Synthesis of high purity narrow-width carbon nanotubes

We have succeeded in controlling the width of multi-walled carbon nanotubes (MWCNT) by physical manipulation and pretreatment of the catalyst prior to reaction in a CO/H₂ reactant mixture. Since the size of the metal catalyst particle determines the width of the nanotube, we have investigated the notion of introducing a dispersing agent into the catalyst formulation that facilitates fragmentation and prevents sintering of the granules during the reduction step. Inclusion of 5 wt.% silica into a Fe–Ni (6:4) catalyst was found to reduce the average width of MWCNT from about 40 to 20 nm, when the bimetallic was reacted in CO/H₂ (1:4) at 670 °C. On the other hand, when 5 wt.% NaCl was used as the dispersant the average width of the MWCNT was decreased to about 11 nm. The impact of both the catalyst pre-treatment and various post-treatment procedures on the width and purity of the final MWCNT product is discussed.     

Decoration of multiwalled carbon nanotubes with protected iron nanoparticles

A method to simultaneously synthesize carbon-encapsulated magnetic iron nanoparticles (Fe-NPs) and attach these particles to multi-walled carbon nanotubes (MWCNT) is presented. Thermal decomposition of cyclopentadienyliron dicarbonyl dimer [(C₅H₅)₂Fe₂(CO)₄], over a range of temperatures from 250 °C to 1200 °C, results in the formation of Fe-NPs attached to MWCNT. At the same time, a protective carbon shell is produced and surrounds the Fe-NPs, covalently attaching the particles to the MWCNT and leading to resistance to acid dissolution. The carbon coating varies in degree of graphitisation, with higher synthesis temperatures leading to a higher degree of graphitisation. The growth model of the nanoparticles and subsequent mechanism of MWCNT attachment is discussed. Adsorption potential of the hybrid material towards organic dyes (Rhodamine B) has been displayed, an indication of potential uses as a material for water treatment. The material has also been electrospun into aligned nanocomposite fibres to produce a soft magnetic composite (SMC) with future applications in sensors and fast switching solenoids.     

The influence of crosslinking and fumed silica nanoparticles on mixed gas transport properties of poly[1-(trimethylsilyl)-1-propyne]

Crosslinking poly[1-(trimethylsilyl)-1-propyne] (PTMSP) films with 3,3′-diazidodiphenylsulfone, a bis(azide) crosslinker, rendered the films insoluble in common solvents for PTMSP such as toluene. At all temperatures, mixed gas CH₄ and n-C₄H₁₀ permeabilities of crosslinked PTMSP were less than those of uncrosslinked PTMSP, which correlates with lower free volume in the crosslinked material. The presence of fumed silica (FS) nanoparticles in both uncrosslinked PTMSP and crosslinked PTMSP increased mixed gas CH₄ and n-C₄H₁₀ permeabilities, consistent with the disruption of polymer chain packing by such nanoparticles. Mixed gas CH₄ permeabilities of all films were significantly less than their corresponding pure gas CH₄ permeabilities. For example, at 35 °C, the mixed gas CH₄ permeabilities were approximately 60–80% less than their pure gas values. The greatest decrease was observed for uncrosslinked PTMSP, while nanocomposite PTMSP films showed the least decrease. The mixed gas n-C₄H₁₀/CH₄ selectivities of crosslinked PTMSP and nanocomposite PTMSP films were less than those of uncrosslinked PTMSP at all temperatures. For example, at 35 °C, the mixed gas n-C₄H₁₀/CH₄ selectivities of uncrosslinked PTMSP, crosslinked PTMSP containing 10 wt% crosslinker, and uncrosslinked PTMSP containing 30 wt% FS were 33, 27, and 17, respectively, when the feed gas contained 2 mol% n-C₄H₁₀ and the total upstream mixture fugacity was 11 atm. For all films, as temperature decreased, mixed gas n-C₄H₁₀ permeabilities increased, and mixed gas CH₄ permeabilities decreased. Consequently, the mixed gas n-C₄H₁₀/CH₄ selectivities increased substantially as temperature decreased and the mixed gas selectivity of uncrosslinked PTMSP increased from 33 to 170 as temperature decreased from 35 °C to ?20 °C when the feed gas contained 2 mol% n-C₄H₁₀ and the total upstream mixture fugacity was 11 atm.     

Metal-catalyzed etching of graphene governed by metal–carbon interactions: A comparison of Fe and Cu

We present a comparative investigation on the etching of graphene catalyzed by Fe and Cu. When Fe or Cu thin film deposited on graphene is rapidly annealed in either N₂ or forming gas (10% H₂/90% N₂), particles are produced due to the dewetting of thin films. Low-voltage scanning electron microscopy reveals different morphology for Fe and Cu particles and their strikingly different catalytic etching behaviors. For the Fe thin film on graphene annealed at 950 °C in either gas environment, graphene is severely damaged, suggesting that the etching could occur through catalytic carbon hydrogenation or carbon dissolution into Fe due to the strong Fe–C interactions. In contrast, while no etching takes place for Cu particles on graphene at 1050 °C in N₂, Cu particles catalytically etch channels in graphene in forming gas through carbon hydrogenation, and the width of the channel is much narrower than the diameter of Cu particle due to the non-wetting behavior of Cu on graphene. The weak interactions between Cu and graphene, along with the low solubility of carbon in Cu, make Cu particles ideal for tracking their etching paths on graphene. This work provides new insights into the metal-catalyzed etching of graphene.     

Characterization of Li–Zn–Fe crystalline phases in low temperature ceramic glaze

Ceramic glaze containing Li₂O and ZnO was prepared at a low firing temperature of 1100 °C. Addition of 0–30 wt.% iron oxide content developed brown color with a metallic sparkling effect from crystallization after soaking at 980–1080 °C. Using XRD, SEM/EDS and Raman microscopy the crystalline phases were determined as lithium zinc ferrite (Li_xZn_1?2xFe_2+xO₄ where x = 0.05–0.20), hematite (α-Fe₂O₃) and anorthite (CaAl₂Si₂O₈). The most preferable metallic sparkling effect was caused by the lithium zinc ferrite phase obtained from the glaze containing 10 wt.% of iron oxide. Thermal analysis by STA after heat treatment indicated that crystallization temperature of lithium zinc ferrite and the effective soaking temperature depended on the iron oxide content in the glaze. The influence of excessive iron oxide content on the crystallization behavior of lithium zinc ferrite, anorthite and hematite phases is discussed.     

Extraordinary mechanical flexibility in composite thin films composed of bimetallic AgPt nanoparticle-decorated multi-walled carbon nanotubes

Flexible, transparent, and conducting composite thin films, constructed from multi-walled carbon-nanotube-supported silver–platinum alloy nanoparticles (AgPt–MWCNT) on a flexible polyethylene terephthalate (PET) substrate through the combination of a two-step polyol process for synthesizing composites of carbon nanotubes (CNTs) and metallic nanoparticles (NPs) with an ultrasonic atomization-spin coating method for preparing thin films, have been fabricated. AgPt NPs with an average size of approximately 26 nm were uniformly attached to the sidewalls of MWCNTs to form an effective and strongly mechanical conductive network. These composites were then exposed to microwave plasma irradiation, which can lower the contact resistance between the metallic NPs and CNTs and reinforce the network bridges. The resulting AgPt–MWCNT–PET thin films exhibit improved optoelectronic and mechanical properties, and they possess a sheet resistance of 154 Ω/sq with a transmittance of 80% at 550 nm. These values are competitive with those of most other CNT-based films. Most importantly, the corresponding sheet conductivity does not decrease even after 500 bending cycles. Therefore, the as-produced AgPt–MWCNT–PET films may be direct alternatives to indium tin oxide and other transparent conducting oxide films.     

The role of inert gas in MW-enhanced plasmas for the deposition of nanocrystalline diamond thin films

Nanocrystalline diamond thin films have been deposited using microwave plasma enhanced deposition with gas mixtures of composition H₂/CH₄/X, where X was one of the inert gases He, Ne, Ar and Kr and typically constituted > 90% of the total gas flow. The diamond films obtained with each gas mixture deposited at approximately the same rate (0.15–0.5 µm h^? 1), and all showed similar morphologies and average grain sizes, despite very obvious differences in the appearance and gas temperatures of the respective plasmas. These plasmas were probed by optical emission and cavity ring-down spectroscopy, and results from companion 2D chemical kinetic modelling of the Ar/H₂/CH₄ and He/H₂/CH₄ plasma were used to guide interpretation of the experimental observations. We conclude that the inert gas, though acting primarily as a buffer, also has significant effects on the thermal conduction of the gas mixtures, the electron temperature and electron energy distribution, and thereby changes the main channels of ionization and input power absorption. As a result, inert gas dilution elevates the electron and gas temperatures, enhances the hydrogen dissociation degree and affects the H/C mixture composition and deposition mechanisms.     

Catalytic decomposition of ammonia gas with metal cations present naturally in low rank coals

A novel hot gas cleanup method to decompose a low concentration of NH₃ to N₂ with metal cations present inherently in low rank coals has been studied with a quartz reactor under the conditions of 750–850 °C, 0.1 MPa and high space velocity of 45,000 h⁻¹. Each coal is pyrolyzed at 900 °C to prepare the char, which is subjected to the decomposition of 2000 ppm NH₃ after pretreatment with H₂. All of five chars examined promote NH₃ decomposition in inert gas, but the promotion effect depends strongly on the kind of char and can correlate more closely with the Fe content than with the Ca content. This result may indicate that the Fe plays a crucial role in the reaction. A commercial activated carbon with a very low Fe content of <0.05 wt% exhibits lower conversion of NH₃ to N₂ than five chars. The TEM pictures reveal the formation of nanoscale particles of Fe and Ca components on a brown coal char that provides the largest catalytic performance. The char maintains the high conversion level of 80% during 25 h reaction at 750 °C and achieves the complete decomposition of NH₃ at 850 °C. The co-feeding of a mixture of H₂, CO, and CO₂ does not change significantly the catalytic activity of the char at a steady state, whereas the coexistence of 2000 ppm H₂S lowers it in the whole range of time on stream. It is proposed by combining the XRD and TPD observations with our previous results that the catalytic decomposition of NH₃ in inert gas with the chars derived from low rank coals proceeds through two cycle mechanisms involving iron metal, iron nitrides, CaO and CaCN₂.     

Synthesis of a graphene–carbon nanotube composite and its electrochemical sensing of hydrogen peroxide

Graphene, whose structure consists of a single layer of sp²-hybridized carbon atoms, provides an excellent platform for designing composite nanomaterials. In this study, we have demonstrated a facile process to synthesize graphene–multiwalled carbon nanotube (MWCNT) composite. The graphene–MWCNT composite material is endowed with a large electrochemical surface area and fast electron transfer properties in Fe(CN)₆^3?/4? redox species. A graphene–MWCNT composite modified electrode exhibits good performance in terms of the electrocatalytic reduction of H₂O₂; a sensor constructed from such an electrode shows a good linear dependence on H₂O₂ concentration in the range of 2 × 10^?5 to 2.1 × 10^?3 mol L^?1. The detection limit is estimated to be 9.4 × 10^?6 mol L^?1. This study provides a new kind of composite modified electrode for electrochemical sensors.     

H2 response characteristics for sol–gel-derived WO3-SnO2 dual-layer thin films

This paper describes the deposition of SnO₂ and WO₃ thin films and WO₃-SnO₂ dual-layer thin films using the sol-gel process. The microstructure and morphology of these three thin films were analyzed with FE-SEM and X-ray diffraction. The H₂ response characteristics, including response magnitude, time and transients of the three samples, were investigated at different operation temperatures and H₂ gas concentrations. Although the maximum response magnitude of 29.31 towards 1000 ppm H₂ gas appeared at 225 °C,the WO₃-SnO₂ dual-layer films still had a response magnitude of 24.23 at 175 °C, which is much higher than those of the SnO₂ (4.19) and WO₃ (6.73) thin films. The linear response magnitude profile of the WO₃-SnO₂ dual-layer thin films toward H₂ gas concentration was obtained. The mechanism of the enhanced gas response characteristics was explained by the band bending theory.     

Linkers and coordinated solvent molecules; the two effective factors on formation of zinc oxide nanoparticles from metal–organic frameworks

The host and the apohost frameworks of Zn₂(ndc)₂(DMF)₂ ∙(H₂O)₄ (1 ∙ DMF ∙ H₂O) and Zn₂(bdc)₂(H₂O)₂ ∙(DMF)₂ (2·H₂O·DMF), (H₂ndc = 2,6-naphthalene dicarboxylic acid, H₂bdc = benzene-1,4-dicarboxylic acid and DMF = N,N-Dimethylformamide), were synthesized, characterized and subsequently used for preparing of ZnO nanoparticles. The morphology of initial precursors has direct influence on agglomeration tendency of resulting ZnO nanoparticles. Linkers and coordinated solvent molecules are the two effective factors on the formation of zinc oxide nanoparticles from these metal–organic frameworks.     

Effect of Fe doping on TiO2 films prepared by spin coating

Iron-doped titanium dioxide thin films were coated on fluorine-doped tin oxide coated glass using the spin coating technique. The concentration of the dopant was varied up to 7 mol% iron (metal base). The films were characterised for their structural, morphological, and optical properties. Glancing angle X-ray diffraction and laser Raman microspectroscopy indicate that the films consisted solely of the anatase polymorph of titanium dioxide, without any contamination phases, such as iron oxide. Field emission scanning electron microscopy indicates that the films were microstructurally homogeneous and fully dense, with grains in the size range of ～10–20 nm. UV-VIS spectrophotometry shows that the optical indirect band gap of the films decreased with increasing iron doping (3.36 eV for undoped and 2.95 eV for 7 mol% Fe).     

Catalytic decomposition of biomass tars with iron oxide catalysts

Catalytic gasification of wood (Cedar) biomass was carried out using a specially designed flow-type double beds micro reactor in a two step process: temperature programmed non-catalytic steam gasification of biomass was performed in the first (top) bed at 200–850 °C followed by catalytic decomposition gasification of volatile matters (including tars) in the second (bottom) bed at a constant temperature, mainly 600 °C. Iron oxide catalysts, which transformed to Fe₃O₄ after use possessed catalytic activity in biomass tar decomposition. Above 90% of the volatile matters was gasified by the use of iron oxide catalyst (prepared from FeCl₃ and NH_3aq) at SV of 4.5 × 10³ h^?1. Tar was decomposed over the iron oxide catalysts followed by water gas shift reaction. Surface area of the iron oxide seemed to be an important factor for the catalytic tar decomposition. The activity of the iron oxide catalysts for tar decomposition seemed stable with cyclic use but the activity of the catalysts for the water gas shift reaction decreased with repeated use.     

Novel method for synthesis of Fe core and C shell magnetic nanoparticles

Using a newly developed method, carbon-encapsulated iron (Fe) nanoparticles were synthesized by plasma due to ultrasonication in toluene. Fe core with carbon shell nanoparticles were characterized using Transmission Electron Microscopy (TEM) and High Resolution Transmission Electron Microscopy (HRTEM). Fe nanoparticles of diameter 7–115 nm are encapsulated by 7–8 nm thick carbon layers. There was no iron carbide formation observed between the Fe core and the carbon shell. The Fe nanoparticles have body centered cubic (bcc) crystal structure. Synthesized nanoparticles showed a saturation magnetization of 9 A m²/kg at room temperature. After thermal treatment crystalline order of the nanoparticles improved and saturation magnetization increased to 24 A m²/kg. We foresee that the carbon-encapsulated Fe nanoparticles are biologically friendly and could have potential applications in Magnetic Resonance Imaging (MRI) and photothermal cancer therapy.     

Thermally evaporated copper oxide films: A view of annealing effect on physical and gas sensing properties

The present paper reports a facile approach to prepare copper oxide (CuO) films directly onto a glass substrate by thermal evaporation method and their chemiresistive properties towards hazardous nitrogen dioxide (NO₂). The influence of annealing temperature on structural, morphological, and gas sensing properties of the CuO films has been thoroughly investigated and reported. Structural and morphological analyses has confirmed the formation of polycrystalline monoclinic CuO with uniformly distributed nanoparticles over the substrate surface. Gas sensing measurements on CuO films reveal the high response, excellent selectivity, fast response-recovery time signatures, good repeatability, and stability towards lower concentration of NO₂ gas @150 °C. A maximum response of 48% towards 100 ppm NO₂ has been achieved. Gas sensing results demonstrate an influence of morphology on the NO₂ sensing performance of CuO films. In addition, the interactions between CuO sensor film and NO₂ gas molecules are studied through an impendence spectroscopy analysis.     

A facile method for preparation of iron based catalysts for high temperature water gas shift reaction

Nanocrystalline Fe₃O₄ based catalysts with theoretical particle size of 31–78 nm were synthesized by a facile direct pyrolysis method and employed in high temperature water gas shift reaction. XRD analysis showed that this method led to obtaining the catalysts directly in the active phase with chromium and copper incorporated into magnetite lattice. The results showed that the addition of chromium significantly increases the BET surface area of the pure iron oxide from 14.87 to 35.42 m² g⁻¹. Among the catalysts evaluated, Fe–Cr–Cu catalyst revealed higher activity compared to commercial catalyst and showed high stability during 10 h time on stream.     

High performance electrochemical H2O2 sensor based on MWCNT thin films fabricated by novel electron beam evaporation

High quality multi-walled carbon nanotubes (MWCNT) were grown by electron beam evaporation (EBE) under a high vacuum of 10⁻⁶ mtorr. The influence of deposition thickness on the orientation, morphology and vibrational bands of MWCNT films fabricated on tantalum (Ta) substrate was discussed. XRD patterns of the film revealed the presence of (002) preferential plane of carbon. Raman spectral analysis show the G-band Raman feature corresponding to high frequency E₂g of first order mode, suggesting that CNTs were composed of crystalline carbon. SEM image of 200 nm thick MWCNT film shows well shaped homogenous fine nanotubes of length ~300 nm and diameter ~70 nm with high purity. The electrochemical performance of the MWCNTs/Ta electrodes was studied by cyclic voltammetry. The sensor prepared with optimum thickness can detect H₂O₂ in the wide range covering 5 µM to 0.025 mM, with the detection limit as low as 0.09 µM. The results demonstrate that the fabrication of MWCNTs/Ta electrode by EBE is a very interesting and useful approach, likely to be a focus of upcoming research efforts in electrochemical sensing.     

Methane steam reforming in the absence and presence of H2S over Ce0.8Pr0.2O2 − δ, Ce0.85Sm0.15O2 − δ and Ce0.9Gd0.1O2 − δ SOFCs anode materials

We report here on the activity and stability of low-content praseodymium–, samarium– and gadolinium–cerium oxide catalysts for the steam reforming of methane under water deficient conditions. These materials display different methane reforming activities, and remain free of praseodymium, samarium and gadolinium oxide phases respectively after use in a reaction gas stream composed of 50% CH₄–5% H₂O – (in the absence and presence of 50 or 200 ppm H₂S) – balance He at 740 °C. The results show that Ce_0.8Pr_0.2O_2 − δ, Ce_0.85Sm_0.15O_2 − δ and Ce_0.9Gd_0.1O_2 − δ are effective catalysts for reforming of methane and H₂S in the feed promotes the catalytic activity. Ce_0.8Pr_0.2O_2 − δ appeared to attain the highest activity for methane reforming, a feature that is associated with the ability of praseodymium to undergo a red–ox (Pr^4 +/Pr^3 +) and spreading action in the cerium oxide host structure, possibly resulting in a red–ox relationship between the components.     

Synthesis and electrochemical performance of reduced graphene oxide/maghemite composite anode for lithium ion batteries

Reduced graphene oxide (rGO) tethered with maghemite (γ-Fe₂O₃) was synthesized using a novel modified sol–gel process, where sodium dodecylbenzenesulfonate was introduced into the suspension to prevent the undesirable formation of an iron oxide 3D network. Thus, nearly monodispersed and homogeneously distributed γ-Fe₂O₃ magnetic nanoparticles could be obtained on surface of graphene sheets. The utilized thermal treatment process did not require a reducing agent for reduction of graphene oxide. The morphology and structure of the composites were investigated using various characterization techniques. As-prepared rGO/Fe₂O₃ composites were utilized as anodes for half lithium ion cells. The 40 wt.%-rGO/Fe₂O₃ composite exhibited high reversible capacity of 690 mA h g⁻¹ at current density of 500 mA g⁻¹ and good stability for over 100 cycles, in contrast with that of the pure-Fe₂O₃ nanoparticles which demonstrated rapid degradation to 224 mA h g⁻¹ after 50 cycles. Furthermore, the composite showed good rate capability of 280 mA h g⁻¹ at 10C (∼10,000 mA g⁻¹). These characteristics could be mainly attributed to both the use of an effective binder, poly(acrylic acid) (PAA), and the specific hybrid structures that prevent agglomeration of nanoparticles and provide buffering spaces needed for volume changes of nanoparticles during insertion/extraction of Li ions.     

Thermal annealing induced mazy structure on MoO3 thin films and their high sensing performance to NO gas at room temperature

MoS₂ thin films were prepared by radio frequency (RF) magnetron sputtering and then annealed in air. X-ray diffraction (XRD), field-emission electron scanning microscopy (FESEM) and transmission electron microscopy (TEM) were adopted to characterize the phase structure and surface morphology. Interestingly, upon thermal annealing in air, MoS₂ thin films changed into α-MoO₃ with mazy morphology, and the thin films were covered by MoO₃ nano-sheets with a length of 30–50 nm and a width of 10 nm. α-MoO₃ thin films with mazy morphology showed excellent response to NO gas at room temperature. The response of 5% and 92% was obtained at 5 ppm and 200 ppm, respectively, and the response and recovery times were 30 s and 1500 s. Moreover, the mazy structure of MoO₃ exhibited good selectivity to NO gas with respect to SO₂, NH₃ and H₂ gases. The high surface-to-volume ratio was the dominant factor for high sensing performance.