Keith L. Hohn

Partial oxidation of methane to syngas at high space velocities over Rh-coated spheres

Abstract The effect of space velocity on the partial oxidation of methane using different support geometries has been studied. While on a foam alumina monolith syngas selectivity drops as space velocity is increased above 4×10 5 h −1 , the use of non-porous alumina spheres as the support allows high reactant conversions and syngas selectivities even at space velocities of 1.8×10 6 h −1 . The differences between monoliths and spheres are discussed in order to understand why spheres give superior results. It is suggested that differences in heat transfer within the two support geometries may play a major role in the different results between spheres and monoliths. A convective heat transfer model suggests that higher rates of convection in a monolith will lead to lower front temperatures than in a sphere bed, a trend that becomes important at high space velocities in leading to blowout and lower syngas selectivities.

A multifunctional biocide/sporocide and photocatalyst based on titanium dioxide (TiO2) codoped with silver, carbon, and sulfur.

Composite nanostructured samples of Ag (0.5-20%)/(C, S)-TiO(2) were synthesized and characterized by EDX, XRD, FT-IR, UV-vis, BET, XPS, and zeta potential measurements. Photocatalytic and biocidal tests revealed that the amount of the codoped silver (Ag(+)) in (C, S)-TiO(2) played a crucial, distinctive role in the photodegradation of gas-phase acetaldehyde as well as in the inactivation of Escherichia coli cells and Bacillus subtilis spores. Very interestingly, Ag/(C, S)-TiO(2) nanoparticles (crystallite size <10 nm) have shown very strong antimicrobial properties without light activation against both E. coli (log kill >8) and B. subtilis spores (log kill >5) for 30 min exposures, compared with P25-TiO(2). Thus, for the first time, we have demonstrated that titanium dioxide (an environmentally friendly photocatalyst) codoped with silver, carbon, and sulfur can serve as a multifunctional generic biocide as well as a visible light activated photocatalyst.

Catalytic Partial Oxidation of Methanol and Ethanol for Hydrogen Generation

Hydrogen-powered fuel cell vehicles feature high energy efficiency and minor environmental impact. Liquid fuels are ideal hydrogen carriers, which can catalytically be converted into syngas or hydrogen to power vehicles. Among the potential liquid fuels, alcohols have several advantages. The hydrogen/carbon ratio is higher than that of other liquid hydrocarbons or oxygenates, especially in the case of methanol. In addition, alcohols can be derived from renewable biomass resources. Catalytic partial oxidation of methanol or ethanol offers immense potential for onboard hydrogen generation due to its rapid reaction rate and exothermic nature. These benefits stimulate a burgeoning research community in catalyst design, reaction engineering, and mechanistic investigation. The purpose of this Minireview is to provide insight into syngas and hydrogen production from methanol and ethanol partial oxidation, particularly highlighting catalytic chemistry.

Self-Assembled Monolayers of Alkylphosphonic Acid on GaN Substrates

In this paper we describe the formation and characterization of self-assembled monolayers of octadecylphosphonic acid (ODPA) on epitaxial (0001) GaN films on sapphire. By immersing the substrate in its toluene solution, ODPA strongly adsorbed onto UV/O 3-treated GaN to give a hydrophobic surface. Spectroscopic ellipsometry verified the formation of a well-packed monolayer of ODPA on the GaN substrate. In contrast, adsorption of other primarily substituted hydrocarbons (C n H 2 n+1 X; n = 16-18; X = -COOH, -NH 2, -SH, and -OH) offered less hydrophobic surfaces, reflecting their weaker interaction with the GaN substrate surfaces. A UV/O 3-treated N-polar GaN had a high affinity to the -COOH group in addition to ODPA, possibly reflecting the basic properties of the surface. These observations suggested that the molecular adsorption was primarily based on hydrogen bond interactions between the surface oxide layer on the GaN substrate and the polar functional groups of the molecules. The as-prepared ODPA monolayers were desorbed from the GaN substrates by soaking in an aqueous solution, particularly in a basic solution. However, ODPA monolayers heated at 160 degrees C exhibited suppressed desorption in acidic and neutral aqueous solution maybe due to covalent bond formation between ODPA and the surface. X-ray photoelectron spectroscopy provided insight into the effect of the UV/O 3 treatment on the surface composition of the GaN substrate and also the ODPA monolayer formation. These results demonstrate that the surface of a GaN substrate can be tailored with organic molecules having an alkylphosphonic acid moiety for future sensor and device applications.

Partial oxidation of methanol at millisecond contact times

Abstract The partial oxidation of methanol has been carried out on Pt- and Rh-coated α-alumina monoliths in an autothermal, short contact time reactor. This is seen as a possible first step in converting methanol to hydrogen for use in fuel cells for mobile applications. Methanol was readily converted to primarily CO and H 2 at CH 3 OH/O 2 ratios from two to five. Higher ratios produced lower temperatures, lower methanol conversions, and higher H 2 selecitivities. CO selectivity on both catalysts increased from CH 3 OH/O 2 =2 to 3–3.5, but decreased beyond this ratio. This was attributed to the water-gas shift reaction where equilibrium of this reaction becomes more favorable at higher ratios due to the decrease in reaction temperature. Platinum and rhodium gave very similar trends, suggesting that thermodynamic equilibrium, not catalyst properties, determines product composition.

Transformation of indium nanoparticles to β-indium sulfide: digestive ripening and visible light-induced photocatalytic properties.

We report the transformation of polydispersed dodecanethiol stabilized indium nanoparticles, obtained from bulk indium shot by evaporation/condensation solvated metal atom dispersion (SMAD) technique, into highly monodispersed partially alkyl thiolate-capped β-indiumsulfide (In(2)S(3)) by a postpreparative digestive ripening in high boiling point t-butyltoluene (190 °C) solvent. Upon digestive ripening, the as-prepared polydispersed black indium nanoparticles showed a characteristic color transition from black to cream, pale yellow, yellow, and finally to brown, indicating the transformation of the indium metal nanoparticles into intermediates composed of indium thiolates, sulfides, and polysulfides, and finally into the product In(2)S(3) nanoparticles whose surfaces are partially capped with thiolates. The transformed product (In(2)S(3)) was characterized with UV-vis, XRD, EDX, SEM, XPS, and TEM. From XRD and TEM measurements, the average size of the transformed In(2)S(3) nanoparticles is 5 nm. The optical absorbance of the as-prepared sample showed absorption peaks around 538 and 613 nm; upon digestive ripening these two peaks disappeared and stabilized at 375 nm, providing evidence of strong quantum confinement of excitons. The visible light-induced photocatalytic activity test with the In(2)S(3) nanoparticles showed that 95% of Rhodamine B (RhB) dye degraded after 100 min of irradiation with visible light.

Synthesis and Characterization of Amphiphilic Reduced Graphene Oxide with Epoxidized Methyl Oleate

Amphiphilic reduced graphene oxide is obtained by oleo-functionalization with epoxidized methyl oleate (renewable feedstock) using a green process. The excellent diverse solvent-dispersivity of the oleo-reduced amphiphilic graphene and its reduction chemistry are confirmed in this study. Oleo-reduction of amphiphilic graphene is amenable to industrially viable processes to produce future graphene-based polymer composites and systems.

Catalytic ignition of light hydrocarbons

Catalytic ignition refers to phenomenon where sufficient energy is released from a catalytic reaction to maintain further reaction without additional external heating. This phenomenon is important in the development of catalytic combustion and catalytic partial oxidation processes, both of which have received extensive attention in recent years. In addition, catalytic ignition studies provide experimental data which can be used to test theoretical hydrocarbon oxidation models. For these reasons, catalytic ignition has been frequently studied. This review summarizes the experimental methods used to study catalytic ignition of light hydrocarbons and describes the experimental and theoretical results obtained related to catalytic ignition. The role of catalyst metal, fuel and fuel concentration, and catalyst state in catalytic ignition are examined, and some conclusions are drawn on the mechanism of catalytic ignition.

Hexagonal magnetite nanoprisms: preparation, characterization and cellular uptake

The capacity of iron oxide nanocrystals to heat tissue when subjected to an alternating magnetic field (AMF hyperthermia) is shape-selective. Although iron oxide nanostructures with numerous shapes have been synthesized to date, hexagonal Fe3O4 prisms of low toxicity remained elusive. Here, we report the use of a dual ligand system permitting feasible reaction conditions to synthesize nearly perfect hexagonal Fe3O4 nanoplatelet structures, with edge length of 45 ± 5 nm and thickness of 5 to 6 nm. Their Specific Absorption Rate (SAR) is >750 W g(Fe)-1. The Fe3O4 hexagons were coated with a dopamine-based ligand to increase dispersibility in aqueous buffers. The Fe3O4 hexagons were only minimally toxic to RAW264.7 cells, which can be utilized in cell-based cancer targeting approaches.

Acid monolayer functionalized iron oxide nanoparticles as catalysts for carbohydrate hydrolysis

Superparamagnetic iron oxide nanoparticles were functionalized with a quasi-monolayer of 11-sulfoundecanoic acid and 10-phosphono-1-decanesulfonic acid ligands to create separable solid acid catalysts. The ligands are bound through carboxylate or phosphonate bonds to the magnetite core. The ligand-core bonding surface is separated by a hydrocarbon linker from an outer surface with exposed sulfonic acid groups. The more tightly packed monolayer of the phosphonate ligand corresponded to a higher sulfonic acid loading by weight, a reduced agglomeration of particles, a greater tendency to remain suspended in solution in the presence of an external magnetic field, and a higher catalytic activity per sulfonic acid group. The particles were characterized by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), potentiometric titration, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), inductively coupled plasma optical emission spectrometry (ICP-OES), and dynamic light scattering (DLS). In sucrose catalysis reactions, the phosphonic–sulfonic nanoparticles (PSNPs) were seen to be incompletely recovered by an external magnetic field, while the carboxylic–sulfonic nanoparticles (CSNPs) showed a trend of increasing activity over the first four recycle runs. The activity of the acid-functionalized nanoparticles was compared to the traditional solid acid catalyst Amberlyst-15 for the hydrolysis of starch in aqueous solution. Catalytic activity for starch hydrolysis was in the order PSNPs > CSNPs > Amberlyst-15. Monolayer acid functionalization of iron oxides presents a novel strategy for the development of recyclable solid acid catalysts.