Bruno F. Machado

Graphene-based materials for catalysis

Graphene is one of the most promising materials in nanotechnology. From a theoretical point of view, it provides the ultimate two-dimensional model of a catalytic support. Its unique physical, chemical and mechanical properties are outstanding, and could allow the preparation of composite-materials with unprecedented characteristics. Even though the use of a single graphene sheet as a catalytic support has not yet been reported, some promising results have already been obtained with few-layer graphene. In this review, we will briefly discuss the most relevant synthetic routes to obtain graphene. Then, we will focus our attention on the properties and characterization techniques of graphene that are of relevance to catalysis, with emphasis on adsorption. After presenting an overview of the most common and effective preparation methods, we will discuss the catalytic application of graphene and graphene-based composites, with particular attention on energy conversion and photocatalysis.

Catalytic properties of carbon materials for wet oxidation of aniline

A mesoporous carbon xerogel with a significant amount of oxygen functional groups and a commercial activated carbon, were tested in the catalytic wet air oxidation of aniline at 200 degrees C and 6.9 bar of oxygen partial pressure. Both carbon materials showed high activity in aniline and total organic carbon removal, a clear increase in the removal efficiency relatively to non-catalytic wet air oxidation being observed. The best results in terms of aniline removal were obtained with carbon xerogel, an almost complete aniline conversion after 1h oxidation with high selectivity to non-organic compounds being achieved. The materials were characterized by thermogravimetric analysis, temperature programmed desorption, N(2) adsorption and scanning electron microscopy, in order to relate their performances to the chemical and textural characteristics. It was concluded that the removal efficiency, attributed to both adsorption and catalytic activity, is related to the mesoporous character of the materials and to the presence of specific oxygen containing functional groups at their surface. The effect of catalytic activity was found to be more important in the removal of aniline than the effect of adsorption at the materials surface. The results obtained indicate that mesoporous carbon xerogels are promising catalysts for CWAO processes.

Hydrogenation of p‐Chloronitrobenzene over Nanostructured‐Carbon‐Supported Ruthenium Catalysts

Carbon nanotubes (CNTs) and carbon nanofibers (CNFs) have been used for the first time to support ruthenium nanoparticles for the hydrogenation of p-chloronitrobenzene (p-CNB) to produce selectively p-chloroaniline. The preparation of well-dispersed ruthenium catalysts from the [Ru(3)(CO)(12)] precursor required activation of the purified supports by nitric acid oxidation. The supports, purified and functionalized, and the supported catalysts have been characterized by a range of techniques. The catalytic activity of these materials for the hydrogenation of p-CNB at 35 bar and 60 °C is shown to reach as high as 18 mol(p-CNB)g(Ru)(-1) h(-1), which is one order of magnitude higher than a commercial Ru/Al(2)O(3) catalyst. Selectivities between 92 and 94 % are systematically obtained, the major byproduct being aniline.

Liquid‐Phase Hydrogenation of Unsaturated Aldehydes: Enhancing Selectivity of Multiwalled Carbon Nanotube‐Supported Catalysts by Thermal Activation

Platinum and iridium organometallic precursors are used to prepare nanosized, thermally stable multiwalled carbon nanotube‐supported catalysts. The materials are characterized by N2 adsorption at 77 K, temperature‐programmed desorption coupled with mass spectrometry, H2 chemisorption, transmission electron microscopy and thermogravimetric analysis; they are tested in the selective hydrogenation of cinnamaldehyde to cinnamyl alcohol under mild conditions (363 K and 1 MPa). A thermal activation at 973 K is found to have a very positive effect over both activity and selectivity, leading to selectivities of approximately 70 %, at 50 % conversion, regardless of the active metal phase (Pt or Ir). Since no noticeable differences in the metal particle sizes are detected, the results are interpreted in light of an enhanced metal/support interaction. This effect, induced by the removal of oxygenated surface groups, is thought to change the adsorption mechanism of the cinnamaldehyde molecule.

Synergistic effect between few layer graphene and carbon nanotube supports for palladium catalyzing electrochemical oxidation of alcohols

Abstract Few layer graphene (FLG), multi-walled carbon nanotubes (CNTs) and a nanotube-graphene composite (CNT-FLG) were used as supports for palladium nanoparticles. The catalysts, which were characterized by transmission electron microscopy, Raman spectroscopy and X-ray diffraction, were used as anodes in the electrooxidation of ethanol, ethylene glycol and glycerol in half cells and in passive direct ethanol fuel cells. Upon Pd deposition, a stronger interaction was found to occur between the metal and the nanotube-graphene composite and the particle size was significantly smaller in this material (6.3 nm), comparing with nanotubes and graphene alone (8 and 8.4 nm, respectively). Cyclic voltammetry experiments conducted with Pd/CNT, Pd/FLG and Pd/CNT-FLG in 10 wt% ethanol and 2 M KOH solution, showed high specific currents of 1.48,2.29 and 2.51 mA·µg−1Pd, respectively. Moreover, the results obtained for ethylene glycol and glycerol oxidation highlighted the excellent electrocatalytic activity of Pd/CNT-FLG in terms of peak current density (up to 3.70 mA·µg−1Pd for ethylene glycol and 1.84 mA·μg−1Pd for glycerol, respectively). Accordingly, Pd/CNT-FLG can be considered as the best performing one among the electrocatalysts ever reported for ethylene glycol oxidation, especially considering the low metal loading used in this work. Direct ethanol fuel cells at room temperature were studied by obtaining power density curves and undertaking galvanostatic experiments. The power density outputs using Pd/CNT, Pd/FLG and Pd/CNT-FLG were 12.1, 16.3 and 18.4 mW·cm−2, respectively. A remarkable activity for ethanol electrooxidation was shown by Pd/CNT-FLG anode catalyst. In a constant current experiment, the direct ethanol fuel cell containing Pd/CNT-FLG could continuously deliver 20 mA·cm−2 for 9.5 h during the conversion of ethanol into acetate of 30%, and the energy released from the cell was about 574 J.

Oxidized few layer graphene and graphite as metal-free catalysts for aqueous sulfide oxidation

Few layer graphene and natural graphite were chemically modified by oxidation with HNO3 at 80 and 140 °C and used to promote the oxidation of sulfide ions in aqueous solutions. TEM, potentiometric titration, XRD, BET and Raman spectroscopy show that HNO3 treatment even at 140 °C did not modify the graphene and graphite morphologies but produced significant amounts of different oxygen surface groups. The presence of these groups on few layer graphene and graphite strongly increased the Saq2− oxidation, showing activities comparable to a high surface area activated carbon with a similar amount of oxygen surface groups. The obtained results suggest that the sulfide oxidation efficiency requires a balance between two important effects, i.e. the presence of oxygen functionalities to initiate the Saq2− oxidation and the electrical conductivity that is important to further transfer the electrons removed from sulfide.

Properties of Carbon Nanotubes

After a brief reminder of the basics of carbon nanotubes regarding their morphology, structure, texture, and nanotexture, this chapter attempts to summarize the knowledge gathered on every aspect of their properties as the result of the extensive investigation carried out in this field since the 1990s. The properties covered include electrical, thermal, optical, electronic, and adsorptive (chemical reactivity) completed by a summary of the behavior of carbon nanotubes in biological environment, both from the point of view of eco- and cytotoxicity and that of positive (e.g., therapeutic) interactions. An abundant literature is cited for enabling the reader to deepen any selected topic among those addressed here.

Role of nitrogen doping on the performance of carbon nanotube catalysts: a catalytic wet peroxide oxidation application

Four magnetic carbon nanotube (CNT) samples (undoped, completely N‐doped, and two selectively N‐doped) were synthesized by chemical vapor deposition. The materials were tested in the catalytic wet peroxide oxidation (CWPO) of highly concentrated 4‐nitrophenol solutions (4‐NP, 5 g L−1). Relatively mild operating conditions were considered (atmospheric pressure, T=50 °C, pH 3), using a catalyst load of 2.5 g L−1 and the stoichiometric amount of H2O2 needed for the complete mineralization of 4‐NP. N‐doping was identified to influence considerably the CWPO performance of the materials. In particular, undoped CNTs, with a moderate hydrophobicity, favor the controllable and efficient decomposition of H2O2 into highly reactive hydroxyl radicals (HO.), thus showing high catalytic activity for 4‐NP degradation. On the other hand, the completely N‐doped catalyst, fully hydrophilic, favors a quick decomposition of H2O2 into nonreactive O2 and H2O species. The selectively N‐doped amphiphilic catalysts, that is, hybrid structures containing undoped sections followed by N‐doped ones, provided intermediate results, namely, a higher N content favored H2O2 decomposition towards nonreactive H2O and O2 species, whereas a lower N content resulted in the formation of HO., increasing 4‐NP mineralization. Catalyst stability and reusability were also investigated by consecutive CWPO runs.