Co-pyrolysis of chicken feathers and macadamia nut shells, a promising strategy to create nitrogen-enriched electrode materials for supercapacitor applications.

Global food waste emits substantial quantities of nitrogen to the environment (6.3 Mtons annually), chicken feather (CF) waste is a major contributor to this. Pyrolysis, in particular co-pyrolysis of nitrogen-rich and lignocellulosic waste streams is a promising strategy to improve the extent of pyrolytic nitrogen retention by incorporating nitrogen in its solid biochar structure. As such, this biochar can serve as a precursor for nitrogen-enriched activated carbons for application in supercapacitors. Therefore, this study investigates the co-pyrolysis of CF with macadamia nut shells (MNS) to create nitrogen-rich activated carbons. Co-pyrolysis increased nitrogen retention during pyrolysis from 9 % to 18 % compared to CF mono-pyrolysis, while the porosity was maintained. After removing undesirable inorganic impurities by dilute acid washing, this led to a specific capacitance of 21F/g using a scan rate of 20 mV/s. Finally, cycling stability tests demonstrated good stability with 73 % capacitance retention after 10 000 cycles.

Magnetostructural effects in ligand stabilized Pd13 clusters: a density functional theory study.

We show computationally that ligation allows tuning of the magnetostructural properties of the Pd(13) cluster. The bare, phosphine and thiol capped clusters were investigated at the density functional level. The most stable conformers of the bare cluster are of high spin, septet and nonet and of distorted C(3v), C(s) and I(h) geometries. Ligation stabilizes the I(h) geometry and quenches the high spin states, down to a triplet for Pd(13)(PH(3))(12) and to a quintet for Pd(13)(SCH(3))(12).The influence of the two capping systems on the magnetostructural properties of the ligated clusters is analyzed in connection with their different bonding properties. The mixed ligand species Pd(13)(SCH(3))(6)(PH(3))(6) is also characterized. Due to the multiple energetically accessible spin states, unusual thermal behaviour of the average magnetic moment is predicted for these clusters.

Controlling the interparticle spacing of Au-salt loaded micelles and Au nanoparticles on flat surfaces.

The self-organization of diblock copolymers into micellar structures in an appropriate solvent allows the deposition of well ordered arrays of pure metal and alloy nanoparticles on flat surfaces with narrow distributions in particle size and interparticle spacing. Here we investigated the influence of the materials (substrate and polymer) and deposition parameters (temperature and emersion velocity) on the deposition of metal salt loaded micelles by dip-coating from solution and on the order and inter-particle spacing of the micellar deposits and thus of the metal nanoparticle arrays resulting after plasma removal of the polymer shell. For identical substrate and polymer, variation of the process parameters temperature and emersion velocity enables the controlled modification of the interparticle distance within a certain length regime. Moreover, also the degree of hexagonal order of the final array depends sensitively on these parameters.

Enhanced orbital magnetism in Fe(50)Pt(50) nanoparticles.

X-ray absorption and magnetic circular dichroism spectra at both the Fe and Pt L(3,2) edges were measured on wet-chemically synthesized monodisperse Fe(50)Pt(50) particles with a mean diameter of 6.3 nm before and after complete removal of the organic ligands and the oxide shell covering the particles by soft hydrogen plasma resulting in a pure metallic state. After thermal treatment of the metallic particles, the coercive field increased by a factor of 6, the orbital magnetic moment at the Fe site increased by 330% and is reduced at the Pt site by 30%, while the effective spin moments did not change. A decrease of the frequency of oscillations in the extended x-ray absorption fine structure at the Pt L(3,2) edges provides evidence for crystallographic changes towards the L1(0) phase.

Alloy formation of supported gold nanoparticles at their transition from clusters to solids: does size matter?

Gold nanoclusters of a size approaching the molecular limit (<3 nm) were prepared on Si substrates in order to study alloy formation on the nanometer scale. For this purpose, indium atoms are deposited on top of the gold particles at room temperature and the formation of AuIn(2) is studied by x-ray photoelectron spectroscopy in situ. It is observed that the alloy formation takes place independent of whether the particles electronically are in an insulating molecular or in a metallic state. Most important, however, closed packed full-shell clusters containing 55 Au atoms are found to exhibit an outstanding stability against alloying despite a large negative heat of formation of the bulk Au-In system. Thus, Au(55) clusters may play a significant role in the design of nanoscaled devices where chemical inertness is of crucial importance.

Nanostructured surfaces from size-selected clusters.

The deposition of ionized beams of size-selected atomic clusters onto well-defined substrates represents a new method of preparing nanostructured surfaces, with lateral feature sizes in the range 1-10 nm. 'Pinning' of the incident clusters prevents the diffusion of the clusters on the surface, and thus preserves the gas-phase cluster size, even at room temperature and above. At the same time, advances in diblock copolymer techniques allow the preparation of ordered two-dimensional arrays of clusters. Here we discuss the creation and applications of these nanostructured surfaces, ranging from the fabrication of semiconductor nanostructures to the immobilization of protein molecules.

Epitaxy of cubic boron nitride on (001)-oriented diamond.

Cubic boron nitride (c-BN), although offering a number of highly attractive properties comparable to diamond, like hardness, chemical inertness and a large electronic bandgap, up to now has not found the attention it deserves. This mostly has to do with preparational problems, with easy chemical routes not available and, instead, the necessity to apply ion-bombardment-assisted methods. Hence, most of the c-BN samples prepared as thin films have been nanocrystalline, making the prospect of using this material for high-temperature electronic applications an illusion. Although heteroepitaxial nucleation of c-BN on diamond substrates has been demonstrated using the high-pressure-high-temperature technique, none of the low-pressure methods ever succeeded in the epitaxial growth of c-BN on any substrate. Here, we demonstrate that heteroepitaxial c-BN films can be prepared at 900 degrees C on highly (001)-oriented diamond films, formed by chemical vapour deposition, using ion-beam-assisted deposition as a low-pressure technique. The orientation relationship was found to be c-BN(001)[100]||diamond(001)[100]. High-resolution transmission electron microscopy additionally proved that epitaxy can be achieved without an intermediate hexagonal BN layer that is commonly observed on various substrates.

Chemically induced metal-to-insulator transition in Au55 clusters: effect of stabilizing ligands on the electronic properties of nanoparticles.

The cluster compound Au55(PPh3)12Cl6 has been reanalyzed by photoelectron spectroscopy giving direct evidence for a nonmetallic behavior of the individual Au clusters as long as their ligand shell remains intact. The exposure to x-rays during the measurements is found to partly decompose the shell by removal of the chlorine atoms, resulting in a metallic behavior of the clusters as demonstrated by a steplike intensity at the Fermi energy. These observations resolve a long-standing controversy about the metallic behavior of ligated Au clusters emphasizing, in addition, the influence of the local environment on the electronic properties of nanoscaled materials.

Oxidation-resistant gold-55 clusters.

Gold nanoparticles ranging in diameter from 1 to 8 nanometers were prepared on top of silicon wafers in order to study the size dependence of their oxidation behavior when exposed to atomic oxygen. X-ray photoelectron spectroscopy showed a maximum oxidation resistance for "magic-number" clusters containing 55 gold atoms. This inertness is not related to electron confinement leading to a size-induced metal-to-insulator transition, but rather seems to be linked to the closed-shell structure of such magic clusters. The result additionally suggests that gold-55 clusters may act as especially effective oxidation catalysts, such as for oxidizing carbon monoxide.