S and steam-free dehydrogenation of ethylbenzene. The N-CNTs/SiC catalyst exhibited extremely good desulfurization performance compared to a Fe2O3/SiC catalyst under less conducive reaction conditions such as low temperature, high space velocity, and a low O2-to-H2S molar ratio. For the dehy-drogenation of ethylbenzene, a higher dehydrogenation activity was obtained with the N-CNTs/SiC catalyst compared to a commercial K-Fe/Al2O3 catalyst. The N-CNTs/SiC catalyst also displayed good stability as a function of time on stream for both reactions, which was attributed to the strong anchoring of the nitrogen dopant in the carbon matrix. The extrudate shape of the SiC support allowed the direct macroscopic shaping of the catalyst for use in a conventional fixed-bed reactor without the problems of catalyst handling, transportation, and pressure drop across the catalyst bed that are encountered with nanoscopic carbon-based catalysts.     

CeO2纳米管负载Pd纳米颗粒催化CO低温氧化

高效负载型Pd催化剂的制备及其在CO低温氧化反应中的机理探究是近年来的研究热点.普遍认为,Pd催化剂上的CO氧化反应遵循Langmuir-Hinshelwood机理:首先,CO吸附于Pd物种表面;然后,CO与催化剂表面的晶格氧发生反应转化为CO2,反应发生在金属-载体界面.另外,高分散的Pd活性物种有利于CO氧化反应.同时载体的形貌、暴露的晶面、氧空位以及孔结构等都是影响催化剂活性的重要因素.CeO2纳米管具有独特的管状特征和较高的比表面积,是一种潜在的CO低温氧化催化剂载体.本文利用乙醇还原法,以CeO2纳米管为载体,制备不同Pd含量的Pd/CeO2-nanotube纳米催化剂,并利用N2吸附脱附、X射线衍射(XRD)、透射电子显微镜(TEM)、CO程序升温脱附(CO-TPD)、X射线光电子能谱(XPS)等表征手段,探索纳米催化剂载体形貌对CO氧化反应活性的影响.氮气吸脱附结果表明,Pd/CeO2-nanotube具有较高的比表面积(58.0 m2/g),且存在介孔结构.XRD表征发现,Pd/CeO2-nanotube的衍射峰对应立方萤石型结构的CeO2的(111),(200),(220),(311)等品面.TEM结果表明,Pd/CeO2-nanotube具有均匀的纳米管形貌,其外径为40-60 nm,Pd纳米颗粒均匀分散在其表面.CO-TPD结果表明,Pd/CeO2-nanotube在1 10℃附近具有很强的脱附峰,在370℃和600℃附近分别具有较宽和较弱的脱附峰,这表明该催化剂具有较多的吸附位,且具有很强的CO吸附能力;CO不可逆吸附量计算结果表明,该催化剂上的Pd具有很高的表面分散度(23.3％),Pd颗粒尺寸为7.3 nm.XPS表征显示,Pd以pd2+的形式分散于CeO2纳米管的表面,且与载体发生相互作用,存在Pd-O-Ce键;同时该催化剂表面存在丰富的Ce3+,为反应提供更多的氧空位.0.9Pd/CeO2-nanotube纳米催化剂在CO氧化反应中表现出优良的活性,能在100℃实现CO的完全转化;通过计算发现,该催化剂具有较高的TOF值(0.63 s-1),由Arrhenius 曲线可得到该催化剂的活化能为26.5 kJ/mol.综上可见:金属活性组分的尺寸和分散度、载体的结构特征、CO吸附能力以及金属-载体间的相互作用决定催化剂的性能.Pd/CeO2-nanotube的高比表面积有利于Pd的分散;其强CO吸附能力有利于CO吸附于Pd物种表面;催化剂表面丰富的Ce3+能为反应提供更多的氧空位,Pd-O-Ce键的形成能增强金属-载体间的相互作用,有利于CO与催化剂表面品格氧发生反应.同时催化剂介孔结构有利于反应气体和产物气体的吸附和扩散,因此,Pd/CeO2-nanotube纳米催化剂在CO氧化反应中表现出优良的活性.     

Electrocatalytic oxidation of hydrazine at a glassy carbon electrode modified with nickel ferrite and multi-walled carbon nanotubes

A hydrothermal technique was used to synthesize nickel ferrite nanoparticles (NF-NPs) deposited on multi-walled carbon nanotubes (MWCNTs). The material was characterized by scanning electron microscopy, energy dispersive spectrometry, and X-ray powder diffraction which showed that the NF-NPs are located on the surface of the carboxylated MWCNTs. The material was used to modify a glassy carbon electrode which then was characterized via cyclic voltammetry, electrochemical impedance spectroscopy, and amperometry. The electrode displays strong electrochemical response to hydrazine. A potential hydrazine sensing scheme is suggested.

掺氮纳米炭球担载高分散钯纳米催化剂的制备及其苯甲醇氧化性能(英文)

负载型贵金属纳米催化剂中的金属纳米粒子易发生团聚或流失,因此提高金属活性组分的分散性和稳定性很重要。我们报道了一种制备高分散钯纳米催化剂的方法,通过浸泡法将氯钯酸前驱体负载到苯并噁嗪聚合物上,再经过惰性气氛一步热解得到纳米炭球担载钯催化剂.催化剂性能通过温和条件下苯甲醇氧化反应进行评价.经过500℃热处理制备的催化剂,从TEM图可以看出Pd纳米粒子均匀分散在载体上,尺寸大小约为3 nm,这是由于载体和钯活性组分的配位作用有利于提高钯纳米粒子的分散性和稳定性.通过调控金属负载量及负载时间,尽可能地实现活性组分分布在载体外表面,制备的催化剂上最高TOF为690 h-1.此催化剂同时具有较好的循环稳定性,失活后的催化剂经过200℃焙烧即可实现再生.     

Synthesis of diameter controlled carbon nanotubes using self-assembled catalyst nanoparticles

Vertically-aligned diameter-controlled carbon nanotubes (CNTs) are synthesised by the plasma enhanced chemical vapour deposition (PECVD) method using multi-layers of self-assembled catalytic ligand-coated iron oxide nanoparticles. We find that the mono-dispersed nanoparticles play a vital role for the production of diameter-controlled CNTs. A new growth model is also proposed based on the experimental results. The present results may make a great contribution to the development and design of mechanical, electronic and biomedical devices, in which diameter-controlled CNTs are utilised.     

A new recyclable Pd catalyst supported on vertically aligned carbon nanotubes for microwaves-assisted Heck reactions

Palladium supported on vertically aligned multi-walled carbon nanotubes (Pd/VA-CNTs) is used as catalyst for the C-C coupling reactions of p-iodonitrobenzene with styrene and ethyl acrylate under microwaves irradiation. Pd/VA-CNTs catalyst exhibits higher activity compared to Pd supported on activated charcoal, under the same reaction conditions. Due to the microwaves irradiation, the kinetics of the reaction is strongly accelerated compared to that obtained with a traditional heating mode. The macroscopic form of aligned CNTs support allows an easy recovery of the catalyst, avoiding a costly post-reaction filtration. In addition, the interaction between the active phase and the support leads to the negligible leaching of palladium during recycling tests. The observed results indicate that Pd/CNTs is a recyclable and stable heterogeneous catalytic system.     

Molecular level dispersed Pd clusters in the carbon walls of ordered mesoporous carbon as a highly selective alcohol oxidation catalyst

Ordered mesoporous carbon containing molecular-level dispersed Pd clusters in the carbon walls can be synthesized by the nanocasting pathway, which shows high selectivity for the oxidation of alcohols to aldehydes.     

苯甲酰肼在多壁碳纳米管修饰玻碳电极上的电催化氧化及其电化学动力学性质

研究了苯甲酰肼(BH)在MWCNT/GCE上的电化学行为。实验结果表明,BH在GCE上的直接电化学氧化十分迟缓,无氧化峰出现,但在MWCNT/GCE上BH在0.20 V处出现了一个不可逆氧化峰,且峰电流大幅度增大,表明MWCNT/GCE对BH电化学氧化具有良好的催化作用。同时用计时库仑法(Chro-nocoulometry,CC)和计时电流法(Chronoamperometry,CA)测定了电极过程动力学参数:扩散系数D=8.73×10-5cm2.s-1,电子转移系数α=0.85,电极反应速率常数kf=1.45×10-3s-1。稳态电流-时间实验结果表明,电流响应信号随其浓度成比例增长,响应时间小于6 s,最低响应浓度为1×10-6mol/L。该方法可用于BH电化学定量测定。     

Co3O4-decorated carbon nanotubes as a novel efficient catalyst in the selective oxidation of benzoins

An efficient and facile air oxidation of benzoins in the presence of the heterogeneous catalyst, Co₃O₄–CNTs nanocomposite, has been developed. It thus constitutes a very simple, clean, economical and selective method for the aerobic preparation of benzils from the corresponding benzoins. The catalyst can be re-used a number of times without losing its catalytic activity to a greater extent.     

Novel preparation of polyphosphazene-coated carbon nanotubes as a Pt catalyst support

This study reports a noncovalent functionalization of MWCNTs with a fluorinated cross-linked polymer coating of poly[cyclotriphosphazene-co-(4,4'-(hexafluoroisopropylidene)diphenol)] and their application as the support of Pt for electrocatalytic oxidation of methanol.     

Partially unzipped carbon nanotubes as a superior catalyst support for PEM fuel cells

Partially unzipped carbon nanotubes prepared by strong oxidation and thermal expansion of carbon nanotubes were explored as an advanced catalyst support for PEM fuel cells. The unique hybrid structure of 1D nanotube and 2D double-side graphene resulted in an outstanding electrocatalytic performance.