Theoretical Studies on Interaction Between Methanol and Functionalized Single-Walled Carbon Nanotubes

We study the adsorption of a methanol molecule on single-walled carbon nanotubes (SWCNTs) with various diameters and chiral angles by using the density functional theory based calculations. We find that methanol prefers to be adsorbed physically on the exterior surface of chiral nanotubes in comparison to the armchair and zigzag tubes with binding energy of about-2.76 kcal/mol, which is consistent with recent experimental andtheoretical investigation results. We further consider the adsorption of methanol on the exterior surface and edge site of functionalized SWCNTs. The obtained results indicate that the binding energy of methanol is significantly increased for adsorption on the sidewall of functionalized nanotubes. It is also found that the adsorption of methanol at the edge site of both functionalizedand pristine SWCNT is remarkably different (chemisoption process) incomparison to the exterior sidewall of the tubes. Furthermore, the electronic structures and Mulliken charge population of the considered complexes at their ground state are discussed within the context.     

Exploring the possibility of GaPNTs as new materials for hydrogen storage

The possibility of hydrogen storage in gallium phosphate nanotubes (GaPNTs) as a high-capacity hydrogen storage media is studied by employing ab-initio density functional theory (DFT) calculations with a van der Waals (VdW) correction. The binding energy, the distance of the adsorbed hydrogen molecules and the charge transfer were particularly calculated. The obtained results indicate that hydrogenation of the GaPNTs is sensitive to the curvatures and chiralities of the nanotubes. It is found that the binding energy of hydrogen physisorption on GaP nanotubes is higher that on carbon nanotubes. These results are useful in the search for a proper media for hydrogen storage at ambient conditions.     

A study of nitric oxide adsorbed on nickel oxide,cobalt oxide,and graphite by X-ray photoelectron spectroscopy

The nitrogen 1s binding energy of nitric oxide adsorbed on nickel oxide, cobalt oxide and graphite was measured at several temperatures by X-ray photoelectron spectroscopy. For the oxides, a temperature dependent range of binding energies was observed, but for graphite the nitrogen 1s binding energy was independent of temperature. The values obtained suggest that significant back donation of electrons occurs from the oxides to the adsorbed nitric oxides, but no back donation occurs from graphite to adsorbed nitric oxide. However, adsorption did not cause changes in the binding energy of substrate core electrons. It is believed that unless the mean free path of electrons is short, the total photoelectron signal will not reveal changes in binding energy of electrons from substrate atoms at the surface.     

Density-functional study of methanol adsorption on the Al(100) surface

The interaction of methanol (CH₃OH) molecules with the Al(100) surface is investigated in the framework of the density-functional theory. Numerical parameters, such as the decrease in the kinetic energy, number of special points used for integration over the Brillouin zone, broadening of the filling function, and number of atomic metal layers, are determined. The density-functional theory calculations with these parameters offer reliable data on the total energy and structural optimization of the system under consideration. The geometric characteristics of a methanol molecule in both isolated and adsorbed states on the metal surface are calculated. It is shown that the electron pseudodensity at the metal surface changes in the presence of an adsorbed molecule. The influence of the orientation of the methanol molecule (with respect to the metal surface and nearest neighbor methanol molecules) on the total energy of the system is analyzed. It is found that the total energy of the system is affected by the metal deformation and the interaction of adsorbed molecules with each other.     

Elastic properties of SWCNTs with curved morphology: Density functional tight binding based treatment

The self-consistent charge density functional based tight-binding method is used to calculate the effect of curvature on the structure, average energy of atoms and Young's modulus of armchair single-wall carbon nanotubes (SWCNTs) under axial strains. We found that as the amount of curvature increases, the average energy of atoms and the Young's modulus decrease and the equilibrium CC distance increases for (7,7) SWCNTs. However, we also found that the average energy of atoms and Young's modulus of (5,5) SWCNTs are weakly affected by increasing the amount of curvature. Our results also show that the average energy of atoms and Young's modulus of smaller diameter armchair nanotubes are smaller than that of the larger diameter ones.     

XPS,UPS and thermal desorption studies of alcohol adsorption on Cu(110): II. Higher alcohols

Preceding work dealing with the adsorption of methanol on Cu(110) has been extended to include ethanol, n- and iso-propanol and a diol, ethylene glycol. In common with the simplest alcohol, all these molecules are able to form a stable alkoxy species on the surface, that is, the alcohol dissociated at the O-H group. However, in contrast to methanol on the clean surface for which the dissociated methoxy and hydrogen recombined to desorb as methanol, all the higher alcohols reacted further with the surface, dehydrogenating to yield the corresponding aldehyde or ketone in the gas phase. Ethylene glycol reacted to form the most strongly bound intermediate of all, decomposing near 390 K to produce the dialdehyde, glyoxal, with little evidence of monoaldehyde formation or C-C bond breakage. The influence of pre-adsorbed oxygen on these reactions was to generally increase the amount of alkoxy formed on the surface by enhancing the amount of dissociative adsorption (water is formed by the deprotonation of adsorbed alcohol molecules by oxygen atoms). The alkoxide decomposition peaks were shifted to slightly higher temperatures and considerably broadened in such experiments. The decomposition peak temperatures of the different surface alkoxides correlate fairly well with literature values of the αC-H bond strength, which is weaker in iso-propanol than in methanol. XPS showed broad O(1s) spectra for all the molecules adsorbed at 140 K, probably due to hydrogen-bonding effects in the adlayer, with peak emissions at around 533 eV. When the surface was warmed to 250 K, the O(1s) spectra narrowed to close to instrumental linewidths with a concomitant shift to a lower binding energy near 531 eV. C(1s) spectra showed little change between the adsorbed alcohol and alkoxy species. The UPS showed low temperature spectra similar to the gas phase, but the highest occupied orbitals, which are essentially O(2p) orbitals, showed a chemisorption bonding shift of several tenths of an electron volt. UPS for these molecules is shown to have considerable less utility than for the simplest molecule, methanol, due to the masking of possible orbital shifts during chemical changes on the surface by the presence of overlapping emissions in the spectra.     

缺陷碳纳米管限域金属Ti原子的理论研究

基于密度泛函第一性原理研究了金属原子Ti在原始、单空位缺陷(SV)、Stone-Wales(SW)缺陷碳纳米管内外的吸附情况.我们的计算结果表明金属Ti原子在缺陷碳纳米管内外结合能的排列顺序为:SVSW-zSW-xpristine(外吸附),SVSW-xSW-zpristine(内吸附).同时,我们通过吸附结构、电子密度和态密度等分析了Ti原子与碳纳米管的作用机制.其中,SV缺陷碳纳米管由于失去一个碳原子而形成了的三个悬键具有很强的结合能力,金属原子Ti在SV缺陷碳纳米管内外的吸附能力都是最强的.对于SW缺陷的碳纳米管,由于缺陷的位置不同,对于金属原子Ti内外吸附的能力也是不同的.因此,缺陷的存在能调节碳纳米管载体对Ti原子的吸附性能.     

Interaction of alkanethiols with single-walled carbon nanotubes: First-principles calculations

We report the results of our first-principles study based on density functional theory on the interaction of alkanethiols with both defected and defect-free single-walled carbon nanotube (SWCNT). The adsorption energies are calculated for various configurations such as alkanethiol molecule approaching to defect sites heptagon, hexagon, and pentagon in defective tube, and another case where the alkanethiol approaching to hexagon in defect-free nanotube. The calculated results showed that alkanethiols are rather strongly bound to the outer surface of both the defected and defect-free carbon nanotubes with the binding energy of about −50.58 kcal/mol, consistent with the experimental result. We also find that alkanethiols prefer to be adsorbed on the hexagon ring site of defect-free nanotube. Furthermore, the effect of alkanethiols chain length on the adsorption of alkanethiols on carbon nanotubes has been investigated, and the obtained results reveal that the longer alkanethiols bind rather more strongly to the nanotube surface.     

Adsorption of TCDD molecule onto CNTs and BNNTs: Ab initio van der Waals density-functional study

2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCCD) is one of the most dangerous compounds that infect the environment and hence its removal is crucial for safety in human life. In this work, we have investigated the interaction of TCDD with boron nitride nanotubes (BNNTs) and carbon nanotubes (CNTs) by using the density functional theory (DFT) calculations. Our first-principles results have been validated by experiment and also other theoretical values for the similar system. The adsorption energies for TCDD molecule on the BNNTs and CNT are calculated. It was found that TCDD adsorption ability of BNNT is slightly stronger than that of CNT and TCDD molecule prefers to be adsorbed on BNNTs with molecular axis parallel to the tube axis. The results obtained indicate that TCDD is weakly bound to the outer surface of all the considered nanotubes and the obtained adsorption energy values and binding distance are typical for the physisorption. We also evaluated the influence of curvature and introduced defects on the TCDD adsorption ability of BNNTs. Furthermore, we have analyzed the electronic structure and charge population for the energetically most favorable complexes and the results indicate that no significant hybridization between the respective orbitals of the two entities was accomplished.     

Structure and properties of BeO nanotubes

The structure of a new non-carbon (beryllium oxide BeO) nanotube consisting of a rolled-up graphene sheet is proposed, and its physical properties are described. Ab initio calculations of the binding energy, the electronic band structure, the density of states, the dependence of the strain energy of the nanotube on the nanotube diameter D, and the Young’s modulus Y for BeO nanotubes of different diameters are performed in the framework of the density functional theory (DFT). From a comparison of the binding energies calculated for BeO nanotubes and crystalline BeO with a wurtzite structure, it is inferred that BeO nanotubes can be synthesized by a plasma-chemical reaction or through chemical vapor deposition. It is established that BeO nanotubes are polar dielectrics with a band gap of ～5.0 eV and a stiffness comparable to that of the carbon nanotubes (the Young’s modulus of the BeO nanotubes Y _BeO is approximately equal to 0.7Y _C, where Y _C is the Young’s modulus of the carbon nanotubes). It is shown that, for a nanotube diameter D > 1 nm, the (n, n) armchair nanotubes are energetically more favorable than the (n, 0) zigzag nanotubes.     

Magnetic and binding properties of metal-divacancy complexes at MgO (0 0 1) surface: DFT calculations

We have analyzed the magnetic and binding properties of Ni, Cr, Mo, and Pt metals deposited on the defect free and defect containing surfaces of MgO by means of density functional theory calculations and embedded cluster model. Clusters of moderate sizes with no border anions, to avoid artificial polarization effects, were embedded in the simulated Coulomb fields that closely approximate the Madelung fields of the host surfaces. Spin quenching occurs for Cr and Mo complexes at the defect free (terrace) surface, and Cr, Mo, and Pt complexes at the defect containing “pit” divacancy surface. The binding energies of the metals are significantly enhanced on the cationic vacancy end of the divacancy. The adsorption energies of the low spin states of spin quenched complexes are always greater than those of the high spin states. The metal-support interactions stabilize the low spin states of the adsorbed metals with respect to the isolated metals, but the effect is not always enough to quench the spin. The encountered variations in magnetic properties of free metals and of metal complexes are correlated with the energy gaps of the frontier orbitals. Spin contamination affect the adsorbate-substrate distances, Mulliken charges, Mulliken spin densities, natural charge, natural orbital population, and provide rationalization for the reported magnetic and binding properties. The electrostatic potential energy curves provide clearer understanding of the nature of magnetic and binding interactions. The magnetic and binding properties of a single metal atom adsorbed on a particular surface result from a competition between Hund's rule for the adsorbed metal, and the formation of a chemical bond at the interface.     

Excitons in optical spectra of boron-nitride (BN) nanotubes

Exciton effects are studied in single-wall boron-nitride nanotubes. The Coulomb interaction dependence of the band gap, the optical gap, and the binding energy of excitons are discussed. The optical gap of the (5,0) nanotube is about 6 eV at the on-site interaction U=2t with the hopping integral t=1.1 eV. The binding energy of the exciton is 0.50 eV for these parameters. This energy agrees well with that of other theoretical investigations. We find that the energy gap and the binding energy are almost independent of the geometries of nanotubes. This novel property is in contrast with that of the carbon nanotubes, which show metallic and semiconducting properties depending on the chiralities.     

Adsorption on the graphene surface of carbon nanotubes and their energy spectrum

The conditions of formation of local states in the energy spectra of semi-infinite carbon nanotubes with regularly arranged atoms adsorbed on the outer surface are studied in the π-electron approximation. The influence of the adsorption type (physical and chemical), the donor-acceptor properties of adsorbed atoms, their concentration on the graphene surface, and the nanotube diameter on the characteristics of the local states that arise is considered. It is shown that both physical and chemical adsorptions cause a decrease in the band gap separating the upper filled energy band and the lower vacant band. This effect can significantly change the electrical and optical properties of the nanotubes under consideration in comparison with the initial “pure” tubulene.     

Methanol adsorption on Pd(1 1 0) and Ag/Pd(1 1 0) studied by high-resolution photoelectron spectroscopy

Adsorption of methanol on clean Pd(1 1 0) and on an alloyed Ag/Pd(1 1 0) surface has been studied by high-resolution photoelectron spectroscopy. On Pd(1 1 0) two different chemisorbed methanol species were observed for temperatures up to 200 K, with the one at lower binding energy remaining at low coverage. These species were attributed to methanol adsorbed in two different adsorption sites on the Pd(1 1 0) surface. As is well established for this system, heating to 250 K resulted in decomposition of methanol into CO. The adsorption and decomposition behaviour of methanol on the Ag/Pd(1 1 0) surface alloy formed by depositing Ag on Pd(1 1 0) at elevated temperature was similar to that of the pure Pd(1 1 0) surface. This suggests that the amount of Ag present in the Pd(1 1 0) surface in this study does not affect the decomposition behaviour of methanol as compared to pure Pd(1 1 0). Complementary density functional theory calculations also show little influence of Ag on the binding of methanol to Pd. These calculations predict an on-top adsorption site for low methanol coverages.     

On the existence and stability of double-walled armchair silicon carbide nanotubes

A systematic study of type 1 armchair double-walled SiC nanotubes (DWNTs) (n,n)@(m,m) (3≤n≤6;7≤m≤12) using the finite cluster approximation is presented. The geometries of the tubes have been spin optimized using the hybrid functional B3LYP (Becke’s three-parameter exchange functional and the Lee-Yang-Parr correlation functional) and the all-electron 3-21G* basis set. The study indicates that the stabilities of the double-walled SiC nanotubes are of the same order as those of single-walled SiC nanotubes suggesting the possibilities of experimental synthesis of both single-walled and double-walled SiC nanotubes. The binding energy per atom or the cohesive energy of the double-walled nanotubes depends not only on the number of atoms but also on the coupling of the constituent single-walled nanotubes. The formation energy of the DWNTs is found to be maximum when the interlayer separation is about 3.5 Å. The DWNTs (n,n)@(n+4,n+4) are found to have large formation energies. In particular, (5,5)@(9,9) DWNT is the most stable tube in our study with a binding energy per atom of 5.07 eV, the largest formation energy of 12.39 eV, an interlayer separation of 3.58 Å and a “band gap” of 1.97 eV. All double-walled SiC nanotubes are found to be semiconductors, with the band gaps decreasing from single-walled nanotubes to double-walled nanotubes.     

Development of new composite biosorbents from olive pomace wastes

In this study olive pomace was used as a source of binding substances for the development of composite biosorbents to be used in heavy metal removal from aqueous solutions. The aim was to obtain biosorbent material with an increased concentration of binding sites. The effects of two different extraction procedures (one using only methanol and the other one hexane followed by methanol) on the binding properties of olive pomace were tested by potentiometric titrations and batch biosorption tests for copper and cadmium removal. Titration modelling evidenced that both kinds of extractions generated a solid with a reduced amount of protonatable sites. Biosorption tests were organized according to full factorial designs. Analysis of variance denoted that both kinds of extractions determined a statistically significant negative effect on metal biosorption. In the case of cadmium extractions also determined a significant decrease of selectivity with respect to olive pomace.When the acid-base and binding properties of the substances extracted were determined, they were adsorbed onto a synthetic resin (octadecylsilane) and calcium alginate beads. In this way two kinds of composite biosorbents have been obtained both having an increased concentration of binding substances with respect to native olive pomace, also working more efficiently in metal removal.     

单壁碳纳米管能带及其电子特性研究

从能带理论出发,采用电子紧束缚能量色散关系,推导锯齿,扶手椅和手性单壁碳纳米管(SWCNT)的电子能带结构表达式,指出单壁碳纳米管或为金属或为半导体的判据。结果表示:单壁碳纳米管的电子结构与其几何结构密切相关,如扶手椅型单壁碳纳米管是金属性的,而对其它类型的单壁碳纳米管是与碳纳米管的手性指数有关,只有手性指数n和m的差别等于3的倍数时,单壁碳纳米管是金属性的,否则会显出有带隙的半导体特性。这意味着单壁碳纳米管是由特殊的电子传输和光学性质,在纳米电子学领域具有巨大的潜在应用价值。     

Enhancement of single-walled nanotubes luminescence intensity upon dithiothreitol doping

In the present work the influence of reducing agent dithiothreitol doping on photoluminescence spectra of nanotubes with adsorbed biopolymers (single-stranded DNA and polyC) in aqueous suspensions and films was studied. It is revealed that greater intensity enhancement at 10^?3 mol/L dithiothreitol concentration is observed for (7,5) and (6,5) nanotubes in suspension with single-stranded DNA (by more than 150% of initial intensity) comparing to polyC suspension (less than 60%) while for (6,4) and (9,1) nanotubes enhancement is less than 50% for both suspensions. Photoluminescence intensity increasing for nanotube film with DNA is less than 50% without noticeable dependence on nanotube chirality. It is assumed, that different influence of biopolymers on nanotube luminescence intensity enhancement is due to their different coverage of nanotube surface.     

Preparation and Characterization of Linear Low Density Polyethylene/Carbon Nanotube Nanocomposites

Linear low‐density polyethylene (LLDPE)/multiwalled carbon nanotube (MWNT) nanocomposites were prepared via melt blending. The morphology and degree of dispersion of nanotubes in the polyethylene matrix were investigated using scanning electron microscopy (SEM). Both individual and agglomerates of MWNTs were evident. The rheological behavior and mechanical and electrical properties of the nanocomposites were studied using a capillary rheometer, tensile tester, and Tera ohm‐meter, respectively. Both polyethylene and its nanocomposites showed non‐Newtonian behavior in almost the whole range of shear rate. Addition of carbon nanotubes increased shear stress and shear viscosity. It was also found that the materials experience a fluid‐solid transition below 1 wt% MWNT. Flow activation energy for the nanocomposites was calculated using an Arrhenius type equation. With increasing nanotube content, the activation energy of flow increases. A decrease of about 7 orders of magnitude was obtained in surface and volume resistivity upon addition of 5 wt% MWNT. In addition, a difference between electrical and rheological percolation thresholds was observed. The results confirm the expected nucleant effect of nanotubes on the crystallization process of polyethylene. A slight increase in Young's modulus was also observed with increasing MWNT content.     

水分子链受限于单壁碳纳米管结构的密度泛函理论研究

本文采用第一性原理的密度泛函理论,主要以(6,6)Armchair型,(11,0)Zigzag型单壁碳纳米管为研究对象,研究了水分子链在碳纳米管内部吸附的稳定结构,以及结合能随其结构的变化.结果表明:当水分子链受限于碳纳米管内部时,引起碳纳米管直径收缩,这主要是由于水分子链与碳纳米管之间的氢键作用以及范德华弱相互作用所引起的.随着碳纳米管半径的增加,两种单体之间的结合能逐渐减小,但当碳纳米管半径增加至6.78时,其结合能又有所增加,这是由于在优化过程中,水分子链单体之间的氢键作用大于水分子链与碳纳米管之 关键词： 水分子链/单壁碳纳米管 密度泛函理论 结构稳定性