Features of the chemical bonding in fluorinated and hydrogenated carbon: Nanotubes analysis of polarized NEXAFS spectra

The carbon K-edge NEXAFS spectra of initial and fluorinated and hydrogenated single-wall carbon nanotubes (SWCNTs) are analyzed theoretically with regard to the polarization dependence. Differences in the polarized theoretical spectra of SWCNTs with zigzag and chair chiralities are shown. As a result of the comparison of experimental and theoretical carbon K-edge NEXAFS spectra of hydrogenated and fluorinated SWCNTs it is found that it is most probable that hydrogen atoms attach to the outer surface of the tube wall and fluorine atoms to the outer and inner surfaces of the SWCNT wall. Based on the analysis of polarized theoretical spectra of fluorinated and hydrogenated SWCNTs differences in the symmetry of the final states of C-H and C-F bonds are shown.     

单壁纳米碳管的纯化及表征

利用微孔膜及空气氧化法逐步除去电弧放电法制备的单壁纳米碳管(SWCNTs)中的金属催化剂粒子、碳纳米粒子、无定形碳等杂质,并利用热重分析（TGA）、高分辨透射电子显微镜（HRTEM）及拉曼（Raman）光谱,对每一步得到的产物进行分析表征.实验证明,该方法对单壁纳米碳管的纯化是比较有效的,可以得到纯度在90％以上的单壁纳米碳管.     

单壁纳米碳管的纯化研究

A purification method to remove the metal catalysts and impurity carbon materials from arc-discharge-grown single-walled carbon nanotubes (SWCNTs) has been developed. Microporous membrane and the oxidation in the air for the crude SWCNTs were used to eliminate the coexisting metal catalysts nanoparticles，carbon nanoparticles and amorphous carbon. Then we used the high resolution transmission electron microscopy (HRTEM) to characterize the crude SWCNTs prepared by arc-discharge method and the purified SWCNTs. The Raman spectra and the thermogravimetric analysis (TGA) were also utilized to analyze the approach of our purification for SWCNTs. With this method the SWCNTs with the purity more than 95% could be obtained.     

Probing the Chemical Functionalization of Single‐Walled Carbon Nanotubes with Multiple Carbon Ad‐Dimer Defects

Drying‐tube‐shaped single‐walled carbon nanotubes (SWCNTs) with multiple carbon ad‐dimer (CD) defects are obtained from armchair (n,n,m) SWCNTs (n=4, 5, 6, 7, 8; m=7, 13). According to the isolated‐pentagon rule (IPR) the drying‐tube‐shaped SWCNTs are unstable non‐IPR species, and their hydrogenated, fluorinated, and chlorinated derivatives are investigated. Interestingly, chemisorptions of hydrogen, fluorine, and chlorine atoms on the drying tube‐shaped SWCNTs are exothermic processes. Compared to the reaction energies for binding of H, F, and Cl atoms to perfect and Stone–Wales‐defective armchair (5,5) nanotubes, binding of F with the multiply CD defective SWCNTs is stronger than with perfect and Stone–Wales‐defective nanotubes. The reaction energy for per F₂ addition is between 85 and 88 kcal mol^?1 more negative than that per H₂ addition. Electronic structure analysis of their energy gaps shows that the CD defects have a tendency to decrease the energy gap from 1.98–2.52 to 0.80–1.17 eV. After hydrogenation, fluorination, and chlorination, the energy gaps of the drying‐tube‐shaped SWCNTs with multiple CD defects are substantially increased to 1.65–3.85 eV. Furthermore, analyses of thermodynamic stability and nucleus‐independent chemical shifts (NICS) are performed to analyze the stability of these molecules.     

Solubilization of carbon nanoparticles,nanotubes, nano-onions,and nanodiamonds through covalent functionalization with sucrose

Water solubilization of carbon nanoparticles (nanocarbons), single-walled nanotubes (SWCNTs), nano-onions (NOs) and nanodiamonds (NDs) has been achieved through their covalent functionalization by fluorination and subsequent derivatization with sucrose. The covalent bonding of sucrose to the surface of the fluorinated nanocarbons was attained by a one-step fluorine substitution reaction with sucrose-derived lithium monosucrate under sonication in DMF at room temperature. This chemical process provides a simple, inexpensive, and easily scalable method for hydrophilic chemical modification of SWCNT, NO, and ND surfaces to produce sucrose-functionalized nanocarbons that become soluble in water, DMF, ethanol, and other polar solvents. The sucrose-functionalized nanocarbon particles are expected to be biocompatible due to the abundance of hydroxyl groups available for hydrogen bonding and further chemical modification. Relevant examples have been given.     

A comparative study of argon ion irradiated pristine and fluorinated single-wall carbon nanotubes

Effect of Ar(+) ion irradiation on the structure of pristine and fluorinated single-wall carbon nanotubes (SWCNTs) was examined using transmission electron microscopy (TEM), Raman, and x-ray photoelectron spectroscopy (XPS). The TEM analysis revealed retention of tubular structures in both irradiated samples while Raman spectroscopy and XPS data indicated a partial destruction of nanotubes and formation of oxygen-containing groups on the nanotube surface. From similarity of electronic states of carbon in the irradiated pristine and fluorinated SWCNTs observed by XPS, it was suggested that defluorination of nanotubes proceeded with breaking of C-F bonds.     

Rearrangement routes to selectively fluorinated compounds

Fluoroallylic alcohols are easy to synthesise by a variety of routes using one or two carbon fluorinated building blocks. Sigmatropic rearrangement then transforms these intermediates into species in which the fluorine atom (or atoms) is borne on an sp³-hybridised carbon. Alternatively, allylic alcohols can be transformed into fluorinated vinyl ether derivatives; rearrangement then affords products in which the fluorine atoms occupy a different and complementary location with respect to a carbonyl function.     

Efficient Chemical Modification of Carbon Nanotubes with Metallacarboranes

As‐produced single‐walled carbon nanotubes (SWCNTs) tend to aggregate in bundles due to π–π interactions. Several approaches are nowadays available to debundle, at least partially, the nanotubes through surface modification by both covalent and noncovalent approaches. Herein, we explore different strategies to afford an efficient covalent functionalization of SWCNTs with cobaltabisdicarbollide anions. Aberration‐corrected HRTEM analysis reveals the presence of metallacarboranes along the walls of the SWCNTs. This new family of materials presents an outstanding water dispersibility that facilitates its processability for potential applications.     

Electrochemical defluorination of carbon nanotubes

An electrochemical procedure for the removal of fluorine from the walls of fluorinated monolayer carbon nanotubes was suggested. According to element analysis data, fluorine was completely removed. According to UV-Vis-Nir and Raman spectroscopic studies, the initial structure of fluorinated carbon nanotubes was almost completely restored.     

Fluorine containing phosphazene polymers

In this paper we highlighted the synthesis, characterization, and practical exploitation of different types of polyphosphazenes substituted with fluorinated groups. There are several ways in which fluorine atoms can be inserted into polyphosphazenes, all of which leading to different polymers showing a wide range of characteristics. In general it is true that the insertion of fluorine atoms into phosphazene macromolecules leads to an enhancement of the thermal stability, flame resistance, low-temperature elastomericity, and chemical inertness of the phosphazenes obtained. The contribution of Italian research groups to the preparation and exploitation of organic commercial macromolecules grafted onto fluorinated polyphosphazenes is also reviewed.     

Surface and bulk properties of severely fluorinated carbon fibres

The development of ultra-inert composites using fluorinated carbon fibres as the reinforcement requires fluorinated carbon fibres with a durable surface composition. Here we report the effect of direct fluorination using an F₂/N₂ mixture at 653 K on the surface and bulk properties of two types of high strength carbon fibres. These were treated up to a surface fluorine content of ∼64 at.% and a bulk fluorine content of ∼15 mass%. A colour change was observed after fluorination caused by the changes in the graphitic band structure of the carbon fibres by the introduction of carbon sp³ hybridisation. The tensile strength and Young's modulus decrease after fluorination by up to 33 and 22%, respectively. XRD shows marginal changes in the interlayer distance but the crystallite size increases. Changes in the electrical conductivity of the fluorinated carbon fibres indicate that the modification is confined to the near surface volume. Predominantly covalent C-F bonds are formed as shown by X-ray photoelectron spectroscopy (XPS) and measured zeta (ζ)-potentials. Hence the fluorinated fibres are hydrophobic and have low surface tensions. This and the large increase in fibre surface area, as determined by nitrogen adsorption, is expected to facilitate interfacial interaction between fluorinated carbon fibres and fluoropolymers.     

13C-NMR spectra of fluorinated molecules using 19F-13C polarization transfer

¹³C-NMR spectra of fluorinated molecules are difficult to observe under conventional broad-band proton decoupling. The large coupling constants involved make polarization transfer between fluorine and carbon, using INEPT or DEPT experiments very effective while broad band fluorine decoupling collapses the multiplet pattern.     

蒿甲醚在单壁碳纳米管修饰电极上的电催化还原

研制了单壁碳纳米管(SWCNTs)修饰玻碳电极。用交流阻抗谱法(EIS)和扫描电镜(SEM)研究了电极膜性能,应用循环伏安法(CV)、计时库仑法(CC)、计时电流法(CA)研究了蒿甲醚在修饰电极上的电化学行为。结果表明,SWCNTs修饰电极对蒿甲醚的还原有良好的电催化活性,其还原反应为双电子过程,电极反应的扩散系数及速率常数分别为6·67×10-4cm2·s-1及8·54×10-2mol·L-1·s-1。在优化实验条件下,还原峰的峰电位位于-0·85V,其峰电流与蒿甲醚浓度在6·71×10-7~2·45×10-4mol·L-1范围内呈良好线性,检出限达4·02×10-7mol·L-1,相对标准偏差(n=10)为4·2%,可用于蒿甲醚样品的含量测定。     

Using the 19F NMR chemical shift anisotropy tensor to differentiate between the zigzag and chiral forms of fluorinated single-walled carbon nanotubes

The structural characterization of different kinds of zigzag and chiral single-walled carbon nanotubes (SWNTs) has been investigated theoretically using (19)F NMR spectroscopy. The chemical shift anisotropy (CSA) tensor is computed at different levels of theory for the (19)F nuclei in different forms of functionalized fluorinated carbon nanotubes (CNT). A set of fluorine CSA parameters comprising the span, skew, and isotropic chemical shift is computed for each form of the fluoronanotubes and multidimensional CSA parameter correlation maps are constructed. We show that these correlations are able to clearly distinguish between the chiral and zigzag forms of fluorinated carbon nanotubes (F-SWNTs). Implications for solid-state and liquid-state NMR experiments are discussed.     

含氟液晶研究进展

本文简述了含氟液晶的研究进展。根据小分子含氟液晶中氟原子或含氟基团的位置不同,将其分为3类：末端是氟原子或含氟基团的液晶、苯环上氢原子被氟原子取代的液晶、中心桥键上的氢原子被氟原子取代的液晶。根据小分子含氟液晶特点,归纳了氟原子或含氟基团对液晶分子物理性质的影响。同时对高分子含氟液晶的研究进展也做了介绍。     

Decomposition of Fluorinated Graphene under Heat Treatment

Fluorination modifies the electronic properties of graphene, and thus it can be used to provide material with on‐demand properties. However, the thermal stability of fluorinated graphene is crucial for any application in electronic devices. Herein, X‐ray photoelectron spectroscopy (XPS), temperature‐programmed desorption (TPD), and Raman spectroscopy were used to address the impact of the thermal treatment on fluorinated graphene. The annealing, at up to 700 K, caused gradual loss of fluorine and carbon, as was demonstrated by XPS. This loss was associated with broad desorption of CO and HF species, as monitored by TPD. The minor single desorption peak of CF species at 670 K is suggested to rationalize defect formation in the fluorinated graphene layer during the heating. However, fluorine removal from graphene was not complete, as some fraction of strongly bonded fluorine can persist despite heating to 1000 K. The role of intercalated H₂O and OH species in the defluorination process is emphasised.     

Preparation and Surface Properties of Fluorine‐Containing Diblock Copolymers PLMA‐Block‐PFAEA

A series of fluorine‐containing diblock copolymers based on lauryl methacrylate and 1H,1H,2H,2H‐perfluoroalkyl acrylate have been prepared by atom transfer radical polymerization (ATRP). The preparation process of PLMA‐Br macroinitiators was controlled within a reasonable time corresponding to the ln [M₀]/[M_t]～time plot of the reaction. FTIR, ¹H‐NMR, GPC and fluorine‐element analysis (FEA) were used to characterize the synthesized block copolymers. The solid surface activity of these polymers was demonstrated by contact angle measurement. The polymer films prepared by block copolymers with more than three fluorinated units showed low dispersion force contributions to the surface energy indicating the presence of the fluorinated block at the surface. The surface activity in solutions was measured by drop‐weight method. Ii is interesting to find, when the fluorine weight percentage is controlled constant, that PLMA‐b‐PFAEA with larger molecular size is more prominent in exploiting the fluorinated structure to reduce the surface tension of solutions. The block copolymer's ability in reducing surface tension of solutions also depends on the type of solvent.     

Poly(γ‐benzyl‐L‐glutamate)‐functionalized single‐walled carbon nanotubes from surface‐initiated ring‐opening polymerizations of N‐carboxylanhydride

Single‐walled carbon nanotubes (SWCNTs) have been functionalized with poly(γ‐benzyl‐L ‐glutamate) (PBLG) by ring‐opening polymerizations of γ‐benzyl‐L ‐glutamic acid‐based N‐carboxylanhydrides (NCA‐BLG) using amino‐functionalized SWCNTs (SWCNT‐NH₂) as initiators. The SWCNT functionalization has been verified by FTIR spectroscopy and transmission electron microscopy. The FTIR study reveals that surface‐attached PBLGs adopt random‐coil conformations in contrast to the physically absorbed or bulk PBLGs, which exhibit α‐helical conformations. Raman spectroscopic analysis reveals a significant alteration of the electronic structure of SWCNTs as a result of PBLG functionalization. The PBLG‐functionalized SWCNTs (SWCNT‐PBLG) exhibit enhanced solubility in DMF. Stable DMF solutions of SWCNT‐PBLG/PBLG with a maximum SWCNTs concentration of 259 mg L^?1 can be readily obtained. SWCNT‐PBLG/PBLG solid composites have been characterized by differential scanning calorimetry, thermogravimetric analysis, wide/small‐angle X‐ray scattering (W/SAXS), scanning electron microscopy, and polarized optical microscopy for their thermal or morphological properties. Microfibers containing SWCNT‐PBLG and PBLG can also be prepared via electrospinning. WAXS characterization reveals that SWCNTs are evenly distributed among PBLG rods in solution and in the solid state where PBLGs form a short‐range nematic phase interspersed with amorphous domains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2340–2350, 2010     

Photooxidation of copolymers of fluorinated olefins and allyl or vinyl ethers

This article reports the results on the photooxidation mechanisms of two copolymers of fluorinated olefins and allyl or vinyl ethers. It is shown that the presence of the fluorine atoms influences strongly both the orientation of the reaction and the photooxidation kinetics. Due to the neighbouring fluorine atoms, the methylene groups in α-position of the oxygen of the ether groups are not equivalent regarding oxidation and the secondary carbon becomes more oxidable than the tertiary one. Because these unexpected results were obtained, the study has been extended to non fluorinated polyethers. On the basis of the results obtained, a general mechanism of the primary oxidation of polyethers is given, and the role played by the fluorine atoms on the orientation of the reactions is discussed.     

Synthesis of fluorine‐containing star‐shaped poly(vinyl ether)s via arm‐linking reactions in living cationic polymerization

Various types of fluorine‐containing star‐shaped poly(vinyl ether)s were successfully synthesized by crosslinking reactions of living polymers based on living cationic polymerization. Star polymers with fluorinated arm chains were prepared by the reaction between a divinyl ether and living poly(vinyl ether)s with fluorine groups (C₄F₉, C₆F₁₃, and C₈F₁₇) at the side chain using cationogen/Et_1.5AlCl_1.5 in a fluorinated solvent (dichloropentafluoropropanes), giving star‐shaped fluorinated polymers in high yields with a relatively narrow molecular weight distribution. The concentration of living polymers for the crosslinking reaction and the molar feed ratio of a bifunctional vinyl ether to living polymers affected the yield and molecular weight of the star polymers. Star polymers with block arms were prepared by a linking reaction of living block copolymers of a fluorinated segment and a nonfluorinated segment. Heteroarm star‐shaped polymers containing two‐ or three‐arm species were synthesized using a mixture of different living polymer species for the reaction with a bifunctional vinyl ether. The obtained polymers underwent temperature‐induced solubility transitions in various organic solvents, and their concentrated solutions underwent sol–gel transitions, based on the solubility transition of a thermoresponsive fluorinated segment. Furthermore, a slight amount of fluorine groups were shown to be effective for physical gelation when those were located at the arm ends of a star polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012