Preparation and electrocatalytic activities of platinum nanoclusters deposited on modified multi-walled carbon nanotubes supports

Multi-walled carbon nanotubes (MWNTs) were modified by oxyfluorination treatment at several different temperatures of 20, 100, 200, and 300 °C. The changes of surface properties of oxyfluorinated MWNTs were investigated using X-ray photoelectron spectroscopy (XPS) method. As a result, it was found that surface fluorine contents were varied with changing an oxyfluorination temperature and showed a maximum value at 100 °C. By changing the treatment temperature in the process of oxyfluorination for carbon supports, the surface characteristics of MWNTs had been modified, resulting that the size and loading content of deposited Pt on the modified carbon supports could be changed. Consequently, Pt deposited MWNTs that were treated at 100 °C (Pt/100-MWNTs) showed the best electroactivity among samples. The enhanced electroactivity was dependent on the higher surface area of electrochemical reaction for metal catalyst, which was related to the particle size and the morphology of the deposited particle catalysts.     

Electro-responsive transdermal drug delivery behavior of PVA/PAA/MWCNT nanofibers

The electro-responsive transdermal drug delivery system was prepared by electrospinning of poly(vinyl alcohol)/poly(acrylic acid)/multi-walled carbon nanotubes (MWCNTs) nanocomposites. The surface modification of MWCNTs was carried out by oxyfluorination to introduce the functional groups on the hydrophobic MWCNTs. The dispersion of MWCNTs and the compatibility with polymer matrices were improved by oxyfluorination. The MWCNT content and oxyfluorination condition played important roles in the swelling and drug release characteristics of nanofibers. The conductivity of nanofibers increased by increasing the content of MWCNTs and performing oxyfluorination with higher oxygen content. Uniform distribution of the oxyfluorinated MWCNTs in the nanofibers was crucial to the electro-responsive swelling and drug releasing behaviors of nanofibers.     

A comparative study on properties of multi-walled carbon nanotubes (MWCNTs) modified with acids and oxyfluorination

In this study, the surface modification of multi-walled carbon nanotubes (MWCNTs) with acid and oxyfluorination has been examined. Acid treatment of multi-walled CNTs produces many functionalized groups on the surface of MWCNTs, such as C-N stretching and the asymmetric carboxylate group (-COO-). It can be concluded that nitrogen doping of the graphite sheets may take place and a C-N bond identical to the sp³-bonded carbon nitride may form during the acid treatment process. In addition, oxyfluorinated MWCNTs exhibit higher BET specific surface area and mesopore volume than those of the as-received and acid treated MWCNTs. Therefore, acid and oxyfluorination treatments are more effective methods for enhancing the chemical and textural properties of MWCNTs.     

Functionalisation of polypropylene non-woven fabrics (NWFs)

Surface oxyfluorination had been carried out on polypropylene non-woven fabric (PP NWF) samples of different morphologies and pore sizes. The modified surfaces were characterised by Attenuated Total Reflectance Fourier Transform InfraRed (ATR-FTIR)-spectroscopy, FTIR imaging microscopy, X-Ray Photoelectron Spectroscopy (XPS), Electron Spin Resonance (ESR) spectroscopy, Differential Scanning Calorimetry (DSC), X-Ray Diffraction (XRD) analysis, Scanning Electron Microscopy (SEM), dynamic rheometry and Thermo-Gravimetry (TG). ATR-FTIR and XPS techniques revealed the presence of ?CCF, ?CCF₂, ?CCHF and ?CC(O)F groups. The formed ?CC(O)F groups mostly got hydrolysed to ?CCOOH groups. The C=O groups of alpha-haloester, and the C=C stretching of the formed ?CCF=C(OH)?C groups could also be detected. Long-lived radicals could be detected on the functionalised surfaces as middle-chain peroxy radicals by ESR spectroscopy. SEM micrographs showed slight roughening of the oxyfluorinated surfaces. Oxyfluorination had no significant effect on the crystalline structure and phase composition of the PP NWF samples supported by DSC and XRD measurements. The molecular mass of the samples were unaffected by the oxyfluorination treatment as proved by oscillating rheometry. The surface modification, however, significantly affected the thermal decomposition but not affected the thermo-oxidative decomposition of PP NWFs. Different morphologies and pore sizes of PP NWF samples resulted in reproducibility of the findings, although did not substantially affect surface functionalisation.     

Effect of oxyfluorination on electromagnetic interference shielding behavior of MWCNT/PVA/PAAc composite microcapsules

Composite microcapsules of poly(vinyl alcohol)/poly(acrylic acid)/multi-walled carbon nanotubes were prepared and the electromagnetic interference shielding behavior was evaluated for the composite microcapsules. The dispersion and adhesion of multi-walled carbon nanotubes in microcapsules were improved by the surface modification through direct oxyfluorination which introduced polar groups on the multi-walled carbon nanotubes. The composite microcapsules containing the oxyfluorinated multi-walled carbon nanotubes showed significant increases in permittivity, permeability, and electromagnetic interference shielding efficiency. The electromagnetic interference shielding efficiency of composite microcapsule increased up to 51 dB mainly base on the absorption mechanism.     

Ammonia removal of activated carbon fibers produced by oxyfluorination

In this study, activated carbon fibers (ACFs) were produced by an oxyfluorination treatment to enhance the capacity of ammonia gas removal. The introduction of polar groups, such as CF, CO, and COOH, on the ACFs was confirmed by a XPS analysis, and N2/77 K adsorption isotherm characteristics including specific surface area and total and micropore volumes were studied by the BET and t-plot methods. The ammonia-removal efficiency was confirmed by a gas-detecting tube technique. As a result, the specific surface area and micropore volume of ACFs were slightly destroyed as the surface treatment time was increased. However, the oxyfluorinated ACFs led to an increase of fluorine and oxygen-containing polar functional groups in ACF surfaces, resulting in an increase in the ammonia-removal efficiency of the ACFs produced.     

Surface characteristics of low-density polyethylene films modified by oxyfluorination-assisted graft polymerization

In this study, a unique two-step process, i.e., an oxyfluorination-assisted graft polymerization (OAGP), was used to modify the surface properties of low-density polyethylene (LDPE) films. Based on the results of the 1,1-diphenyl-2-picrylhydrazyl (DPPH) method, which was performed to estimate the amount of hydroperoxides generated by oxyfluorination, oxyfluorination conditions that maximize the amount of hydroperoxide groups were selected. Hydroperoxides were generated by oxyfluorination to provide active sites for the OAGP of the different monomers. Depending on the type of monomers used, two different graft polymerization behaviors were observed. Hydrophilic methacrylic acid (MA) monomers were graft polymerized onto the oxyfluorinated LDPE (OFPE) surface in a perpendicular direction, forming a spike-shaped morphology. On the other hand, hydrophobic styrene (ST) monomers were graft polymerized parallel to the OFPE surface, forming a valley-shaped morphology. By changing the type of vinyl monomers, two different surfaces could be prepared using the hydroperoxides generated by oxyfluorination. After OAGP with MA monomers, a hydrophilic surface following the Wenzel model was obtained, whereas after OAGP with ST monomers, a hydrophobic surface following the Cassie–Baxter model was obtained. Therefore, the OAGP process may be an efficient method for preparing two different surfaces by changing the monomer used.     

Effect of oxyfluorination on electromagnetic interference shielding of polyaniline-coated multi-walled carbon nanotubes

Highly conducting polyaniline (PANi)-coated multi-walled carbon nanotubes (MWCNTs) were prepared by in situ polymerization method for electromagnetic interference shielding. The thickness of the PANi coatings was controlled by the oxyfluorination treatment on the multi-walled carbon nanotubes and analyzed with both SEM and TEM. The oxyfluorination with higher oxygen content produced more hydrophilic functional groups on the surface of multi-walled carbon nanotubes. The functional groups led to the well distribution and coating of PANi on the multi-walled carbon nanotubes resulting in the higher interfacial affinity between them. The uniform coating of PANi on MWCNTs by controlling the oxyfluorination conditions also played a crucial role in increasing the electrical conductivity of nanocomposites. The improved interfacial affinity resulted in the higher electromagnetic interference (EMI) SE of 47.03?dB based on the synergistic combination of the conductive components. The EMI shielding mechanism of PANi on MWCNTs suggested that EMI was mainly shielded by adsorption to avoid secondary EMI.     

Vibrational analysis of H2 and D2 adsorption on Pt/SiO2

Vibrational properties of surface species formed upon H2 and D2 exposure of silica supported platinum particles have been investigated with in situ diffuse reflection infrared Fourier transform spectroscopy. Experiments have been performed at 50-250 degrees C, using different platinum loading of the samples in the absence and presence of oxygen. In addition, electronic structure calculations and vibrational analysis have been performed within the density functional theory for H adsorption on a silica cluster, (HO)3SiOSi(OH)3. The spectroscopy experiments showed reversible formation of isolated OH and OD groups on the silica surface when the samples were exposed to H2 and D2, respectively. In addition to the absorption peak corresponding to isolated OH and OD groups, an intense broad band was observed around 3270 cm(-1) (2500 cm(-1)) during H2 (D2) exposure. Supported by the calculations, this band was assigned to perturbed OH groups on the silica surface. The surface coverage of new OH groups was found to correlate to the platinum loading in the samples, indicating that the new silanol groups were formed in the vicinity of the Pt particles. In the investigated temperature interval, the formation rate of OH groups was not found to be temperature dependent.     

Surface characterization and electrical property of carbon fibers modified by air oxidation

Polyacrylonitrile‐based carbon fibers were modified by oxidation in air, and a systematic study of surface groups and surface resistance at different treated temperatures was made. Progressive fiber weight loss occurred with increasing extents of air oxidation, and it was approximately proportional to the extent of air oxidation from the onset of oxidation up to 400 °C. At this point 4.4% of the initial fiber weight had been lost. A faster loss of weight occurred as the extent of air oxidation increased from 400 °C to 700 °C. X‐ray photoelectron spectroscopy studies (C 1s and O 1s) indicated that the oxygen/carbon atomic ratio rose rapidly from 2.64% (as‐received carbon fiber) to 42.83% as the oxidation temperature was increased to 400 °C. Fourier transform infrared spectra showed the relative intensity of the peaks at about 3440 cm^?1 from ―OH stretching vibrations and at 1634 cm^?1 from ―C?O stretching vibrations increased significantly at 400 °C. FESEM micrographs showed that as‐received fibers show relatively smooth surface. With oxidation temperature increasing, the fiber surface was rougher. The surface resistance of treated carbon fibers decreased obviously with increasing oxidation temperatures. The most decrease was about 100% at 400 °C. Copyright © 2014 John Wiley & Sons, Ltd.     

原位合成纳米SiO2增强阴离子聚酯型上浆剂及其对碳纤维复合材料层间剪切强度的影响

采用溶胶-凝胶法, 在侧链带有羧基的线性不饱和聚酯中加入正硅酸乙酯(TEOS), 使TEOS在酸性条件下发生水解反应, 原位合成纳米SiO₂增强阴离子型聚酯乳液(SEAPE). 利用傅里叶变换红外光谱(FTIR)仪、 激光粒度分析仪和冷冻扫描电子显微镜(Cryo-SEM)对SEAPE进行分析与表征. 将SEAPE与聚乙二醇单油酸酯润滑剂、 非离子型表面活性剂FC-4430及抗氧剂1010进行复配, 原位制备纳米SiO₂增强阴离子型聚酯乳液上浆剂(SEAPEs), 用扫描电子显微镜(SEM)、 视频动态接触角测量仪、 X射线能谱(EDS)仪和纤维强力仪对SEAPEs上浆后碳纤维的表面形貌、 表面能、 碳纤维(CF)表面元素及碳纤维增强不饱和聚酯(UPR)复合材料(CF/UPR)的层间剪切强度(ILSS)进行测试与表征. 结果表明, 当TEOS添加质量分数为5%时, SEAPEs上浆后的碳纤维有效增强了其与UPR的结合强度, CF/UPR复合材料的ILSS达到40.03 MPa, 与市售环氧树脂型上浆剂上浆后碳纤维增强UPR复合材料相比, ILSS提高90.1%. SEAPEs中原位生成的纳米SiO₂分散均匀, 乳液储存稳定, 上浆后SiO₂均匀吸附在碳纤维表面, 增加碳纤维表面能, 改善碳纤维与树脂间的浸润性, 可有效提高碳纤维增强不饱和聚酯树脂复合材料的ILSS.     

葡萄糖加氢用Ru/活性炭催化剂: 改性方法对活性炭表面性能的影响

分别采用超临界甲醇流体、浓硝酸氧化、浓硝酸结合超临界甲醇流体等不同手段对椰壳活性炭进行了表面处理,用N2物理吸附、Boehm滴定、X光电子能谱仪(XPS)、电感耦合等离子原子发射光谱分析(ICP)、透射电镜(TEM)等手段研究了处理方法对活性炭表面孔结构及表面基团的影响;并以活性炭为载体,三氯化钌为活性前驱体,采用等容水浸渍法制备了钌炭催化剂,以葡萄糖加氢生产山梨醇为模型反应对制备的钌基催化剂的催化活性进行了评价.结果表明:各种处理方法对活性炭的比表面、孔径等孔结构性能影响不大;但超临界甲醇处理活性炭可明显减少活性炭表面含氧酸性基团的含量,尤其是羧基等不稳定基团的含量;而硝酸处理活性炭则可大幅度提高活性炭表面含氧酸性基团的含量,尤其是羧基等不稳定基团的含量增加更大.ICP分析结果表明:超临界甲醇处理活性炭并不改变活性炭样品对钌的吸附量,但硝酸氧化处理活性炭却能明显提高样品对钌的吸附能力.活性炭表面的这些含氧基团虽然有利于钌离子的吸附,但却不利于钌在活性炭表面的分散.由于超临界甲醇流体处理活性炭时的表面反应及萃取作用,可有效清除活性炭表面的不稳定含氧酸性基团,避免还原过程中钌的迁移聚集,使负载钌的分散度提高,有利于增强钌与活性炭间的相互作用,使钌部分缺失电子,钌的结合能升高;可明显提高负载钌炭催化剂葡萄糖催化加氢的活性.     

Formation and reactivity of 3-diazopyridinium cations and influence on their reductive electrografting on glassy carbon

The in situ generation of 3-diazonium cations from 3-aminopyridine and their subsequent stability under experimental conditions used for electrografting of pyridine groups were investigated by spectroscopy and electrochemistry. UV spectroscopy revealed the rapid kinetics for the reaction of 3-aminopyridine with sodium nitrite in HCl to form the 3-diazopyridinium cation with a second-order rate constant of 550 ± 20 L mol(-1) s(-1) at 22 °C. UV spectroscopy showed that the 3-diazopyridinium ion was relatively unstable and its transformation into 3-hydroxypyridine was proven by (1)H NMR. Its hydrolytic decomposition was investigated by NMR and followed first-order kinetics with a rate constant of (53 ± 5) × 10(-3) s(-1) at 22 °C. These results enable us to establish the appropriate conditions for the electrografting of pyridine from the corresponding diazonium cations generated in situ. The electrochemical modification of glassy carbon electrodes with pyridine was characterized by cyclic voltammetry and the resulting grafted layer by electrochemical impedance spectroscopy in the presence of Fe(CN)(6)(3-/4-) as redox probes. The effect of diazotization time before electrochemical reduction on the blocking effect of the grafted layer was investigated and showed that an increase of the diazotization time led to less efficient grafting. The presence of immobilized pyridine on the electrode surface was demonstrated by X-ray photoelectron spectroscopy measurements, and a surface coverage of 8.8 × 10(-10) mol cm(-2) was estimated for the grafted pyridine groups. The significance of these results for researchers using the in situ generation approach for electrochemical and chemical grafting is discussed.     

Infrared plus vacuum ultraviolet spectroscopy of neutral and ionic methanol monomers and clusters: new experimental results

We present new observations of the infrared (IR) spectrum of neutral methanol and neutral and protonated methanol clusters employing IR plus vacuum ultraviolet (vuv) spectroscopic techniques. The tunable IR light covers the energy ranges of 2500-4500 cm(-1) and 5000-7500 cm(-1). The CH and OH fundamental stretch modes, the OH overtone mode, and combination bands are identified in the vibrational spectrum of supersonic expansion cooled methanol (2500-7500 cm(-1)). Cluster size selected IR plus vuv nonresonant infrared ion-dip infrared spectra of neutral methanol clusters, (CH(3)OH)(n) (n=2,[ellipsis (horizontal)],8), demonstrate that the methanol dimer has free and bonded OH stretch features, while clusters larger than the dimer display only hydrogen bonded OH stretch features. CH stretch mode spectra do not change with cluster size. These results suggest that all clusters larger than the dimer have a cyclic structure with OH groups involved in hydrogen bonding. CH groups are apparently not part of this cyclic binding network. Studies of protonated methanol cluster ions (CH(3)OH)(n)H(+) n=1,[ellipsis (horizontal)],7 are performed by size selected vuv plus IR photodissociation spectroscopy in the OH and CH stretch regions. Energies of the free and hydrogen bonded OH stretches exhibit blueshifts with increasing n, and these two modes converge to approximately 3670 and 3400 cm(-1) at cluster size n=7, respectively.     

Inelastic state-to-state scattering of OH (2Pi3/2, J=3/2,f) by HCl

Parity resolved state-to-state cross sections for inelastic scattering of OH (X2Pi) by HCl were measured in a crossed molecular beam experiment at the collision energy of 920 cm(-1). The OH (X2Pi) radicals were prepared in a single quantum state, Omega=3/2, J=3/2, MJ=3/2, f, by means of electrostatic state selection in a hexapole field. The rotational distribution of the scattered OH radicals by HCl was probed by saturated LIF spectroscopy of the 0-0 band of the A 2Sigma+ - X 2Pi transition. Relative state-to-state cross sections were measured for rotational excitations up to J=9/2 within the Omega=3/2 spin-orbit manifold and up to J=7/2 within the Omega=1/2 spin-orbit manifold. A propensity for spin-orbit conserving transitions was found, but no propensity for excitation into a particular Lambda-doublet component of the same rotational state was evident. The data are presented and discussed in comparison with results previously obtained for collisions of OH with CO (Ecoll=450 cm(-1)) and N2 (Ecoll=410 cm(-1)) and with new data we have measured for the OH+CO system at a comparable collision energy (Ecoll=985 cm(-1)). This comparison suggests that the potential energy surface (PES) governing the interaction between OH and HCl is more anisotropic than the PES's governing the intermolecular interaction of OH with CO and N2.     

Conformation of L-tyrosine studied by fluorescence-detected UV-UV and IR-UV double-resonance spectroscopy

The laser-induced fluorescence spectrum of jet-cooled L-tyrosine exhibits more than 20 vibronic bands in the 35450-35750 cm(-1) region. We attribute these bands to eight conformers by using results of UV-UV hole-burning spectroscopy. These isomers are classified into four groups; each group consists of two rotational isomers that have a similar side-chain conformation but different orientations of the phenolic OH. The splitting of band origins of rotational isomers is 31, 21, 5, and 0 cm(-1) for these groups. IR-UV spectra suggest that conformers belonging to two of the four groups have an intramolecular OH...N hydrogen bond between the COOH and NH2 groups. By comparing experimental and theoretical results of L-tyrosine with those of L-phenylalanine, we propose probable conformers of L-tyrosine.     

Characterization of aerogel prepared high-surface-area alumina: in situ FTIR study of dehydroxylation and pyridine adsorption

Mesoporous high-surface-area alumina was prepared by a modified aerogel procedure. Specific surface areas between 530-685 m(2)g(-1) were obtained after heat treatment at 500 degrees C. Nitrogen adsorption studies have shown that surface areas and pore characteristics change upon decomposition of aluminum hydroxide to oxide as well as upon compaction of oxide powders. The surface area of aluminum hydroxide increased to a maximum, while the pore volume and diameter decreased as the hydroxide was heated to a temperature of 400 degrees C. Heating at higher temperatures resulted in sintering of the particles accompanied by a decline in the surface area. Compaction of activated alumina into pellets was accompanied by a relatively gradual change in the surface area and pore characteristics at pressures below 6.9 x 10(7) Pa, while severe changes took place at a pressure of 1.4 x 10(8) Pa. In situ IR studies of the dehydroxylation of the alumina surface, showed nu(OH) absorptions for isolated surface hydroxy groups centering at 3670, 3714, and 3765 cm(-1), which are shifted to lower frequencies than common literature values. Pyridine was found to adsorb on Al(3+) ions as well as through hydrogen bonding to relatively acidic surface OH groups, and IR spectra indicated the presence of strong Lewis acid sites.     

Spectroelectrochemical examination of the interaction between bacterial cells and gold electrodes

The interaction between bacterial cells of Pseudomonas fluorescens (ATCC 17552) and gold electrodes was analyzed by cyclic voltammetry (CV) and attenuated total reflection-surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS). The voltammetric evaluation of cell adsorption showed a decrease in the double-layer capacitance of polyoriented single-crystal gold electrodes with cell adhesion. As followed by IR spectroscopy in the ATR configuration, the adsorption of bacterial cells onto thin-film gold electrodes was mainly indicated by the increase in intensity with time of amide I and amide II protein-related bands at 1664 and 1549 cm(-1), respectively. Bands at 1448 and 2900 cm(-1) corresponding to the scissoring and the stretching bands of CH2 were also detected, together with a minor peak at 1407 cm(-1) due to the vs COO- stretching. Weak signals at 1237 cm(-1) were due to amide III, and a broad band between 1100 and 1200 cm(-1) indicated the presence of alcohol groups. Bacteria were found to displace water molecules and anions coadsorbed on the surface in order to interact with the electrode intimately. This fact was evidenced in the SEIRAS spectra by the negative features appearing at 3450 and 3575 cm-1, corresponding to interfacial water directly interacting with the electrode and water associated with chloride ions adsorbed on the electrode, respectively. Experiments in deuterated water confirmed these assignments and allowed a better estimation of amide absorption bands. In CV experiments, an oxidation process was observed at potentials higher than 0.4 V that was dependent on the exposure time of electrodes in concentrated bacterial suspensions. Adsorbed bacterial cells were found to get closer to the gold surface during oxidation, as indicated by the concomitant increment in the main IR bacterial signals including amide I, a sharp band at 1240 cm(-1), and a broad one at 1120 cm(-1) related to phosphate groups in the bacterial membranes. It is proposed to be due to the oxidation of lipopolysaccharides on the outermost bacterial surface.     

In situ IR study of surface hydroxyl species of dehydrated TiO2: towards understanding pivotal surface processes of TiO2 photocatalytic oxidation of toluene

The surface species on P25-TiO(2) were characterized by FTIR after evacuation at 50-550 °C. The functions of OH groups on P25-TiO(2) catalysts have been tested by the adsorption and photooxidation of toluene in an in situ IR cell. FTIR studies show that the hydroxyl species on P25-TiO(2) are clearly temperature-dependent and P25-TiO(2) has six isolated hydroxyls with bands at 3734, 3715, 3688, 3671, 3658 and 3640 cm(-1). The OH groups on P25 play different roles in the photo-oxidation process: surface hydroxyls with bands at 3688, 3671, 3658 and 3640 cm(-1) act as adsorption sites while surface hydroxyls with bands at 3734 and 3715 cm(-1) act as sources of the ˙OH radical.     

Effect of mordenite dealumination on the structure of encapsulated molybdenum catalysts

A series of dealuminated mordenites treated under various conditions of acid leaching was impregnated in an aqueous solution of ammonium heptamolybdate to achieve a loading of 12 wt% Mo. These samples were characterized by XRD, UV-DRS, N(2) adsorption, TGA, and FTIR techniques. Special attention was given to the far-IR measurements and IR study of surface hydroxyl groups before and after dealumination. A polymolybdate species was recognized by the appearance of bands at 344, 319, and 236 (229) cm(-1) due to the vibrational modes of delta(Mo-O) and delta(Mo-O-Mo), respectively. The disappearance of the 236 cm(-1) band as well as that at 344 cm(-1) in favor of the 319 cm(-1) band, with the dealumination, was related to the high dispersion of Mo species in the produced mesopore surface assessed by the N(2) adsorption at 77 K. No bands due to bulk MoO(3) were detected from the IR and XRD results. A strong interaction between Mo species and dealuminated mordenite surfaces (OH groups) was recognized by a decrease in intensity and a marked shift of the band at 3745 to 3727 cm(-1) as well as the appearance of a new band at 3668 cm(-1). The latter band was produced by the interaction of the framework Al-OH with Mo species. The BET surface areas of Mo-dealuminated mordenite samples were higher than the corresponding Mo-free ones. The diffuse reflectance measurements suggested that Mo cations are predominantly present as an octahedrally coordinated Mo(6+), along with some tetrahedral Mo(6+). New spectral features as a consequence of dealumination events in the far-IR range were evaluated and discussed.