Browsing by Subject "Surface active agents"

Now showing 1 - 20 of 22

Open Access
Colloidal nanoplatelet/conducting polymer hybrids: excitonic and material properties
(American Chemical Society, 2016) Guzelturk, B.; Menk, F.; Philipps, K.; Kelestemur Y.; Olutas M.; Zentel, R.; Demir, Hilmi Volkan
Here we present the first account of conductive polymer/colloidal nanoplatelet hybrids. For this, we developed DEH-PPV-based polymers with two different anchor groups (sulfide and amine) acting as surfactants for CdSe nanoplatelets, which are atomically flat semiconductor nanocrystals. Hybridization of the polymers with the nanoplatelets in the solution phase was observed to cause strong photoluminescence quenching in both materials. Through steady-state photoluminescence and excitation spectrum measurements, photoluminescence quenching was shown to result from dominant exciton dissociation through charge transfer at the polymer/nanoplatelet interfaces that possess a staggered (i.e., type II) band alignment. Importantly, we found out that sulfide-based anchors enable a stronger emission quenching than amine-based ones, suggesting that the sulfide anchors exhibit more efficient binding to the nanoplatelet surfaces. Also, shorter surfactants were found to be more effective for exciton dissociation as compared to the longer ones. In addition, we show that nanoplatelets are homogeneously distributed in the hybrid films owing to the functional polymers. These nanocomposites can be used as building blocks for hybrid optoelectronic devices, such as solar cells.
Open Access
Continuous mesoporous pd films by electrochemical deposition in nonionic micellar solution
(American Chemical Society, 2017) Iqbal, M.; Li C.; Wood, K.; Jiang B.; Takei, T.; Dag, Ö.; Baba, D.; Nugraha, A. S.; Asahi, T.; Whitten, A. E.; Hossain, M. S. A.; Malgras, V.; Yamauchi, Y.
Mesoporous metals that combine catalytic activity and high surface area can provide more opportunities for electrochemical applications. Various synthetic methods, including hard and soft templating, have been developed to prepare mesoporous/nanoporous metals. Micelle assembly, typically involved in soft-templates, is flexible and convenient for such purposes. It is, however, difficult to control, and the ordering is significantly destroyed during the metal deposition process, which is detrimental when it comes to designing precisely mesostructured materials. In the present work, mesoporous Pd films were uniformly electrodeposited using a nonionic surfactant, triblock copolymer poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide), as a pore-directing agent. The interaction between micelles and metal precursors greatly influences the metal growth and determines the final structure. The water-coordinated species interact with the ethylene oxide moiety of the micelles to effectively drive the Pd(II) species toward the working electrode surface. From small-angle neutron scattering data, it is found that spherical P123 micelles, with an average diameter of ∼14 nm, are formed in the electrolyte, and the addition of Pd ions does not significantly modify their structure, which is the essence of the micelle assembly approach. The uniformly sized mesopores are formed over the entire mesoporous Pd film and have an average pore diameter of 10.9 nm. Cross-sectional observation of the film also shows mesopores spanning continuously from the bottom to the top of the film. The crystallinity, crystal phase, and electronic coordination state of the Pd film are also confirmed. Through this study, it is found that the optimized surfactant concentration and applied deposition potential are the key factors to govern the formation of homogeneous and well-distributed pores over the entire film. Interestingly, the as-prepared mesoporous Pd films exhibit superior electrocatalytic activity toward the ethanol oxidation reaction by fully utilizing the accessible active surface area. Our approach combines electrochemistry with colloidal and coordination chemistry and is widely applicable to other promising metals and alloy electrocatalysts.
Open Access
Controlled optical transition rates in nanodroplets
(IEEE, 2000) Özçelik, Serdar
The time-resolved fluorescence measurements of 3,3′-diethyl-5,5′-dichloro-9-phenylthiacarbocyanine (DDPT) in bulk solvents and methanol-in-oil reverse micellar systems is presented which include nano-sized methanol droplets stabilized with anionic surfactant aerosol-OT (AOT) in n-heptane, at room temperature. Relative fluorescence intensities of DDPT increase with a factor of 16 in m/o reverse micelles in comparison to those in bulk methanol. The radiative and nonradiative rate constants decreases in methanol dispersions, indicating that internal motions of DDPT in the droplets is reduced due to strong electrostatic interactions between the positively charged DDPT and the negatively charged sulfonate head-groups of AOT.
Open Access
Cytotoxicity of multifunctional surfactant containing capped mesoporous silica nanoparticles
(Royal Society of Chemistry, 2016) Yildirim, A.; Turkaydin, M.; Garipcan, B.; Bayındır, Mehmet
This paper reports the synthesis of silica capped surfactant (cetyltrimethylammonium bromide; CTAB) and dye (Rose Bengal; RB) containing mesoporous silica nanoparticles (MSNs). Capping the pores of the surfactant containing MSNs with a thin silica layer decreased the immediate surfactant originated cytotoxicity of these particles without affecting their long term (3 days) cytotoxicity. Also, the silica capping process almost completely prevented the hemolytic activity of the surfactant containing MSNs. In addition, improved uptake of silica capped MSNs compared to the uncapped particles by cancer cells was demonstrated. The delayed cytotoxicity, low hemolytic activity, and better cellular uptake of the silica capped MSNs make them promising for the development of safe (i.e. with fewer side effects) yet efficient theranostic agents. These nanocarriers may release the loaded cytotoxic molecules (CTAB) mostly after being accumulated in the tumor site and cause so minimal damage to the normal tissues and blood components. In addition, the nanoscale confinement of RB molecules inside the pores of MSNs makes the particles brightly fluorescent. Furthermore, it was demonstrated that due to the singlet oxygen generation capability of the RB dye the silica capped MSNs can be also used for photodynamic therapy of cancer. © 2016 The Royal Society of Chemistry.
Open Access
The effect of anions of transition metal salts on the structure of modified mesostructured silica films and monoliths
(Elsevier, 2007) Demirörs, A. F.; Arslan, M.; Dag, Ö.
The structure of the preformed LC mesophase of water:transition metal salt ([M(H2O)6]X2):acid (HX):oligo(ethylene oxide) (or Pluronics):tetramethylorthosilicate (TMOS) mixture during hydrolysis and partial polymerization of the silica source is maintained upon further polymerization and condensation of the silica species in the solid state. The liquid mixture in early stage of the silica polymerization could be casted or dip coated to a surface of a glass or silicon wafer to produce mesostructured silica monoliths and films, respectively. The silica species and ions (metal ions and anions) influence the structure of the LC mesophases (as a result, the structure of silica) and the hydrophilic and hydrophobic balance in the reaction media. The silica structure can be changed from hexagonal to cubic by increasing, for example, the nitrate salt concentration in the nitrate salt systems. A similar transformation takes place in the presence of very low perchlorate salt concentration. The salt concentration in the mesostructured silica can be increased up to 1.1/1.0 salt/SiO2 w/w ratio, in mesostructured silica materials by maintaining its lamella structure in P123 and cubic in the CnEOm systems. However, the materials obtained from the P123 systems undergo transformation from lamella to 2D hexagonal upon calcinations. The method developed in this work can be used to modify the internal surface of the pores with various transition metal ions and metal oxides that may find application in catalysis. © 2006 Elsevier Inc. All rights reserved.
Open Access
Effects of ions on the liquid crystalline mesophase of transition-metal salt: surfactant (CnEOm)
(American Chemical Society, 2004) Dag, Ö.; Alayoǧlu, S.; Uysal, İ.
The transition-metal aqua complex salts [M(H2O) x]Y2 (where M is some of the first- and second-row transitionmetal ions and Y is Cl-, NO3-, and ClO4- counteranions) form liquid crystalline (LC) mesophases with oligo(ethylene oxide) nonionic surfactants (CnH 2n+1(CH2CH2O)mOH, denoted as C nEOm). The structure of the [M(H2O) x]Y2:CnEOm mesophase is usually 2D hexagonal in nitrate systems, cubic in perchlorate systems, and absent in the chloride systems. The solubility of the metal aqua complex salt follows the Hofmeister series in a [M(H2O)x]Y2:C nEOm mesophase. However, the nitrate ion interacts with the metal center as a bidentate and/or unidentate ligand, therefore reducing the ion density (and/or ionic strength) of the LC medium and further enhancing the solubility of nitrate salt in the LC systems. The cobalt chloride salt is the only soluble chloride salt that undergoes ligand-exchange reactions in the [Co(H2O)6]Cl2:CnEOm system. In an LC mesophase, anions have a greater influence on the hydrophilicity of nonionic surfactants than do cations. The structure and stability of the LC mesophase can be controlled by controlling either the hydrophilicity of the nonionic surfactant (by choosing the right anion type) or the ion density of the medium (by either influencing the equilibrium between the free and coordinated anions or balancing between the coordinating and noncoordinating anions in the medium).
Open Access
Facile route to produce spherical and highly luminescent Tb3+doped Y2O3 nanophosphors
(Elsevier, 2017) Kumar, D.; Sharma, M.; Haranath, D.; Pandey, O. P.
Terbium doped yttrium oxide (Y2O3:Tb3+) nanophosphor has been synthesized via a facial yet modified co-precipitation method. To get maximum luminescence output from Y2O3:Tb3+nanophosphors, surfactants namely, Cetyl trimethylammonium bromide (CTAB) and Trioctylphosphine oxide (TOPO) were added during synthesis. Further, it has been observed that combined addition of surfactant (CTABï¿½+ï¿½TOPO) at the time of synthesis has resulted in nearly spherical morphology of the nanophosphor. Furthermore, these optimized material are observed to have enhanced integrated photoluminescence (PL) intensity of ∼23% as compared to the one synthesized without the addition of any surfactant. The results are further supported by detailed structural and optical studies. Optimum use of surfactants during synthesis shows for the first time that both nano-sized distribution and high crystallinity can be achieved simultaneously which has resulted in bright green emission in Tb3+doped Y2O3nanophosphors.
Open Access
Liquid crystalline mesophases of pluronics (L64, P65, and P123) and transition metal nitrate salts ([M(H2O)6](NO 3)2)
(American Chemical Society, 2005) Demirörs, A. F.; Eser, B. E.; Dag, Ö.
The triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) copolymers, Pluronics (L64, P65, and P123), form liquid crystalline (LC) mesophases with transition metal nitrate salts (TMS), [M(H2O) n] (NO3)2, in the presence and absence of free water in the media. In this assembly process, M-OH2 plays an important role as observed in a TMS:CnEOm (C nEOm is oligo(ethylene oxide) nonionic surfactants) system. The structure of the LC mesophases and interactions of the metal ion-nitrate ion and metal ion-Pluronic were investigated using microscopy (POM), diffraction (XRD), and spectroscopy (FTIR and micro-Raman) techniques. The TMS:L64 system requires a shear force for mesophase ordering to be observed using X-ray diffraction. However, TMS:P65 and TMS:P123 form well structured LC mesophases. Depending on the salt/Pluronic mole ratio, hexagonal LC mesophases are observed in the TMS:P65 systems and cubic and tetragonal LC mesophases in the TMS:P123 systems. The LC mesophase in the water/salt/Pluronic system is sensitive to the concentration of free (H2O) and coordinated water (M-OH2) molecules and demonstrates structural changes. As the free water is evaporated from the H2O:TMS:Pluronic LC mesophase (ternary mixture), the nitrate ion remains free in the media. However, complete evaporation of the free water molecules enforces the coordination of the nitrate ion to the metal ion in all TMS:Pluronic systems. © 2005 American Chemical Society.
Unknown
Lithium salt-nonionic surfactant lyotropic liquid crystalline gel-electrolytes with redox couple for dye sensitized solar cells
(Royal Society of Chemistry, 2016) Yılmaz, E.; Olutaş, E. B.; Barım, G.; Bandara, J.; Dag, Ö.
Lithium salt (LiCl, LiBr, LiI, or LiNO3) and a non-ionic surfactant (such as 10-lauryl ether, C12E10) form lyotropic liquid crystalline (LLC) mesophases in the presence of a small amount of water. The mesophases can be prepared as gels by mixing all the ingredients in one pot or in the solution phase that they can be prepared by coating over any substrate where the LLC phase is formed by evaporating excess solvent. The second method is easier and produces the same mesophase as the first method. A typical composition of the LLC phases consists of 2-3 water per salt species depending on the counter anion. The LiI-C12E10 mesophases can also be prepared by adding I2 to the media to introduce an I-/I3 - redox couple that may be used as a gel-electrolyte in a dye-sensitized solar cell. Even though the mesophases contain a large amount of water in the media, this does not affect the cell performance. The water molecules in the mesophase are in the hydration sphere of the ions and do not act like bulk water, which is harmful to the anode of the dye-sensitized solar cells (DSSC). There are two major drawbacks of the salt-surfactant LLC mesophases in the DSSCs; one is the diffusion of the gels into the pores of the anode electrode and the other is the low ionic conductivity. The first issue was partially overcome by introducing the gel content as a solution and the gelation was carried in/over the pores of the dye modified titania films. To increase the ionic conductivity of the gels, other salts (such as LiCl, LiBr, and LiNO3) with better ionic conductivity were added to the media, however, those gels behave less effectively than pure LiI/I2 systems. Overall, the DSSCs constructed using the LLC electrolyte display high short circuit current (Isc of around 10 mA), high open circuit voltage (Voc of 0.81 V) and good fill factor (0.69) and good efficiency (3.3%). There is still room for improvement in addressing the above issues in order to enhance the cell efficiency by developing new methods of introducing the gel-electrolytes into the mesopores of the anode electrode.
Unknown
Lyotropic liquid-crystalline mesophase of lithium triflate-nonionic surfactant as gel electrolyte for graphene optical modulator
(American Chemical Society, 2023) Balci, F. M.; Balci, S.; Kocabas, C.; Dag, Ö.
Lithium salt (noncoordinating anions, such as lithium triflate (Ltf)) gel electrolytes may be key for the practical use of electrochemical devices. We introduce a new lyotropic liquid-crystalline (LLC) mesophase using Ltf, a small amount of water (as low as 1.3 water per Ltf), and nonionic surfactant (C18H37(OCH2CH2)10OH, C18E10). The LLC phase forms over a broad range of Ltf/C18E10 mole ratios, 2-18. The clear ethanol solution of the ingredients can be either directly spin-coated over a glass substrate to form a gel phase or it can be prepared as a gel by mixing Ltf, water, and C18E10. The mesophase leaches out surfactant molecules at low salt concentrations, but at a salt/surfactant mole ratio of above 8, the phase is homogeneous with a cubic mesostructure, fully transparent in the visible optical region, mechanically flexible, and an effective gel electrolyte. We have observed a large electrostatic doping on graphene with the Fermi energy level of ∼1.0 eV using Ltf-C18E10 gel electrolytes. The Ltf-based gels demonstrate better properties than commonly used ionic liquid electrolyte in graphene optical modulators. The stability of the new gel electrolytes and their superior performance make them suitable electrolytes for use in graphene-based optical modulators.
Unknown
Lyotropic liquid-crystalline mesophases of [Zn(H2O)6](NO3)2-C12EO10-CTAB-H2O and [Zn(H2O)6](NO3)2-C12EO10-SDS-H2O systems
(2008) Albayrak, C.; Soylu, A. M.; Dag, Ö.
The mixture of two surfactants (C12EO10-CTAB and C 12EO10-SDS) forms lyotropic liquid-crystalline (LLC) mesophases with [Zn(H2O)6](NO3)2 in the presence of a minimum concentration of 1.75 H2O per C 12EO10. The metal ion/C12EO10 mole ratio can be increased up to 8.0, which is a record high metal ion density in an LLC mesophase. The metal ion concentration can be increased in the medium by increasing the CTAB/C12EO10 or SDS/C12EO 10 mole ratio at the expense of the stability of the LLC mesophase. The structure and some thermal properties of the new mesophase have been investigated using XRD, POM, FTIR, and Raman techniques. © 2008 American Chemical Society.
Open Access
Lyotropic liquid-crystalline phase of oligo(ethylene oxide) surfactant/transition metal salt and the synthesis of mesostructured cadmium sulfide
(American Chemical Society, 2003) Dag, Ö.; Alayoǧlu, S.; Tura, C.; Çelik, Ö.
Lyotropic liquid-crystalline (LLC), transition metal salt: oligo(ethylene oxide) nonionic surfactant (CnH2n+1(CH2CH2O)mOH, denoted as CnEOm), systems have been studied by means of diffraction, microscopy, and spectroscopy to elucidate the structural, thermal, and templating properties. In the system, the lyotropic salts of transition metal aqua complexes, such as chlorides and sulfates, are insoluble and do not form a LC phase in CnEOm-type nonionic surfactants. However, the transition metal aqua complexes of nitrates and perchlorates are soluble and form 2D and 3D hexagonal and cubic mesophases. These phases are stable in a very broad range of salt:surfactant mole ratios (1.0 and 3.6). The nitrate salts form a hexagonal mesophase. However, in high nitrate salt concentrations (above 3.2 salt:surfactant mole ratio), the salt crystals are either insoluble or the salt:surfactant mixtures are in a cubic mesophase. The structure and thermal properties of the new system are determined by the solubility of the transition metal salts, the concentration of the salt, and the surfactant type. The LC [Cd(H2O)4](NO3)2: C12EO10 mesophase has been reacted with H2S gas to produce solid mesostructured CdS (meso-CdS). The meso-CdS particles are spherical in morphology and are made up of hierarchical organization of 2-4-nm CdS particles. The salt:surfactant LLC systems and the solid meso-CdS have been investigated using polarized optical microscopy, X-ray diffraction, Fourier transform infrared, Fourier transform Raman, and UV-vis absorption spectroscopy, scanning electron microscopy, and transmission electron microscopy.
Open Access
Model study of a surfactant on the GaAs(100) surface
(Elsevier, 2002-11-01) Consorte, C. D.; Fong, C. Y.; Watson, M. D.; Yang, L. H.; Çıracı, Salim
Based on the facts that: (a) the transverse acoustic vibrational branch frequency is softened at the Brillouin zone boundaries of crystalline GaAs; (b) at the surface, the Ga-As bond is stronger than Ga-Te bond; and (c) the requirement that the final bond orientation of the Te surfactant should be rotated by 90degrees with respect to its initial orientation, we carried out a model study of an exchange process in epitaxial growth of GaAs (100). Even with very restrictive conditions imposed on the atomic movements, this study explains why Te is an effective surfactant for this type of growth. (C) 2002 Elsevier Science B.V. All rights reserved.
Open Access
A new lyotropic liquid crystalline system: oligo(ethylene oxide) surfactants with [M(H2O)n]Xm transition metal complexes
(Wiley, 2001) Çelik, Ö.; Dag, Ö.
Coordinated water molecules induce the aggregation and self-assembly of the lyotropic liquid crystalline phase formed from non-ionic surfactants CnH2n+1(CH2CH2O)mOH and transition metal aqua complexes ([Ni(H2O)6](NO3)2, [Co(H2O)6](NO3)2, [Cd(H2O)4](NO3)2, and [Co(H2O)6]Cl2) into hexagonal (see schematic representation) and/or cubic structures. While the NiII and CoII complexes undergo recrystallization and phase separation at high complex concentrations, the ZnII and CdII complexes form cubic phases above metal/surfactant molar ratios of 3.2/1 at room temperature.
Open Access
One-pot synthesis of CdS nanoparticles in the channels of mesosructured silica films and monoliths
(American Chemical Society, 2005) Tura, C.; Coombs, N.; Dag, Ö.
Cd(II)-modified mesoporous silica films and/or monoliths synthesized in one pot using a true liquid crystalline (TLC) approach have been reacted with H2S gas to produce CdS-modified mesostructured nanocomposite materials (Nano-CdS/meso-SiO2). During this process, both the TLC and the metallotropic liquid crystalline (MLC) mesophase of metal salt ([Cd(H 2O)4](NO3)2)-nonionic surfactant (CnH2n+1- (OCH2CH2)mOH, CnEOm) systems were collectively used to incorporate large quantities of metal ions into the mesoporous silica film and monoliths. The effect of the cadmium nitrate concentration on the formation and structure of the mesoporous silica has also been investigated. The results show that at low salt concentrations, the mesoporous silica is anisotropic (hexagonal); however, at high salt concentration, the structure is isotropic (cubic or disordered). The freshly prepared CdS nanoparticles are reactive toward the surface acids that form during the H2S treatment. These surface acids also promote the degradation of the CdS nanopaticles. However, the CdS particles in the mesopores can be stabilized by washing out the acid sides or aging the samples for a period of time before the H2S reaction. The optical absorption edge of the CdS nanoparticle in the pores is sensitive to the composition and structure of the host. In this context, the materials were characterized using FTIR, micro-Raman, UV-visible absorption spectroscopy, POM, TEM, and PXRD techniques.
Open Access
Production and structural characterization of biosurfactant produced by newly isolated staphylococcus xylosus STF1 from petroleum contaminated soil
(Elsevier BV, 2015) Keskin, N. O. S.; Han, D.; Ozkan A.D.; Angun, P.; Umu, O. C. O.; Tekinay, T.
Petroleum-contaminated soil was used to isolate and characterize biosurfactant producing bacteria. The strain could produce higher amount of biosurfactant in medium supplemented with motor oil as sole source of carbon and energy. A new biosurfactant producing bacterium, designated as Staphylococcus xylosus STF1 based on morphological, physiological, biochemical tests and 16S rRNA gene sequencing. The isolated bacterium was first screened for the ability to produce biosurfactant. Partial sequence of STF1 strain of 16S rDNA gene was highly similar to those of various members of the family Staphylococcaceae. Biochemical characterizations including FT-IR, Raman spectroscopy and Mass spectroscopy studies suggested the biosurfactant to be lipopeptide. Study also confirmed that the cell free supernatant exhibited high emulsifying activity against the different hydrocarbons. Moreover, the partially purified biosurfactant exhibited antimicrobial activity by inhibiting the growth of several bacterial species. The strain could be a potential candidate for the production of polypeptide biosurfactant which could be useful in a variety of biotechnological and industrial processes, particularly in the food and oil industry. © 2015 Elsevier B.V.
Open Access
Role of organic and inorganic additives on the assembly of CTAB-P123 and the morphology of mesoporous silica particles
(2009) Poyraz, A. S.; Dag, Ö.
Mesoporous silica particles with various morphologies and structures have been synthesized by controlling the solubility, micellization, and assembly of a charged surfactant (cethyltrimethylammonium bromide, CTAB) and a pluronic (PEO20PPO70PEO20, P123) couple using an organic (benzene) or an inorganic (SO4 2-, NO3 -, or Cl-) additive. The effect of CTAB, with or without one of the Hofmeister ions or benzene in various concentrations, on the morphology, pore-size, pore-structure and the nature of the silica particles has been investigated. Increasing the lyotropic anion (SO4 2-) or benzene concentration of the synthesis media creates wormlike particles with enlarged pores and reduced wall thickness. However, the hydrotropic anion (NO3 -) influenced the solubility of the charged surfactant and increased the CTAB concentration in the CTAB-P123 micelles, and as a result, in the mesoporous silica particles. The surface area, unit cell, and pore size of the silica particles are diminished by increasing the nitrate ion centration. The effects of the Cl- ion are between the SO4 2- and NO3 -ions. It influenced the P123 at low and CTAB at high concentrations. At low CTAB/ P123 mol ratios, the Cl- ion affects mainly the P123, but at high CTAB/P123 it affects both the CTAB and P123. By carefully adjusting these ingredients (CTAB, SO4 2-, Cl-, NO3 - and benzene), not only the morphology of the particles, but also the pore-size and pore-structure of the mesoporous silica particles could be adjusted. The investigations were carried out by preparing a series of powder samples and, by varying the CTAB/P123 mol ratio (between 3.0 and 6.0) and the concentration of the organic (0.17 to 0.90 M) or inorganic (at 0.25, 0.50, or 1.00 M) additive in the synthesis media. The powder samples were analyzed using microscopy (SEM, TEM, and POM), diffraction (PXRD), and spectroscopy (FTIR, Raman, UV-vis, and EDS) techniques toward above goals. © 2009 American Chemical Society.
Open Access
Silver nitrate/oligo(ethylene oxide) surfactant/mesoporous silica nanocomposite films and monoliths
(Academic Press, 2001) Samarskaya, O.; Dag, Ö.
A lyotropic, liquid crystalline (LC) phase of a silver nitrate/oligo(ethylene oxide), water, and acid mixture was used for one-pot synthesis of mesoporous silica materials in which Ag+ ions are uniformly distributed. We established that the AgNO3-to-surfactant mole ratio is very important in a 50 wt% surfactant/water system to preserve the hexagonal LC phase before and after the addition of the silica source. Below a 0.6 AgNO3-to-surfactant mole ratio, the mixture is liquid crystalline and serves as a template for silica polymerization. However, between 0.6 and 0.8 AgNO3-to-surfactant mole ratios, one must control the composition of the mixture during the polymerization processes. Above a 0.8 mole ratio, Ag+ ions undergo phase separation from the reaction mixture by complexing with the surfactant molecules. The resulting silica materials obtained from AgNO3/surfactant ratio above 0.8 have anisotropy but without a hexagonal mesophase. Here, we establish a AgNO3 concentration range in which the LC phase is preserved to template the synthesis of mesoporous silica, and we discuss the structural behavior of the mixtures at AgNO3/surfactant mole ratios of 0.00-2.00, using POM, PXRD, FTIR, and UV-Vis absorption spectroscopy. © 2001 Academic Press.
Open Access
Solventless acid-free synthesis of mesostructured titania: nanovessels for metal complexes and metal nanoclusters
(Wiley - V C H Verlag GmbH & Co. KGaA, 2003) Dag, Ö.; Soten, I.; Çelik, Ö.; Polarz, S.; Coombs, N.; Ozin, G. A.
A new and highly reproducible method to obtain mesostructured titania materials is introduced in this contribution. The meso-structured titania is obtained by employing self-assembled structures of non-ionic alkyl-poly(ethylene oxide) surfactants as templates. The materials are produced without additional solvents such as alcohols, or even water. Only the titanium(iv) ethoxide and the surfactant (C12EO10) are needed. Water, in the form of that attached to the surfactant and from the atmosphere, induces growth of titania nanoclusters in the synthesis sol. It is indicated that these nanoclusters interact with the surfactant EO-head groups to form a new titanotropic amphiphile. The new amphiphiles self-assemble into titanium nanocluster-surfactant hybrid lyotropic phases, which are transformed to the final mesostructured materials by further condensation of the titania network. The titania materials can be obtained also with noble-metal particles immobilized in the mesostructured framework. It is seen that when different metal salts are used as the metal precursors, different interactions with the titania walls are found. The materials are characterized by X-ray diffraction (XRD), polarization optical microscopy (POM), transmission electron microscopy (TEM), UV-vis spectroscopy, and micro-Raman analysis.
Open Access
Strong acid-nonionic surfactant lyotropic liquid-crystalline mesophases as media for the synthesis of carbon quantum dots and highly proton conducting mesostructured silica thin films and monoliths
(American Chemical Society, 2015) Olutaş, E. B.; Balcı, F. M.; Dag, Ö.
Lyotropic liquid-crystalline (LLC) materials are important in designing porous materials, and acids are as important in chemical synthesis. Combining these two important concepts will be highly beneficial to chemistry and material science. In this work, we show that a strong acid can be used as a solvent for the assembly of nonionic surfactants into various mesophases. Sulfuric acid (SA), 10-lauryl ether (C12E10), and a small amount of water form bicontinuous cubic (V1), 2Dhexagonal (H1), and micelle cubic (I1) mesophases with increasing SA/ C12E10 mole ratio. A mixture of SA and C12E10 is fluidic but transforms to a highly ordered LLC mesophase by absorbing ambient water. The LLC mesophase displays high proton conductivity (1.5 to 19.0 mS/cm at room temperature) that increases with an increasing SA content up to 11 SA/ C12E10 mole ratio, where the absorbed water is constant with respect to the SA amount but gradually increases from a 2.3 to 4.3 H2O/C12E10 mole ratio with increasing SA/C12E10 from 2 to 11, respectively. The mixture of SA and C12E10 slowly undergoes carbonization to produce carbon quantum dots (c-dots). The carbonization process can be controlled by simply controlling the water content of the media, and it can be almost halted by leaving the samples under ambient conditions, where the mixture slowly absorbs water to form photoluminescent c-dot-embedded mesophases. Over time the c-dots grow in size and increase in number, and the photoluminescence frequency gradually shifts to a lower frequency. The SA/C12E10 mesophase can also be used as a template to produce highly proton conducting mesostructured silica films and monoliths, as high as 19.3 mS/cm under ambient conditions. Aging the silica samples enhances the conductivity that can be even larger than for the LLC mesophase with the same amount of SA. The presence of silica has a positive effect on the proton conductivity of SA/C12E10 systems.