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

Perspectives on carbon materials as powerful catalysts in continuous anaerobic bioreactors

Supplementary data related to this article can be found at http:// dx.doi.org/10.1016/j.watres.2016.06.004.The catalytic effect of commercial microporous activated carbon (AC) and macroporous carbon nanotubes (CNT) is investigated in reductive bioreactions in continuous high rate anaerobic reactors, using the azo dye Acid Orange 10 (AO10) as model compound as electron acceptor and a mixture of VFA as electron donor. Size and concentration of carbon materials (CM) and hydraulic retention time (HRT) are assessed. CM increased the biological reduction rate of AO10, resulting in significantly higher colour removal, as compared to the control reactors. The highest efficiency, 98%, was achieved with a CNT diameter (d) lower than 0.25 mm, at a CNT concentration of 0.12 g per g of volatile solids (VS), a HRT of 10 h and resulted in a chemical oxygen demand (COD) removal of 85%. Reducing the HRT to 5 h, colour and COD removal in CM-mediated bioreactors were above 90% and 80%, respectively. In the control reactor, thought similar COD removal was achieved, AO10 decolourisation was just approximately 20%, demonstrating the ability of CM to significantly accelerate the reduction reactions in continuous bioreactors. AO10 reduction to the correspondent aromatic amines was proved by high performance liquid chromatography (HPLC). Colour decrease in the reactor treating a real effluent with CNT was the double comparatively to the reactor operated without CNT. The presence of AC in the reactor did not affect the microbial diversity, as compared to the control reactor, evidencing that the efficient reduction of AO10 was mainly due to AC rather than attributed to changes in the composition of the microbial communities.This study was supported by the Portuguese Foundation for Science and Technology (FCT) under the scope of the strategic funding of UID/BIO/04469/2013 unit and COMPETE 2020 (POCI-01- 0145-FEDER-006684). Raquel Pereira had a fellowship (SFRH/BD/ 72388/2010) and Luciana Pereira has the fellowship (SFRH/BPD/ 110235/2015) from FCT. The authors thank the FCT exploratory EXPL/AAG-TEC/0898/2013 project

Use of facile mechanochemical method to functionalize carbon nanofibers with nanostructured polyaniline and their electrochemical capacitance

A facile approach to functionalize carbon nanofibers [CNFs] with nanostructured polyaniline was developed via in situ mechanochemical polymerization of polyaniline in the presence of chemically treated CNFs. The nanostructured polyaniline grafting on the CNF was mainly in a form of branched nanofibers as well as rough nanolayers. The good dispersibility and processability of the hybrid nanocomposite could be attributed to its overall nanostructure which enhanced its accessibility to the electrolyte. The mechanochemical oxidation polymerization was believed to be related to the strong Lewis acid characteristic of FeCl3 and the Lewis base characteristic of aniline. The growth mechanism of the hierarchical structured nanofibers was also discussed. After functionalization with the nanostructured polyaniline, the hybrid polyaniline/CNF composite showed an enhanced specific capacitance, which might be related to its hierarchical nanostructure and the interaction between the aromatic polyaniline molecules and the CNFs

Vapor grown carbon nanofiber based cotton fabrics with negative thermoelectric power

Vapor grown carbon nanofiber (CNF) based ink dispersions were used to dip-coat woven cotton fabrics with different constructional parameters, and their thermoelectric (TE) properties studied at room temperature. Unlike the positive thermoelectric power (TEP) observed in TE textile fabrics produced with similar carbon-based nanostructures, the CNF-based cotton fabrics showed negative TEP, caused by the compensated semimetal character of the CNFs and the highly graphitic nature of their outer layers, which hinders the p-type doping with oxygen groups onto them. A dependence of the electrical conductivity (r) and TEP as a function of the woven cotton fabric was also observed. The cotton fabric with the largest linear density (tex) showed the best performance with negative TEP values around - 8 lV K-1 , a power factor of 1.65 9 10-3 lW m-1 K-2 , and a figure of merit of 1.14 9 10-6 . Moreover, the possibility of a slight e- charge transfer or n-doping from the cellulose onto the most external CNF graphitic shells was also analysed by computer modelling. This study presents n-type carbon-based TE textile fabrics produced easily and without any functionalization processes to prevent the inherent doping with oxygen, which causes the typical p-type character found in most carbon-based TE materialsFEDER funds through COMPETE and by national funds through FCT – Foundation for Science and Technology within the project POCI-01-0145- FEDER-007136. E. M. F. Vieira is grateful for financial support through FCT with CMEMS-UMinho Strategic Project UIDB/ 04436/202

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

Development of ClearPEM-Sonic, a multimodal mammography system for PET and Ultrasound

International audience; ClearPEM-Sonic is an innovative imaging device specifically developed for breast cancer. The possibility to work in PEM-Ultrasound multimodality allows to obtain metabolic and morphological information increasing the specificity of the exam. The ClearPEM detector is developed to maximize the sensitivity and the spatial resolution as compared to Whole-Body PET scanners. It is coupled with a 3D ultrasound system, the SuperSonic Imagine Aixplorer that improves the specificity of the exam by providing a tissue elasticity map. This work describes the ClearPEM-Sonic project focusing on the technological developments it has required, the technical merits (and limits) and the first multimodal images acquired on a dedicated phantom. It finally presents selected clinical case studies that confirm the value of PEM information

Optimizing the synthesis of cobalt based catalysts for the selective growth of multiwalled carbon nanotubes under industrially relevant conditions

An industrially applicable cobalt-based catalyst was optimized for the production of multiwalled carbon nanotubes (CNTs) from ethene in a hot-wall reactor. A series of highly active Co-Mn-Al-Mg spinel-type oxides with systematically varied Co : Mn ratios was synthesized by precipitation and calcined at different temperatures. The addition of Mn drastically enhanced the catalytic activity of the Co nanoparticles resulting in an extraordinarily high CNT yield of up to 249 gCNT/gCat. All quaternary catalysts possessed an excellent selectivity towards the growth of CNTs. The detailed characterization of the obtained CNTs by electron microscopy, Raman spectroscopy and thermogravimetry demonstrated that a higher Mn content results in a narrower CNT diameter distribution, while the morphology of the CNTs and their oxidation resistance remains rather similar. The temperature-programmed reduction of the calcined precursors as well as in-situ X-ray absorption spectroscopy investigations during the growth revealed that the remarkable promoting effect of the Mn is due to the presence of monovalent Mn(II) oxide in the working catalyst, which enhances the catalytic activity of the metallic Co nanoparticles by strong metal-oxide interactions. The observed correlations between the added Mn promotor and the catalytic performance are of high relevance for the production of CNTs on an industrial scale