Synthesis of Gold Nanoparticles Attached to Polypyrrole Nanofibers

Polypyrrole is a frequently studied conducting polymer due to its application in sensing and catalysis.1 Polypyrrole is considered among the most promising conductive polymers due to its stability and ease of conversion between conducting and insulating forms.2 Different chemical and electrochemical methods are generally used in the synthesis of polypyrrole.2 Despite many interesting applications, the use of polypyrrole is limited because of difficulty in processing it. Several approaches have been explored to improve the ability to process polypyrrole, including the use of emulsion, inverse emulsion, steric stabilizer, and microemulsion methods.1 Several reports have also been published on the synthesis of polypyrrole-metal nanocomposites.3 the sensing and catalytic abilities of the polypyrrole composites are significantly better than those for polymer alone.4 as most of the important properties of the noble metals depend on their dispersion and surface properties in the surrounding medium, it is important to obtain evenly distributed Au nanoparticles in conducting polymer matrix. Here we report a simple and convenient procedure for the synthesis of polypyrrole and gold composites, where both polymer and metal morphologies can be controlled in a single set-up

Bimetallic Pt-Ag and Pd-Ag Nanoparticles

We report studies of bimetallic nanoparticles with 15%-16% atomic crystal parameters size mismatch. The degree of alloying was probed in a 2-nm Pt core (smallest attainable core size) of Pt-Ag nanoparticles (completely immiscible in bulk) and 20-nm-diameter Pd-Ag nanowires (completely miscible in bulk). Particles were synthesized radiolytically, and depending on the initial parameters, they assume spherical or cylindrical (nanowire) morphologies. In all cases, the metals are seen to follow their bulk alloying characteristics. Pt and Ag segregate in both spherical and wire forms, which indicates that strain due to crystallographic mismatch overcomes the excess surface free energy in the small particles. The Pd-Ag nanowires alloy similar to previously reported spherical Pd-Ag particles of similar diameter and composition

Polyaniline Nanofiber-Based Gas Sensors

There has been recent interest in conducting polymers that have very promising chemical and electrical applications. Some of these polymers have shown great potential for use in sensors.1 Polyaniline is one particular example of a prospective material. In our laboratory, we have studied the synthesis of polyaniline nanofibers. We have carried out one-pot syntheses to obtain polyaniline nanofibers in aqueous solutions where the polymerization was influenced by γ-radiation2 or UV-radiation.3 This polymer can also be patterned with an appropriate photo mask. In our present report, polyaniline nanofiber thin film sensors have been fabricated in one step by employing UV-irradiation and those sensors showed high sensitivity. Changes in conductivity were monitored with an electrometer as a function of time after the materials had been exposed to different gases. This simple gas sensing device can be used to detect many different gaseous types

Ferromagnetism in Li doped ZnO nanoparticles: The role of interstitial Li

ZnO nanoparticles doped with Li (Zn1−yLiyO, y ≤ 0.1) have been investigated with emphasis on the correlation between their magnetic, electronic, and structural properties. In particular, defects such as interstitial Li and Zn atoms, substitutional Li atoms, and oxygen vacancies have been identified by X-ray photoelectron spectroscopy(XPS) and their respective roles in stabilization of the magnetic moment are discussed. X-ray diffraction(XRD) and XPS give clear evidence of Li presence at both substitutional and interstitial sites. XPS studies further show that the amount of substitutional Li defects (Lizn) and interstitial Li defects (Lii) vary non-monotonically with the Li concentration, with the Lii defects being noticeably high for the y = 0.02, 0.08, and 0.10 concentrations, in agreement with the XRD results. Magnetization studies show room temperature ferromagnetism in these nanoparticles with the moment being largest for the particles with high concentration of interstitial lithium and vice versa. Both interstitialZn(Zni) defects and Zn-O bonds were determined from the Zn LMM Auger peaks; however, the variation of these with Li concentrations was not large. Oxygen vacancies (Vo) concentrations are estimated to be relatively constant over the entire Li concentration range. We relate the Lii and Zni defects to the formation and stabilization of Znvacancies and thus stabilizing the p-type ferromagnetism predicted for cation (zinc)vacancy in the ZnO type oxides

Irradiation and Metal-Containing Conjugated-Polymer Nanocomposites

In recent years, there has been considerable interest in inorganic/organic hybrid materials that combine the desirable properties of both classes. These composite materials may find significant application in a variety of applications such as sensors, memory and energy conversion, to name just a few. In our laboratories, we have recently made a series of studies on the production of polymer nanofibers and their composites with nanometals. Much of this work has focused on the production of polyaniline (PANI) nanofibers that have been made from one-pot syntheses in aqueous solutions where the polymerization was influenced by -radiation1 or UV-radiation.2 in the latter case, the polymer can be patterned with an appropriate mask. It has also been shown that if certain metal salts are added to the precursor solutions, metal nanocomposites can be produced. For example, we have been able to make polyaniline composites using -irradiation with silver 3,4 and gold 4 nanoparticles

Mesopore etching under supercritical conditions – A shortcut to hierarchically porous silica monoliths

Hierarchically porous silica monoliths are obtained in the two-step Nakanishi process, where formation of a macro microporous silica gel is followed by widening micropores to mesopores through surface etching. The latter step is carried out through hydrothermal treatment of the gel in alkaline solution and necessitates a lengthy solvent exchange of the aqueous pore fluid before the ripened gel can be dried and calcined into a mechanically stable macro mesoporous monolith. We show that using an ethanol water (95.6/4.4, v/v) azeotrope as supercritical fluid for mesopore etching eliminates the solvent exchange, ripening, and drying steps of the classic route and delivers silica monoliths that can withstand fast heating rates for calcination. The proposed shortcut decreases the overall preparation time from ca. one week to ca. one day. Porosity data show that the alkaline conditions for mesopore etching are crucial to obtain crack-free samples with a narrow mesopore size distribution. Physical reconstruction of selected samples by confocal laser scanning microscopy and subsequent morphological analysis confirms that monoliths prepared via the proposed shortcut possess the high homogeneity of silica skeleton and macropore space that is desirable in adsorbents for flow-through applications

Nanometal Containing Nanocomposites and Photolithographic Polyaniline Nanofibers

A report on recent progress from our laboratories on the nanostructures produced from novel synthesis techniques will be discussed. Using high-energy radiation (γ-rays) we have been able to produce conducting polymer nanofibers and nanorods of polyaniline and polypyrrole without the use of a separate template or capping agent. This technique has been extended, with the addition of metal ions, to a one pot synthesis, producing conducting nanocomposites. These nanocomposites contain metal nanoparticles which decorate the conducting nanofibers. We have also recently shown that these systems can be photopatterned to produce novel structures. We believe that these systems will be useful in novel or significantly improved electronic devices

Facile syntheses of monodisperse ultrasmall Au clusters

During our effort to synthesize the tetrahedral Au 20 cluster, we found a facile synthetic route to prepare monodisperse suspensions of ultrasmall Au clusters Au N (N < 12) using diphosphine ligands. In our monophasic and single-pot synthesis, a Au precursor ClAu(I)PPh 3 (Ph ) phenyl) and a bidentate phosphine ligand P(Ph) 2 (CH 2 ) M P(Ph) 2 are dissolved in an organic solvent. Au(I) is reduced slowly by a borane-tert-butylamine complex to form Au clusters coordinated by the diphosphine ligand. The Au clusters are characterized by both high-resolution mass spectrometry and UV-vis absorption spectroscopy. We found that the mean cluster size obtained depends on the chain length M of the ligand. In particular, a single monodispersed Au 11 cluster is obtained with the P(Ph) 2 (CH 2 ) 3 P(Ph) 2 ligand, whereas P(Ph) 2 (CH 2 ) M P(Ph) 2 ligands with M ) 5 and 6 yield Au 10 and Au 8 clusters. The simplicity of our synthetic method makes it suitable for large-scale production of nearly monodisperse ultrasmall Au clusters. It is suggested that diphosphines provide a set of flexible ligands to allow size-controlled synthesis of Au nanoparticles

X-Ray Lithography of Metal and Semiconductor Nanoparticles

In the last few years, a considerable amount of research has focused on the three-dimensional fabrication of contacts and electronic devices. Most techniques, however, are essentially based on photoreduction, and are limited to noble- and semi-noble metals. We present here a general method that allows patterning of porous matrices in 3D with metal, but also with semiconductor nanoparticles which is of potential relevance for microfabrication applications. In our method, the pore-filling solvent of a sol-gel material is exchanged with a solution of precursors. The precursors are photodissociated and nanoparticles are formed when the monoliths are irradiated. In a series of previous publications we showed that noble metals but also semiconductor quantum dots can be produced with our technique. Here we focus on the Xray variation of our technique and show that monoliths can be patterned with metals and also with semiconductor nanoparticles. The patterns have the same resolution than the masks, i.e., around 10 μm, and extend into the bulk of the monoliths for up to a depth of 12 mm. Our method possesses several attractive features. Sample preparation is very simple; the technique has a bottom-up character; it allows access to a wide number of materials, such as noble metals and II-VI semiconductor materials; and it has a 3D character. With additional developments, our technique could be possibly used to complement more established techniques such as LIGA and multiphoton fabrication techniques which are currently used for 3D microfabrication

Laser Writing of Semiconductor Nanoparticles and Quantum Dots

Silica aerogels were patterned with CdS using a photolithographic technique based on local heating with infrared (IR) light. The solvent of silica hydrogels was exchanged with an aqueous solution of the precursors CdNO3 and NH4 OH, all precooled to a temperature of 5°C. Half of the bathing solution was then replaced by a thiourea solution. After thiourea diffused into the hydrogels, the samples were exposed to a focused IR beam from a continuous wave, Nd-YAG laser. The precursors reacted in the spots heated by the IR beam to form CdS nanoparticles. We lithographed features with a diameter of about 40 µm, which extended inside the monoliths for up to 4 mm. Samples were characterized with transmission electron microscopy and optical absorption, photoluminescence, and Raman spectroscopies. Spots illuminated by the IR beam were made up by CdS nanoparticles dispersed in a silica matrix. The CdS nanoparticles had a diameter in the 4-6 nm range in samples exposed for 4 min to the IR beam, and of up to 100 nm in samples exposed for 10 min