Ultrafine anatase TiO2 nanoparticles produced in premixed ethylene stagnation flame at 1 atm

Nano-sized titanium oxide particles were synthesized in a stationary, laminar, premixed, stagnation flame burning an ethylene–oxygen–argon mixture at an equivalence ratio of 0.36 under the atmospheric pressure. The titanium precursor, titanium tetraisopropoxide (TTIP), was fed into the flame by a carrier argon flow through a heated TTIP bath. Particles synthesized in this flame were characterized for their size distribution, morphology, phase purity, and crystal structure, by scanning mobility particle sizer, transmission electron microscopy, and X-ray diffraction. It was found that the mean diameter of the particles was highly controllable and ranged from 3 to 6 nm depending on TTIP loading. The particle size was nearly uniform, and particles appeared to be single crystals without excessive aggregation. XRD analyses show that particles directly synthesized in the flame are pure anatase. Upon sintering and size growth on the flame stabilizer, a notable portion of particles transformed into rutile with much larger crystal sizes.     

Preparation of bimetal incorporated TiO2 photocatalytic nano-powders by flame method and their photocatalytic reactivity for the degradation of diluted 2-propanol

Bimetal incorporated TiO₂ photocatalysts (FeZn–TiO₂) prepared by a flame method showed high photocatalytic activity for the degradation of 2-propanol dissolved in water as compared with mono-metal incorporated or unincorporated TiO₂. By using this flame method, parameters such as uniform particle size, crystallinity as well as the anatase and rutile phase ratio (anatase/rutile) could be controlled without calcination of the catalysts at high temperatures, the parameters being important to achieve a high photocatalytic activity. The presence of a small amount of bimetals such as Fe and Zn plays a vital role as a catalyst in the formation of highly crystalline, small and uniform size particles with defined anatase/rutile phase ratio of around 60/40, this being similar to that of P-25 which is well known as a highly active photocatalyst.     

Study on the lattice distortion of the As-prepared nanosized TiO2 particles via detonation method

Quantitative XRD measurements of the nanosized TiO₂ particles obtained from the detonation soot have been carried out. The lattice parameters, such as grain size, cell volume, lattice constants and lattice strain were obtained. The relationships between the change ratio of cell volume (the reciprocal of the particles size, or the mass ratio of explosive and TiO₂ precursor) and the lattice strain of the different TiO₂ phases were also discussed. The relationship between the change ratio of cell volume and the particle size of TiO₂ particles was also studied. The results demonstrated that with the decreasing of the particles size, the lattice strain of anatase phase increased, while the lattice strain of rutile phase increased firstly and then decreased to some extent. It is different from the linear relationship between the lattice distortion and the reciprocal of the particles size reported in other literatures. In the meantime, the lattice strains were different with the different mass contents of RDX in the microstructures of the TiO₂ particles. The direct reflection of microstructure changes is the changes of the particle size of TiO₂ particles. Based on the XRD results, the particular characteristics of the detonation process and interfacial effects of nanocrystalline materials, a crude explanation was also given.     

Effect of silver addition on the formation and deposition of titania nanoparticles produced by liquid flame spray

In this study, liquid flame spray (LFS) was used to produce titania, silver and silver–titania deposits of nanoparticles. Titanium(IV)ethoxide (TEOT) and silver nitrate in ethanol solutions were used as precursors and sprayed into turbulent hydrogen–oxygen flame. Production rates of 1.5–40 mg/min of titania were used with silver additions of 1, 2, 4, and 8 wt% compared to titania. Nanoparticle deposits were collected by thermophoretic sampling at six different axial distances from the flame torch head: 3, 5, 10, 12, 15, and 20 cm, of which the all but the last one occurred inside the flame. The deposit samples were analysed by TEM and SAED analysis. The powder samples of the particles were also collected by electric precipitator to XPS and specific surface area analysis. Particle size and effective density after the flame in the aerosol were analysed with SMPS and ELPI. The results from the previous studies i.e. controlling the particle size by setting the production rates of the particles were seen to apply also for this binary system. Characterisation of the deposits showed that when the substrate is inserted into the flame, in the beginning of the flame the deposit is formed by gas phase deposition whereas further down the flame the particles are first formed in the gas phase and then deposited. The location of the transition from gas phase deposition to gas phase nucleation prior to deposition depends on chemical/physical properties (e.g. thermodynamics and gas phase interactions) of the precursor, precursor concentration in the flame and also flame temperature profile. Therefore, the deposit collection distance from the burner also affected the collected particle size and degree of agglomeration. The two component deposits were produced in two different ways: one-step method mixing both precursors in the same solute, and two-step method spraying each precursor separately. The particle morphology differs between these two cases. In one-step method the primary (d _TEM) and agglomerate particle size (d _SMPS) decreased with the amount of silver addition, verifying the fact that when present, the silver has a clear effect on the titania nanoparticle formation and growth.     

Effect of Particle Size and Phase Composition of Titanium Dioxide Nanoparticles on the Photocatalytic Properties

Titanium dioxide (TiO₂) nanoparticles were prepared by the oxidation of titanium tetrachloride (TiCl₄) in a diffusion flame reactor. The average diameter of particles was 15–30 nm and mass fraction of anatase ranged from 40% to 80%. Effects of particle size and phase composition of those TiO₂ nanoparticles on photocatalytic properties such as decomposition of methylene blue, bacteria and ammonia gas were investigated. The degree of decomposition of methylene blue by the TiO₂ nanoparticles under the illumination of the black light was directly proportional to the anatase mass fraction, but inversely to the particle size. The decomposition of bacteria and ammonia gas by the TiO₂ nanoparticles under the illumination of the fluorescent light showed the same trend as in the case of the methylene blue.     

Brownmillerite-Type Crystalline Ca2FeCoO5 Ultrasmall Particles with Single-Nanometer Dimensions as an Active Cocatalyst for Oxygen Photoevolution Reaction

Brownmillerite-type Ca₂FeCoO₅ (CFCO) is one of the most effective catalysts for oxygen evolution reaction (OER), comparable with noble metal oxides. In this study, crystalline CFCO ultrasmall particles with nanometric dimension are synthesized by a reverse micelle method on TiO₂ nanoparticles. The particle size decreases with decreasing molar ratio of water to surfactant. The precursors of CFCO must be calcined after loading on TiO₂ nanoparticles to achieve CFCO ultrasmall particles with several nanometers in size. Interaction between the precursors and TiO₂ is speculated to suppress aggregation of the precursors during calcination. The photocatalytic activity of TiO₂ for OER is improved by loading of CFCO ultrasmall particles with 5 nm, whereas the activity decreases by loading of CFCO with more than 15 nm. Photocatalytic activity of the most active CFCO/TiO₂ is comparable to that of RuO₂/TiO₂. Both the lower edge of conduction band and higher edge of valence band of CFCO are lower and higher than those of TiO₂, respectively, leading to transfer of excited holes and electrons transferred to CFCO and recombination. When the particle size of CFCO becomes several nanometric dimensions, the transferred holes rapidly reach the surface of CFCO and oxidize water molecules before recombination with electrons.     

Particle Sampling and Real Time Size Distribution Measurement in H2/O2/TEOS Diffusion Flame

Growth characteristics of silica particles have been studied experimentally using in situ particle sampling technique from H₂/O₂/Tetraethylorthosilicate (TEOS) diffusion flame with carefully devised sampling probe. The particle morphology and the size comparisons are made between the particles sampled by the local thermophoretic method from the inside of the flame and by the electrostatic collector sampling method after the dilution sampling probe. The Transmission Electron Microscope (TEM) image processed data of these two sampling techniques are compared with Scanning Mobility Particle Sizer (SMPS) measurement. TEM image analysis of two sampling methods showed a good agreement with SMPS measurement. The effects of flame conditions and TEOS flow rates on silica particle size distributions are also investigated using the new particle dilution sampling probe. It is found that the particle size distribution characteristics and morphology are mostly governed by the coagulation process and sintering process in the flame. As the flame temperature increases, the effect of coalescence or sintering becomes an important particle growth mechanism which reduces the coagulation process. However, if the flame temperature is not high enough to sinter the aggregated particles then the coagulation process is a dominant particle growth mechanism. In a certain flame condition a secondary particle formation is observed which results in a bimodal particle size distribution.     

The effects of activated carbon supports on the structure and properties of TiO2 nanoparticles prepared by a sol-gel method

TiO₂-coated activated carbon (TiO₂/AC) composites and pure TiO₂ powders were prepared by a sol-gel method using tetrabutylorthotitanate as a precursor. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), differential thermal analysis (DTA), X-ray photoelectron spectrum (XPS) and nitrogen absorption. The photoactivity of samples was evaluated by methylene blue (MB) degradation. The analysis results show that compared with pure TiO₂ powders, the spherical-shaped TiO₂ particles are well-dispersed in the AC matrix and the size of the resulting TiO₂ crystallites decreases to below 40 nm with increasing phase transformation temperature. The AC matrix creates anti-calcination effects and shows interfacial energy effects that control the growth of the TiO₂ particles, baffle the anatase to rutile phase transition, and cumber the TiO₂ particles to agglomerate. Compared with the surface areas of TiO₂ powders, the combination of TiO₂ and AC forms composites with high surface areas which are slightly affected by calcination temperature. By AC support, the photoactivity of TiO₂ is increased in MB photocatalytic course, possible because active carbon increases photocatalytic activity of TiO₂ particles by producing high concentration of organic compound near TiO₂, and small-size TiO₂ particles are well-dispersed on the surface of AC.     

Synthesis of titania/carbon nanocomposites by polymeric precursor method

Here we describe a single chemical route to obtain highly dispersed nanometric Ni particles embedded in titania/carbon matrixes (amorphous and crystalline). The synthesis of these nanocomposites is based on a polymeric precursor method. The metallic Ni nanoparticles (1-15 nm) were obtained in a single process. We also present the results of photocatalytic experiments involving a series of nanocrystalline composites based on TiO₂/carbon with embedded Ni nanoparticles as nanocatalysts for rhodamine 6G degradation in aqueous solution and investigate the effects of the structure and properties of the nanocomposites on their photocatalytic applications. The effect of the different annealing treatments on the formation of TiO₂ nanophases (anatase and/or rutile), the size of Ni particles and the role of the residual carbon phase on the final solid are also described.     

Dye sensitized solar cells prepared by flames stabilized on a rotating surface

A previously developed flame synthesis method was applied to the preparation of mesoporous titania films for application in dye sensitized solar cells (DSSC). The method combines the synthesis of narrowly sized, ultrafine metal oxide particles with controllable chemical and phase purity and the deposition of these particles into a uniform, porous thin film in a single step. The current work used a series of ethylene–oxygen–argon flames to produce DSSC anode films of wide ranging properties. The performance of the solar cells prepared with these anode films was studied at the fundamental level with respect to variations of the titania crystal phase purity and content resulting from changes primarily from flame stoichiometry changes. Based on the basic relationship established among flame synthesis condition-material property-cell performance, a highly efficient DSSC was designed, which shows photocurrent densities better than some of the best performing cells reported to date. Additional studies have focused on a demonstration of the suitability of the flame process in engineering TiO₂ films structurally and chemically with the potential of further improved DSSC efficiency.     

Measurement of radiative gas and particle emissions in biomass flames

Radiation is the dominant mode of heat transfer near the burner of coal and biomass-fired boilers. Predicting and measuring heat transfer is critical to the design and operation of new boiler concepts. The individual contributions of gas and particle phases are dependent on gas and particle concentration, particle size, and gas and particle temperature which vary with location relative to the flame. A method for measuring the contributions of both gas and particle radiation capable of being applied in harsh high temperature and pressure environments has been demonstrated using emission from particles and water vapor using an optical fiber probe transmitting a signal to a Fourier Transform Infrared (FTIR) spectrometer. The method was demonstrated in four environments of varying gas and particle loading using natural gas and pulverized wood flames in a down-fired 130?kW_th cylindrical reactor. The method generates a gas and particle temperature, gas concentrations (H₂O and CO₂), total gas and particle intensities, and gas and particle total effective emissivity from line-of-sight emission measurements. For the conditions measured, downstream of the luminous flame zone, water vapor and CO₂ radiation were the dominant modes of heat transfer (effective emissivity 0.13–0.19) with particles making a minor contribution (effective emissivity 0.01–0.02). Within a lean natural gas flame, soot emission was low (effective emissivity 0.02) compared to gas (0.14) but within a luminous flame of burning wood particles (500?µm mean diameter) the particles (soot and burning wood) produced a higher effective emissivity (0.17) than the gas (0.12). The measurement technique was therefore found to be effective for several types of combustion environments.     

Synthesis of TiO2 nanoparticles by premixed stagnation swirl flames

A new turbulent, premixed, stagnation swirl flame (SSF) is used to synthesize titanium dioxide (TiO₂) nanopowders. Synthesis conditions under two flame modes, i.e., burner- and substrate-stabilized SSF, are investigated, for the same equivalence ratio, but different inert-dilution ratios. The particles (collected on the substrate) have high anatase purity, with mean diameters of 5–10 nm, determined using BET and TEM, for all cases studied. For the same mean nanoparticle diameter synthesized, the SSF can accommodate higher precursor loading fluxes than that produced by others using laminar premixed stagnation flat flames. Particles in the flow field are determined to be non-agglomerated. For the particles deposited on the substrate, molecular dynamics simulations support the experimental results that sintering and growth of TiO₂ nanoparticles do not occur on the substrate after the deposition, and the high anatase-phase purity is maintained.     

A comparative study of nanoparticles in premixed flames by scanning mobility particle sizer, small angle neutron scattering, and transmission electron microscopy

Scanning mobility particle sizer (SMPS) and transmission electron microscopy (TEM) studies were conducted for TiO₂ and soot particles. The TiO₂ particles were produced from a premixed stagnation ethylene-oxygen-argon flame (? = 0.36) doped with titanium tetraisopropoxide. Soot was generated from a burner-stabilized premixed ethylene-oxygen-argon flame (? = 2.5). The close agreement among SMPS, TEM, and X-ray diffraction results for TiO₂ nanoparticles demonstrates that the probe sampling/mobility measurement technique is accurate for on-line analysis of the size distribution of particles as small as 3 nm in diameter. In the case of soot, notable disagreement between the SMPS and TEM sizes was found and attributable to the fact that the soot taken from the flame studied herein is liquid-like and that upon deposition on the TEM grid, the primary particles do not retain their sphericity. This interpretation is supported by measurements with photo ionization aerosol mass spectrometry, small angle neutron scattering, and thermocouple particle densitometry.     

SnO2/TiO2 mixed oxide particles synthesized in doped premixed H2/O2/Ar flames

SnO₂/TiO₂ mixed oxides with primary particle size ranging between 5 nm d_p 12 nm were synthesized by doping a H₂/O₂/Ar flame with Sn(CH₃)₄ and Ti(OC₃H₇)₄ co-currently. The effects of “flow coordinate,” concentration and flame configurations were investigated with respect to particle size and morphology of the generated mixed oxides. In situ characterization of the mixed oxides was performed using the particle mass spectrometer (PMS), while XRD, TEM, BET and UV–Vis were performed ex situ. Results obtained showed that primary particle size of mixed oxides can be controlled by varying experimental parameters. The mixed oxides have interesting properties compared to those of the pure oxides of TiO₂ and SnO₂, which were also synthesized in flames earlier. Band gap tuning opportunities are possible using mixed oxides.     

Porous TiO2 microspheres with tunable properties for photocatalytic air purification

The synthesis of highly-crystalline porous TiO₂ microspheres is reported using ultrasonic spray pyrolysis (USP) in the presence of colloidal silica as a template. We have exploited the interactions between hot SiO₂ template particles surface and TiO₂ precursor that occur during reaction inside the droplets, to control the physical and chemical properties of the resulting particles. Varying the SiO₂ to titanium precursor molar ratio and the colloidal silica dimension, we obtained porous titania microspheres with tunable morphology, porosity, BET surface area, crystallite size, band-gap, and phase composition. In this regard, we have also observed the preferential formation of anatase vs. rutile with increasing initial surface area of the silica template. The porous TiO₂ microspheres were tested in the photocatalytic degradation of nitrogen oxides (NO_x) in the gas phase. USP prepared nanostructured titania samples were found to have significantly superior specific activity per surface area compared to a commercial reference sample (P25 by Evonik-Degussa).     

Methane-assisted combustion synthesis of nanocomposite tin dioxide materials

Combustion synthesis of tin dioxide (SnO₂) was studied using a new synthesis approach where the combustion environment was augmented to control the temperature and flow conditions using methane as a supplemental fuel. The experiments were carried out at atmospheric pressure using a multi-element diffusion flame burner with a gas-phase precursor for SnO₂ and solid-phase precursor for metal additives. In the methane-assisted (MA) system, the inert carrier gas was replaced with methane as the transport gas for the SnO₂ and metal additive precursors. Two additive precursors were investigated: gold acetate and aluminum acetate. Particle morphology, primary particle size, crystallinity, phase, molecular and elemental composition were studied using transmission electron microscopy, X-ray diffraction, and energy-dispersive spectroscopy. Particle imaging velocimetry and thermocouple measurements provided velocity and temperature data for the synthesis environment experienced by particles. The MA system provided conditions for rapid sintering of particles into large faceted single crystals of SnO₂ (d_p = 46 nm) compared to methane unassisted system (d_p = 19 nm), thus offering a degree of control over grain size. Additionally, large aspect ratio (2.6 ± 0.9) single crystal SnO₂ particles were produced using the MA system. Gold-doped SnO₂ produced using the MA system yielded gold particles encapsulated in a layer of SnO₂. The characteristic reaction-, coagulation- and sintering-times were investigated for nanoparticle formation in the two systems using simplified models. The analysis provided qualitative justification for the trends observed in particle morphology. The modification of characteristic times in this study demonstrates a route for controlling size and morphology of single or multicomponent systems.     

In Situ Charge Characterization of TiO<Subscript>2</Subscript> and Cu–TiO<Subscript>2</Subscript> Nanoparticles in a Flame Aerosol Reactor

Charge distribution characteristics were investigated for nanoparticles synthesized in a diffusion flame aerosol reactor. The nanoparticles considered were pristine TiO₂ and Cu–TiO₂, with Cu dopant concentrations ranging from 1 to 5 wt% with particle size from 25 to 60 nm. In situ measurements were conducted by integrating a tandem differential mobility analyzer (TDMA) experimental setup with the flame aerosol reactor. A charging model was used to identify the important parameters that govern the two charging mechanisms (diffusion and thermo-ionization) in the flame and their relative importance at different operating parameters. The results indicate that TiO₂ and Cu–TiO₂ nanoparticles carry single as well as double unit charges. The charged fraction depends on particle size as well as on dopant concentration. The charged fraction increased with increasing particle size and decreased with copper dopant concentration. Measured charged fractions were similar for both the polarities at different mobility diameters. Based on the flame operating parameters, the calculations indicate that diffusion charging is dominant in the flame, which is consistent with the experimental results.     

Silica-based composite and mixed-oxide nanoparticles from atmospheric pressure flame synthesis

Binary TiO₂/SiO₂ and SnO₂/SiO₂ nanoparticles have been synthesized by feeding evaporated precursor mixtures into an atmospheric pressure diffusion flame. Particles with controlled Si:Ti and Si:Sn ratios were produced at various flow rates of oxygen and the resulting powders were characterized by BET (Brunauer–Emmett–Teller) surface area analysis, XRD, TEM and Raman spectroscopy. In the Si–O–Ti system, mixed oxide composite particles exhibiting anatase segregation formed when the Si:Ti ratio exceeded 9.8:1, while at lower concentrations only mixed oxide single phase particles were found. Arrangement of the species and phases within the particles correspond to an intermediate equilibrium state at elevated temperature. This can be explained by rapid quenching of the particles in the flame and is in accordance with liquid phase solubility data of Ti in SiO₂. In contrast, only composite particles formed in the Sn–O–Si system, with SnO₂ nanoparticles predominantly found adhering to the surface of SiO₂ substrate nanoparticles. Differences in the arrangement of phases and constituents within the particles were observed at constant precursor mixture concentration and the size of the resultant segregated phase was influenced by varying the flow rate of the oxidant. The above effect is due to the variation of the residence time and quenching rate experienced by the binary oxide nanoparticles when varying the oxygen flow rate and shows the flexibility of diffusion flame aerosol reactors.     

Uniform nanoparticles by flame-assisted spray pyrolysis (FASP) of low cost precursors

A new flame-assisted spray pyrolysis (FASP) reactor design is presented, which allows the use of inexpensive precursors and solvents (e.g., ethanol) for synthesis of nanoparticles (10–20 nm) with uniform characteristics. In this reactor design, a gas-assisted atomizer generates the precursor solution spray that is mixed and combusted with externally fed inexpensive fuel gases (acetylene or methane) at a defined height above the atomizing nozzle. The gaseous fuel feed can be varied to control the combustion enthalpy content of the flame and onset of particle formation. This way, the enthalpy density of the flame is decoupled from the precursor solution composition. Low enthalpy content precursor solutions are prone to synthesis of non-uniform particles (e.g., bimodal particle size distribution) by standard flame spray pyrolysis (FSP) processes. For example, metal nitrates in ethanol typically produce nanosized particles by gas-to-particle conversion along with larger particles by droplet-to-particle conversion. The present FASP design facilitates the use of such low enthalpy precursor solutions for synthesis of homogeneous nanopowders by increasing the combustion enthalpy density of the flame with low-cost, gaseous fuels. The effect of flame enthalpy density on product properties in the FASP configuration is explored by the example of Bi₂O₃ nanoparticles produced from bismuth nitrate in ethanol. Product powders were characterized by nitrogen adsorption, X-ray diffraction, X-ray disk centrifuge, and transmission electron microscopy. Homogeneous Bi₂O₃ nanopowders were produced both by increasing the gaseous fuel content and, most notably, by cutting the air entrainment prior to ignition of the spray.     

热处理对爆轰合成的纳米TiO_2混晶的结构相变的影响

采用爆轰法制备了纳米TiO2混晶体,初步研究了不同煅烧温度(600℃和720℃)和不同煅烧时间(1 h,2 h,3.5 h和5 h)对其微结构和结构相变行为的影响,并应用热动力学理论讨论了从锐钛矿相到金红石相的结构相变过程和相变机理.研究表明:随着煅烧温度的升高和煅烧时间的增加,纳米TiO2的粒径逐渐增大,混晶中金红石相的含量逐渐提高.与常规方法制备的纳米TiO2不同的是,在相同煅烧温度和煅烧时间下金红石相的平均生长速率明显低于锐钛矿相.锐钛矿相完全相变为金红石的温度也明显低于常规方法报道的相变温度.该研究会对控制纳米TiO2晶体尺寸和批量合成提供一定的理论和实验指导.