Bio-hydrogen production based on catalytic reforming of volatiles generated by cellulose pyrolysis: an integrated process for ZnO reduction and zinc nanostructures fabrication

The paper presents a process of cellulose thermal degradation with bio-hydrogen generation and zinc nanostructures synthesis. Production of zinc nanowires and zinc nanoflowers was performed by a novel processes based on cellulose pyrolysis, volatiles reforming and direct reduction of ZnO. The bio-hydrogen generated in situ promoted the ZnO reduction with Zn nanostructures formation by vapor–solid (VS) route. The cellulose and cellulose/ZnO samples were characterized by thermal analyses (TG/DTG/DTA) and the gases evolved were analyzed by FTIR spectroscopy (TG/FTIR). The hydrogen was detected by TPR (Temperature Programmed Reaction) tests. The results showed that in the presence of ZnO the cellulose thermal degradation produced larger amounts of H2 when compared to pure cellulose. The process was also carried out in a tubular furnace with N2 atmosphere, at temperatures up to 900 °C, and different heating rates. The nanostructures growth was catalyst-free, without pressure reduction, at temperatures lower than those required in the carbothermal reduction of ZnO with fossil carbon. The nanostructures were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The optical properties were investigated by photoluminescence (PL). One mechanism was presented in an attempt to explain the synthesis of zinc nanostructures that are crystalline, were obtained without significant re-oxidation and whose morphologies are dependent on the heating rates of the process. This route presents a potential use as an industrial process taking into account the simple operational conditions, the low costs of cellulose and the importance of bio-hydrogen and nanostructured zinc.

Flexible array sensors based on zinc oxide nanowires for touch displays

Recent efforts towards the fabrication of touch sensing systems are presented, in which zinc oxide nanowire arrays are embedded in a polymer matrix to produce an engineered composite material. In the future, these sensor systems will be fully flexible and multi-touch as intended for Nokia's 'Morph' concept device.

Local synthesis and alignment of zinc oxide nanowires in aqueous solution using microheaters

A bottom-up technique for synthesizing transversely suspended zinc oxide nanowires (ZnO NWs) under a zinc nitrate (Zn(NO 3) 2· 6H 2O) and hexamethylenetetramine (HMTA, (CH 2) 6·N 4) solution within a microfabricated device is reported in this paper. The device consists of a microheater which is used to initially create an oxidized ZnO seed layer. ZnO NWs are then locally synthesized by the microheater and electrodes embedded within the devices are used to drive electric field directed horizontal alignment of the nanowires within the device. The entire process is carried out at low temperature. This approach has the potential to considerably simplify the fabrication and assembly of ZnO nanowires on CMOS compatible substrates, allowing for the chemical synthesis to be carried out under near-ambient conditions by locally defining the conditions for nanowire growth on a silicon reactor chip. © 2012 IEEE.

Phase perfection in zinc Blende and Wurtzite III-V nanowires using basic growth parameters.

Controlling the crystallographic phase purity of III-V nanowires is notoriously difficult, yet this is essential for future nanowire devices. Reported methods for controlling nanowire phase require dopant addition, or a restricted choice of nanowire diameter, and only rarely yield a pure phase. Here we demonstrate that phase-perfect nanowires, of arbitrary diameter, can be achieved simply by tailoring basic growth parameters: temperature and V/III ratio. Phase purity is achieved without sacrificing important specifications of diameter and dopant levels. Pure zinc blende nanowires, free of twin defects, were achieved using a low growth temperature coupled with a high V/III ratio. Conversely, a high growth temperature coupled with a low V/III ratio produced pure wurtzite nanowires free of stacking faults. We present a comprehensive nucleation model to explain the formation of these markedly different crystal phases under these growth conditions. Critical to achieving phase purity are changes in surface energy of the nanowire side facets, which in turn are controlled by the basic growth parameters of temperature and V/III ratio. This ability to tune crystal structure between twin-free zinc blende and stacking-fault-free wurtzite not only will enhance the performance of nanowire devices but also opens new possibilities for engineering nanowire devices, without restrictions on nanowire diameters or doping.

Electronic structure and g factors of narrow-gap zinc-blende nanowires and nanorods

The Hamiltonian in the framework of eight-band effective-mass approximation of the zinc-blende nanowires and nanorods in the presence of external homogeneous magnetic field is given in the cylindrical coordinate. The electronic structure, optical properties, magnetic energy levels, and g factors of the nanowires and nanorods are calculated. It is found that the electron states consist of many hole-state components, due to the coupling of the conduction band and valence band. For the normal bands which are monotone functions of |k(z)|, long nanorods can be modeled by the nanowires, the energy levels of the nanorods approximately equal the values of the energy band E(k(z)) of the nanowires with the same radius at a special k(z), where k(z) is the wave vector in the wire direction. Due to the coupling of the states, some of the hole energy bands of the nanowires have their highest points at k(z)=0. Especially, the highest hole state of the InSb nanowires is not at the k(z)=0 point. It is an indirect band gap. For these abnormal bands, nanorods can not be modeled by the nanowires. The energy levels of the nanorods show an interesting plait-like pattern. The linear polarization factor is zero, when the aspect ratio L/2R is smaller than 1, and increases as the length increases. The g(z) and g(x) factors as functions of the k(z), radius R and length L are calculated for the wires and rods, respectively. For the wires, the g(z) of the electron ground state increases, and the g(z) of the hole ground state decreases first, then increases with the k(z) increasing. For the rods, the g(z) and g(x) of the electron ground state decrease as the R or the L increases. The g(x) of the hole ground state decreases, the g(z) of the hole ground state increases with the L increasing. The variation of the g(z) of the wires with the k(z) is in agreement with the variation of the g(z) of the rods with the L.

Charge Separation in Wurtzite/Zinc-Blende Heterojunction GaN Nanowires

The electronic properties of wurtzite/zinc-blende (WZ/ZB) heterojunction GaN are investigated using first-principles methods. A small component of ZB stacking formed along the growth direction in the WZ GaN nanowires does not show a significant effect on the electronic property, whereas a charge separation of electrons and holes occurs along the directions perpendicular to the growth direction in the ZB stacking. The later case provides an efficient way to separate the charge through controlling crystal structure. These results have significant implications for most state of the art excitonic solar cells and the tuning region in tunable laser diodes.

HRTEM assessment of Wurtzite and Zinc-Blende phases in GaAs nanowires for optoelectronic devices

Màster en Nanociència i Nanotecnologia. Curs 2007-2008. Directors: Francesca Peiró i Martínez and Jordi Arbiol i Cobos

Fabrication of Zinc Oxide Nanowires/Polymer Composites by Two-Photon Polymerization

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Tailoring the visible photoluminescence of mass-produced ZnO nanowires

We have grown defect-rich ZnO nanowires on a large scale by the vapour phase reaction method without using any metal catalyst and vacuum system. The defects, including zinc vacancies, oxygen interstitials and oxygen antisites, are related to the excess of oxygen in ZnO nanowires and are controllable. The nanowires having high excess of oxygen exhibit a brown-colour photoluminescence, due to the dominant emission band composed by violet, blue and green emissions. Those having more balanced Zn and O show a dominant green emission, giving rise to a green colour under UV light illumination. By O2-annealing treatment the violet luminescence after the band-edge emission UV peak can be enhanced for as-grown nanowires. However, the green emission shows different changing trends under O2-annealing treatment, associated with the excess of oxygen in the nanowires.