Carbonaceous Carriers Research Articles

Ultraviolet electronic spectroscopy of heavily substituted naphthalene derivatives

Context. The so-called bump spectral signature observable on interstellar extinction curves, peaking at 217.5 nm, is commonly assigned to π* ← π transitions from carbonaceous carriers, but the exact nature of the carbonaceous carriers remains debated. Aims. To constrain the chemical structures associated with the bump carriers, we record and compare the UV spectra of a large variety of carbonaceous molecules to this interstellar feature. Methods. Large carbonaceous molecules, such as polycyclic aromatic hydrocarbons (PAHs), were produced by a combustion process stabilized at low pressure under rich flame conditions. Species were extracted and probed through resonance enhanced multiphoton ionization spectroscopy coupled to a time-of-flight mass spectrometer. Masses and absorption profiles of the carbonaceous molecules were measured, and their spectra were compared to the bump feature. Results. Species showing a specific mass progression starting at mass 128 u visible up to mass 394 u with a characteristic progression of +14 u present a common electronic absorption band profile peaking asymptotically around 220 nm. The first masses were assigned to a naphthalene C10H8 molecule and two of its derivatives: C10H7CH3 and C10H7C2H5. The mass progression of +14 u is explained by successive H atom substitutions by CH3 functional groups. This mass distribution was thus assigned to naphthalene derivatives with large aliphatic carbon substitution. This derivative family shows an electronic band assigned to S3 ← S0 transitions involving electron promotion within the π aromatic orbitals of the naphathlene chromophore. More importantly, after a few substitutions, the position of the band converges asymptotically to a value close to the interstellar bump signature, independent of the molecule size. Conclusions. Based on the asymptotic behavior of the larger members in the species distribution, a similar band position is expected from double aromatic ring substructures within hydrogenated amorphous carbons (HACs). Similar to the conclusions of previous works, we find substituted naphthalene units as substructures of interstellar HACs to be good candidates as carriers of the bump feature.

Review and Development of Anode Electrocatalyst Carriers for Direct Methanol Fuel Cell

Direct methanol fuel cell (DMFC) can be used as a promising portable power device due to its excellent energy conversion efficiency and low pollutant emissions. The performance of DMFC largely depends on the anode electrocatalyst for methanol oxidation reaction (MOR). As an important part of the electrocatalyst, the carrier greatly affects the activity and stability of the electrocatalyst. Herein, the research progress of carbonaceous carriers (such as activated carbon, nanostructured carbon), noncarbonaceous carriers (metal compounds), and conducting polymers in DMFC is reviewed. Furthermore, an overview of the development of self‐supporting carriers for flexible DMFC electronics is presented. Its role as the most ideal DMFC carrier in the future provides new ideas for the challenges and development of the commercialization of flexible DMFC.

Embedding Fe2P nanocrystals in bayberry-like N, P-enriched carbon nanospheres as excellent oxygen reduction electrocatalyst for zinc-air battery

Transition metal phosphide/carbon composites are promising electrocatalysts for oxygen reduction reaction (ORR). Herein, we propose a facile process to fabricate a bayberry-like N, P-enriched carbon nanospheres embedded with Fe2P nanocrystals (Fe2P/NPCs). Bayberry-like polyaniline nanospheres (PANI-NS) are firstly synthesized through microemulsion template method. Then, Fe is incorporated in PANI-NS during the hydrothermal treatment. Lastly FexP nanocrystals and N, P-enriched carbonaceous carriers are obtained by pyrolyzing the hydrothermal-treated PANI-NS. The resultant FexP/NPCs exhibit a uniform particle size (~250 nm), a large specific surface area (523 m2 g−1) and a homogeneous mesoporous structure (~3.46 nm). The phase structure of FexP depends on the Fe/P (molar ratio) during hydrothermal treatment. When Fe/P is around 0.2, a preferable Fe2P phase is obtained. The Fe2P/NPCs exhibit outstanding ORR electrocatalytic activity with a half-wave potential of 0.820 V (vs. RHE) and a diffusion-limited current density of 5.58 mA cm−2, comparable with commercial Pt/C. Moreover, Fe2P/NPCs possess a good duration stability and higher methanol tolerance than commercial Pt/C. When assembled in zinc-air batteries, Fe2P/NPCs contribute to an open circuit voltage of 1.449 V, a maximum power density of 128.38 mW cm−2, and a specific capacity of 691.0 mAh g−1, superior to the commercial Pt/C-based zinc-air battery.

Role of Carbonaceous Supports and Potassium Promoter on Higher Alcohols Synthesis over Copper–Iron Catalysts

The identification of an effective copper–iron catalyst for the direct conversion of synthesis gas into higher alcohols is hindered by the low solubility limit of Cu in Fe and the limited understanding of structural and electronic descriptors in such multicomponent systems. Here, commercial carbonaceous carriers are shown to produce an efficient material only if they enable control of the size and location of metal species through confinement in adequately sized channels, with conical carbon nanofibers being more adequate than carbon nanotubes. Application of a sol–gel route was preferred to other deposition methods to avoid excessive Cu aggregation, associated with enhanced CO2 formation. A bulk Cu/Fe ratio of 2 permitted one to balance the different tendencies of Cu and Fe toward agglomeration, i.e., to form numerous Cu particles of moderate size and hinder the dispersion of the Fe phase and in turn the Fischer–Tropsch activity. Promotion by tiny amounts of potassium was instrumental to further increase...

Polyaromatic disordered carbon grains as carriers of the UV bump: Far-UV to mid-IR spectroscopy of laboratory analogs

Context. A multiwavelength study of laboratory carbons with varying degrees of hydrogenation and sp2 hybridization is required to characterize the structure of the carbonaceous carriers of interstellar and circumstellar extinction. Aims. We study the spectral properties of carbonaceous dust analogs from the far-ultraviolet to the mid-infrared and correlate features in both spectral ranges to the aromatic/aliphatic degree. Methods. Analogs to carbonaceous interstellar dust encountered in various phases of the interstellar medium have been prepared in the laboratory. These are amorphous hydrogenated carbons (a-C:H), analogs to the diffuse interstellar medium component, and soot particles, analogs to the polyaromatic component. Thin films (d < 100 nm) have been measured in transmission in the vacuum-ultraviolet (VUV; 120–210 nm) within the atmospheric pressure experiment (APEX) chamber of the DISCO beam line at the SOLEIL synchrotron radiation facility. Spectra of these films were further measured through the UV-Vis (210 nm–1 μm) and in the mid-infrared (3–15 μm). Results. Tauc optical gaps, Eg, are derived from the visible spectra. The major spectral features are fitted through the VUV to the mid-infrared to obtain positions, full-widths at half maximum (FWHM), and integrated intensities. These are plotted against the position of the π-π∗ electronic transitions peak. Unidentified or overlapping features in the UV are identified by correlations with complementary infrared data. A correlation between the optical gap and position of the π-π∗ electronic transitions peak is found. The latter is also correlated to the position of the sp3 carbon defect band at ~8 μm, the aromatic C=C stretching mode position at ~6 μm, and the H/C ratio. Conclusions. Ultraviolet and infrared spectroscopy of structurally diverse carbon samples are used to constrain the nanostructural properties of carbon carriers of both circumstellar and interstellar extinction, such as the associated coherent lengths and the size of polyaromatic units. Our study suggests that carriers of the interstellar UV bump should exhibit infrared bands akin to the A/B classes of the aromatic infrared bands, while the circumstellar bump carriers should exhibit bands corresponding to the B/C classes.

The Genesis solar xenon composition and its relationship to planetary xenon signatures

The fluence and isotopic composition of solar wind xenon have been determined from silicon collector targets flown on the NASA Genesis mission. A protocol was developed to extract gas quantitatively from samples of ∼9–25mm2, and xenon measured using the RELAX mass spectrometer. The fluence of implanted solar wind xenon is 1.202(87)×106 atoms 132Xecm−2, which equates to a flux of 5.14(21)×106 atoms 132Xecm−2year−1 at the L1 point. This value is in good agreement with those reported in other studies. The isotopic composition of the solar wind is consistent with that extracted from the young lunar regolith and other Genesis collector targets.The more precise xenon isotopic data derived from the Genesis mission confirm models of relationships among planetary xenon signatures. The underlying composition of Xe-Q is mass fractionated solar wind; small, varying contributions of Xe-HL and 129Xe from 129I decay are present in reported meteorite analyses. In contrast, an s-process deficit is apparent in Xe-P3, which appears to have been mass fractionated to the same extent as Xe-Q from a precursor composition, suggesting similar trapping mechanisms. Solar wind xenon later evolved by the addition of ∼1% (at 132Xe) of s-process xenon to this precursor. As an alternative model to a single source reservoir for Xe-P3, we propose that trapping of xenon onto carbonaceous carriers has been an ongoing process across galactic history, and that preparation of the residues in which Xe-P3 has been identified preferentially preserves longer lived host phases; a higher proportion of these sample xenon isotopic compositions from earlier in galactic chemical evolution, allowing the s-process deficit to become apparent. The relationships among SW-Xe, Xe-Q and Xe-P3 predict that the 124Xe/132Xe ratio for the solar wind is 0.00481(6).

On the carbonaceous carriers of infrared plateau and continuum emission

This study explores the molecular origins of plateaus and continua underlying the infrared and far-infrared (far-IR) bands emitted by compact nebulae, especially protoplanetary nebulae. Computational organic chemistry codes are used to deliver the vibrational integrated band intensities of various large, typical carbonaceous structures. These spectra are composed of a rather continuous distribution of weak modes from which emerge the fingerprints. The 6–18 μm region is interspersed with a great many weak lines, to which the plateaus are assigned. Similarly, the far-IR spectrum is ascribed to the phonon (skeletal) spectrum which is readily identified beyond 18 μm. The absorptivities and absorption cross-sections per interstellar H atom deduced from these spectra are comparable with those of laboratory dust analogues and astronomical measurements, respectively. Moreover, the 5–35 μm spectra of two typical protoplanetary nebulae were reasonably well simulated with combinations of molecules containing functional groups which carry the 21- and 30-μm bands, and molecules devoid of these but carrying strong phonon spectra. These results may help understand the emergence of plateaus, the origin of continua underlying far-IR bands, as well as the composition of circumstellar dust.

Nanogold‐Loaded Sharp‐Edged Carbon Bullets as Plant‐Gene Carriers

AbstractThe higher DNA delivery efficiency into plants by gold nanoparticles embedded in sharp carbonaceous carriers is demonstrated. These nanogold‐embedded carbon matrices are prepared by heat treatment of biogenic intracellular gold nanoparticles. The DNA‐delivery efficiency is tested on a model plant, Nicotiana tabacum, and is further extended to the monocot, Oryza sativa, and a hard dicot tree species, Leucaena leucocephala. These materials reveal good dispersion of the transport material, producing a greater number of GUS foci per unit area. The added advantages of the composite carrier are the lower plasmid and gold requirements. Plant‐cell damage with the carbon‐supported particles is very minimal and can be gauged from the increased plant regeneration and transformation efficiency compared with that of the commercial micrometer‐sized gold particles. This is ascribed to the sharp edges that the carbon supports possess, which lead to better piercing capabilities with minimum damage.

Effect of the functionalizing of carbon nanotubes on the electrodeposited catalysts’ structure and catalytic properties

The structure and hydrophilic-hydrophobic properties of functionalized single-wall carbon nanotubes are studied by the standard porosimetry method. It is shown that the functionalized nanotubes have highly hydrophilic surface; at that the summary surface area measured “by octane” decreased, as a result of the functionalizing, due to the blocking of the nanotubes’ inner channels by the functional groups located at the nanotubes’ ends. The nanotubes’ capacitive properties are studied; their charging-discharging curves appeared being highly reversible, unlike those of other carbonaceous materials. Catalytic properties of the functionalized nanotubes are studied, with particular tendency toward their using as a carrier of platinum catalysts for the methanol oxidation and oxygen electroreduction reactions. When minor amounts (5–10 µg cm−2) of platinum or platinum-ruthenium alloy are deposited onto the nanotubes’ hydrophilic surface, uniform layer of the catalyst is formed, with specific surface area up to 150–300 m2 g−1; high current of the methanol oxidation or oxygen electroreduction is observed at these catalysts. When the catalyst deposit mass increased, its specific surface area decreased, as well as the specific current of the reactions occurring thereon. When the current is related to the electrochemically active unit surface, the catalytic activity is nearly the same both for different catalyst mass deposited onto the nanotubes and the same catalyst mass at different carbonaceous carriers.

Preparation of nanosized metal (oxides) by gas phase hydrolysis using mesoporous materials as nanoreactors

Immobilized nanosized metal (oxides) on carbonaceous carriers were prepared by hydrolysis under mild conditions by using the carrier pores as a kind of nanoreactor. Metal alkoxide vapor was adsorbed on the carrier and then formed the product upon exposure to water vapor. With this facile method, Titania, Vanadia, Rhodium (oxide), and Platinum (oxide) nanostructures were prepared at high yields, high loadings, and good dispersion in the carrier material. High number concentrations of spheroidal nanoparticles of uniform size (diameter ca. 5 nm) were obtained from less reactive precursors, whereas with highly reactive precursors, such nanoparticles occurred only after subsequent calcination. Nanoparticles appeared to be the thermodynamically stable form of the metal (oxide) produced in the pores. Highly reactive precursors formed metastable seeds, which nucleated and restructured into nanoparticles upon subsequent exposure to heat. The presented method allows for preparation of metal (oxide) nanostructures and effective control of their size and shape.

Effect of Carbonaceous Carrier and Promoter on Electrocatalytical Properties of Composite Cathodes in Fuel Cells with Alkaline Electrolyte

The activity of composite catalysts, Pt and Co-porphyrin- or Fe-phthalocyanine-based pyropolymers on low-disperse carbonaceous carriers (graphite, carbon black), in the oxygen and H2O2electroreduction in 1 M KOH is studied. Kinetic parameters of oxygen electroreduction are determined from experiments with rotating disk and model floating electrodes. Possible mechanism of the oxygen electroreduction reaction is discussed; it includes a slow stage of attachment of the second electron on the pyropolymer/carbonaceous carrier or joining the first electron (under the conditions of Temkin adsorption) on the platinum/graphite catalysts.

Trapped xenon in ordinary chondrites

A trapped component of heavy noble gases representing a distinct solar system (presumably asteroid belt) reservoir is known to be concentrated in carbonaceous carriers of chondritic meteorites. The isotopic signature of trapped Xe in separates of the H4 chondrite Forest Vale (FV) was determined by combusting its carrier phases at 600°C in oxygen, discriminating against in situ produced nucleogenic components which are released above 600°C. The isotopic abundances of FVC (combustion)‐Xe are compared to signatures of bulk trapped Xe in chondritic meteorites. We conclude that FVC‐Xe represents the predominant trapped component in ordinary chondrites (OC) for which we adopt the term OC‐Xe. Its isotopic signature differs from Xe in ureilites, in “average carbonaceous chondrites”, in Earth's atmosphere, and in the solar wind. Additional minor Xe components were identified in type 3 chondrites and in the metal phase of chondrites. We discuss relationships among solar system Xe reservoirs and show that the OC‐Xe signature is consistent with a mixture of HL‐Xe with slightly mass fractionated solar‐type Xe.

Determination of Biomass in Activated Sludge Containing Large Quantities of Carbonaceous Solid Carriers

Abstract The exact estimation of biomass in the presence of carbonaceous carriers is an unresolved problem. Inaccuracy arises from the use of mixed liquor volatile suspended solids (MLVSS) determination as the measure of biomass, due to the volatilization properties of some carrier particles at 550°C. Problems are also associated with the differential ignition technique and nitric acid digestion technique, which are used instead of the MLVSS determination. Therefore, a method of calculating the biomass content by the determination of nitrogen in the mixed liquor suspended solids is proposed. In this paper, the proposed method is compared with the differential ignition technique. The Nitric acid digestion technique was not used in this study due to the explosive nature of one of the carbonaceous carriers when digested with nitric acid. It was found that calculation based on the nitrogen analysis gave a more reliable estimate of biomass in systems containing carbonaceous particles than the differential ignition technique.