Understanding of the finite size effects on lattice vibrations and electronic transitions of nano alpha-Fe2O3

Alpha-Fe(2)O(3) nanocrystals with controlled diameters ranging from 10 to 63 nm were successfully prepared. The finite size effects in alpha-Fe(2)O(3) nanocrystals were probed by X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, UV-visible spectrum, and magnetization measurements. With a size reduction, alpha-Fe(2)O(3) nanocrystals showed a lattice expansion and an enlarged axial ratio of c/a that is in apparent contradiction to the previous conjecture of high lattice symmetry for alpha-Fe(2)O(3) nanocrystals at small sizes. The surface terminations of alpha-Fe(2)O(3) nanocrystals were found to be highly hydrated with a size dependence that surprisingly follows the surface hydration chemistry of anatase TiO2 nanocrystals reported recently by us. The lattice vibrations, electronic transitions, and magnetic properties of alpha-Fe(2)O(3) nanocrystals were significantly modified by surface hydration and lattice expansion. The finite size effects that occurred in alpha-Fe(2)O(3) nanocrystals at small sizes were first found to give a red shift in frequencies of perpendicular mode at 540 cm(-1), a blue shift in the electronic transition of double exciton process in visible region, and a significant decrease in the coercive force.     

Self-assembled FePt nanocrystals with large coercivity: reduction of the fcc-to-L1(0) ordering temperature

Herein we report the synthesis and properties of Fe(55)Pt(45) nanoparticles, both monodisperse and self-assembled into hexagonal close-packed and cubic arrays of 4.0 +/- 0.2 nm size in an L1(0) structure, obtained by a modified polyol process. The new synthetic route improved the control over the particle composition, thereby reducing the temperature required to convert from face-centered cubic (fcc) to face-centered tetragonal (fct) phase by some 30-50 degrees C without additives. Annealing at 550 degrees C for 30 min converts the self-assembled nanoparticles into ferromagnetic nanocrystals with large coercivity, H(C) = 11.1 kOe. Reducing the fcc-to-fct (L1(0)) ordering temperature avoided particle coalescence and decreased the loss in particle positional order without compromising the magnetic properties, as is generally observed when additives are used.     

Synthesis of branched gold nanocrystals by a seeding growth approach

Synthesis of branched gold nanocrystals by a seeding growth approach is described. In this process, HAuCl4 aqueous solution was supplied stepwise to grow the gold seeds (approximately 2.5 nm) into larger nanoparticles with a highly faceted particle structure (approximately 15-20 nm in diameter). Sodium dodecyl sulfate (SDS) served as a capping agent to facilitate the formation of highly faceted nanoparticles, and ascorbic acid was used as a weak reducing agent. The highly faceted nanoparticles then transformed into branched nanocrystals (approximately 40 nm in length) by further addition of the SDS-HAuCl4 solution and ascorbic acid for particle growth. The branched nanocrystals show bipod, tripod, tetrapod, and pentapod structures and are composed of mainly (111) lattice planes. These multipods appear to grow along the twin boundaries of the initially formed highly faceted gold nanoparticles, as the twin boundaries on the pods originate from the centers of the branched nanocrystals. The concentration of ascorbate ions in the solution was found to have a profound influence on branch formation. These branched nanocrystals are stable to storage at low temperature (that is, 4 degrees C), but they may slowly evolve into a multitwinned faceted crystal structure (that is, pentagonal-shaped decahedral structure) when stored at 30 degrees C.     

Synthesis of uniform anatase TiO2 nanoparticles by gel-sol method. 3. Formation process and size control

Uniform anatase-type TiO(2) nanoparticles were prepared by the gel-sol process from a condensed Ti(OH)(4) gel preformed by the hydrolysis of a Ti-triethanolamine (TEOA) complex. The particle size of the anatase TiO(2) was increased from ca. 5 to 30 nm with pH increasing from 0.6 to 12 by aging the Ti(OH)(4) gel at 140 degrees C for 72 h, while the yield of the anatase TiO(2), 100% below pH 9.6, started to decrease from pH 10, to 67% at pH 11.5 and only 9% at pH 12.2. These results reveal a significant reduction of the nucleation rate of the anatase TiO(2) with increasing pH, as is explained by the reduction of the concentration of a precursor complex, Ti(OH)(3)(+), and the adsorption of hydroxide ion onto the embryos of TiO(2). Triethanolamine appeared to enhance the pH effect on the nucleation rate of anatase TiO(2) particles by adsorption onto their embryos, leading to the wide range of the size control. Triethanolamine was also found to act as a shape controller of the anatase TiO(2) particles for yielding ellipsoidal particles from Ti(OH)(4) gel at a relatively high pH above 11. The particle size was also controlled by seeding of anatase TiO(2). Moreover, the seeding experiment suggested that the rate-determining step of the gel-sol process was not the dissolution of the hydroxide gel, but the deposition of the monomeric precursor from the solution phase.     

Multigram scale synthesis and characterization of monodisperse tetragonal zirconia nanocrystals

A new and simple method has been developed to synthesize large quantities of highly monodisperse tetragonal zirconia nanocrystals. In this synthesis, a nonhydrolytic sol-gel reaction between zirconium(IV) isopropoxide and zirconium(IV) chloride at 340 degrees C generated 4 nm sized zirconia nanoparticles. A high-resolution transmission electron microscopic (HRTEM) image showed that the particles have a uniform particle size distribution and that they are highly crystalline. These monodisperse nanoparticles were synthesized without any size selection process. X-ray diffraction studies combined with Rietveld refinement revealed that the ZrO(2) nanocrystals are the high-temperature tetragonal phase, and very close to a cubic phase. When zirconium(IV) bromide is used as a precursor instead of zirconium chloride, zirconia nanoparticles with an average size of 2.9 nm were obtained. The UV-visible absorption spectrum of 4 nm sized zirconia nanoparticles exhibited a strong absorption starting at around 270 nm. A fluorescence spectrum with excitation at 300 nm showed a broad fluorescence band centered around 370 nm. FTIR spectra showed indication of TOPO binding on the ZrO(2) nanoparticle surface. These optical studies also suggest that the nanoparticles are of high quality in terms of narrow particle size distribution and relatively low density of surface trap states.     

Controlled synthesis of highly dispersed TiO2 nanoparticles using SBA-15 as hard template

Highly dispersed TiO2 nanoparticles were successfully synthesized by a wet impregnation method using SBA-15 as hard template for confining the growth of TiO2 nanocrystals, and then calcined at 550 degrees C in muffle furnace for 2 h. The as-synthesized samples were characterized with Fourier transform infrared spectra (FTIR), Raman spectroscopy, diffuse reflectance UV-visible spectroscopy (UV-vis), powder X-ray diffraction (XRD), small-angle X-ray diffraction (SAXRD), nitrogen adsorption, transmission electron microscopy (TEM) and photoluminescence spectra (PL). It was found that SBA-15 contained abundant silanol groups after removal of triblock copolymers by ethanol extraction and could easily adsorb a great number of titanium alkoxide via chemisorption. After subsequent hydrolysis of the anchored Ti complexes and calcination of the amorphous TiO2, anatase TiO2 nanocrystals with spherical shape and uniform particle diameter of about 6 nm were formed. A blue shift was observed in UV-vis absorption spectra due to the quantum size effect of TiO2 nanoparticles. Moreover, the as-prepared TiO2 nanoparticles showed a high PL intensity due to an increase in the recombination rate of photogenerated electrons and holes under UV light irradiation.     

Colloidal synthesis and structural control of PtSn bimetallic nanoparticles

PtSn bimetallic nanoparticles with different particle sizes (1-9 nm), metal compositions (Sn content of 10-80 mol %), and organic capping agents (e.g., amine, thiol, carboxylic acid and polymer) were synthesized by colloidal chemistry methods. Transmission electron microscopy (TEM) measurements show that, depending on the particle size, the as-prepared bimetallic nanocrystals have quasi-spherical or faceted shapes. Energy-dispersive X-ray (EDX) analyses indicate that for all samples the signals of both Pt and Sn can be detected from single nanoparticles, confirming that the products are actually bimetallic but not only a physical mixture of pure Pt and Sn metal nanoparticles. X-ray diffraction (XRD) measurements were also conducted on the bimetallic particle systems. When compared with the diffraction patterns of monometallic Pt nanoparticles, the bimetallic samples show distinct shifts of the Bragg reflections to lower degrees, which gives clear proof of the alloying of Pt with Sn. However, a quantitative analysis of the lattice parameter shifts indicates that only part of the Sn atoms are incorporated into the alloy nanocrystals. This is consistent with X-ray photoelectron spectroscopy (XPS) measurements that reveal the segregation of Sn at the surfaces of the nanocrystals. Moreover, short PtSn bimetallic nanowires were synthesized by a seed-mediated growth method with amine-capped bimetallic particles as precursors. The resulting nanowires have an average width of 2.3 nm and lengths ranging from 5 to 20 nm.     

Effect of digestion time and alkali addition rate on physical properties of magnetite nanoparticles

We investigate the effect of digestion time and alkali addition rate on the size and magnetic properties of precipitated magnetite nanoparticles. It is observed that the time required to complete the growth process for magnetite nanocrystals is very short (approximately 300 s), compared to long digestion times (20-190 min) required for MnO and CdSe nanocrystals. The rapid growth of magnetite nanoparticles suggests that Oswald ripening is insignificant during the precipitation stage, due to the low solubility of the oxides and the domination of a solid-state reaction where high electron mobility between Fe2+ and Fe3+ ions drives a local cubic close-packed ordering. During the growth stage (0-300 s), the increase in the particle size is nominal (6.7-8.2 nm). The effect of alkali addition rate on particle size reveals that the nanocrystal size decreases with increasing alkali addition rate. The particle size decreases from 11 to 6.8 nm as the alkali addition rate is increased from 1 to 80 mL/s. During the size decrease, the lattice parameter decreases from 0.838 to 0.835 nm, which is attributed to an increase in the amount of Fe3+ atoms at the surface due to oxidation. As the alkali addition rate increases, the solution reaches supersaturation state rapidly leading to the formation of large number of initial nuclei at the nucleation stage, resulting in large number of particles with smaller size. When alkali addition rate is increased from 1 to 80 mL/s, the saturation magnetization of the particles decreases from 60 to 46 emu/g due to the reduced particle size.     

Control of the morphology and particle size of boehmite nanoparticles synthesized under hydrothermal conditions

The spontaneous nucleation under hydrothermal conditions often leads to aggregation of crystallizing particles, which is an undesired phenomenon when the goal is the preparation of nanocrystals with narrow particle size distribution. The present paper reports on the synthesis of boehmite nanocrystals under hydrothermal conditions. An aqueous aluminum chloride salt solution was first prepared, and the pH was increased to 11 using a 5 M sodium hydroxide solution. The hydrothermal treatment was performed at 160 degrees C for different periods of time. The system yielded relatively small (15-40 nm) boehmite crystallites aggregated into larger (160 nm) particles. To avoid the aggregation, a biocompatible polymer, sodium polyacrylate (NaPa) 2100, was employed as a size-/morphology-controlling agent. Thus, stable colloidal suspensions of rounded boehmite nanoparticles having a size between 15 and 40 nm were obtained at 160 degrees C for 24 h. Further, the effect of synthesis time on the morphological features of boehmite synthesized in such a NaPa-containing system was investigated. The increase of the synthesis time from 24 to 168 h resulted in the formation of very long boehmite fibers (1000-2000 nm) with an average diameter of about 10 nm. The boehmite samples were characterized by XRD, DLS, TEM, IR, N2 adsorption, and zeta potential measurements. The colloidal stability of the obtained suspension was also studied.     

Synthesis and structural characterization of sol–gel derived titania/poly (vinyl pyrrolidone) nanocomposites

Non hydrolytic sol–gel method was employed to synthesize pure anatase TiO₂ nanocrystals using tetra isopropyl orthotitanate and poly vinylpyrrolidone as precursors. The structural analyses of the prepared samples were carried out using Fourier transform infrared spectroscopy (FT-IR), thermo gravimetric and differential thermal analysis (TG–DTA), X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS). The capping of PVP around TiO₂ nanoparticles was confirmed by FT-IR spectroscopy, the interaction being via bridging oxygens of the carbonyl (C=O) and the nanoparticle surface. The XRD, Raman and TEM results indicate that the prepared samples had a pure anatase nano-TiO₂ structure. The particle size analysed by TEM ranged between 7 and 12 nm. The size of the nanocrystals evaluated from the XRD spectra and TEM micrograph is well in agreement. The spacing for the crystal planes was also determined using the ImageJ program applied to the TEM micrographs.     

Low temperature synthesis and characterization of porous anatase TiO2 nanoparticles

An ethanol solution of Ti-peroxy compounds was prepared from the ethanol solution of titanium isopropoxide (Ti(O-iPr)4) and H2O2. Heating of the ethanol solution of the Ti-peroxy compounds at 348 K formed a Ti-peroxy gel, and heat treatment of the gel at 348 K for more than 6 h formed gels that consisted of anatase nanoparticles. The diameter of the anatase nanoparticles increased from 9 to 15 nm as the heating time increased from 6 to 48 h. According to the results of the N2 adsorption measurement, the anatase nanoparticles had micropores, and the specific surface area (SBET) was in the range of 254 to 438 m2/g. The particle size, lattice strain, specific surface area, and photocatalytic activity of the anatase nanoparticles can be regulated by the heating time of the Ti-peroxy gel at 348 K.     

Adsorption of cadmium on anatase nanoparticles-effect of crystal size and pH

The adsorption and desorption of Cd(2+) to large and nanometer-scale anatase crystals have been studied to determine the relationship between heavy metal adsorption properties and anatase particle size. A solvothermal method was used to synthesize very fine anatase nanocrystals with average grain sizes ranging from 8 to 20 nm. On a surface area basis, it was found that large and nanometer-scale anatase particles had similar maximum Cd(2+) adsorption capacities, while their adsorption slopes differed by more than 1 order of magnitude. The particle-size effect on adsorption is constant over a pH range of 4-7.5. The desorption of Cd(2+) from both particle sizes is completely reversible. The adsorption data have been modeled by the Basic Stern model using three monodentate surface complexes. It is proposed that intraparticle electrostatic repulsion may reduce the adsorption free energy significantly for nanometer-sized particles.     

Hydrothermal routes to prepare nanocrystalline mesoporous SnO2 having high thermal stability

We report simple hydrothermal routes to prepare thermally stable SnO2 particles having high specific surface areas and mesoporosity. The preparation method includes a new combination of synthetic processes: hydrolysis of tin(IV) chloride at 95 degrees C in the absence of alkaline solutions (aqueous NH3 or NaOH), formation of nanocrystalline SnO2, and subsequent hydrothermal treatments at temperatures between 100 and 200 degrees C. After annealing treatments of the hydrothermally treated SnO2 particles at 400 or 500 degrees C, their crystallite sizes remained smaller than 7.7 nm and their specific surface areas were still higher than 110 m2/g, indicative of the high thermal stability against particle growth and sintering. Furthermore, mesoporosity evolved with a relatively narrow pore size distribution typically in the range of 3.0-4.3 nm. The effects of the hydrothermal treatment were explained by uniformization of the particle size that was beneficial to the suppression of particle growth.     

Aged titania nanoparticles: the simultaneous control of local and long-range properties

TiO(2) nanoparticles are obtained by combining a sol-gel preparative route with hydrothermal aging steps, performed in mild conditions, of varying time lengths. Both aged and un-aged samples are thermally treated at 300 and 600 degrees C, for the same length of time. The crystal structures, the phase composition, and crystallite sizes are analyzed by powder X-ray diffraction. Raman spectra of anatase nanocrystals with average sizes of 7-10 nm are reported and the correlation between the Raman band shape of the main feature at 144 cm(-1) and the crystallite size is discussed. Nitrogen physisorption by Brunauer-Emmett-Teller (BET) method is adopted to evaluate the particles surface area and mesopore size and size distribution. The role played by the hydrothermal step in affecting the physicochemical properties of the powders is discussed also with respect to the H(2)O/TiO(2) interactions as apparent from Raman spectroscopy investigations of the O-H stretching range (3000-3800 cm(-1)).     

Revealing the mechanisms behind SnO2 nanoparticle formation and growth during hydrothermal synthesis: an in situ total scattering study

The formation and growth mechanisms in the hydrothermal synthesis of SnO(2) nanoparticles from aqueous solutions of SnCl(4)·5H(2)O have been elucidated by means of in situ X-ray total scattering (PDF) measurements. The analysis of the data reveals that when the tin(IV) chloride precursor is dissolved, chloride ions and water coordinate octahedrally to tin(IV), forming aquachlorotin(IV) complexes of the form [SnCl(x)(H(2)O)(6-x)]((4-x)+) as well as hexaaquatin(IV) complexes [Sn(H(2)O)(6-y)(OH)(y)]((4-y)+). Upon heating, ellipsoidal SnO(2) nanoparticles are formed uniquely from hexaaquatin(IV). The nanoparticle size and morphology (aspect ratio) are dependent on both the reaction temperature and the precursor concentration, and particles as small as ~2 nm can be synthesized. Analysis of the growth curves shows that Ostwald ripening only takes place above 200 °C, and in general the growth is limited by diffusion of precursor species to the growing particle. The c-parameter in the tetragonal lattice is observed to expand up to 0.5% for particle sizes down to 2-3 nm as compared to the bulk value. SnO(2) nanoparticles below 3-4 nm do not form in the bulk rutile structure, but as an orthorhombic structural modification, which previously has only been reported at pressures above 5 GPa. Thus, adjustment of the synthesis temperature and precursor concentration not only allows control over nanoparticle size and morphology but also the structure.     

Metallorganic routes to nanoscale iron and titanium oxide particles encapsulated in mesoporous alumina: formation, physical properties, and chemical reactivity

Iron and titanium oxide nanoparticles have been synthesized in parallel mesopores of alumina by a novel organometallic "chimie douce" approach that uses bis(toluene)iron(0) (1) and bis(toluene)titanium(0) (2) as precursors. These complexes are molecular sources of iron and titanium in a zerovalent atomic state. In the case of 1, core shell iron/iron oxide particles with a strong magnetic coupling between both components, as revealed by magnetic measurements, are formed. M?ssbauer data reveal superparamagnetic particle behavior with a distinct particle size distribution that confirms the magnetic measurements. The dependence of the M?ssbauer spectra on temperature and particle size is explained by the influence of superparamagnetic relaxation effects. The coexistence of a paramagnetic doublet and a magnetically split component in the spectra is further explained by a distribution in particle size. From M?ssbauer parameters the oxide phase can be identified as low-crystallinity ferrihydrite oxide. In agreement with quantum size effects observed in UV-visible studies, TEM measurements determine the size of the particles in the range 5-8 nm. The particles are mainly arranged alongside the pore walls of the alumina template. TiO2 nanoparticles are formed by depositing 2 in mesoporous alumina template. This produces metallic Ti, which is subsequently oxidized to TiO2 (anatase) within the alumina pores. UV-visible studies show a strong quantum confinement effect for these particles. From UV-visible investigations the particle size is determined to be around 2 nm. XPS analysis of the iron- and titania- embedded nanoparticles reveal the presence of Fe2O3 and TiO2 according to experimental binding energies and the experimental line shapes. Ti4+ and Fe3+ are the only oxidation states of the particles which can be determined by this technique. Hydrogen reduction of the iron/iron-oxide nanoparticles at 500 degrees C under flowing H2/N2 produces a catalyst, which is active towards formation of carbon nanotubes by a CVD process. Depending on the reaction conditions, the formation of smaller carbon nanotubes inside the interior of larger carbon nanotubes within the alumina pores can be achieved. This behavior can be understood by means of selectively turning on and off the iron catalyst by adjusting the flow rate of the gaseous carbon precursor in the CVD process.     

Hydrothermal Synthesis and Characterization of Ce_(1-x)Mn_xO_(2-δ) Solid Solutions

Nanocrystals of Ce1-xMnxO2-δ(x=0.00,0.05,0.10,0.15,and 0.20) were synthesized by a hydrothermal reaction route.The solid solutions crystallized in a cubic fluorite structure with a particle size in the range of 11～15 nm.The incorporation of Mn ions in CeO2 resulted in a lattice volume reduction.Mn ions showed a mixed valence state of +2,+3 and +4 in CeO2 lattice.An obvious red-shift of the absorption threshold edge was observed from the UV-visible spectrum.Compared with the bulk CeO2,Ce1-xMnxO2-δ nanocrystals exhibited a lower releasing oxygen temperature as indicated by TPR technique.     

Nanoscale Pt(0) particles prepared in imidazolium room temperature ionic liquids: synthesis from an organometallic precursor,characterization, and catalytic properties in hydrogenation reactions

The reaction of Pt(2)(dba)(3) (dba = bis-dibenzylidene acetone) dispersed in room temperature 1-n-butyl-3-methylimidazolium (BMI) hexafluorophosphate ionic liquid with molecular hydrogen (4 atm) at 75 degrees C leads to stable and isolable nanometric Pt(0) particles. The X-ray diffraction analysis (XRD) of the material indicated that it is constituted of Pt(0). Transmission electron microscopy (TEM) analysis of the particles dispersed in the ionic liquid shows the formation of [Pt(0)](n) nanoparticles of 2.0-2.5 nm in diameter. A detailed examination of the nanoparticles imbibed in the ionic liquid and their environment shows an interaction of the BMI.PF(6) ionic liquid with the Pt(0) nanoparticles. The isolated [Pt(0)](n) nanoparticles can be redispersed in the ionic liquid or in acetone or used in solventless conditions for liquid-liquid biphasic, homogeneous, or heterogeneous hydrogenation of alkenes and arenes under mild reaction conditions (75 degrees C and 4 atm). The recovered platinum nanoparticles can be reused as a solid or redispersed in the ionic liquid several times without any significant loss in catalytic activity.     

Synthesis of titanium dioxide nanoparticles with mesoporous anatase wall and high photocatalytic activity

Mesoporous titanium dioxide nanosized powder with high specific surface area and anatase wall was synthesized via hydrothermal process by using cetyltrimethylammonium bromide (CTAB) as surfactant-directing agent and pore-forming agent. The resulting materials were characterized by XRD, nitrogen adsorption, FESEM, TEM, and FT-IR spectroscopy. The as-synthesized mesoporous TiO2 nanoparticles have mean diameter of 17.6 nm with mean pore size of 2.1 nm. The specific surface area of the as-synthesized mesoporous nanosized TiO2 exceeded 430 m2/g and that of the samples after calcination at 600 degrees C still have 221.9 m2/g. The mesoporous TiO2 nanoparticles show significant activities on the oxidation of Rhodamine B (RB). The large surface area, small crystalline size, and well-crystallized anatase mesostructure can explain the high photocatalytic activity of mesoporous TiO2 nanoparticles calcined at 400 degrees C.     

Supercritical Propanol-Water Synthesis and Comprehensive Size Characterisation of Highly Crystalline anatase TiO2 Nanoparticles

Highly crystalline anatase TiO₂ nanoparticles have been synthesised in less than 1 min in a supercritical propanol-water mixture using a continuous flow reactor. The synthesis parameter space (T, P, concentration) has been explored and the average particle size can be accurately controlled within 10-18 nm with narrow size distributions (2-3 nm). At subcritical conditions amorphous products are obtained, whereas a broad range of T and P in the supercritical regime gives 11-14 nm particles. At high temperature and pressure, the particles size increase to 18 nm. The nanoparticles have been extensively characterised with powder X-ray diffraction (PXRD), transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) with excellent agreement on size and size distribution parameters. The SAXS analysis suggests disk-shaped particles with diameters that are approximately double the height. For comparison, a series of conventional autoclave sol-gel syntheses have been carried out. These also produce phase-pure anatase nanoparticles, but with much broader size distributions and at much longer synthesis times (hours). The study demonstrates that synthesis in supercritical fluids is a very promising method for manipulating the size and size distribution of nanoparticles, thus removing one of the key limitations in many applications of nanomaterials.