Chemical and structural characterization of carbon nanotube surfaces

To utilize carbon nanotubes (CNTs) in various commercial and scientific applications, the graphene sheets that comprise CNT surfaces are often modified to tailor properties, such as dispersion. In this article, we provide a critical review of the techniques used to explore the chemical and structural characteristics of CNTs modified by covalent surface modification strategies that involve the direct incorporation of specific elements and inorganic or organic functional groups into the graphene sidewalls. Using examples from the literature, we discuss not only the popular techniques such as TEM, XPS, IR, and Raman spectroscopy but also more specialized techniques such as chemical derivatization, Boehm titrations, EELS, NEXAFS, TPD, and TGA. The chemical or structural information provided by each technique discussed, as well as their strengths and limitations. Particular emphasis is placed on XPS and the application of chemical derivatization in conjunction with XPS to quantify functional groups on CNT surfaces in situations where spectral deconvolution of XPS lineshapes is ambiguous.      

Cobalt particle size effects in the Fischer-Tropsch reaction studied with carbon nanofiber supported catalysts

The influence of cobalt particle size in the range of 2.6-27 nm on the performance in Fischer-Tropsch synthesis has been investigated for the first time using well-defined catalysts based on an inert carbon nanofibers support material. X-ray absorption spectroscopy revealed that cobalt was metallic, even for small particle sizes, after the in situ reduction treatment, which is a prerequisite for catalytic operation and is difficult to achieve using traditional oxidic supports. The turnover frequency (TOF) for CO hydrogenation was independent of cobalt particle size for catalysts with sizes larger than 6 nm (1 bar) or 8 nm (35 bar), while both the selectivity and the activity changed for catalysts with smaller particles. At 35 bar, the TOF decreased from 23 x 10(-3) to 1.4 x 10(-3) s(-1), while the C5+ selectivity decreased from 85 to 51 wt % when the cobalt particle size was reduced from 16 to 2.6 nm. This demonstrates that the minimal required cobalt particle size for Fischer-Tropsch catalysis is larger (6-8 nm) than can be explained by classical structure sensitivity. Other explanations raised in the literature, such as formation of CoO or Co carbide species on small particles during catalytic testing, were not substantiated by experimental evidence from X-ray absorption spectroscopy. Interestingly, we found with EXAFS a decrease of the cobalt coordination number under reaction conditions, which points to reconstruction of the cobalt particles. It is argued that the cobalt particle size effects can be attributed to nonclassical structure sensitivity in combination with CO-induced surface reconstruction. The profound influences of particle size may be important for the design of new Fischer-Tropsch catalysts.     

Mechanochemical Immobilisation of Metathesis Catalysts in a Metal–Organic Framework

A simple, one‐step mechanochemical procedure for immobilisation of homogeneous metathesis catalysts in metal–organic frameworks was developed. Grinding MIL‐101‐NH₂(Al) with a Hoveyda–Grubbs second‐generation catalyst resulted in a heterogeneous catalyst that is active for metathesis and one of the most stable immobilised metathesis catalysts. During the mechanochemical immobilisation the MIL‐101‐NH₂(Al) structure was partially converted to MIL‐53‐NH₂(Al). The Hoveyda–Grubbs catalyst entrapped in MIL‐101‐NH₂(Al) is responsible for the observed catalytic activity. The developed synthetic procedure was also successful for the immobilisation of a Zhan catalyst.     

Stability and activity of carbon nanofiber-supported catalysts in the aqueous phase reforming of ethylene glycol

Nickel, cobalt, copper and platinum nanoparticles supported on carbon nano-fibers were evaluated with respect to their stability, catalytic activity and selectivity in the aqueous phase reforming of ethylene glycol (230 C, autogenous pressure, batch reactor). The initial surface-specific activities for ethylene glycol reforming were in a similar range but decreased in the order of Pt (15.5 h1 ) >Co(13.0 h1 ) >Ni(5.2 h1 ) while the Cu catalyst only showed low dehydrogenation activity. The hydrogen molar selectivity decreased in the order of Pt (53%)>Co(21%)>Ni (15%) as a result of the production of methane over the latter two catalysts. Over the Co catalyst acids were formed in the liquid phase while alcohols were formed over Ni and Pt. Due to the low pH of the reaction mixture, especially in the case of Co (as a result of the formed acids), significant cobalt leaching occurs which resulted in a rapid deactivation of this catalyst. Investigations of the spent catalysts with various techniques showed that metal particle growth is responsible for the deactivation of the Pt and Ni catalysts. In addition, coking might also contribute to the deactivation of the Ni catalyst.     

Toward a physical understanding of electron-sharing two-center bonds. I. General aspects

In 1916, Lewis and Kossel laid the empirical ground for the electronic theory of valence, whose quantum theoretical foundation was uncovered only slowly. We can now base the classification of the various traditional chemical bond types in a threefold manner on the one- and two-electron terms of the quantum-physical Hamiltonian (kinetic, atomic core attraction, electron repulsion). Bond formation is explained by splitting up the real process into two physical steps: (i) interaction of undeformed atoms and (ii) relaxation of this nonstationary system. We aim at a flexible bond energy partitioning scheme that can avoid cancellation of large terms of opposite sign. The driving force of covalent bonding is a lowering of the quantum kinetic energy density by sharing. The driving force of heteropolar bonding is a lowering of potential energy density by charge rearrangement in the valence shell. Although both mechanisms are quantum mechanical in nature, we can easily visualize them, since they are of one-electron type. They are however tempered by two-electron correlations. The richness of chemistry, owing to the diversity of atomic cores and valence shells, becomes intuitively understandable with the help of effective core pseudopotentials for the valence shells. Common conceptual difficulties in understanding chemical bonds arise from quantum kinematic aspects as well as from paradoxical though classical relaxation phenomena. On this conceptual basis, a dozen different bond types in diatomic molecules will be analyzed in the following article. We can therefore examine common features as well as specific differences of various bonding mechanisms.     

Click synthesis of triazole-linked calix[4]arene ionophores. Potentiometric and ESI-MS screening of ion-selectivity

A series of 1,2,3-triazole-linked calix[4]arene ionophores comprised of different O-donor groups (OH, COOEt, CONEt₂) attached either to the lower rim of calix or to the triazole moieties were synthesized to explore their ion-selectivity for the first time in potentiometric transduction. Plasticized PVC membrane electrodes (ISEs) were fabricated, and their potentiometric selectivities were measured toward a series of mono- and divalent metal ions. Structure-ion-selectivity relationship and the structural requirements of the coordination sphere for selective binding were established. ISEs made of calix[4]arene-bis-triazoles were found generally to exhibit distinct Ag⁺ selectivity in the order 3 ≈ 4 > 2 > 1, indicating the beneficial effect of the carboxamide or ester groups in the complexing site. In contrast, calix[4]arene-tetratriazole 5 comprised only sp ² N-donor atoms displayed excellent Cu²⁺ selectivity over a series of alkali-, alkaline earth- and transition metal ions. A unique feature of the outstanding Ag⁺ selective electrodes made of 3 and 4 was recognized and suggested their potential application as Na⁺ ISEs in systems not containing silver ions. Further, the potential use of competitive ESI-MS experiments for screening the binding affinities of ionophores 3–6 to different metal ions was also demonstrated.     

Chemoselective ring closure of thiacalix[4]arene-1,3-bis(N-ω-hydroxyalkylamides) via the Mitsunobu reaction

Chemoselective intramolecular ring closure on the phenolic OH groups of p-tert-butylthiacalix[4]arene-1,3-bis(N-ω-hydroxyalkylamides) attained under Mitsunobu conditions affords inherently chiral macrocycles capped by carboxamide bridges. Oxazoline or oxazine cyclization products derived from self-condensation of the hydroxyalkylamide moieties were not isolated. In one case the detection of enantiomers was achieved by chiral HPLC.     

Lactose oxidation over palladium catalysts supported on active carbons and on carbon nanofibres

Liquid-phase lactose oxidation was investigated over supported Pd/C and Pd-carbon nanofibre catalysts, which were characterized by several methods. A complex relationship between catalyst activity and catalyst acidity was established, i.e. optimum catalyst acidity resulted in the highest activity in lactose oxidation. In-situ catalyst potential measurements during lactose oxidation gave information about the extent of accumulation of oxygen on the metal surface. These results could be correlated with catalyst deactivation, which was extensive over the most acidic catalysts at low reaction temperatures. Selectivity for the desired product, lactobionic acid, was a maximum of approximately 83% at 93% conversion. The main side-product was lactulose formed via isomerisation of lactose. Lower selectivity toward lactobionic acid was obtained when the rate of oxidation of lactose was low.     

Fluorescent iminodiacetamide derivatives as potential ionophores for optical zinc ion-selective sensors.

Fluorescent sensor molecules were synthesized by conjugation of iminodiacetamide derivatives with fluorescent moieties of different structures and their UV-visible and fluorescent properties were characterized in acetonitrile solvent. The fluorescent measurements revealed that the N-(2-naphthyl) and N-phenyl derivatives exhibit a distinct zinc ion-selectivity over alkali and alkaline earth metal ions, while N-(anthrylmethyl) and N-(3-methoxyphenyl) derivatives do not possess any ion-selectivities. In contrast to the fluorescent measurements, all ligands show Zn(2+) selectivity over Ca(2+) and Mg(2+) ions in plasticized PVC membranes using potentiometric signal transduction. This observation found for N-(anthrylmethyl) and N-(3-methoxyphenyl) derivatives can be ascribed to the more hindered interaction between the signalling group of the ionophore and the central metal ion in PVC membranes than in acetonitrile solution upon complexation. From the fluorescent measurements it can also be concluded that the ligands with metal ions form complexes mainly with 2:1 stoichiometry (L(2)M). On complex formation a considerable decrease in the fluorescent intensity was observed for all ligands except the N-(anthrylmethyl) derivative, where a 25 - 30 fold fluorescence enhancement was found, which is explained by the photoinduced electron transfer (PET) mechanism. All ionophores exhibited serious hydrogen ion interference, therefore complexation-induced spectral changes were measured in aprotic acetonitrile solution.