The role and structure of carbonaceous materials in dehydrogenation reactions

The catalytic dehydrogenation (DH) and oxidative dehydrogenation (ODH) of light alkanes is widely studied as a route to the formation of alkenes and di-alkenes, important precursor molecules for synthetic rubbers, plastics and a variety of other products [1,2]. Recent studies have focused on the non-oxidative DH of butane over alumina-supported vanadia catalysts [3-5]. In the present work, we provide a detailed understanding of both the role and structure of coke deposited on VOx/Al2O3 during reaction. A range of characterisation techniques have been employed including the first application of terahertz time domain spectroscopy (THz-TDS) to the study of coke. Complementary THz-TDS characterisation of carbonaceous materials including carbon nanofibres (CNFs) has also been conducted. For such materials THz-TDS spectra can be correlated with their catalytic performance in the oxidative dehydrogenation of ethylbenzene to form styrene

The structure and mechanistic impact of carbon deposits in dehydrogenation reactions

The catalytic dehydrogenation (DH) and oxidative dehydrogenation (ODH) of light alkanes is widely studied as a route to the formation of alkenes and di-alkenes, important precursor molecules for synthetic rubbers, plastics and a variety of other products [1-4]. Recent studies have focused on the non-oxidative DH of butane over alumina-supported vanadia catalysts [5-7]. In the present work, we provide a detailed understanding of both the role and structure of coke deposited on VOx/Al2O3 during reaction. A range of characterisation techniques have been employed including the first application of terahertz time domain spectroscopy (THz-TDS) to the study of coke. Complementary THz-TDS characterisation of carbonaceous materials including carbon nanofibres (CNFs) has also been conducted

Analysis of the structure and chemical properties of some commercial carbon nanostructures

For many years the scientific community has believed in a promising future for carbon nanotubes for various applications in such diverse fields as polymer reinforcement, adsorption, catalysis, electronics and medicine. Industrial production of carbon nanotubes and -fibers and the subsequent availability and decrease of price, have rendered this vision feasible. In the last years, several carbon nanomaterial products have been marketed by major chemical companies. In this work, we present an extensive characterization of a representative set of commercially available carbon nanomaterials. Special focus has been put on their quality, i.e. presence of metal or carbonaceous impurities but also homogeneity and structural integrity. The observations are of importance for subsequent use in catalysis where the presence of impurities or defects in the nanostructure can dramatically modify the activity of the catalytic material

Iron-filled multiwalled carbon nanotubes surface-functionalized with paramagnetic Gd (III): A candidate dual-functioning MRI contrast agent and magnetic hyperthermia structure

The authors are grateful for the financial support from the Engineering and Physical Science Research Council, UK

Control of steam input to the pyrolysis-gasification of waste plastics for improved production of hydrogen or carbon nanotubes

Carbon nanotubes (CNTs) have been proven to be possible as high-value by-products of hydrogen production from gasification of waste plastics. In this work, steam content in the gasification process was investigated to increase the quality of CNTs in terms of purity. Three different plastics-low density polyethylene (LDPE), polypropylene (PP) and polystyrene (PS) were studied in a two stage pyrolysis-gasification reactor. Plastics samples were pyrolysed in nitrogen at 600°C, before the evolved gases were passed to a second stage where steam was injected and the gases were reformed at 800°C in the presence of a nickel-alumina catalyst. To investigate the effect that steam plays on CNT production, steam injection rates of 0, 0.25, 1.90 and 4.74gh-1 were employed. The CNTs produced from all three plastics were multiwalled CNTs with diameters between 10 and 20nm and several microns in length. For all the plastic samples, raising the steam injection rate led to increased hydrogen production as steam reforming and gasification of deposited carbon increased. High quality CNTs, as observed from TEM, TPO and Raman spectroscopy, were produced by controlling the steam injection rate. The largest yield for LDPE was obtained at 0gh-1 steam injection rate, whilst PP and PS gave their largest yields at 0.25gh-1. Overall the largest CNT yield was obtained for PS at 0.25gh-1, with a conversion rate of plastic to CNTs of 32wt%

The phase of iron catalyst nanoparticles during carbon nanotube growth

We study the Fe-catalyzed chemical vapor deposition of carbon nanotubes by complementary in situ grazing-incidence X-ray diffraction, in situ X-ray reflectivity, and environmental transmission electron microscopy. We find that typical oxide supported Fe catalyst films form widely varying mixtures of bcc and fcc phased Fe nanoparticles upon reduction, which we ascribe to variations in minor commonly present carbon contamination levels. Depending on the as-formed phase composition, different growth modes occur upon hydrocarbon exposure: For γ-rich Fe nanoparticle distributions, metallic Fe is the active catalyst phase, implying that carbide formation is not a prerequisite for nanotube growth. For α-rich catalyst mixtures, Fe3C formation more readily occurs and constitutes part of the nanotube growth process. We propose that this behavior can be rationalized in terms of kinetically accessible pathways, which we discuss in the context of the bulk iron–carbon phase diagram with the inclusion of phase equilibrium lines for metastable Fe3C. Our results indicate that kinetic effects dominate the complex catalyst phase evolution during realistic CNT growth recipes.S.H. acknowledges funding from ERC grant InsituNANO (No. 279342). We acknowledge the European Synchrotron Radiation Facility (ESRF) for provision of synchrotron radiation facilities. We acknowledge the use of facilities within the LeRoy Eyring Center for Solid State Science at Arizona State University. C.T.W. and C.S.E. acknowledge funding from the EC project Technotubes. A.D.G. acknowledges funding from the Marshall Aid Commemoration Commission and the National Science Foundation. R.S.W. acknowledges funding from EPSRC (Doctoral training award) and B.C.B. acknowledges a Research Fellowship at Hughes Hall, Cambridge.This is the accepted manuscript. The final version is available from ACS at http://pubs.acs.org/doi/abs/10.1021/cm301402g

Effect of Covalent Functionalisation on Thermal Transport Across Graphene-Polymer Interfaces

This paper is concerned with the interfacial thermal resistance for polymer composites reinforced by various covalently functionalised graphene. By using molecular dynamics simulations, the obtained results show that the covalent functionalisation in graphene plays a significant role in reducing the graphene-paraffin interfacial thermal resistance. This reduction is dependent on the coverage and type of functional groups. Among the various functional groups, butyl is found to be the most effective in reducing the interfacial thermal resistance, followed by methyl, phenyl and formyl. The other functional groups under consideration such as carboxyl, hydroxyl and amines are found to produce negligible reduction in the interfacial thermal resistance. For multilayer graphene with a layer number up to four, the interfacial thermal resistance is insensitive to the layer number. The effects of the different functional groups and the layer number on the interfacial thermal resistance are also elaborated using the vibrational density of states of the graphene and the paraffin matrix. The present findings provide useful guidelines in the application of functionalised graphene for practical thermal management.Comment: 8 figure