Surface-enhanced Raman scattering of suspended monolayer graphene

Abstract

The interactions between phonons and electrons induced by the dopants or the substrate of graphene in spectroscopic investigation reveal a rich source of interesting physics. Raman spectra and surface-enhanced Raman spectra of supported and suspended monolayer graphenes were measured and analyzed systemically with different approaches. The weak Raman signals are greatly enhanced by the ability of surface-enhanced Raman spectroscopy which has attracted considerable interests. The technique is regarded as wonderful and useful tool, but the dopants that are produced by depositing metallic nanoparticles may affect the electron scattering processes of graphene. Therefore, the doping and substrate influences on graphene are also important issues to be investigated. In this work, the peak positions of G peak and 2D peak, the I_2D/I_G ratios, and enhancements of G and 2D bands with suspended and supported graphene flakes were measured and analyzed. The peak shifts of G and 2D bands between the Raman and SERS signals demonstrate the doping effect induced by silver nanoparticles by n-doping. The I_2D/I_G ratio can provide a more sensitive method to carry out the doping effect on the graphene surface than the peak shifts of G and 2D bands. The enhancements of 2D band of suspended and supported graphenes reached 138, and those of G band reached at least 169. Their good enhancements are helpful to measure the optical properties of graphene. The different substrates that covered the graphene surface with doping effect are more sensitive to the enhancements of G band with respect to 2D band. It provides us a new method to distinguish the substrate and doping effect on graphene.

PACS

78.67.Wj (optical properties of graphene); 74.25.nd (Raman and optical spectroscopy); 63.22.Rc (phonons in graphene)     

Surface-enhanced Raman scattering of carbazole-based covalent triazine framework

A kind of carbazole-based covalent triazine framework (CTF-Cz) has been synthesized from a carbazole derivative. The porous polymer can efficiently adsorb probe molecules due to the strong intermolecular interactions caused by the polar triazine moiety. CTF-Cz directly serves as the surface-enhanced Raman scattering substrate without any post proceeding techniques. The enhancement factor of CTF-Cz is ~10⁵ for detecting rhodamine 6G (R6G). The lowest unoccupied molecular orbital energy level of CTF-Cz (−3.93 eV) is much lower than that of R6G, which is in favor of the charge transfer from R6G to CTF-Cz for illumination under a 532 nm laser, which is proved by time resolved photoluminescence spectra. The efficient charge transfer induced by the strong intermolecular π–π interactions and large molecular-orbital delocalization contribute to the enhanced Raman signals of R6G on CTF-Cz.     

On the interaction of nano-sized organic carbon particles with model lipid membranes

The cytotoxic character of atmospheric ultra-fine-particles (UFPs) has been reported in numerous, mainly epidemiological, investigations. However, the detailed mechanism, at the molecular level, leading to UFP cytotoxicity is not yet fully understood. To address this question, a better characterization of UFP toxicity in relation to chemical composition, surface area and particle number is needed. To follow this bottom-up approach, we have investigated the interaction of nano-sized organic carbon particles (NOCs), produced in ordinary combustion processes, with cell-sized unilamellar vesicles. These particles have a size in the 1-5 nm range and constitute an abundant fraction of the total carbon emission to the environment due to human activity. The investigation was performed by spectroscopically analyzing the chemical modifications of membrane lipid tails in optically trapped vesicles after exposure to NOCs. Our experimental outcomes demonstrate that they are able to induce oxidative damage to liposome membranes. This modification, in turn, leads to a change in membrane permeability, as observed by surface enhanced Raman scattering. It should be noticed that the method reported herein paves the way for a deeper comprehension of the interaction of nanomaterials with lipid membranes, in relation to both nanoparticles characteristics and membrane lipid composition.     

Surface-enhanced Raman scattering studies on C60 fullerene self-assemblies

Surface-enhanced Raman scattering (SERS) was used to investigate C₆₀ self-assembling in solvents like pyrrolidine (Py) and N-methyl-2-pyrrolidinone (NMP) as well as in binary mixtures of o-dichlorobenzene (DCB)/acetonitrile (ACN) and DCB/NMP. For a correct evaluation of the modifications of Raman spectra induced by the C₆₀ aggregation, we have also presented the variations due to the measuring method, i.e., the signal dependence of the metallic support type and the surface roughness. The interaction between C₆₀ and the Au substrate, appearing as a chemical component in SERS generation, is mainly evidenced by a band at ∼342 cm⁻¹. In the aggregated phase, the intermolecular interactions lead to a reduction in the parent I_h C₆₀ symmetry as observed by a modified phonon spectrum. As a general feature, the spectral range below 800 cm⁻¹ is the most diagnostic for the aggregate assignment, the main indicative being the disappearance of the Raman bands associated to the radial vibration modes. SERS measurements have revealed two stages in the self-assembling of C₆₀ in NMP. In the beginning, charge-transfer molecular complexes that associate slowly in stable aggregates are formed by the binding of an NMP molecule to the C₆₀ cage. These complexes are noticed in the SERS spectrum by the replacement of the original H_g(1) band at ∼269 cm⁻¹ with two others at ∼255 and ∼246 cm⁻¹. In the aggregated phase, when using NMP and P as a solvent, the Raman spectrum reveals new bands that appear around 94 and 110-118 cm⁻¹, which are associated with the interball interactions. In a DCB/ACN solvent mixture, the self-assembling process is driven by weak van der Waals type forces and resembles a precipitation, yielding C₆₀ clusters of different size.     

Raman scattering in a new carbon material

Samples of a new carbon material, Diamonite-B, were fabricated under high pressure from a commercial carbon black — identified as mixed fullerenes. The new material is neither graphite-like nor diamond-like, but exhibits electrical properties close to graphite and mechanical properties close to diamond. The use of Raman spectroscopy to investigate the vibrational dynamics of this new carbon material and to provide structural characterization of its short-, medium- and long-range order is reported. We also provide the results of investigations of these samples by high resolution electron microscopy and X-ray diffraction. Hardness, electrical conductivity, thermal conductivity and other properties of this new material are compared with synthetic graphite-like and diamond-like materials, two other phases of synthetic bulk carbon.     

Surface-enhanced Raman scattering in local optical fields of silver and gold nanoaggregates-from single-molecule Raman spectroscopy to ultrasensitive probing in live cells

This Account discusses surface-enhanced Raman scattering at extremely high enhancement levels that can occur for molecules attached to silver and gold nanoclusters. Strongly enhanced and highly confined local optical fields enable surface-enhanced Stokes and anti-Stokes Raman spectroscopy of single molecules even under nonresonant excitation conditions as well as extremely large effective cross sections in two-photon excited Raman spectroscopy. The ability for very sensitive and spatially confined molecular structural probing makes gold and silver nanoclusters very promising tools for studies of small structures in biological materials, such as cellular compartments.     

Spectroscopic study of the combustion of solitary magnesium particles in air and in carbon dioxide

The combustion spectra of loose magnesium particles in air and in carbon dioxide at atmospheric pressure are investigated. Experimental graphs of the combustion time as a function of the initial particle size are plotted. It is shown that the luminescence time of the metal and oxide vapors are always shorter than the total particle luminescence time. It is observed for the first time that the magnesium oxide vapor disappears before the vapor of the metal itself when combustion takes place in carbon dioxide gas. This is attributable to the fact that the rate of the gas-phase reaction of magnesium with carbon dioxide decreases as the production of carbon monoxide increases during the combustion stage.Institute of Chemical Physics, Chernogolovka 142432. Translated from Fizika Goreniya i Vzryva, Vol. 30, No. 4, pp. 29–35, July–August, 1994.     

Diffusion and kinetic combustion regimes for carbon particles

Moscow. Translated from Fizika Goreniya i Vzryva, Vol. 27, No. 5, pp. 67–73, September–October, 1991.     

Study of combustion of monodisperse metallic particles produced by impulse arc

Odessa. Translated from Fizika Goreniya i Vzryva, Vol. 26, No. 4, pp. 25–27, July–August, 1990.     

Raman scattering study of the thermal conversion of bundled carbon nanotubes into graphitic nanoribbons

Raman scattering is used to study the temperature-driven structural transformations of bundled single-walled carbon nanotubes (SWCNTs) observed in HiPCO and ARC synthesis by electron microscopy, i.e., tube-tube coalescence ∼1300-1400 °C, coalesced tubes to multi-walled tubes (MWCNT) at ∼1600-1800 °C and finally (only ARC tubes) MWCNT to graphitic nanoribbons (GNRs) at ∼1800 °C. All these transformations occurred in vacuum. Here, we present the details of these transformations as seen through the “eyes” of Raman scattering via changes in the radial (R) SWCNT band, the G-band (and its substructure) and the relative intensity of the disorder-induced D- and D′-band scattering. The Raman spectrum of GNRs is also discussed in detail. For 514.5 nm laser excitation, five relatively broad GNR Raman bands are observed: 1350, 1580, 1620, 2702 and 3250 cm⁻¹. A Knight plot is used to estimate the GNR width and we find w ∼ 9 nm, which is in reasonable agreement with the estimate of 7.6 nm based on TEM and the model that a GNR is a collapsed MWCNT.     

Photoluminescent carbon nanoparticles produced by confined combustion of aromatic compounds

We report new photoluminescent carbon nanoparticles having an average particle size of 50 nm. When dispersed in chloroform and excited with 325 nm wavelength, the solution showed strong photoluminescence at 475 nm with 12–13% quantum yield. A well dispersed photoluminescent solution can also be prepared with ethanol, xylene or hexane using the nanoparticles. The nanoparticles were prepared by a simple confined combustion of an aromatic compound such as benzene, toluene, xylene or a mixture thereof in air.     

超临界水热合成制备纳米微粒材料

简述了超临界水热合成法制备纳米微粒材料技术的微粒形成机理、过程基本工艺及目前所取得的研究成果。讨论了未来需要解决的问题。     

Attrition of spherical electrode carbon particles during batch fluidized combustion

Spherical electrode carbon particles prepared from carbon rods of dry cell batteries have been used to study the attrition behaviour in a bubbling fluidized bed combustor. Experiments have been conducted in a 40 mm I.D. and 1 m high fluidized bed combustor operated at 1 m/s superficial velocity. The bed was operated with nitrogen and with two different oxygen concentrations at 850°C to study the effect of combustion on attrition of these particles. The experimental technique used allowed the time resolution of attrited fines generation, providing detailed curves of attrition rates as a function of time. Attrition rate constants have been evaluated. Results show an enhancement of attrition due to combustion even for spherical, homogeneous and smooth particles.     

Physicochemical properties and oxidative potential of fine particles produced from coal combustion

Abstract

The physical and chemical properties as well as the oxidative potential (OP) of water soluble components of coal combustion fine particles were examined. A laboratory-scale pulverized-coal burning system was used to produce coal combustion particles at different burning temperatures of 550?°C, 700?°C, 900?°C, and 1,100?°C. Few studies have reported the effects of burning temperature on both the chemistry and toxicity of coal combustion particles. The highest mass emission factor of particulate matter less than 2.5?µm (PM_2.5) was found to be produced at 700?°C (3.51?g/kg), owing to strong elemental carbon (EC) emission and ash formation (ions and elements) resulting from the incomplete combustion of tar and char, and mineral fragmentation. The highest organic carbon in PM_2.5 was found at 550?°C. At a temperature higher than 700?°C, the fraction of carbonaceous species decreased while the fractions of ions and elements increased owing to ash formation. Sulfate was found to be the dominant ionic species, followed by sodium, calcium, and magnesium. The highest emission of elements (Al, As, Ba, Cd, Co, Cu, Fe, Mn, Ni, Pb, Sr, Ti, V, and Zn) and the highest fractions of Fe and Al were observed at 700?°C. Intrinsic OP activities obtained from dithiothreitol (DTT) and electron spin resonance (ESR) assays showed the highest values at 550?°C, suggesting that fine particles from low-temperature coal combustion had the highest reactive oxygen species generation capability (potentially toxic) among various tested burning temperatures. The results of principal component analysis suggested a correlation between OP-DTT activity and OC, EC, Cd, Co, V, and Zn, while OP-ESR activity was associated with chloride, nitrate, Ba, Pb, Sr, and Ti.

© 2018 American Association for Aerosol Research     

Kinetics of heterogeneous reactions of carbon and oxygen during combustion of porous carbon particles in oxygen

A model of combustion of a high-porosity carbon particle in oxygen is considered, which takes into account heterogeneous and homogeneous chemical reactions inside the particles and radiative heat transfer. The boundaries of the domain where the burning rate depends on the particle temperature are determined. The possibility of two combustion regimes is demonstrated: regime with a high burning rate, where the carbon-oxygen reaction proceeds in a layer adjacent to the particle surface, and regime with a low burning rate, where the reaction proceeds in the entire particle volume. In the regime with a high burning rate, the main product of the reaction between carbon and oxygen is carbon monoxide, whereas both carbon monoxide and carbon dioxide can be formed in the regime with a low burning rate. The kinetic equations of heterogeneous reactions C + O₂ = CO₂ and 2C + O₂ = 2CO are determined, which reveal the retarding effect of carbon monoxide and dioxide on the rates of these reactions. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 3, pp. 11–22, May–June, 2006.     

Raman scattering study of RETiTaO6 dielectric ceramics

In this work we have investigated microwave-dielectric ceramics RETiTaO₆ (RE=Al, Y, In, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er or Yb) by Raman scattering measurements at room temperature. The observed Raman-active phonons were analysed in conformity with two orthorhombic structures proposed for these ceramics, namely aeschynite (for lanthanide ions with atomic number between 58 and 66) or euxenite (for Y, Ho, Er and Yb). The results indicate that the phonon spectra remained relatively unchanged with respect to the RE ion substitution within each structure. For the three remaining materials with RE=La, Al and In, which are known to present multiphases, the Raman phonon spectra showed significant differences in comparison with those of ceramics with aeschynite and euxenite structure.     

Development of copper matrix composite reinforced with FeAl particles produced by combustion synthesis

This work focuses on the synthesis of FeAl intermetallic compound by combustion synthesis (SHS process) and its inclusion as dispersoids in a copper matrix to develop a metal matrix composite (MMC) by sintering. In the first step, FeAl compound was produced by the sintering of Fe-50 at.%Al at 1100 °C. Then, after grinding and mixing with copper powder, it was sintered in solid phase and liquid phase to obtain a metal matrix composite. The Scanning Electron Microscopy and Energy Dispersive X-ray Spectroscopy (SEM and EDS-X) analysis showed that copper diffuses in the microporosity of the FeAl particles and leaves porosity in the matrix. FeAl was milled by high energy to reduce the size of particles. It was then co-milled with copper to coat its particles in order to achieve higher density. The results showed that copper coats the FeAl particles which become finer and less porous. However, a low porosity persists in the matrix after sintering.     

Microstructural study of titanium carbonitride produced by combustion synthesis

The self-propagating high-temperature synthesis (S.H.S.) process, which is promising for the fabrication of ceramic materials, was chosen to elaborate titanium carbonitride materials. The influence of parameters such as nitrogen gas pressure and carbon ratio on the microstructure was studied. A single phase product of Ti(C,N) is obtained for a carbon ratio under 15 at.% and a nitrogen pressure of 36 MPa. The increase of the carbon ratio corresponds to a decrease of the maximum temperature reached during the synthesis. Time resolved X-ray diffraction measurements (TRXRD) with the synchrotron radiation were used to determine the reaction mechanisms. We could observe that the synthesis of Ti(C,N) is preceded by the formation of titanium nitride. This reaction is initiated by the allotropic transition of -Ti phase into β-Ti. In the final material the presence of sub-stoichiometric phases such as Ti₂N and -Ti was observed.