New hybrid materials based on the grafting of Pd(II)-amino complexes on the graphitic surface of AC: preparation, structures and catalytic properties

A novel procedure for the preparation of solid Pd(II)-based catalysts consisting of the anchorage of designed Pd(II)-complexes on an activated carbon (AC) surface is reported. Two molecules of the Ar–S–F type (where Ar is a plane-pyrimidine moiety, F a Pd(II)-ligand and S an aliphatic linker) differing in F, were grafted on AC by π–π stacking of the Ar moiety and the graphene planes of the AC, thus favouring the retaining of the metal-complexing ability of F. Adsorption of Pd(II) by the AC/Ar–S–F hybrids occurs via Pd(II)-complexation by F. After deep characterization, the catalytic activities of the AC/Ar–S–F/Pd(II) hybrids on the hydrogenation of 1-octene in methanol as a catalytic test were evaluated. 100% conversion to n-octane at T = 323.1 K and P = 15 bar, was obtained with both catalysts and most of Pd(II) was reduced to Pd(0) nanoparticles, which remained on the AC surface. Reusing the catalysts in three additional cycles reveals that the catalyst bearing the F ligand with a larger Pd-complexing ability showed no loss of activity (100% conversion to n-octane) which is assigned to its larger structural stability. The catalyst with the weaker F ligand underwent a progressive loss of activity (from 100% to 79% in four cycles), due to the constant aggregation of the Pd(0) nanoparticles. Milder conditions, T = 303.1 K and P = 1.5 bar, prevent the aggregation of the Pd(0) nanoparticles in this catalyst allowing the retention of the high catalytic efficiency (100% conversion) in four reaction cycles.

Proof of Concept of the Electrochemical Sensing of 3-Iodothyronamine (T1AM) and Thyronamine (T0AM)

Recent studies have shown that, besides the well-recognized T3 and T4 hormones, there are other relevant thyroid hormones circulating in the human body. In particular, this is the case for 3-iodothyronamine (T1AM) and thyronamine (T0AM). One of the reasons for the lack of studies showing their precise importance is the absence of analytical methodologies available. Herein, for the first time, T1AM and T0AM are electrochemically characterized. T0AM was sensed by means of a glassy carbon electrode; furthermore, T1AM was sensed both with a graphitic surface (oxidatively) as well as with mercury (reductively). For both compounds, after oxidation, it was possible to observe the reversible redox reaction concerning the benzoquinone/hydroquinone couple, thus increasing the specificity of the electroanalysis. Therefore, this work provides the basis for an ‘at-point-of-use’ electrochemical strip test for T1AM and T0AM.

Graphene-like nano-sheets for surface acoustic wave gas sensor applications

The gas sensing properties of graphene-like nano-sheets deposited on 36° YX lithium tantalate (LiTaO3) surface acoustic wave (SAW) transducers are reported. The thin graphene-like nano-sheets were produced via the reduction of graphite oxide which was deposited on SAW interdigitated transducers (IDTs). Their sensing performance was assessed towards hydrogen (H2) and carbon monoxide (CO) in a synthetic air carrier gas at room temperature (25 °C) and 40 °C. Raman and X-ray photoelectron spectroscopy (XPS) revealed that the deposited graphite oxide (GO) was not completely reduced creating small, graphitic nanocrystals ∼2.7 nm in size. © 2008 Elsevier B.V.

Oriented graphitic carbon films for hydrogen gas sensors

An oriented graphitic nanostructured carbon film has been employed as a conductometric hydrogen gas sensor. The carbon film was energetically deposited using a filtered cathodic vacuum arc with a -75 V bias applied to a stainless steel grid placed 1cm from the surface of the Si substrate. The substrate was heated to 400°C prior to deposition. Electron microscopy showed evidence that the film consisted largely of vertically oriented graphitic sheets and had a density of 2.06 g/cm3. 76% of the atoms were bonded in sp2 or graphitic configurations. A change in the device resistance of >; 1.5% was exhibited upon exposure to 1 % hydrogen gas (in synthetic, zero humidity air) at 100°C. The time for the sensor resistance to increase by 1.5 % under these conditions was approximately 60 s and the baseline (zero hydrogen exposure) resistance remained constant to within 0.01% during and after the hydrogen exposures.

Graphitic Carbon as Durable Cathode-Catalyst Support for PEFCs

Long-term deterioration in the performance of PEFCs is attributed largely to reduction in active area of the platinum catalyst at cathode, usually caused by carbon-support corrosion. It is found that the use of graphitic carbon as cathode-catalyst support enhances its long-term stability in relation to non-graphitic carbon. This is because graphitic-carbon-supported- Pt (Pt/GrC) cathodes exhibit higher resistance to carbon corrosion in-relation to non-graphitic-carbon-supported- Pt (Pt/Non-GrC) cathodes in PEFCs during accelerated stress test (AST) as evidenced by chronoamperometry and carbon dioxide studies. The corresponding change in electrochemical surface area (ESA), cell performance and charge-transfer resistance are monitored through cyclic voltammetry (CV), cell polarisation and impedance measurements, respectively. The degradation in performance of PEFC with Pt/GrC cathode is found to be around 10% after 70 h of AST as against 77% for Pt/Non-GrC cathode. It is noteworthy that Pt/GrC cathodes can withstand even up to 100 h of AST with nominal effect on their performance. Xray diffraction (XRD), Raman spectroscopy, transmission electron microscopy and cross-sectional field-emission scanning electron microscopy (FE-SEM) studies before and after AST suggest lesser deformation in catalyst layer and catalyst particles for Pt/GrC cathodes in relation to Pt/Non-GrC cathodes, reflecting that graphitic carbon-support resists carbon corrosion and helps mitigating aggregation of Pt-particles.

A Durable Graphitic-Carbon Support for Pt and Pt3Co Cathode Catalysts in Polymer Electrolyte Fuel Cells

The high efficiency of fuel-cell-powered electric vehicles makes them a potentially viable option for future transportation. Polymer Electrolyte Fuel Cells (PEFCs) are most promising among various fuel cells for electric traction due to their quick start-up and low-temperature operation. In recent years, the performance of PEFCs has reached the acceptable level both for automotive and stationary applications and efforts are now being expended in increasing their durability, which remains a major concern in their commercialization. To make PEFCs meet automotive targets an understanding of the factors affecting the stability of carbon support and platinum catalyst is critical. Alloying platinum (Pt) with first-row transition metals such as cobalt (Co) is reported to facilitate both higher degree of crystallinity and enhanced activity in relation to pristine Pt. But a major challenge for the application of Pt-transition metal alloys in PEFCs is to improve the stability of these binary catalysts. Dissolution of the non-precious metal in the acidic environment could alleviate the activity of the catalysts and hence cell performance. The use of graphitic carbon as cathode-catalyst support enhances the long-term stability of Pt and its alloys in relation to non-graphitic carbon as the former exhibits higher resistance to carbon corrosion in relation to the latter in PEFC cathodes during accelerated-stress test (AST). Changes in electrochemical surface area (ESA), cell performance and charge-transfer resistance are monitored during AST through cyclic voltammetry, cell polarization and impedance measurements, respectively. Studies on catalytic electrodes with X-ray diffraction, Raman spectroscopy and transmission electron microscopy reflect that graphitic carbon-support resists carbon corrosion and helps mitigating aggregation of Pt and Pt3Co catalyst particles. (C) 2012 The Electrochemical Society. DOI: 10.1149/2.051301jes] All rights reserved.

Investigations on high enthalpy shock wave exposed graphitic carbon nanoparticles

The impact of high enthalpy shock wave on graphitic carbon nanoparticle (GCNP) films has been investigated and discussed in view of space and chemical engineering applications. The GCNP films were developed by using spray method and exposed to high enthalpy shock wave under an inert atmosphere. Upon shock wave treatment, two typical amendments such as weight loss in the deposited material and growth of second order nanostructures (SONS) have been observed. While increasing test gas pressure, the loss of material and density of SONs are gradually increased. Most of the shock wave induced SONS are highly crystalline and belong to the cubic diamond structure. Upon shock treatment as well as with increase of test gas pressure, a considerable improvement in the quality of GCNP films has been observed. Further, ablation of GCNPs exclusively on the top surface of the coatings and formation of hierarchical NPs (diamond NPs on GCNPs) has been observed.

Enhanced Gas Adsorption on Graphitic Substrates via Defects and Local Curvature: A Density Functional Theory Study

Using van-der-Waals-corrected density functional theory calculations, we explore the possibility of engineering the local structure and morphology of high-surface-area graphene-derived materials to improve the uptake of methane and carbon dioxide for gas storage and sensing. We test the sensitivity of the gas adsorption energy to the introduction of native point defects, curvature, and the application of strain. The binding energy at topological point defect sites is inversely correlated with the number of missing carbon atoms, causing Stone-Wales defects to show the largest enhancement with respect to pristine graphene (similar to 20%). Improvements of similar magnitude are observed at concavely curved surfaces in buckled graphene sheets under compressive strain, whereas tensile strain tends to weaken gas binding. Trends for CO2 and CH4 are, similar, although CO2 binding is generally stronger by similar to 4 to 5 kJ mol(-1). However, the differential between the adsorption of CO2 and CH4 is much higher on folded graphene sheets and at concave curvatures; this could possibly be leveraged for CH4/CO2 flow separation and gasselective sensors.

Surface atomic properties of tetrahedral amorphous carbon

The surface energy and surface atomic structure of tetrahedral amorphous carbon has been calculated by an ab-initio method. The surface atoms are found to reconstruct into sp2 sites often bonded in graphitic rings. Placing the dangling bonds on adjacent surface atoms lower their energy by π-bonding and this is the source of the low surface energy. The even lower surface energy of hydrogenated amorphous carbon (a-C:H) is due to the hydrogenation of all broken surface bonds. © 2005 Elsevier B.V. All rights reserved.

Influence of ion energy and deposition temperature on the surface morphology of carbon films deposited by ion beams

Carbon films were deposited by mass-selected ion beam technique with ion energies 50-200eV at a substrate temperature from room temperature to 80 degreesC,. For the energies used, smooth diamond-like carbon films were deposited at room temperature. When the substrate temperature was 600 degreesC,rough graphitic films were produced. But highly oriented carbon tubes were observed when the energies were larger than 140eV at 800 degreesC. They were perpendicular to the surface and parallel to each other. preferred orientation of graphite basic plane was observed by high-resolution electron microscopy. Shallow ion implantation and stress are responsible for this orientation.

Uniformly carbon-covered alumina and its surface characteristics

Uniformly carbon-covered alumina (CCA) was prepared via the carbonization of sucrose highly dispersed on the alumina surface. The CCA samples were characterized by XRD, XPS, DTA-TG, UV Raman, nitrogen adsorption experiments at 77 K, and rhodamine B (RB) adsorption in aqueous media. UV Raman spectra indicated that the carbon species formed were probably conjugated olefinic or polycyclic aromatic hydrocarbons, which can be considered molecular subunits of a graphitic plane. The N(2) adsorption isotherms, pore size distributions, and XPS results indicated that carbon was uniformly dispersed on the alumina surface in the as-prepared CCA. The carbon coverage and number of carbon layers in CCA could be controlled by the tuning of the sucrose content in the precursor and impregnation times. RB adsorption isotherms suggested that the monolayer adsorption capacity of RB on alumina increased drastically for the sample with uniformly dispersed carbon. The as-prepared CCA possessed the texture of alumina and the surface properties of carbon or both carbon and alumina depending on the carbon coverage.

Ultrathin graphitic structures and carbon nanotubes in a purified synthetic graphite

A new class of carbon structure is reported, which consists of microscale graphitic shells bounded by curved and faceted planes containing two to five layers. These structures were originally found in a commercial graphite produced by the Acheson process, followed by a purification treatment. The particles, which could be several hundreds of nanometres in size, were frequently decorated with nanoscale carbon particles, or short nanotubes. In some cases, nanotubes were found to be seamlessly connected to the thin shells, indicating that the formation of the shells and that of the nanotubes are intimately connected. The structures are believed to form during a purification process which involves passing an electric current through the graphite in the presence of a reactive gas. In support of this, it is shown that similar particles can be produced in a standard carbon arc apparatus. With their extremely thin graphene walls and high surface areas, the new structures may have a range of useful properties.

Production and heat treatment of cast graphitic steels with additions of niobium

The optimal combination of the mechanical characteristics of austempered spheroidal graphitic cast steel together with modern casting techniques yielded an economically promising product. The maximum potential of the usage of these steels is related to fabrication and characterization techniques, among which, one of the most important is the cooling diagram (TTT curve). In this work, 3 heats of graphitic steels with the following nominal compositions were cast: 1.0 % C, 2.3 % Si, 0.4 % Mn, and with niobium contents of. 0.0 %, 0.5 % and 1.0 %. TTT curves were determined by dilatometric testing and test specimens of these steels were austempered. The samples were then characterized by hardness testing and optical and SEM microscopy. Tensile, impact (no notch) and wear testing were also performed. The addition of niobium produced significant alterations in the TTT diagrams. Increasing niobium content moves the pearlite transformation nose to the right and the bainitic transformation nose to the left. Tensile strength of these alloys was high, in the range of 1700 MPa and impact values were around of 45 Joules for alloy with 1 % Nb, 49 Joules for alloy with 0.5 % Nb and fracture did not occur for the alloy without the addition of Nb.

CO2 adsorption on crystalline graphitic nanostructures

CO2 adsorption has been measured in different types of graphitic nanostructures (MWCNTs, acid treated MWCNTs, graphene nanoribbons and pure graphene) in order to evaluate the effect of the different defective regions/conformations in the adsorption process, i.e., sp3 hybridized carbon, curved regions, edge defects, etc. This analysis has been performed both in pure carbon and nitrogen-doped nanostructures in order to monitor the effect of surface functional groups on surface created after using different treatments (i.e., acid treatment and thermal expansion of the MWCNTs), and study their adsorption properties. Interestingly, the presence of exposed defective regions in the acid treated nanostructures (e.g., uncapped nanotubes) gives rise to an improvement in the amount of CO2 adsorbed; the adsorption process being completely reversible. For N-doped nanostructures, the adsorption capacity is further enhanced when compared to the pure carbon nanotubes after the tubes were unzipped. The larger proportion of defect sites and curved regions together with the presence of stronger adsorbent–adsorbate interactions, through the nitrogen surface groups, explains their larger adsorption capacity.