Process and catalysts for the methanation of oxides of carbon

The present invention is directed to catalysts for the conversion of oxides of carbon to methane and/or other hydrocarbons and to precursors of such catalysts. The catalyst precursors include one or more refractory oxides selected from the group consisting of rare earth oxides and rare earth contg. perovskites, the precursor including nickel or nickel cations sufficient for a catalyst obtainable by reducing the precursor to be capable of at least partially reducing an oxide of carbon to a hydrocarbon product. Processes for the prepn. of such catalysts and catalyst precursors are also disclosed, as are processes for the conversion of oxides of carbon to methane and/or other hydrocarbons. [on SciFinder(R)]

In situ Raman studies of the selective oxidation of methanol to formaldehyde and ethene to ethylene oxide on a polycrystalline silver catalyst

The combined techniques of in situ Raman microscopy and scanning electron microscopy (SEM) have been used to study the selective oxidation of methanol to formaldehyde and the ethene epoxidation reaction over polycrystalline silver catalysts. The nature of the oxygen species formed on silver was found to depend critically upon the exact morphology of the catalyst studied. Bands at 640, 780 and 960 cm-1 were identified only on silver catalysts containing a significant proportion of defects. These peaks were assigned to subsurface oxygen species situated in the vicinity of surface dislocations, AgIII=O sites formed on silver atoms modified by the presence of subsurface oxygen and O2 - species stabilized on subsurface oxygen-modified silver sites, respectively. The selective oxidation of methanol to formaldehyde was determined to occur at defect sites, where reaction of methanol with subsurface oxygen initially produced subsurface OH species (451 cm-1) and adsorbed methoxy species. Two distinct forms of adsorbed ethene were identified on oxidised silver sites. One of these was created on silver sites modified by the interaction of subsurface oxygen species, and the other on silver crystal planes containing a surface coverage of atomic oxygen species. The selective oxidation of ethene to ethylene oxide was achieved by the reaction between ethene adsorbed on modified silver sites and electrophilic AgIII=O species, whereas the combustion reaction was perceived to take place by the reaction of adsorbed ethene with nucleophilic surface atomic oxygen species. Defects were determined to play a critical role in the epoxidation reaction, as these sites allowed the rapid diffusion of oxygen into subsurface positions, and consequently facilitated the formation of the catalytically active AgIII=O sites.

A combined environmental scanning electron microscopy and Raman microscopy study of methanol oxidation on silver(I) oxide

The techniques of environmental scanning electron microscopy (ESEM) and Raman microscopy have been used to respectively elucidate the morphological changes and nature of the adsorbed species on silver(I) oxide powder, during methanol oxidation conditions. Heating Ag2O in either water vapour or oxygen resulted firstly in the decomposition of silver(I) oxide to polycrystalline silver at 578 K followed by sintering of the particles at higher temperature. Raman spectroscopy revealed the presence of subsurface oxygen and hydroxyl species in addition to surface hydroxyl groups after interaction with water vapour. Similar species were identified following exposure to oxygen in an ambient atmosphere. This behaviour indicated that the polycrystalline silver formed from Ag2O decomposition was substantially more reactive than silver produced by electrochemical methods. The interaction of water at elevated temperatures subsequent to heating silver(I) oxide in oxygen resulted in a significantly enhanced concentration of subsurface hydroxyl species. The reaction of methanol with Ag2O at high temperatures was interesting in that an inhibition in silver grain growth was noted. Substantial structural modification of the silver(I) oxide material was induced by catalytic etching in a methanol/air mixture. In particular, "pin-hole" formation was observed to occur at temperatures in excess of 773 K, and it was also recorded that these "pin- holes" coalesced to form large-scale defects under typical industrial reaction conditions. Raman spectroscopy revealed that the working surface consisted mainly of subsurface oxygen and surface Ag=O species. The relative lack of sub-surface hydroxyl species suggested that it was the desorption of such moieties which was the cause of the "pin-hole" formation.

Carbon dioxide reforming of methane to produce synthesis gas over metal-supported catalysts: State of the art

Carbon dioxide reforming of methane produces synthesis gas with a low hydrogen to carbon monoxide ratio, which is desirable for many industrial synthesis processes. This reaction also has very important environmental implications since both methane and carbon dioxide contribute to the greenhouse effect. Converting these gases into a valuable feedstock may significantly reduce the atmospheric emissions of CO2 and CH4. In this paper, we present a comprehensive review on the thermodynamics, catalyst selection and activity, reaction mechanism, and kinetics of this important reaction. Recently, research has centered on the development of catalysts and the feasible applications of this reaction in industry. Group VIII metals supported on oxides are found to be effective for this reason. However, carbon deposition causing catalyst deactivation is the major problem inhibiting the industrial application of the CO2/CH4 reaction. Ni-based catalysts impregnated on certain supports show carbon-free operation and thus attract much attention. To develop an effective catalyst for CO2 reforming of CH4 and accelerate the commercial application of the reaction, the following are identified to be the most important areas for future work: (1) selection of metal and support and studying the effect of their interaction on catalyst activity; (2) the effect of different promoter on catalyst activity; (3) the reaction mechanism and kinetics; and (4) pilot reactor performance and scale-up operation.

A fourier-transform infrared study of CO2 and CO2/H2 interactions with caesium-doped copper catalysts

FTIR spectra are reported of CO2 and COi/Hi on a silica-supported caesium-doped copper catalyst. Adsorption of COj on a "caesium"/silica surface resulted in the formation of COj and complexed CO species. Exposure of CO2 to' a caesium-doped reduced copper catalyst produced not only these species but also two forms of adsorbed carboxylate giving bands at 1550, 1510, 1365 and 1345 cm"1. Reaction of carboxylate species with hydrogen at 388 K gave formate species on copper and caesium oxide in addition to methoxy groups associated with caesium oxide. Methoxy species were not detected on undoped copper catalyst suggesting that caesium may be a promoter for the methanol synthesis reaction. Methanol decomposition on a caesium-doped copper catalyst produced a small number of formate species on copper and caesium oxide. Methoxy groups on caesium oxide decomposed to CO and U.2, and subsequent reaction between CO and adsorbed oxygen resulted in carboxylate formation. Methoxy species located at interfacial sites appeared to exhibit unusual adsorption properties.

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.

Characterization of precursors to methanol synthesis catalysts Cu/ZnO system

The composition of a series of hydroxycarbonate precursors to copper/zinc oxide methanol synthesis catalysts prepared under conditions reported as optimum for catalytic activity has been studied. Techniques employed included thermogravimetry (TG), temperature-programmed decomposition (TPD), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and Raman and FTIR spectroscopies. Evidence was obtained for various structural phases including hydrozincite, copper hydrozincite, aurichalcite, zincian malachite and malachite (the concentrations of which depended upon the exact Cu/Zn ratio used). Significantly, previously reported phases such as gerhardite and rosasite were not identified when catalysts were synthesized at optimum solution pH and temperature values, and after appropriate aging periods. Calcination of the hydroxycarbonate precursors resulted in the formation of catalysts containing an intimate mixture of copper and zinc oxides. Temperature-programmed reduction (TPR) revealed that a number of discrete copper oxide species were present in the catalyst, the precise concentrations of which were determined to be related to the structure of the catalyst precursor. Copper hydrozincite decomposed to give zinc oxide particles decorated by highly dispersed, small copper oxide species. Aurichalcite appeared to result ultimately in the most intimately mixed catalyst structure whereas zincian malachite decomposed to produce larger copper oxide and zinc oxide grains. The reason for the stabilization of small copper oxide and zinc oxide clusters by aurichalcite was investigated by using carefully selected calcination temperatures. It was concluded that the unique formation of an 'anion-modified' oxide resulting from the initial decomposition stage of aurichalcite was responsible for the 'binding' of copper species to zinc moieties.

Low temperature synthesis of carbon nanotubes on indium tin oxide electrodes for organic solar cells

The electrical performance of indium tin oxide (ITO) coated glass was improved by including a controlled layer of carbon nanotubes directly on top of the ITO film. Multi-wall carbon nanotubes (MWCNTs) were synthesized by chemical vapor deposition, using ultra-thin Fe layers as catalyst. The process parameters (temperature, gas flow and duration) were carefully refined to obtain the appropriate size and density of MWCNTs with a minimum decrease of the light harvesting in the cell. When used as anodes for organic solar cells based on poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM), the MWCNT-enhanced electrodes are found to improve the charge carrier extraction from the photoactive blend, thanks to the additional percolation paths provided by the CNTs. The work function of as-modified ITO surfaces was measured by the Kelvin probe method to be 4.95 eV, resulting in an improved matching to the highest occupied molecular orbital level of the P3HT. This is in turn expected to increase the hole transport and collection at the anode, contributing to the significant increase of current density and open circuit voltage observed in test cells created with such MWCNT-enhanced electrodes.

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.

Selective growth of carbon nanotubes on bare silicon : MWNT sinthesys on patterned substrates without predeposition of metal catalyst

Carbon nanotubes (CNTs) are expected to become the ideal constituent of many technologes, in particular for future generation electronics. This considerable interest is due to their unique electrical and mechanical properties. They show indeed super-high current-carrying capacity, ballistic electron transport and good field-emission properties. Then, these superior features make CNTs the most promising building blocks for electronic devices, as organic solar cells and organic light emitting devices (OLED). By using Focused Ion Beam (FIB) patterning it is possible to a obtain a high control on position, relative distances and diameter of CNTs. The present work shows how to grow three-dimensional architecture made of vertical-aligned CNTs directly on silicon. Thanks to the higher activity of a pre-patterned surface the synthesis process results very quick, cheap and simple. Such large area growths of CNTs could be used in preliminary test for application as electrodes for organic solar cells.

Controlled growth of carbon nanotubes for electronic and photovoltaic applications

Carbon nanotubes (CNTs), experimentally observed for the first time twenty years ago, have triggered an unprecedented research effort, on the account of their astonishing structural, mechanical and electronic properties. Unfortunately, the current inability in predicting the CNTs’ properties and the difficulty in controlling their position on a substrate are often limiting factors for the application of this material in actual devices. This research aims at the creation of specific methodologies for controlled synthesis of CNTs, leading to effectively employ them in various fields of electronics, e.g. photovoltaics. Focused Ion Beam (FIB) patterning of Si surfaces is here proposed as a means for ordering the assembly of vertical-aligned CNTs. With this technique, substrates with specific nano-structured morphologies have been prepared, enabling a high degree of control over CNTs’ position and size. On these nano-structured substrates, the growth of CNTs has been realized by chemical vapor deposition (CVD), i.e. thermal decomposition of hydrocarbon gases over a heated catalyst. The most common materials used as catalysts in CVD are transition metals like Fe and Ni; however, their presence in the CNT products often results in shortcomings for electronic applications, especially for those based on silicon, being the metallic impurities incompatible with very-large-scale integration (VLSI) technology. In the present work the role of Ge dots as an alternative catalysts for CNTs synthesis on Si substrates has been thoroughly assessed, finding a close connection between the catalytic activity of such material and the CVD conditions, which can affect both size and morphology of the dots. Successful CNT growths from Ge dots have been obtained by CVD at temperatures ranging from 750 to 1000°C, with mixtures of acetylene and hydrogen in an argon carrier gas. The morphology of the Si surface is observed to play a crucial role for the outcome of the CNT synthesis: natural (i.e. chemical etching) and artificial (i.e. FIB patterning, nanoindentation) means of altering this morphology in a controlled way have been then explored to optimize the CNTs yield. All the knowledge acquired in this study has been finally applied to synthesize CNTs on transparent conductive electrodes (indium-tin oxide, ITO, coated glasses), for the creation of a new class of anodes for organic photovoltaics. An accurate procedure has been established which guarantees a controlled inclusion of CNTs on ITO films, preserving their optical and electrical properties. By using this set of conditions, a CNTenhanced electrode has been built, contributing to improve the power conversion efficiency of polymeric solar cells.

Titanium-oxide magneli phases in four chondritic porous interplanetary dust particles

Detailed analytical electron microscope analyses of four fine-grained chondritic porous interplanetary dust particles (IDPs)reveal the presence of titanium oxide Magneli phases, TinO2n-1 (n=4,5,6), and rare Ti-metal. The titanium minerals are indigenous to these chondritic IDPs. The association of Magneli phases, Ti-metal, and carbonaceous material in chondritic IDPs, along with the grain size distributions support in situ solid carbon gasification in these extraterrestrial particles. The active catalyst in this process is titanium metal that we infer may be of interstellar origin. This favorable catalysis uniquely leads to the formation of Magneli phases. As chondritic IDPs may be solid debris of short-period comets, our data indicate that nuclei of short-period comets may show distinctive chemical reactions that lead to Ti-mineral assemblages that typically include Magneli phases. The proposed model provides a plausible mechnism to explain the higher solid carbon content of chondritic IDPs relative to bulk carbon abundances typical for carbonaceous chondrite matrices that represent another type of more evolved, that is, metamorphosed, undifferentiated solar system bodies.

Multi-wall carbon nanotube coating of fluorine-doped tin oxide as an electrode surface modifier for polymer solar cells

A controlled layer of multi-wall carbon nanotubes (MWCNT) was grown directly on top of fluorine-doped tin oxide (FTO) glass electrodes as a surface modifier for improving the performance of polymer solar cells. By using low-temperature chemical vapor deposition with short synthesis times, very short MWCNTs were grown, these uniformly decorating the FTO surface. The chemical vapor deposition parameters were carefully refined to balance the tube size and density, while minimizing the decrease in conductivity and light harvesting of the electrode. As created FTO/CNT electrodes were applied to bulk-heterojunction polymer solar cells, both in direct and inverted architecture. Thanks to the inclusion of MWCNT and the consequent nano-structuring of the electrode surface, we observe an increase in external quantum efficiency in the wavelength range from 550 to 650 nm. Overall, polymer solar cells realized with these FTO/CNT electrodes attain power conversion efficiency higher than 2%, outclassing reference cells based on standard FTO electrodes.

Control of density of self-organized carbon nanotube arrays by catalyst pretreatment through plasma immersion ion implantation

A simple and effective method of controlling the growth of vertically aligned carbon nanotube arrays in a lowerature plasma is presented. Ni catalyst was pretreated by plasma immersion ion implantation prior to the nanotube growth by plasma-enhanced chemical vapor deposition. Both the size distribution and the areal density of the catalyst nanoparticles decrease due to the ion-surface interactions. Consequently, the resulting size distribution of the vertically aligned carbon nanotubes is reduced to 50 ∼ 100 nm and the areal density is lowered (by a factor of ten) to 10 8 cm -2, which is significantly different from the very-high-density carbon nanotube forests commonly produced by thermal chemical vapor deposition. The efficiency of this pretreatment is compared with the existing techniques such as neutral gas annealing and plasma etching. These results are highly relevant to the development of the next-generation nanoelectronic and optoelectronic devices that require effective control of the density of nanotube arrays.

3-Orders-of-magnitude density control of single-walled carbon nanotube networks by maximizing catalyst activation and dosing carbon supply

Tailoring the density of random single-walled carbon nanotube (SWCNT) networks is of paramount importance for various applications, yet it remains a major challenge due to the insufficient catalyst activation in most growth processes. Here we report on a simple and effective method to maximise the number of active catalyst nanoparticles using catalytic chemical vapor deposition (CCVD). By modulating short pulses of acetylene into a methane-based CCVD growth process, the density of SWCNTs is dramatically increased by up to three orders of magnitude without increasing the catalyst density and degrading the nanotube quality. In the framework of a vapor-liquid-solid model, we attribute the enhanced growth to the high dissociation rate of acetylene at high temperatures at the nucleation stage, which can be effective in both supersaturating the larger catalyst nanoparticles and overcoming the nanotube nucleation energy barrier of the smaller catalyst nanoparticles. These results are highly relevant to numerous applications of random SWCNT networks in next-generation energy, sensing and biomedical devices. © 2011 The Royal Society of Chemistry.