Highly Porous Amidoximed Carbon Nanofibers Supported Palladium(0) Nanoparticle Catalyzed Heck Reaction

Highly porous amidoximed carbon nanofibers(AOCNFs), which were fabricated via a conventional electrospinning technique followed by chemically modification, impregnation-reduction and carbonization process, had been used for the immobilization of palladium nanoparticles(Pd NPs) catalyst. During the carbonization process, polystyrene(PS) was selectively decomposed from bicomponent fibers, generating porous fibers. Fourier transform infrared spectroscopy(FTIR) result revealed the functional groups on PAN-PS fibers(PAN=polyacrylonitrile), AOPAN-PS fibers and AOCNFs; scanning electron microscopy(SEM) was used to observe the morphology of all stages of nanofibers; transmission electron microscopy(TEM) result gave the structure of through-hole morphology clearly visible and the dispersion of Pd NPs on the surface of nanofibers; and X-ray photoelectron spectra(XPS) confirmed that Pd nanoparticles on the surface of AOCNFs was of the metallic state. Moreover, the as-prepared catalyst exhibited high catalytic activity and efficient recycle for Heck coupling reactions between iodobenzene and acrylates.     

Templating effect of carbon nanoforms on highly cross‐linked imidazolium network: Catalytic activity of the resulting hybrids with Pd nanoparticles

Two different carbon nanoforms (CNFs), namely multi‐walled carbon nanotubes (MWCNTs) and carbon nanohorns (CNHs), have been chosen as support for the direct polymerization of a bis‐vinylimidazolium salt. Transmission electron microscopy analyses revealed a templating effect of the CNFs on the growth of the polymeric network, which perfectly covers their whole surfaces creating a cylindrical or spherical coating for MWCNTs and CNHs, respectively. Subsequently, the CNFs‐polyimidazolium have been used as stabilizers for Pd nanoparticles (Pd NPs), and the obtained materials have been characterized by means of analytical and spectroscopic techniques and then employed as easily recoverable and recyclable catalysts for Suzuki and Heck reactions. Quantitative conversions have been obtained in almost all the explored reactions, even employing low loading of catalyst (down to 0.007 mol%). Suzuki reactions were carried out in pure water under aerobic conditions. Both materials showed excellent activity and recyclability for the investigated C‐C coupling reactions, with the CNHs‐based material resulting slightly more active than the MWCNTs‐based one due to a higher superficial exposure of Pd NPs.     

Electrochemical Detection of Hydrazine Based on Electrospun Palladium Nanoparticle/Carbon Nanofibers

In this work, we developed an electrochemical method for the detection of hydrazine based on palladium nanoparticle/carbon nanofibers (Pd/CNFs). Pd/CNFs were prepared by electrospinning technique and subsequent thermal treatments. The electrocatalytic behaviors of Pd/CNFs modified glassy carbon electrode (Pd/CNF‐GCE) for hydrazine oxidation were evaluated by cyclic voltammetry (CV), an obvious and well‐defined oxidation peak appeared at ?0.32 V (vs. Ag/AgCl). The mechanism of the oxidation of hydrazine at Pd/CNF‐GCE was also studied, which demonstrated an irreversible diffusion‐controlled electrode process and a four‐electron transfer involved in the overall reaction. Furthermore, the wide linear range, low detection limit, good reproducibility and excellent storage stability were obtained utilizing differential pulse voltammetry (DPV).     

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.     

Palladium nanoparticles encapsulated in a metal-organic framework as efficient heterogeneous catalysts for direct C2 arylation of indoles

Highly dispersed palladium nanoparticles (Pd NPs) encapsulated in the mesoporous cages of the metal-organic framework (MOF) MIL-101(Cr) have been prepared by using the wetness impregnation method. The Pd NPs were characterized by powder X-ray diffraction (PXRD), N(2) adsorption, transmission electron microscopy, inductively coupled plasma atomic emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS). The particles size ((2.6±0.5) nm) of the obtained Pd NPs was in good agreement with the cage diameters (2.9 and 3.4 nm) of the MOF. The resulting Pd/MIL-101(Cr) catalyst exhibited extremely high catalytic activities in the direct C2 arylation of substituted indoles by using only 0.1 mol% of the Pd catalyst. Moreover, the catalyst is easily recoverable and can be reused several times without leaching into solution and loss of activity. The combination of the highly dispersible Pd NPs within the accessible mesoporous cages and the favorable adsorption of the aryl halides on MIL-101 are suspected to be the main reasons for the observed high activities of the Pd/MIL-101(Cr) catalyst in the direct C2 arylation of indoles.     

一维碳纤维承载AgX/TiO2(X=Br,I)三元复合材料的制备及光催化性能

利用静电纺丝技术结合高温煅烧过程制备碳纤维(CNFs)载体材料, 进一步通过溶剂热和化学反应过程获得AgX/TiO₂ /CNFs(X=Br, I)复合光催化剂. 利用X射线衍射(XRD)、 扫描电子显微镜(SEM)、 红外光谱(FTIR)等测试手段表征了材料的结构及形貌. 通过在可见光下降解甲基橙考察了催化材料的光催化性能. 结果表明, 该复合材料具有高吸附性、 良好的传导性以及较好的光敏性, 从而使其具有较好的可见光催化活性; 同时以一维碳纤维作为载体, 使其更容易分离、 回收, 更具有实际应用价值.     

Effect of carbon nanofiber microstructure on oxygen reduction activity of supported palladium electrocatalyst

Palladium electrocatalysts supported on carbon nanofibers (CNFs) with controlled microstructure or on activated carbon (AC) are prepared, and the effects of the carbon materials microstructure on the oxygen reduction reaction (ORR) properties of the electrocatalysts are investigated. The physical properties of the CNFs with different microstructure, i.e. platelet CNF (p-CNF) and fish-bone CNF (f-CNF), are characterized by high resolution transmission electron microscope and N₂ physisorption. From cyclic voltammetric studies, it is found that Pd/p-CNF and Pd/f-CNF are more active than Pd/AC. The effects of CNF microstructure on the ORR activities of Pd/f-CNF and Pd/p-CNF are discussed. The p-CNF has a higher ratio of edge atoms to basal atoms, and therefore Pd/p-CNF has more positive ORR onset reduction potential and ORR peak potential than Pd/f-CNF. The supports also have influences on the reaction process. The ORR is surface reaction controlled when Pd/AC is used, while it becomes diffusion control when Pd/f-CNF is used.     

Highly sensitive hydrogen peroxide sensor based on a glassy carbon electrode modified with platinum nanoparticles on carbon nanofiber heterostructures

We are presenting a sensor for hydrogen peroxide (H₂O₂) that is based on the use of a heterostructure composed of Pt nanoparticles (NPs) and carbon nanofibers (CNFs). High-density Pt NPs were homogeneously loaded onto a three-dimensional nanostructured CNF matrix and then deposited in a glassy carbon electrode (GCE). The resulting sensor synergizes the advantages of the conducting CNFs and the nanoparticle catalyst. The porous structure of the CNFs also favor the high-density immobilization of the NPs and the diffusion of water-soluble molecules, and thus assists the rapid catalytic oxidation of H₂O₂. If operated at a working voltage of −0.2 V (vs. Ag/AgCl), the modified GCE exhibits a linear response to H₂O₂ in the 5 μM to 15 mM concentration range (total analytical range: 5 μM to 100 mM), with a detection limit of 1.7 μM (at a signal-to-noise ratio of 3). The modified GCE is not interfered by species such as uric acid and glucose. Its good stability, high selectivity and good reproducibility make this electrode a valuable tool for inexpensive amperometric sensing of H₂O₂.

The Pt NPs/CNF heterostructure-based H₂O₂ sensor synergizes the advantages of both the conducting carbon nanofibers and the nanoparticle catalyst. The 3D structure of the nanofibers favor high density immobilization of the nanoparticles and penetration by water-soluble molecules, which assists the catalyic oxidation of H₂O₂. The sensor shows outstanding performance in terms of detection range, detection limit, response time, stability and selectivity.

     

The composite catalysts of Cu/CuxO nanoparticles supported on the carbon fibers were prepared for styrene oxidation reaction

In this paper a novel simple method for preparing two different catalysts with various‐valences copper was reported. Carbon nanofibers supported copper‐cuprous oxide nanoparticles (Cu‐Cu₂O NPs/CNFs) and copper oxide nanoparticles (CuO NPs/CNFs) through electrospinning, adsorption and reduction in the high‐pressure hydrogenation and the high‐temperature calcination methods. These catalysts were investigated by a series of characterizations and were applied in reaction in nitrogen atmosphere, which had a good catalytic activity and selectivity of benzaldehyde for the reaction. Above all, the new study has been certified clearly, in which Cu‐Cu₂O NPs/CNFs and CuO NPs/CNFs composite catalysts enhanced the generation of benzaldehydeand the excellent catalytic properties were exhibited.     

Properties of Pd–Ag/C catalysts in the reaction of selective hydrogenation of acetylene

Samples of Pd/C and Pd–Ag/C, where C represents carbon nanofibers (CNFs), are synthesized by methane decomposition on a Ni–Cu–Fe/Al₂O₃ catalyst. The properties of Pd/CNF are studied in the reaction of selective hydrogenation of acetylene into ethylene. It is found that the activity of the catalyst in hydrogenation reaction increases, while selectivity decreases considerably when the palladium content rises. The obtained dependences are caused by the features of palladium’s interaction with the carbon support. At a low Pd content (up to 0.04 wt %) in the catalyst, the metal is inserted into the interlayer space of graphite and the catalytic activity is zero. It is established by EXAFS that the main share of palladium in catalysts of 0.05–0.1 wt % Pd/CNF constitutes the metal in the atomically dispersed state. The coordination environment of palladium atoms consists of carbon atoms. An increase in the palladium content in a Pd/CNF catalyst up to 0.3 wt % leads to the formation of highly dispersed (0.8–1 nm) Pd particles. The Pd/CNF samples where palladium is mainly in the atomically dispersed state exhibit the highest selectivity in the acetylene hydrogenation reaction. The addition of silver to a 0.1 wt % Pd/CNF catalyst initially probably leads to the formation of Pd–Ag clusters and then to alloyed Pd–Ag particles. An increase in the silver content in the catalyst above 0.3% causes the enlargement of the alloyed particles and the palladium atoms are blocked by a silver layer, which considerably decreases the catalytic activity in the selective hydrogenation of acetylene.     

Palladium–cadmium sulfide nanopowder at oil–water interface as an effective catalyst for Suzuki–Miyaura reactions

A simple and effective strategy is described for the synthesis of Pd–CdS nanopowder by the reduction of an organopalladium(II) complex, [PdCl₂(cod)] (cod = cis ,cis ‐1,5‐cyclooctadiene), in the presence of CdS quantum dots (QDs) at a toluene–water interface. We investigated the impact of addition of CdS QDs on catalytic activity of Pd nanoparticles (NPs). The Pd–CdS nanopowder functions as an efficient catalyst for Suzuki–Miyaura reactions for the formation of carbon–carbon bonds. There is a high electron density on Pd NPs and due to their high electron affinity they behave as an electron scavenger from CdS increasing the rate of oxidative addition, which is the rate‐determining step of the catalytic cycle, and, just as we expect, the C─C coupling reaction with the Pd–CdS nanopowder is faster and occurs in less time than that with Pd nanocatalysts. Compared to classical reactions, this method consistently has the advantages of short reaction times, high yields in a green solvent, reusability of the catalyst without considerable loss of catalytic activity and low cost, and is a facile method for the preparation of the catalyst.     

CVD Growth of Carbon Nanotubes and Nanofibers: Big Length and Constant Diameter

Summary: We report mass production of carbon nanotubes (CNTs) and carbon nanofibers (CNFs) with relatively high length and aspect ratio. We synthesized carbon nanomaterials by chemical vapor deposition (CVD) of methane as the feeding gas on Fe/Mo nanoparticles that use alumina-aerogel support. Alumina-aerogel-supported Fe/Mo catalyst was prepared using sol-gel. Drying step performed using rotary evaporation and freeze-drying. CVD was performed using a quartz tube furnace. Samples were analyzed using scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and Raman spectroscopy.     

Palladium nanoparticles stabilized by chitosan/PAAS nanofibers: A highly stable catalyst for Heck reaction

Palladium chloride doped chitosan composite nanofibers were prepared by electrospinning with sodium polyacrylate (PAAS) as the co-spinning agent. The composite nanofibers are subsequently treated at elevated temperature to improve their solvent resistance. The Pd (II) cations inside the composite nanofibers were reduced into uniform palladium nanoparticles (Pd NPs) with mean diameter of ~4.93 nm. These Pd NPs inside the chitosan composite nanofibers exhibited excellent catalytic activity for Heck reactions of aromatic iodides with alkenes with yields over 85%. Moreover, due to the fibrous structure, this novel fibrous palladium catalyst could be readily recovered by simple filtration and reused for 18 times without loss of initial catalytic activity. It was found that the reactants could readily diffuse from the reaction solution to the active Pd NPs inside the nanofibers and the products could departure from composite fibers into the reaction solution, while the Pd NPs were tightly restricted inside the chitosan composite nanofibers.     

Selective Hydrogenation of Citral over a Carbon‐titania Composite Supported Palladium Catalyst

A novel carbon‐titania composite material, C/TiO₂, has been prepared by growing carbon nanofibers (CNFs) on TiO₂ surface via methane decomposition using Ni‐Cu as a catalyst. The C/TiO₂ was used for preparing supported palladium catalyst, Pd/C/TiO₂. The support and Pd/C/TiO₂ catalyst were characterized by BET, SEM, XRD and TG‐DTG. Its catalytic performance was evaluated in selective hydrogenation of citral to citronellal, and compared with that of activated carbon supported Pd catalyst. It was found that the Pd/C/TiO₂ catalyst contains 97% of mesopores. And it exhibited 88% of selectivity to citronellal at citral conversion of 90% in citral hydrogenation, which was much higher than that of activated carbon supported Pd catalyst. This result may be attributed to elimination of internal diffusion limitations, which were significant in activated carbon supported Pd catalyst, due to its microporous structure.     

Stabilization of Palladium Nanoparticles on Nanodiamond–Graphene Core–Shell Supports for CO Oxidation

Nanodiamond–graphene core–shell materials have several unique properties compared with purely sp²‐bonded nanocarbons and perform remarkably well as metal‐free catalysts. In this work, we report that palladium nanoparticles supported on nanodiamond–graphene core–shell materials (Pd/ND@G) exhibit superior catalytic activity in CO oxidation compared to Pd NPs supported on an sp²‐bonded onion‐like carbon (Pd/OLC) material. Characterization revealed that the Pd NPs in Pd/ND@G have a special morphology with reduced crystallinity and are more stable towards sintering at high temperature than the Pd NPs in Pd/OLC. The electronic structure of Pd is changed in Pd/ND@G, resulting in weak CO chemisorption on the Pd NPs. Our work indicates that strong metal–support interactions can be achieved on a non‐reducible support, as exemplified for nanocarbon, by carefully tuning the surface structure of the support, thus providing a good example for designing a high‐performance nanostructured catalyst.     

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.     

Ir–V nanoparticles supported on microstructure controlled carbon nanofibers as electrocatalyst for oxygen reduction reaction

Ir–V nanoparticles supported on microstructure controlled carbon nanofibers (CNFs) or on carbon black, Vulcan XC-72 (XC-72), have been synthesized via chemical reduction, and the oxygen reduction reaction (ORR) properties of catalysts are investigated in this paper. The physico-chemical properties are characterized by high resolution transmission electron microscope (HRTEM), N₂ physisorption and electrochemical analysis. HRTEM results show that the metal nanoparticles are separated on carbon support with well-controlled particle size, dispersity, and composition uniformity. Moreover, the metal nanoparticles on CNFs have a smaller size than those on XC-72. Cyclic voltammetric analysis reveals that Ir–V/CNFs exhibits a higher ORR activity than Ir–V/XC-72, and this may be associated with the smaller metal nanoparticles and the stronger metal-support interaction of Ir–V/CNFs. Linear sweep voltammetric analysis at different rotation rates proves that ORR on the Ir–V/CNFs electrode is a 4e^? process.     

二硫化钼纳米片/碳纳米纤维杂化材料的制备及其析氢性能

以碳纳米纤维(CNFs)作为负载基体和反应器采用静电纺丝技术和碳化工艺生长和调控二硫化钼(MoS_2)纳米片。通过改变前驱体溶液浓度来调控纳米片的形貌和结构,利用MoS_2纳米片的高催化活性和CNFs高比表面积、良好的稳定性以及高电导率的协同作用,研究不同形貌和结构的杂化纳米材料在电催化析氢方面的应用,探索杂化材料形貌与性能之间的潜在规律。运用多种分析测试技术对制备得到的纳米杂化材料进行表征,并对所制备的MoS_2/CNFs杂化材料的电催化析氢性能(HER)进行研究,研究表明近似皮芯结构的MoS_2/CNFs-10杂化材料的电催化析氢性能最好,初始析氢过电位在220 mV,Tafel斜率为110m V·dec~(-1)。     

二硫化钼纳米片/碳纳米纤维杂化材料的制备及其析氢性能

以碳纳米纤维（CNFs）作为负载基体和反应器采用静电纺丝技术和碳化工艺生长和调控二硫化钼（MoS₂）纳米片。通过改变前驱体溶液浓度来调控纳米片的形貌和结构,利用MoS₂纳米片的高催化活性和CNFs高比表面积、良好的稳定性以及高电导率的协同作用,研究不同形貌和结构的杂化纳米材料在电催化析氢方面的应用,探索杂化材料形貌与性能之间的潜在规律。运用多种分析测试技术对制备得到的纳米杂化材料进行表征,并对所制备的MoS₂/CNFs杂化材料的电催化析氢性能（HER）进行研究,研究表明近似皮芯结构的MoS₂/CNFs-10杂化材料的电催化析氢性能最好,初始析氢过电位在220 mV,Tafel斜率为110 mV·dec^-1。     

Electrocatalytic interaction of nano-engineered palladium on carbon nanofibers with hydrogen peroxide and β-NADH

The growing demands for reagentless hydrogen peroxide (H₂O₂) and β-nicotinamide adenine dinucleotide (β-NADH) sensors from food, pharmaceutical, chemical, and biochemical fields have stimulated extensive research interest on nano-engineered Pd. In this paper, Pd/carbon composite nanofibers were prepared by electrodepositing Pd onto electrospun carbon nanofibers to act as a catalyst toward the electrocatalytic redox reactions of H₂O₂ and β-NADH. The morphology of nano-engineered Pd was controlled by selectively adjusting the electrodeposition time and potential. Scanning electron microscopy and transmission electron microscopy results showed that nanocactus- and nanoflower-like Pd depositions were obtained on the surface of carbon nanofibers. Electrocatalytic analysis demonstrated a high electrocatalytic activity of the composite nanofibers for the redox of H₂O₂ and oxidation of β-NADH.