Functionalization of carbon nanotubes using aminobenzene acids and electrochemical methods. Electroactivity for the oxygen reduction reaction

Functionalized carbon nanotubes (CNTs) using three aminobenzene acids with different functional groups (carboxylic, sulphonic, phosphonic) in para position have been synthesized through potentiodynamic treatment in acid media under oxidative conditions. A noticeable increase in the capacitance for the functionalized carbon nanotubes mainly due to redox processes points out the formation of an electroactive polymer thin film on the CNTs surface along with covalently bonded functionalities. The CNTs functionalized using aminobenzoic acid rendered the highest capacitance values and surface nitrogen content, while the presence of sulfur and/or phosphorus groups in the aminobenzene structure yielded a lower functionalization degree. The oxygen reduction reaction (ORR) activity of the functionalized samples was similar to that of the parent CNTs, independently of the functional group present in the aminobenzene acid. Interestingly, a heat treatment in N2 atmosphere with a very low O2 concentration (3125 ppm) at 800 °C of the CNTs functionalized with aminobenzoic acid produced a material with high amounts of surface oxygen and nitrogen groups (12 and 4% at., respectively), that seem to modulate the electron-donor properties of the resulting material. The onset potential and limiting current for ORR was enhanced for this material. These are promising results that validates the use of electrochemistry for the synthesis of novel N-doped electrocatalysts for ORR in combination with adequate heat treatments.

Catchment characteristics and soil and water chemistry of the San Francisco basin and subbasins, Ecuador

In this study, the Mean Transit Time and Mixing Model Analysis methods are combined to unravel the runoff generation process of the San Francisco River basin (73.5 km**2) situated on the Amazonian side of the Cordillera Real in the southernmost Andes of Ecuador. The montane basin is covered with cloud forest, sub-páramo, pasture and ferns. Nested sampling was applied for the collection of streamwater samples and discharge measurements in the main tributaries and outlet of the basin, and for the collection of soil and rock water samples. Weekly to biweekly water grab samples were taken at all stations in the period April 2007-November 2008. Hydrometric data, Mean Transit Time and Mixing Model Analysis allowed preliminary evaluation of the processes controlling the runoff in the San Francisco River basin. Results suggest that flow during dry conditions mainly consists of lateral flow through the C-horizon and cracks in the top weathered bedrock layer, and that all subcatchments have an important contribution of this deep water to runoff, no matter whether pristine or deforested. During normal to low precipitation intensities, when antecedent soil moisture conditions favour water infiltration, vertical flow paths to deeper soil horizons with subsequent lateral subsurface flow contribute most to streamflow. Under wet conditions in forested catchments, streamflow is controlled by near surface lateral flow through the organic horizon. Exceptionally, saturation excess overland flow occurs. By absence of the litter layer in pasture, streamflow under wet conditions originates from the A horizon, and overland flow.

Sorption and desorption behaviour of acetochlor in surface, subsurface and size-fractionated soil

Pesticides leaching through a soil profile will be exposed to changing environmental sorption and desorption conditions as different horizons with distinct physical and chemical properties are encountered. Soil cores were taken from a clay soil profile and samples taken from 0.0 to 0.3 m (surface), 1.0-1.3 m (mid) and 2.7-3.0 m (deep) and treated with the chloroacetanilide herbicide, acetochlor. Freundlich isotherms revealed that sorption and desorption behaviour varied with each depth sampled. As soil depth increased, the extent and strength of sorption decreased, indicating that the potential for leaching was increased in the subsoils compared with the surface soil. Hysteresis was evident at each of the three depths sampled, although no significant correlations between soil properties and the hysteresis coefficients were evident. Desorption studies using soil fractions with diameters of > 2000, 250-2000, 53-250, 20-53, 2-20, 0-2 and 0-1 mum separated from each of the three soil depths showed that differential desorption kinetics occurred and that the retention of acetochlor significantly correlated (R-2 = 0.998) with organic matter content. A greater understanding of the influence of soil components on the overall sorption and desorption potential of surface and subsurface soils is required to allow accurate prediction of acetochlor retention in the soil. In addition, it is likely that the proportion of each size fraction in a soil horizon would influence acetochlor bioavailability and movement to groundwater.

Dissipation of acetochlor and its distribution in surface and sub-surface soil fractions during laboratory incubations

Pesticides in soil are subject to a number of processes that result in transformation and biodegradation, sorption to and desorption from soil components, and diffusion and leaching. Pesticides leaching through a soil profile will be exposed to changing environmental conditions as different horizons with distinct physical, chemical and biological properties are encountered. The many ways in which soil properties influence pesticide retention and degradation need to be addressed to allow accurate predictions of environmental fate and the potential for groundwater pollution. Degradation and sorption processes were investigated in a long-term (100 days) study of the chloroacetanilide herbicide, acetochlor. Soil cores were collected from a clay soil profile and samples taken from 0-30cm (surface), 1.0-1.3m (mid) and 2.7-3.0m (deep) and treated with acetochlor (2.5, 1.25, 0.67 mu g acetochlor g(-1) dry wt soil, respectively). In sterile and non-sterile conditions, acetochlor concentration in the aqueous phase declined rapidly from the surface and subsoil layers, predominantly through nonextractable residue (NER) formation on soil surfaces, but also through biodegradation and biotic transformation. Abiotic transformation was also evident in the sterile soils. Several metabolites were produced, including acetochlor-ethane sulphonic acid and acetochlor-oxanilic acid. Transformation was principally microbial in origin, as shown by the differences between non-sterile and sterile soils. NER formation increased rapidly over the first 21 days in all soils and was mainly associated with the macroaggregate (> 2000 mu m diameter) size fractions. It is likely that acetochlor is incorporated into the macroaggregates through oxidative coupling, as humification of particulate organic matter progresses. The dissipation (ie total loss of acetochlor) half-life values were 9.3 (surface), 12.3 (mid) and 12.6 days (deep) in the non-sterile soils, compared with 20.9 [surface], 23.5 [mid], and 24 days [deep] in the sterile soils, demonstrating the importance of microbially driven processes in the rapid dissipation of acetochlor in soil.

Synthesis and structure characterization of chromium oxide prepared by solid thermal decomposition reaction

Mesoporous chromium oxide (Cr2O3) nanocrystals were first synthesized by the thermal decomposition reaction of Cr(NO3)(3)(circle)9H(2)O using citric acid monohydrate (CA) as the mesoporous template agent. The texture and chemistry of chromium oxide nanocrystals were characterized by N-2 adsorption-desorption isotherms, FTIR, X-ray diffraction (XRD), UV-vis, and thermoanalytical methods. It was shown that the hydrate water and CA are the crucial factors in influencing the formation of mesoporous Cr2O3 nanocrystals in the mixture system. The decomposition of CA results in the formation of a mesoporous structure with wormlike pores. The hydrate water of the mixture provides surface hydroxyls that act as binders, making the nanocrystals aggregate. The pore structures and phases of chromium oxide are affected by the ratio of precursor-to-CA, thermal temperature, and time.

Bio-inspired carbon electro-catalysis for the oxygen reduction reaction

We report the synthesis, characterisation and catalytic performance of two nature-inspired biomass-derived electro-catalysts for the oxygen reduction reaction in fuel cells. The catalysts were prepared via pyrolysis of a real food waste (lobster shells) or by mimicking the composition of lobster shells using chitin and CaCO3 particles followed by acid washing. The simplified model of artificial lobster was prepared for better reproducibility. The calcium carbonate in both samples acts as a pore agent, creating increased surface area and pore volume, though considerably higher in artificial lobster samples due to the better homogeneity of the components. Various characterisation techniques revealed the presence of a considerable amount of hydroxyapatite left in the real lobster samples after acid washing and a low content of carbon (23%), nitrogen and sulphur (<1%), limiting the surface area to 23 m2/g, and consequently resulting in rather poor catalytic activity. However, artificial lobster samples, with a surface area of ≈200 m2/g and a nitrogen doping of 2%, showed a promising onset potential, very similar to a commercially available platinum catalyst, with better methanol tolerance, though with lower stability in long time testing over 10,000 s.

Surface catalysed Suzuki-Miyaura cross-coupling by Pd nanoparticles:an operando XAS study

Size-controlled, catalytically active PVP-stabilised Pd nanoparticles have been studied by operando liquid phase XAS during the Suzuki cross-coupling of iodonanisole and phenylboronic acid in MeOH-toluene using KOMe base. XAS reveals nanoparticles are stable to metal leaching throughout the reaction, with surface density Pd defect sites directly implicated in the catalytic cycle. The efficacy of popular selective chemical and structural poisons for distinguishing heterogeneous and homogeneous contributions in Pd catalysed cross-couplings is also explored. © 2010 The Royal Society of Chemistry.

Anisotropic surface chemistry of aspirin crystals

The wettability of the (001), (100), and (011) crystallographic facets of macroscopic aspirin crystals has been experimentally investigated using a sessile drop contact angle (θ) method. θ for a nonpolar liquid was very similar for all three facets, though significant θ differences were observed for three polar probe liquids. The observed hydrophobicity of the (001) and (100) facets is ascribed to a reduced hydrogen bonding potential at these surfaces, whilst the observed hydrophilicity of facet (011) may be attributed to presence of surface carboxylic functionalities as confirmed by X-ray photoelectron spectroscopy (XPS). The dispersive component of the surface free energy (γ) was similar for all three facets (35 ± 2 mJ/m). The total surface energy, γs varied between 46 and 60 mJ/m due to significant variations in the polar/acid-base components of γ for all facets. Surface polarity as determined by γ measurements and XPS data were in good agreement, linking the variations in wettability to the concentration of oxygen containing surface functional groups. In conclusion, the wettability and the surface energy of a crystalline organic solid, such as aspirin, was found to be anisotropic and facet dependant, and in this case, related to the presence of surface carboxylic functionalities. © 2007 Wiley-Liss, Inc. and the American Pharmacists Association.

Zirconium phosphate supported tungsten oxide solid acid catalysts for the esterification of palmitic acid

A series of zirconium phosphate supported WOx solid acid catalysts with W loadings from 1–25 wt% have been prepared on high surface area zirconium phosphate by a surface grafting method. Catalysts were characterized by N2 adsorption, FTIR, Raman, UV-Vis, 31P MAS NMR, pyridine TPD and X-ray methods. Spectroscopic measurements suggest a Keggin-type structure forms on the surface of zirconium phosphate as a ([triple bond, length as m-dash]ZrOH2+)(ZrPW11O405−) species. All catalysts show high activity in palmitic acid esterification with methanol. These materials can be readily separated from the reaction system for re-use, and are resistant to leaching of the active heteropolyacid, suggesting potential industrial applications in biodiesel synthesis. © The Royal Society of Chemistry 2006.

A Fast XPS study of the surface chemistry of ethanol over Pt{1 1 1}

The adsorption and reaction of ethanol over Pt{1 1 1} has been investigated by Fast XPS and TPD. Ethanol adsorbs molecularly at 100 K, with a saturation coverage of 0.44 ML giving rise to C 1s components with binding energies of 283.7 eV (CH3–) and 284.8 eV (–H2COH). Ethanol multilayers desorb above 150 K, while ∼60% of the monolayer desorbs intact above 200 K in competition with decomposition pathways. Reaction initially proceeds via progressive dehydrogenation to form a metastable acetyl intermediate with components at 283.5 eV (CH3–) and 285.2 eV (-C=O), which in turn undergoes decarbonylation above 250 K to chemisorbed CO and methyl groups. A significant fraction of the latter are hydrogenated above 270 K, desorbing as CH4, with the remainder further decomposing to liberate H2 and surface CHx moeities.

Polymer-lipid interactions:biomimetic self-assembly behaviour and surface properties of poly(styrene-alt-maleic acid) with diacylphosphatidylcholines

Abstract Various lubricating body fluids at tissue interfaces are composed mainly of combinations of phospholipids and amphipathic apoproteins. The challenge in producing synthetic replacements for them is not replacing the phospholipid, which is readily available in synthetic form, but replacing the apoprotein component, more specifically, its unique biophysical properties rather than its chemistry. The potential of amphiphilic reactive hypercoiling behaviour of poly(styrene-alt-maleic acid) (PSMA) was studied in combination with two diacylphosphatidylcholines (PC) of different chain lengths in aqueous solution. The surface properties of the mixtures were characterized by conventional Langmuir-Wilhelmy balance (surface pressure under compression) and the du Noüy tensiometer (surface tension of the non-compressed mixtures). Surface tension values and 31P NMR demonstrated that self-assembly of polymer-phospholipid mixtures were pH and concentration-dependent. Finally, the particle size and zeta potential measurements of this self-assembly showed that it can form negatively charged nanosized structures that might find use as drug or lipids release systems on interfaces such as the tear film or lung interfacial layers. The structural reorganization was sensitive to the alkyl chain length of the PC.

The surface chemistry of nanocrystalline MgO catalysts for FAME production:an in situ XPS study of H2O, CH3OH and CH3OAc adsorption

An in situ XPS study of water, methanol and methyl acetate adsorption over as-synthesised and calcined MgO nanocatalysts is reported with a view to gaining insight into the surface adsorption of key components relevant to fatty acid methyl esters (biodiesel) production during the transesterification of triglycerides with methanol. High temperature calcined NanoMgO-700 adsorbed all three species more readily than the parent material due to the higher density of electron-rich (111) and (110) facets exposed over the larger crystallites. Water and methanol chemisorb over the NanoMgO-700 through the conversion of surface O2 − sites to OH− and coincident creation of Mg-OH or Mg-OCH3 moieties respectively. A model is proposed in which the dissociative chemisorption of methanol occurs preferentially over defect and edge sites of NanoMgO-700, with higher methanol coverages resulting in physisorption over weakly basic (100) facets. Methyl acetate undergoes more complex surface chemistry over NanoMgO-700, with C–H dissociation and ester cleavage forming surface hydroxyl and acetate species even at extremely low coverages, indicative of preferential adsorption at defects. Comparison of C 1s spectra with spent catalysts from tributyrin transesterification suggest that ester hydrolysis plays a key factor in the deactivation of MgO catalysts for biodiesel production.

Progress in the development of mesoporous solid acid and base catalysts for converting carbohydrates into platform chemicals

This chapter provides a general overview of recent studies on catalytic conversion of fructose, glucose, and cellulose to platform chemicals over porous solid acid and base catalysts, including zeolites, ion-exchange resins, heteropoly acids, as well as structured carbon, silica, and metal oxide materials. Attention is focused on the dehydration of glucose and fructose to HMF, isomerization of glucose to fructose, hydrolysis of cellulose to sugar, and glycosidation of cellulose to alkyl glucosides. The correlation of porous structure, surface properties, and the strength or types of acid or base with the catalyst activity in these reactions is discussed in detail in this chapter.

Time series of air chemistry measurements at Georg-von-Neumayer station, Dronning Maud Land, Antarctica in the years 1982 to 1991

The first Air Chemistry Observatory at the German Antarctic station Georg von Neumayer (GvN) was operated for 10 years from 1982 to 1991. The focus of the established observational programme was on characterizing the physical properties and chemical composition of the aerosol, as well as on monitoring the changing trace gas composition of the background atmosphere, especially concerning greenhouse gases. The observatory was designed by the Institut für Umweltphysik, University of Heidelberg (UHEIIUP). The experiments were installed inside the bivouac lodge, mounted on a sledge and put upon a snow hill to prevent snow accumulation during blizzards. All experiments were under daily control and daily performance protocols were documented. A ventilated stainless steel inlet stack (total height about 3-4 m above the snow surface) with a 50% aerodynamic cut-off diameter around 7-10 µm at wind velocities between 4-10 m/s supplied all experiments with ambient air. Contamination free sampling was realized by several means: (i) The Air Chemistry Observatory was situated in a clean air area about 1500 m south of GvN. Due to the fact that northern wind directions are very rare, contamination from the base can be excluded for most of the time. (ii) The power supply (20 kW) is provided by a cable from the main station, thus no fuel-driven generator is operated in the very vicinity. (iii) Contamination-free sampling is controlled by the permanently recorded wind velocity, wind direction and by condensation particle concentration. Contamination was indicated if one of the following criteria were given: Wind direction within a 330°-30° sector, wind velocity <2.2 m/s or >17.5 m/s, or condensation particle concentrations >2500/cm**3 during summer, >800/cm**3 during spring/autumn and >400/cm**3 during winter. If one or a definable combination of these criteria were given, high volume aerosol sampling and part of the trace gas sampling were interrupted. Starting at 1982 through 1991-01-14 surface ozone was measured with an electrochemical concentration cell (ECC). Surface ozone mixing ratio are given in ppbv = parts per 10**9 by volume. The averaging time corresponds to the given time intervals in the data sheet. The accuracy of the values are better than ±1 ppbv and the detection limit is around 1.0 ppbv. Aerosols were sampled on two Whatman 541 cellulose filters in series and analyzed by ion chromatography at the UHEI-IUP. Generally, the sampling period was seven days but could be up to two weeks on occasion. The air flow was around 100 m**3/h and typically 10000-20000 m**3 of ambient air was forced through the filters for one sample. Concentration values are given in nanogram (ng) per 1 m**3 air at standard pressure and temperature (1013 mbar, 273.16 K). Uncertainties of the values were approximately ±10% to ±15% for the main components MSA, chloride, nitrate, sulfate and sodium, and between ±20% and ±30% for the minor species bromide, ammonium, potassium, magnesium and calcium.