Carbon-coated titania nanostructured particles: Continuous, one-step flame-synthesis

Concurrent synthesis of titania-carbon nanoparticles (up to 52 wt.% in C) was studied in a diffusion flame aerosol reactor by combustion of titanium tetraisopropoxide and acetylene. These graphitically layered carbon-coated titania particles were characterized by high-resolution transmission electron microscopy (HRTEM), with elemental mapping of C and Ti, x-ray diffraction (XRD), and nitrogen adsorption [Brunauer-Emmett-Teller (BET)]. The specific surface area of the powder was controlled by the acetylene flow rate from 29 to 62 m2/g as the rutile content decreased from 68 to 17 wt.%. Light blue titania suboxides formed at low acetylene flow rates. The average XRD crystal size of TiO2 decreased steadily with increasing carbon content of the composite powders, while the average BET primary particle size calculated from nitrogen adsorption decreased first and then approached a constant value. The latter is attributed to the formation of individual carbon particles next to carbon-coated titania particles as observed by HRTEM and electron spectroscopic imagin

Uniform nanoparticles by flame-assisted spray pyrolysis (FASP) of low cost precursors

A new flame-assisted spray pyrolysis (FASP) reactor design is presented, which allows the use of inexpensive precursors and solvents (e.g., ethanol) for synthesis of nanoparticles (10-20nm) with uniform characteristics. In this reactor design, a gas-assisted atomizer generates the precursor solution spray that is mixed and combusted with externally fed inexpensive fuel gases (acetylene or methane) at a defined height above the atomizing nozzle. The gaseous fuel feed can be varied to control the combustion enthalpy content of the flame and onset of particle formation. This way, the enthalpy density of the flame is decoupled from the precursor solution composition. Low enthalpy content precursor solutions are prone to synthesis of non-uniform particles (e.g., bimodal particle size distribution) by standard flame spray pyrolysis (FSP) processes. For example, metal nitrates in ethanol typically produce nanosized particles by gas-to-particle conversion along with larger particles by droplet-to-particle conversion. The present FASP design facilitates the use of such low enthalpy precursor solutions for synthesis of homogeneous nanopowders by increasing the combustion enthalpy density of the flame with low-cost, gaseous fuels. The effect of flame enthalpy density on product properties in the FASP configuration is explored by the example of Bi2O3 nanoparticles produced from bismuth nitrate in ethanol. Product powders were characterized by nitrogen adsorption, X-ray diffraction, X-ray disk centrifuge, and transmission electron microscopy. Homogeneous Bi2O3 nanopowders were produced both by increasing the gaseous fuel content and, most notably, by cutting the air entrainment prior to ignition of the spra

Synthesis of bimodally porous titania powders by hydrolysis of titanium tetraisopropoxide

Bimodally porous titania powders with controlled phase composition and porosity were made by hydrolysis of titanium tetraisopropoxide (TTIP) and calcination. The extent of calcination was followed by thermogravimetric differential thermal analysis and Fourier transform infrared spectroscopy. The specific surface area (SSA) of the powders ranged from 10 to 500 m2/g as determined by nitrogen adsorption. The SSA increased by decreasing either the water concentration during hydrolysis or the calcination temperature. The pore size distribution was bimodal with fine intraparticle pore diameters at 1-6 nm and larger interparticle pore diameters at 30-120 nm as determined by nitrogen adsorption isotherms. The particle phase composition as determined by x-ray diffraction ranged from amorphous to crystalline anatase and rutile largely proportional to the calcination temperature and to a lesser extent on the initial H2O/TTIP molar rati

Effect of the Proximity of Pt to Ce or Ba in Pt/Ba/CeO2 Catalysts on NO x Storage-Reduction Performance

The effect of Pt location in Pt/Ba/CeO2 catalysts for NO x storage-reduction (NSR) was analyzed. The Pt location on BaCO3 or CeO2 support was controlled by changing the angle (φ) between the two flame sprays producing these two components. As-prepared flame-made catalysts contain PtO x which must be reduced during the fuel rich phase to become active for NO x storage and reduction of NO x . For Pt on BaCO3 this process was significantly faster than for Pt on CeO2. The increased reduction ability of Pt on Ba is reflected in the light off temperatures: for Pt on CeO2 temperatures around 330°C were needed to combust 20% of C3H6 in air while for Pt on BaCO3 only 250°C were required for the same conversion. The ability to control the location of Pt or other noble metals is, therefore, essential to optimize the catalysts for a given Pt/Ba/CeO2 weight ratio. The best performance was observed when most of the Pt constituent was located near Ba-containing site

Flame-Made Pt/K/Al2O3 for NO x Storage-Reduction (NSR) Catalysts

High surface area Pt/K/Al2O3 catalysts were prepared with a 2-nozzle flame spray method resulting in Pt clusters on γ-Al2O3 and amorphous K storage material as evidenced by Raman spectroscopy. The powders had a high NO x storage capacity and were regenerated fast in a model exhaust gas environment. From 300 to 400°C no excess NO x was detected in the off gas during transition from fuel lean to fuel rich conditions, resulting in a highly effective NO x removal performance. Above 500°C, the NSR activity was lost and not recovered at lower temperatures as K-compounds were partially crystallized on the catalys

Agglomerate-free BaTiO3 particles by salt-assisted spray pyrolysis

Optimum conditions for the synthesis of nonagglomerated BaTiO3 particles by salt-assisted spray pyrolysis (SASP) were investigated. The effect of particle residence time in the reactor and salt concentration on the crystallinity and surface morphology of BaTiO3 was examined by x-ray diffraction and scanning electron microscopy. Mixtures of a metal chloride or nitrate salt, dissolved in aqueous precursor solutions, were sprayed by an ultrasonic atomizer into a five-zone hot-wall reactor. By increasing the salt concentration or the particle residence time in the hot zone, the primary particle size was increased, and its surface texture was improved compared to BaTiO3 particles prepared by conventional spray pyrolysis. The SASP-prepared BaTiO3 crystal was transformed from cubic to tetragonal by simply increasing the salt concentration at constant temperature and residence time. Further thermal treatments such as calcination or annealing are not necessary to obtain nonagglomerated tetragonal BaTiO3 (200-500 nm) particles with a narrow size distribution. Increasing the carrier gas flow rate and decreasing the residence time in the hot zone resulted in cubic BaTiO3 particles about 20 nm in diamete

Size-selected agglomerates of SnO₂ nanoparticles as gas sensors

The effect of nanoparticle structure on gas sensing performance is investigated. Size-selected nanostructured SnO₂ agglomerate particles for gas sensors were made by scalable flame spray pyrolysis. These particles were polydisperse (up to 12μm in diameter) and consisted of primary particles of 10nm in grain and crystal size as measured by transmission electron microscopy, x-ray diffraction, and Berner low pressure impactor (BLPI). The effect of agglomerate size on thermal stability and sensing of ethanol vapor (4–100ppm) and CO (4–50ppm) was investigated by selecting nearly monodisperse fractions of these agglomerates by the BLPI. Sensor layers made with these size-fractionated agglomerates exhibited higher thermal stability and dramatically enhanced sensitivity for both analytes than layers made with polydisperse agglomerates. This is attributed to their aggregate (or hard agglomerate) structure exhibiting small sinter necks between their constituent primary particles of tin dioxide that had also a narrow size distribution as expected for particles generated in flames. Upon further sintering of these optimally sized, nanostructured agglomerates, grain and neck growth degraded their superior sensitivity, supporting the proposed mechanism of their enhanced sensitivity: optimal primary particle necking.Financial support was provided by ETH Zurich FEL-04 08-3, Finnish Academy, Tekes The Finnish National Technology Agency, and Nanoprim

Flame-made Alumina Supported Pd-Pt Nanoparticles: StructuralProperties and Catalytic Behavior in Methane Combustion

Bimetallic palladium-platinum nanoparticles supported on alumina were prepared by flame spray pyrolysis. The as-prepared materials were characterized by scanning transmission electron microscopy (STEM), CO chemisorption, nitrogen adsorption (BET), X-ray diffraction (XRD), temperature programmed reduction (TPR), thermogravimetric analysis (TGA) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The materials were tested for the catalytic combustion of methane with a focus on the thermal stability of the noble metal particles. After flame synthesis the noble metal components of the materials were predominantly in oxidized state and finely dispersed on the alumina matrix. Reduction afforded small bimetallic Pd-Pt alloy particles (< 5nm) supported on Al2O3 ceramic nanoparticles. The addition of small amounts of platinum made the palladium particles more resistant against sintering at high temperatures and further lowered the deactivation observed during methane combustio

Independent Control of Metal Cluster and Ceramic Particle Characteristics During One-step Synthesis of Pt/TiO2

Rapid quenching during flame spray synthesis of Pt/TiO2 (0-10 wt% Pt) is demonstrated as a versatile method for independent control of support (TiO2) and noble metal (Pt) cluster characteristics. Titania grain size, morphology, crystal phase structure, and crystal size were analyzed by nitrogen adsorption, electron microscopy and x-ray diffraction, respectively, while Pt-dispersion and size were determined by CO-pulse chemisorption. The influence of quench cooling on the flame temperature was analyzed by Fourier transform infrared spectroscopy. Increasing the quench flow rate reduced the Pt diameter asymptotically. Optimal quenching with respect to maximum Pt-dispersion (∼60%) resulted in average Pt diameters of 1.7 to 2.3 nm for Pt-contents of 1-10 wt%, respectivel

Shrinking droplets in electrospray ionization and their influence on chemical equilibria

We investigated how chemical equilibria are affected by the electrospray process, using simultaneous in situ measurements by laser-induced fluorescence (LIF) and phase Doppler anemometry (PDA). The motivation for this study was the increasing number of publications in which electrospray ionization mass spectrometry is used for binding constant determination. The PDA was used to monitor droplet size and velocity, whereas LIF was used to monitor fluorescent analytes within the electrospray droplets. Using acetonitrile as solvent, we found an average initial droplet diameter of 10 µm in the electrospray. The PDA allowed us to follow the evolution of these droplets down to a size of 1 µm. Rhodamine B-sulfonylchloride was used as a fluorescent analyte within the electrospray. By spatially resolved LIF it was possible to probe the dimerization equilibrium of this dye. Measurements at different spray positions showed no influence of the decreasing droplet size on the monomer-dimer equilibrium. However, with the fluorescent dye pair DCM and oxazine 1 it was shown that a concentration increase does occur within electrosprayed droplets, using fluorescence resonance energy transfer as a probe for the average pair distanc