Vertical graphene gas- and bio-sensors via catalyst-free, reactive plasma reforming of natural honey

A rapid reforming of natural honey exposed to reactive low-temperature Ar + H2 plasmas produced high-quality, ultra-thin vertical graphenes, without any metal catalyst or external heating. This transformation is only possible in the plasma and fails in similar thermal processes. The process is energy-efficient, environmentally benign, and is much cheaper than common synthesis methods based on purified hydrocarbon precursors. The graphenes retain the essential minerals of natural honey, feature reactive open edges and reliable gas- and bio-sensing performance.

Plasma-enabled, catalyst-free growth of carbon nanotubes on mechanically-written Si features with arbitrary shape

Simple, rapid, catalyst-free synthesis of complex patterns of long, vertically aligned multiwalled carbon nanotubes, strictly confined within mechanically-written features on a Si(1 0 0) surface is reported. It is shown that dense arrays of the nanotubes can nucleate and fully fill the features when the low-temperature microwave plasma is in a direct contact with the surface. This eliminates additional nanofabrication steps and inevitable contact losses in applications associated with carbon nanotube patterns. Using metal catalyst has long been considered essential for the nucleation and growth of surface-supported carbon nanotubes (CNTs) [1] and [2]. Only very recently, the possibility of CNT growth using non-metallic (e.g., oxide [3] and SiC [4]) catalysts or artificially created carbon-enriched surface layers [5] has been demonstrated. However, successful integration of carbon nanostructures into Si-based nanodevice platforms requires catalyst-free growth, as the catalyst nanoparticles introduce contact losses, and their catalytic activity is very difficult to control during the growth [6]. Furthermore, in many applications in microfluidics, biological and molecular filters, electronic, sensor, and energy conversion nanodevices, the CNTs need to be arranged in specific complex patterns [7] and [8]. These patterns need to contain the basic features (e.g., lines and dots) written using simple procedures and fully filled with dense arrays of high-quality, straight, yet separated nanotubes. In this paper, we report on a completely metal or oxide catalyst-free plasma-based approach for the direct and rapid growth of dense arrays of long vertically-aligned multi-walled carbon nanotubes arranged into complex patterns made of various combinations of basic features on a Si(1 0 0) surface written using simple mechanical techniques. The process was conducted in a plasma environment [9] and [10] produced by a microwave discharge which typically generates the low-temperature plasmas at the discharge power below 1 kW [11]. Our process starts from mechanical writing (scribing) a pattern of arbitrary features on pre-treated Si(1 0 0) wafers. Before and after the mechanical feature writing, the Si(1 0 0) substrates were cleaned in an aqueous solution of hydrofluoric acid for 2 min to remove any possible contaminations (such as oil traces which could decompose to free carbon at elevated temperatures) from the substrate surface. A piece of another silicon wafer cleaned in the same way as the substrate, or a diamond scriber were used to produce the growth patterns by a simple arbitrary mechanical writing, i.e., by making linear scratches or dot punctures on the Si wafer surface. The results were the same in both cases, i.e., when scratching the surface by Si or a diamond scriber. The procedure for preparation of the substrates did not involve any possibility of external metallic contaminations on the substrate surface. After the preparation, the substrates were loaded into an ASTeX model 5200 chemical vapour deposition (CVD) reactor, which was very carefully conditioned to remove any residue contamination. The samples were heated to at least 800 °C to remove any oxide that could have formed during the sample loading [12]. After loading the substrates into the reactor chamber, N2 gas was supplied into the chamber at the pressure of 7 Torr to ignite and sustain the discharge at the total power of 200 W. Then, a mixture of CH4 and 60% of N2 gases were supplied at 20 Torr, and the discharge power was increased to 700 W (power density of approximately 1.49 W/cm3). During the process, the microwave plasma was in a direct contact with the substrate. During the plasma exposure, no external heating source was used, and the substrate temperature (∼850 °C) was maintained merely due to the plasma heating. The features were exposed to a microwave plasma for 3–5 min. A photograph of the reactor and the plasma discharge is shown in Fig. 1a and b.

Simulation of carbon arc discharge for the synthesis of nanotubes

Arc discharge ablation with a catalyst-filled carbon anode in a helium background was used for the synthesis of graphene and carbon nanotubes. In this paper, we present the results of the numerical simulation of the distribution of various plasma parameters in discharge, as well as the distribution of carbon flux on the nanotube surface, for the typical discharge with an arc current of 60 A and a background gas pressure of 68 kPa.

Minimizing the Gibbs–Thomson effect in the low-temperature plasma synthesis of thin Si nanowires

An advanced combination of numerical models, including plasma sheath, ion- and radical-induced species creation and plasma heating effects on the surface and within a Au catalyst nanoparticle, is used to describe the catalyzed growth of Si nanowires in the sheath of a low-temperature and low-pressure plasma. These models have been used to explain the higher nanowire growth rates, low-energy barriers, much thinner Si nanowire nucleation and the less effective Gibbs–Thomson effect in reactive plasma processes, compared with those of neutral gas thermal processes. The effects of variation in the plasma sheath parameters and substrate potential on Si nanowire nucleation and growth have also been investigated. It is shown that increasing the plasma-related effects leads to decreases in the nucleation energy barrier and the critical nanoparticle radius, with the Gibbs–Thomson effect diminished, even at low temperatures. The results obtained are consistent with available experimental results and open a path toward the energy- and matter-efficient nucleation and growth of a broad range of one-dimensional quantum structures.

Controlled synthesis of a large fraction of metallic single-walled carbon nanotube and semiconducting carbon nanowire networks

Controlled synthesis of both single-walled carbon nanotube and carbon nanowire networks using the same CVD reactor and Fe/Al2O3 catalyst by slightly altering the hydrogenation and temperature conditions is demonstrated. Structural, bonding and electrical characterization using SEM, TEM, Raman spectroscopy, and temperature-dependent resistivity measurements suggest that the nanotubes are of a high quality and a large fraction (well above the common 33% and possibly up to 75%) of them are metallic. On the other hand, the carbon nanowires are amorphous and semiconducting and feature a controlled sp2/sp3 ratio. The growth mechanism which is based on the catalyst nanoisland analysis by AFM and takes into account the hydrogenation and temperature control effects explains the observed switch-over of the nanostructure growth modes. These results are important to achieve the ultimate control of chirality, structure, and conductivity of one-dimensional all-carbon networks.

Synthesis, mechanical and electrical properties of carbon microcoils and nanocoils

The results on the synthesis, mechanical and electrical properties of carbon microcoils and nanocoils (CMCs, CNCs) synthesized using catalytic CVD and Ni-P and Co-P catalyst alloys, respectively, are reported. SEM analysis reveals that the CMCs and CNCs have unique helical morphologies, and diameters of 5.0-9.0 μm and 450-550 nm, respectively. Moreover, CMCs with flat cross-section can be stretched to 3 times their original coil lengths. Current-voltage characteristics of a single microcoil have also been obtained. It is found that the CMCs have the electrical conductivity between 100 and 160 S/cm, whereas the electrical resistance increases by about 20% during the coil extension. Besides, the microcoils can produce light in vacuum when the test voltage reaches 10 V. The emission intensity increases as the voltage increases. The mechanical and electrical properties of CMCs and CNC make them potentially useful in many applications in micromagnetic sensors, mechanical microsprings and optoelectronics.

Single-step synthesis and magnetic separation of graphene and carbon nanotubes in arc discharge plasmas

The unique properties of graphene and carbon nanotubes made them the most promising nanomaterials attracting enormous attention, due to the prospects for applications in various nanodevices, from nanoelectronics to sensors and energy conversion devices. Here we report on a novel deterministic, single-step approach to simultaneous production and magnetic separation of graphene flakes and carbon nanotubes in an arc discharge by splitting the high-temperature growth and low-temperature separation zones using a non-uniform magnetic field and tailor-designed catalyst alloy, and depositing nanotubes and graphene in different areas. Our results are very relevant to the development of commercially-viable, single-step production of bulk amounts of high-quality graphene.

Effect of plasma environment on synthesis of vertically aligned carbon nanofibers in plasma-enhanced chemical vapor deposition

We present a theoretical model describing a plasma-assisted growth of carbon nanofibers (CNFs), which involves two competing channels of carbon incorporation into stacked graphene sheets: via surface diffusion and through the bulk of the catalyst particle (on the top of the nanofiber), accounting for a range of ion- and radical-assisted processes on the catalyst surface. Using this model, it is found that at low surface temperatures, Ts, the CNF growth is indeed controlled by surface diffusion, thus quantifying the semiempirical conclusions of earlier experiments. On the other hand, both the surface and bulk diffusion channels provide a comparable supply of carbon atoms to the stacked graphene sheets at elevated synthesis temperatures. It is also shown that at low Ts, insufficient for effective catalytic precursor decomposition, the plasma ions play a key role in the production of carbon atoms on the catalyst surface. The model is used to compute the growth rates for the two extreme cases of thermal and plasma-enhanced chemical vapor deposition of CNFs. More importantly, these results quantify and explain a number of observations and semiempirical conclusions of earlier experiments.

Rodlike bimetallic ruthenium and osmium complexes bridged by phenylene spacers. Synthesis, electrochemistry, and photophysics

In the search for light-addressable nanosized compounds we have synthesized 10 dinuclear homometallic trisbipyridyl complexes of linear structure with the general formula [M(bpy)3-BL-M(bpy)3]4+ [M = Ru(II) or Os(II); BL = polyphenylenes (2, 3, 4, or 5 units) or indenofluorene; bpy = 2,2′-bipyridine]. By using a "chemistry on the complex" approach, different sizes of rodlike systems have been obtained with a length of 19.8 and 32.5 Å for the shortest and longest complex, respectively. For one of the ruthenium precursors, [RUbpy-ph2-Si(CH3) 3][PF6]2, single crystals were obtained by recrystallization from methanol. Their photophysical and electrochemical properties are reported. All the compounds are luminescent both at room and low temperature with long excited-state lifetimes due to an extended delocalization. Nanosecond transient absorption showed that the lowest excited state involves the chelating unit attached to the bridging ligand. Electrochemical data indicated that the first reduction is at a slightly more positive potential than for the reference complexes [M(bpy)3]2+ (M = Ru, Os). This result confirms that the best acceptor is the bipyridine moiety connected to the conjugated spacers. The role of the tilt angle between the phenylene units, in the two series of complexes, for the ground and excited states is discussed.

A non-aqueous solution synthesis of boron carbide by control of in-situ carbon

Synthesis of high quality boron carbide (B4C) powder is achieved by carbothermal reduction of boron oxide (B2O3) from a condensed boric acid (H3BO3) / polyvinyl acetate (PVAc) product. Precursor solutions are prepared via polymerisation of vinyl acetate (VA) in methanol in the presence of dissolved H3BO3. With excess VA monomer being removed during evaporation of the solvent, the polymerisation time is then used to manage availability of carbon for reaction.

Sol-gel synthesis and characterization of cubic bismuth zinc niobium oxide nanopowders

Bismuth zinc niobium oxide (BZN) was successfully synthesized by a diol-based sol-gel reaction utilizing metal acetate and alkoxide precursors. Thermal analysis of a liquid suspension of precursors suggests that the majority of organic precursors decompose at temperatures up to 150°C, and organic free powders form above 350°C. The experimental results indicate that a homogeneous gel is obtained at about 200°C and then converts to a mixture of intermediate oxides at 350–400°C. Finally, single-phased BZN powders are obtained between 500 and 900°C. The degree of chemical homogeneity as determined by X-ray diffraction and EDS mapping is consistent throughout the samples. Elemental analysis indicates that the atomic ratio of metals closely matches a Bi1.5ZnNb1.5O7 composition. Crystallite sizes of the BZN powders calculated from the Scherrer equation are about 33–98 nm for the samples prepared at 500–700°C, respectively. The particle and crystallite sizes increase with increased sintering temperature. The estimated band gap of the BZN nanopowders from optical analysis is about 2.60–2.75 eV at 500-600°C. The observed phase formations and measured results in this study were compared with those of previous reports.

Synthesis, characterization and activity of an immobilized photocatalyst : natural porous diatomite supported titania nanoparticles

Diatomite, a porous non-metal mineral, was used as support to prepare TiO2/diatomite composites by a modified sol–gel method. The as-prepared composites were calcined at temperatures ranging from 450 to 950 _C. The characterization tests included X-ray powder diffraction (XRD), scanning electron microscopy (SEM) with an energy-dispersive X-ray spectrometer (EDS), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption/desorption measurements. The XRD analysis indicated that the binary mixtures of anatase and rutile exist in the composites. The morphology analysis confirmed the TiO2 particles were uniformly immobilized on the surface of diatom with a strong interfacial anchoring strength, which leads to few drain of photocatalytic components during practical applications. In further XPS studies of hybrid catalyst, we found the evidence of the presence of Ti–O–Si bond and increased percentage of surface hydroxyl. In addition, the adsorption capacity and photocatalytic activity of synthesized TiO2/diatomite composites were evaluated by studying the degradation kinetics of aqueous Rhodamine B under UV-light irradiation. The photocatalytic degradation was found to follow pseudo-first order kinetics according to the Langmuir–Hinshelwood model. The preferable removal efficiency was observed in composites by 750 _C calcination, which is attributed to a relatively appropriate anatase/rutile mixing ratio of 90/10.

Catalytic activity evaluation of industrial Pd/C catalyst via gray-box dynamic modeling and simulation of hydropurification reactor

In this paper, dynamic modeling and simulation of the hydropurification reactor in a purified terephthalic acid production plant has been investigated by gray-box technique to evaluate the catalytic activity of palladium supported on carbon (0.5 wt.% Pd/C) catalyst. The reaction kinetics and catalyst deactivation trend have been modeled by employing artificial neural network (ANN). The network output has been incorporated with the reactor first principle model (FPM). The simulation results reveal that the gray-box model (FPM and ANN) is about 32 percent more accurate than FPM. The model demonstrates that the catalyst is deactivated after eleven months. Moreover, the catalyst lifetime decreases about two and half months in case of 7 percent increase of reactor feed flowrate. It is predicted that 10 percent enhancement of hydrogen flowrate promotes catalyst lifetime at the amount of one month. Additionally, the enhancement of 4-carboxybenzaldehyde concentration in the reactor feed improves CO and benzoic acid synthesis. CO is a poison to the catalyst, and benzoic acid might affect the product quality. The model can be applied into actual working plants to analyze the Pd/C catalyst efficient functioning and the catalytic reactor performance.

Au-Pd alloy nanoparticle catalyzed selective oxidation of benzyl alcohol and tandem synthesis of imines at ambient conditions

Alloy nanoparticles (NPs) of gold and palladium on ZrO2 support (Au–Pd@ZrO2) were found to be highly active in oxidation of benzyl alcohols and can be used for the tandem synthesis of imines from benzyl alcohols and amines via a one-pot, two-step process at mild reaction conditions. The first step of the process is oxidation of benzyl alcohol to benzaldehyde, excellent yields were achieved after 7 h reaction at 40 °C without addition of any base. In the second step, aniline was introduced into the reaction system to produced N-benzylideneaniline. The benzaldehyde obtained in the first step was completely consumed within 1 h. A range of benzyl alcohols and amines were investigated for the general applicability of the Au–Pd alloy catalysts. It is found that the performance of the catalysts depends on the Au–Pd metal contents and composition. The optimal catalyst is 3.0 wt% Au–Pd@ZrO2 with a Au:Pd molar ratio 1:1. The alloy NP catalyst exhibited superior catalytic properties to pure AuNP or PdNP because the surface of alloy NPs has higher charge heterogeneity than that of pure metal NPs according to simulation of density function theory (DFT)

Multipurpose nanoporous alumina-carbon nanowall bi-dimensional nano-hybrid platform via catalyzed and catalyst-free plasma CVD

Simple, rapid, plasma-assisted synthesis of large-area arrays of vertically-aligned carbon nanowalls on highly-porous, transparent bare and gold-coated alumina membranes with the two pore sizes is reported. It is demonstrated that the complex patterns of vertically aligned nanowalls can nucleate and form different morphologies in the low-temperature plasmas. The process is stable, and the twofold change in the gas flow (10 and 20 sccm) does not noticeably influence the morphology of the nanowall pattern. Application of a thin (5 nm) gold layer to nanoporous membrane prior to the nanowall growth allows controlling the network morphology.