Simultaneous reduction of particulate matter and NOx emissions using 4-way catalyzed filtration systems

The next generation of diesel emission control devices includes 4-way catalyzed filtration systems (4WCFS) consisting of both NOx and diesel particulate matter (DPM) control. A methodology was developed to simultaneously evaluate the NOx and DPM control performance of miniature 4WCFS made from acicular mullite, an advanced ceramic material (ACM), that were challenged with diesel exhaust. The impact of catalyst loading and substrate porosity on catalytic performance of the NOx trap was evaluated. Simultaneously with NOx measurements, the real-time solid particle filtration performance of catalyst-coated standard and high porosity filters was determined for steady-state and regenerative conditions. The use of high porosity ACM 4-way catalyzed filtration systems reduced NOx by 99% and solid and total particulate matter by 95% when averaged over 10 regeneration cycles. A "regeneration cycle" refers to an oxidizing ("lean") exhaust condition followed by a reducing ("rich") exhaust condition resulting in NOx storage and NOx reduction (i.e., trap "regeneration"), respectively. Standard porosity ACM 4-way catalyzed filtration systems reduced NOx by 60-75% and exhibited 99.9% filtration efficiency. The rich/lean cycling used to regenerate the filter had almost no impact on solid particle filtration efficiency but impacted NOx control. Cycling resulted in the formation of very low concentrations of semivolatile nucleation mode particles for some 4WCFS formulations. Overall, 4WCFS show promise for significantly reducing diesel emissions into the atmosphere in a single control device. © 2013 American Chemical Society.

Au-catalyzed InP nanowires: The influence of growth temperature and V/III ratio

Growth of Au-catalyzed InP nanowires (NWs) by metalorganic chemical vapor deposition (MOCVD) has been studied in the temperature range of 400-510 °C and V/III ratio of 44-700. We demonstrate that minimal tapering of InP NWs can be achieved at 400 °C and V/III ratio of 350. Zinc-blende (ZB) or wurtzite (WZ) NWs is obtained depending on the growth conditions. 4K microphotoluminescence (μ-PL) studies show that emission energy is blue-shifted as growth temperature increases. By changing these growth parameters, one can tune the emission wavelength of InP NWs which is attractive for applications in developing novel optoelectronic devices. © 2010 IEEE.

In situ observations of the atomistic mechanisms of Ni catalyzed low temperature graphene growth.

The key atomistic mechanisms of graphene formation on Ni for technologically relevant hydrocarbon exposures below 600 °C are directly revealed via complementary in situ scanning tunneling microscopy and X-ray photoelectron spectroscopy. For clean Ni(111) below 500 °C, two different surface carbide (Ni2C) conversion mechanisms are dominant which both yield epitaxial graphene, whereas above 500 °C, graphene predominantly grows directly on Ni(111) via replacement mechanisms leading to embedded epitaxial and/or rotated graphene domains. Upon cooling, additional carbon structures form exclusively underneath rotated graphene domains. The dominant graphene growth mechanism also critically depends on the near-surface carbon concentration and hence is intimately linked to the full history of the catalyst and all possible sources of contamination. The detailed XPS fingerprinting of these processes allows a direct link to high pressure XPS measurements of a wide range of growth conditions, including polycrystalline Ni catalysts and recipes commonly used in industrial reactors for graphene and carbon nanotube CVD. This enables an unambiguous and consistent interpretation of prior literature and an assessment of how the quality/structure of as-grown carbon nanostructures relates to the growth modes.

Noncatalytic chemical vapor deposition of graphene on high-temperature substrates for transparent electrodes

A noncatalytic chemical vapor deposition mechanism is proposed, where high precursor concentration, long deposition time, high temperature, and flat substrate are needed to grow large-area nanocrystalline graphene using hydrocarbon pyrolysis. The graphene is scalable, uniform, and with controlled thickness. It can be deposited on virtually any nonmetallic substrate that withstands ∼1000 °C. For typical examples, graphene grown directly on quartz and sapphire shows transmittance and conductivity similar to exfoliated or metal-catalyzed graphene, as evidenced by transmission spectroscopy and transport measurements. Raman spectroscopy confirms the sp 2-C structure. The model and results demonstrate a promising transfer-free technique for transparent electrode production. © 2012 American Institute of Physics.

Low partial pressure chemical vapor deposition of graphene on copper

A systematic study of the Cu-catalyzed chemical vapor deposition of graphene under extremely low partial pressure is carried out. A carbon precursor supply of just P CH4∼ 0.009 mbar during the deposition favors the formation of large-area uniform monolayer graphene verified by Raman spectra. A diluted HNO 3 solution is used to remove Cu before transferring graphene onto SiO 2/Si substrates or carbon grids. The graphene can be made suspended over a ∼12 μm distance, indicating its good mechanical properties. Electron transport measurements show the graphene sheet resistance of ∼0.6 kΩ/□ at zero gate voltage. The mobilities of electrons and holes are ∼1800 cm 2/Vs at 4.2 K and ∼1200 cm 2/Vs at room temperature. © 2011 IEEE.

The phase of iron catalyst nanoparticles during carbon nanotube growth

We study the Fe-catalyzed chemical vapor deposition of carbon nanotubes by complementary in situ grazing-incidence X-ray diffraction, in situ X-ray reflectivity, and environmental transmission electron microscopy. We find that typical oxide supported Fe catalyst films form widely varying mixtures of bcc and fcc phased Fe nanoparticles upon reduction, which we ascribe to variations in minor commonly present carbon contamination levels. Depending on the as-formed phase composition, different growth modes occur upon hydrocarbon exposure: For γ-rich Fe nanoparticle distributions, metallic Fe is the active catalyst phase, implying that carbide formation is not a prerequisite for nanotube growth. For α-rich catalyst mixtures, Fe3C formation more readily occurs and constitutes part of the nanotube growth process. We propose that this behavior can be rationalized in terms of kinetically accessible pathways, which we discuss in the context of the bulk iron-carbon phase diagram with the inclusion of phase equilibrium lines for metastable Fe3C. Our results indicate that kinetic effects dominate the complex catalyst phase evolution during realistic CNT growth recipes. © 2012 American Chemical Society.

Twin-free uniform epitaxial GaAs nanowires grown by a two-temperature process.

We demonstrate vertically aligned epitaxial GaAs nanowires of excellent crystallographic quality and optimal shape, grown by Au nanoparticle-catalyzed metalorganic chemical vapor deposition. This is achieved by a two-temperature growth procedure, consisting of a brief initial high-temperature growth step followed by prolonged growth at a lower temperature. The initial high-temperature step is essential for obtaining straight, vertically aligned epitaxial nanowires on the (111)B GaAs substrate. The lower temperature employed for subsequent growth imparts superior nanowire morphology and crystallographic quality by minimizing radial growth and eliminating twinning defects. Photoluminescence measurements confirm the excellent optical quality of these two-temperature grown nanowires. Two mechanisms are proposed to explain the success of this two-temperature growth process, one involving Au nanoparticle-GaAs interface conditions and the other involving melting-solidification temperature hysteresis of the Au-Ga nanoparticle alloy.