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.     

Particle Formation from Single Droplets of Aqueous Solutions of Lead Nitrate

The thermal evolution of droplets of aqueous solution of lead nitrate was studied in a drop-tube furnace, which simulates typical conditions for material synthesis, through spray pyrolysis, and for the thermal destruction of liquid-containing waste. The processes of droplet evaporation, precursor precipitation within the droplet and thermolysis of the precipitated particles were followed by means of the spectral analysis of the ultraviolet light scattered by the aerosol produced during the heating of aqueous droplets (100 μm) of lead nitrate, with different salt concentrations, from ambient temperature up to 1200 K. Dimensions and physico-chemical properties of the droplets/particles were obtained in situ by means of ultraviolet spectra of light scattering (UVSLS) and compared with scanning electron microscopy (SEM) of the sampled material. A plasma generated in the air by an optical breakdown induced by a Nd:YAG laser was employed as the light source in the wavelength range 200–400 nm, thus allowing an exceptionally high photon flux in the ultraviolet region where intense and species-specific interactions with metal species take place. The spray drying process was followed by measuring the light transmitted by the droplets in the backward region. As the drying process progresses, the surface concentration reaches a saturation value and solute is deposited as a solid phase forming a surface crust, which grows steadily. At this point in the process of droplet drying, information was retrieved from the light reflected by the particle interface. Two spectral scattering behaviors were detected at temperatures above the salt precipitation within the droplet. On the basis of Mie calculations and SEM measurements, these behaviors were attributed to lead nitrate particles with typical diameters of the residual droplets (about 50 μm) and to micrometer-sized lead oxide particles. The effect of salt concentration on the drying process and the thermolysis of lead nitrate to oxide was investigated by changing the salt concentration from very dilute conditions up to almost the saturation concentration.     

Multiporous ceria nanoparticles prepared by spray pyrolysis

The morphology of ceria nanoparticles prepared by spray pyrolysis (SP) from cerium (III) acetate and cerium (III) nitrate hydrate precursors were characterized by transmission electron microscopy. It was observed that using the nitrate as a precursor, particles containing multiple pores in the core can be prepared preferentially as opposed to the acetate precursor, when particles with predominantly a single pore were obtained. It was also found that the number of pores in the particles strongly correlates with the particle diameter. It is shown that predominantly multiporous particles for possible catalytic applications may be obtained by selecting particles with diameters between 50 and 100 nm and using cerium nitrate hydrate as a precursor. A mechanism leading to formation of multiporous ceria nanoparticles in the case of using the nitrate precursor in the SP process is discussed based on thermogravimetric analysis (TGA) data.     

Emulsion Combustion and Flame Spray Synthesis of Zinc Oxide/Silica Particles

Two flame spray methods, emulsion combustion method (ECM) and flame spray pyrolysis (FSP), were compared for synthesis of pure and mixed SiO₂ and ZnO nanoparticles. The effect of silicon precursor was investigated using liquid hexamethyldisiloxane (HMDSO) or SiO₂ sol, while for ZnO zinc acetate (ZA) was used. Gas phase reaction took place when using HMDSO as Si precursor, forming nanoparticles, whereas the SiO₂ sol used as Si source was not evaporated in the flame, creating large aggregates of the sol particles (e.g. 1 m). The FSP of ZA produced ZnO homogeneous nanoparticles. Lower flame temperatures in ECM than in FSP resulted in mixed gas and liquid phase reaction, forming ZnO particles with inhomogeneous sizes. The FSP of HMDSO and ZA led to intimate gas-phase mixing of Zn and Si, suppressing each other's particle growth, forming nanoparticles of 19 nm in BET-equivalent average primary particle diameter. Nucleation of ZnO and SiO₂ occurred independently by ECM of HMDSO and ZA as well as by FSP of the SiO₂ sol and ZA, creating a ZnO and SiO₂ mixture. The reaction of ZnO with SiO₂ was likely to be enhanced by ECM of the SiO₂ sol and ZA where both Zn and Si species were not evaporated completely, resulting in ZnO, -willemite and Zn_1.7SiO₄ mixed phase.     

Assisted spray pyrolysis production and characterisation of ZnO nanoparticles with narrow size distribution

Nano-sized ZnO particles with a narrow size distribution and high crystallinity were prepared from aqueous solutions with high concentrations of Zn²⁺ containing salts and citric acid in a conventional spray pyrolysis setup. Structure, morphology and size of the produced material were compared to ZnO material produced by simple spray pyrolysis of zinc nitrates in the same experimental setup. Using transmission electron microscopy and electron tomography it has been shown that citric acid-assisted spray pyrolysed material is made up of micron sized secondary particles comprising a shell of lightly agglomerated, monocrystalline primary ZnO nanoparticles with sizes in the 20–30 nm range, separable by a simple ultrasonic treatment step.     

Homogeneous ZnO Nanoparticles by Flame Spray Pyrolysis

Zinc oxide (ZnO) nanoparticles were made by flame spray pyrolysis (FSP) of zinc acrylate–methanol–acetic acid solution. The effect of solution feed rate on particle specific surface area (SSA) and crystalline size was examined. The average primary particle diameter can be controlled from 10 to 20nm by the solution feed rate. All powders were crystalline zincite. The primary particle diameter observed by transmission electron microscopy (TEM) was in agreement with the equivalent average primary particle diameter calculated from the SSA as well as with the crystalline size calculated from the X-ray diffraction (XRD) patterns for all powders, indicating that the primary particles were rather uniform in diameter and single crystals. Increasing the solution feed rate increases the flame height, and therefore coalescence and/or surface growth was enhanced, resulting in larger primary particles. Compared with ZnO nanoparticles made by other processes, the FSP-made powder exhibits some of the smallest and most homogeneous primary particles. Furthermore, the FSP-made powder has comparable BET equivalent primary particle diameter with but higher crystallinity than sol–gel derived ZnO powders.     

Synthesis of Single Crystalline ZnO Nanoparticles by Salt-Assisted Spray Pyrolysis

LiNO₃ was used as a shield in the preparation of single crystalline ZnO particles by a spray pyrolysis process in order to prevent agglomeration and enhance the crystallinity of the ZnO. LiNO₃ was added to a precursor solution of zinc acetate dihydrate prior to its atomization by means of an ultrasonic transducer. Agglomerate-free particles having a mean particle size of 26 nm were successfully obtained after washing the product. X-ray diffractometry, field-emission scanning electron micrograph and transmission electron micrograph data indicate that the size and morphology of ZnO were strongly influenced by the operating temperature used and the residence time of the particle in the reactor.     

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.     

Immobilized TiO<Subscript>2</Subscript> nanoparticles produced by flame spray for photocatalytic water remediation

Anatase/rutile mixed-phase titanium dioxide (TiO₂) photocatalysts in the form of nanostructured powders with different primary particle size, specific surface area, and rutile content were produced from the gas-phase by flame spray pyrolysis (FSP) starting from an organic solution containing titanium (IV) isopropoxide as Ti precursor. Flame spray-produced TiO₂ powders were characterized by means of X-ray diffraction, Raman spectroscopy, and BET measurements. As-prepared powders were mainly composed of anatase crystallites with size ranging from 7 to 15 nm according to the synthesis conditions. TiO₂ powders were embedded in a multilayered fluoropolymeric matrix to immobilize the nanoparticles into freestanding photocatalytic membranes. The photocatalytic activity of the TiO₂-embedded membranes toward the abatement of hydrosoluble organic pollutants was evaluated employing the photodegradation of rhodamine B in aqueous solution as test reaction. The photoabatement rate of best performing membranes significantly overcomes that of membranes produced by the same method and incorporating commercial P25-TiO₂.     

Size Tunable Synthesis of Highly Crystalline BaTiO3 Nanoparticles using Salt-Assisted Spray Pyrolysis

Highly crystalline, dense BaTiO₃ nanoparticles in a size range from 30 to 360nm with a narrow size distribution (_g = 1.2–1.4) were prepared at various synthesis temperatures using a salt-assisted spray pyrolysis (SASP) method without the need for post-annealing. The effect of synthesis temperature on particle size, crystallinity and surface morphology of the nanoparticles were characterized by X-ray diffraction and scanning/transmission electron microscopy. The nature of the crystalline structure was analyzed by Rietveld refinement and Raman spectroscopy. The particle size decreased with decreasing operation temperature. The crystal phase was transformed from tetragonal to cubic at a particles size of about 50nm at room temperature. SASP can be used to produce high weight fraction of tetragonal BaTiO₃ nanoparticles down to 64nm in a single step.     

Synthesis and characterization of indium–tin oxide (ITO) nanoparticles

Synthesis and characterization of ITO nanoparticles were investigated in the present study. To synthesize the ITO nanoparticles flame spray pyrolysis was introduced. The average particle diameter increased with an increase in the molar concentration of the precursor. Raising the maximum flame temperature by controlling the gas flow rates also led to an increase in the average diameter of the particles. The crystalline ITO nanoparticles were synthesized, and their average primary particle diameters ranged from 11 to 20 nm. ITO thin films were prepared with a sol consisted of the ITO nanoparticles and a polymer binder. Effect of average particle diameter of the ITO nanoparticles on the transparency and the surface resistance of the ITO thin films were measured. As the average particle diameter increased, the transparency and the surface resistance decreased from 92 to 83% and from 1.0 × 10⁴ to 0.8 × 10⁴Ω/□, respectively.     

Incorporation of film theory in single droplet combustion model for prediction of precursor release in flame spray pyrolysis

The precursor release rate during flame synthesis has been shown to influence the uniformity of synthesized particles. However, its quantification through single droplet combustion modeling was based on its immediate release from the droplet without considering the effect of the mass boundary layer surrounding the droplet. Here, the film theory is applied with the single droplet combustion model to understand the precursor release in the droplet. The resulting mass boundary layer thickness is coupled with droplet temperature to qualitatively investigate precursor release in flame spray pyrolysis. It is shown that small droplets can enhance the precursor release rate due to their small mass boundary layer thickness and higher heating rate. Increasing the EHA content in the EHA/toluene solvent mixture reduces the mass boundary layer thickness and increases the droplet temperature due to EHA's low specific heat capacity. Using droplet sizes estimated by the phase Doppler interferometry, the model shows that the temporal droplet temperature profile remains relatively constant for six synthesis conditions. Concurrently, the mass boundary layer thickness is increased when the liquid and oxygen flow rates are reduced, and atomizing pressure drop is enhanced, resulting in the overall suppression of precursor release from the droplet and consequently increased formation of smaller-size primary particles. Insight into the relative tendencies of the pure gas-to-particle formation route during the synthesis was also derived as a function of the synthesis conditions. This new methodology for the characterization of precursor release is essential for a more accurate understanding and design of homogeneous nanomaterial using flame spray pyrolysis.     

UV-Broadband Light Scattering Measurements During Metallic Particle Formation in a Combustion-Like Environment

The thermal evolution of aqueous solution droplets of lead and nickel nitrate was studied experimentally in a drop-tube furnace operated up to 1300 K. Dimensions and physico-chemical properties of the droplets/particles were obtained by coupling the analysis of the spectra of ultraviolet light scattered by the produced aerosol with scanning electron microscopy and numerical simulation of the scattering spectra by Mie theory. Lead nitrate forms solid hollow particles with sizes of the order of the original droplets during the drying process, whereas at higher temperature it decomposes, forming spherical micrometer-sized particles of lead oxide and even submicrometer-sized particles of pure lead. Nickel nitrate never forms solid particles owing to its high solubility in water, but precipitates as nickel hydroxide particles in the temperature range where this intermediate decomposition product is formed. At higher temperatures the decomposition of nickel hydroxide and the formation of oxide particles in the micrometer size range is observed. The mutual interaction of the salt properties were analyzed by studying the behavior of a lead–nickel nitrate mixture in the drop-tube reactor. The main peculiarity of the mixture evolution is the formation of composite particles of lead nitrate in a nickel hydroxide shell. The combined use of in situ ultraviolet spectral scattering and ex-situ scanning electron microscopy, along with the simulations of the scattering spectra by Mie theory, allows us to compile a database of scattering spectra attributed to specific droplets or particles of given chemical properties and size which may be useful for the continuous detection and speciation of metallic aerosols at the exit of real plants.     

Production of cobalt and nickel particles by hydrogen reduction

Cobalt and nickel nanoparticles were produced by hydrogen reduction reaction from cobalt or nickel chloride precursor vapour in nitrogen carrier gas. This aerosol phase method to produce nanoparticles is a scalable one-step process. Two different setups were introduced in particle production: a batch type reactor and a continuously operated reactor. Common feature in these setups was hydrogen mixing in a vertical flow reactor. The process was monitored on-line for particle mass concentration and for gas phase chemical reactions. Tapered element oscillating microbalance measured the particle mass concentration and Fourier transform infrared spectroscopy was used to monitor relevant gas phase species. The produced cobalt and nickel particles were characterised using transmission electron microscopy and x-ray diffraction. The produced cobalt and nickel particles were crystalline with cubic fcc structure. Twinning was often observed in cobalt particles while nickel particles were mostly single crystals. The cobalt particles formed typically long agglomerates. No significant neck growth between the primary particles was observed. The primary particle size for cobalt and nickel was below 100 nm.     

Size‐Dependence of the Melting Temperature of Individual Au Nanoparticles

Nanoparticles have an immense importance in various fields, such as medicine, catalysis, and various technological applications. Nanoparticles exhibit a significant depression in melting point as their size goes below ≈10 nm. However, nanoparticles are frequently used in high temperature applications such as catalysis where temperatures often exceed several 100 degrees which makes it interesting to study not only the melting temperature depression, but also how the melting progresses through the particle. Using high‐resolution transmission electron microscopy, the melting process of gold nanoparticles in the size range of 2–20 nm Au nanoparticles combined with molecular dynamics studies is investigated. A linear dependence of the melting temperature on the inverse particle size is confirmed; electron microscopy imaging reveals that the particles start melting at the surface and the liquid shell formed then rapidly expands to the particle core.     

Nanoparticle Microreactor: Application to Synthesis Of Titania by Thermal Decomposition of Titanium Tetraisopropoxide

The nanoparticle microreactor (NPMR) is a new concept that we have introduced to describe a very small-scale system capable of converting an aerosol precursor to solid particles. The liquid precursor of about 1 µl is injected by a syringe through a septum into a tubular evaporator of 1.0 cm³ in volume with stopcocks at both ends. The evaporator has been preheated by a heating tape to a temperature sufficiently high for vaporization to occur in half a minute. By opening the stopcocks, the vaporized precursor is transported by a carrier gas stream into a quartz tube which is mounted along the axis of a tubular furnace. The nanoparticle aggregates produced in the reactor are sampled by deposition on an electron micrograph grid at the reactor exit. The NPMR was applied first to the synthesis of TiO₂ particles by thermal decomposition of titanium tetraisopropoxide (TTIP) in a nitrogen carrier gas, with TTIP concentrations varying from 1.0 to 7.0 mol% or 2.35×10^–6 to 1.65×10^–5 in TiO₂ volume loading, and decomposition temperatures from 300°C to 1000°C. Studies were made with a 2 mm reaction tube and a 4 mm tube with sheath gas. With the 2 mm tube, a considerable fraction of the TTIP precursor was consumed at the wall by surface reaction, resulting in very small particles. With the 4 mm tube, the primary particle size was comparable to that reported in the literature for steady flow experiments using a 22.2 mm tube. Primary particle sizes ranged from 200 to 400 nm. Depending on TTIP concentration and reactor temperature, the particles exhibited a bimodal size distribution, probably due to a two-stage nucleation. A fourfold increase in the gas flow rate had little effect on particle size, indicating that particle growth ended early, within one-fourth the tube length. Residence time in the reactor was between 0.35 and 1.4 s, and total run time about 1 min. The NPMR has potential for rapid assembly of large databases and is adaptable to combinatorial discovery of nanoparticles with novel properties. Design requirements for an ideal aerosol microreactor are discussed briefly.     

A new dual matrix burner for one-dimensional investigation of aerosol flames

In spray-flame synthesis of nanoparticles, a precise understanding of the reaction processes is necessary to find optimal process parameters for the formation of the desired products. Coupling the chemistries of flame, solvent, and gas-phase species initially formed from the particle precursor in combination with the complex flow geometry of the spray flame means a special challenge for the modeling of the reaction processes. A new burner has been developed that is capable to observe the reaction of precursor solutions frequently used in spray-flame synthesis. The burner provides an almost flat, laminar, and steady flame with homogeneous addition of a fine aerosol and thus enables detailed investigation and modeling of the coupled reactions independent of spray formation and turbulent mixing. With its two separate supply channel matrices, the burner also enables the use of reactants that would otherwise react with each other already before reaching the flame. These features enable the investigation of a wide range of flame-based synthesis methods for nanoparticles and, due to the flat-flame geometry, kinetics models for these processes can be developed and validated. This work describes the matrix burner development and its gas flow optimization by simulation. Droplet-size distributions generated by ultrasonic nebulization and their interaction with the burner structure are investigated by phase-Doppler anemometry. As an example for nanoparticle-forming flames from solutions, iron-oxide nanoparticle-generating flames using iron(III) nitrate nonahydrate dissolved in 1-butanol were investigated. This effort includes measurements of two-dimensional maps of the flame temperature by a thermocouple and height-dependent concentration profiles of the main species by time-of-flight mass spectrometry. Experimental data are compared with 1D simulations using a reduced reaction mechanism. The results show that the new burner is well suited for the development of reaction models for precursors supplied in the liquid phase usually applied in spray-flame synthesis configurations.     

Microflow reactor synthesis of palladium nanoparticles stabilized with poly(benzyl ether) dendron ligands

A simple glass capillary microflow reactor system has been applied for the synthesis of palladium nanoparticles by thermal decomposition of palladium acetate (Pd(OAc)₂) in diphenyl ether in the presence of poly(benzyl ether) dendron ligands (PBED Gn-NH₂, n = 1–3) as a stabilizer. Effect of hydrodynamic parameters (capillary diameter, linear flow rate, volume flow rate, and reaction temperature) and concentrations (precursor and stabilizer) on the particle size was investigated. The particle size can be controlled by varying linear flow rate and temperature as well as ligand/precursor concentration ratio. Volume flow rate does not affect the particle size when the linear flow rate is held constant for different capillary diameters (150–320 μm). Unlike batch systems, in this microreactor system, smaller particles are produced at low ligand concentrations when the molar ratio of the ligand to metal precursor ranged from 1 to 5. As another characteristic of the microreactor synthesis, the concentration of the Pd precursor can be increased (up to 27 mM) with maintaining a constant particle size (3.1 ± 0.2 nm) and a good monodispersity, while in the batch system a significant increase and broadening in the particle size are observed with increasing precursor concentration.     

Y2Si2O7:Eu/SiO2 core shell phosphor particles prepared by flame spray pyrolysis

This paper reports the synthesis of core shell phosphor particles (Y₂Si₂O₇:Eu/SiO₂) produced by flame spray pyrolysis with yttrium and europium nitrates and colloidal silica dispersed precursor solutions. Particles of various structures were produced, including heterogeneous, core shell and non-spherical core shell particles, depending on the synthesis conditions; the ideal core shell structure was obtained under the highest flame temperature and high silicon concentration in the precursor solution. Based on the phase diagram, the formation of the core shell structure was caused by the separation of each component at the liquid phase in the synthesis route. In the energy-dispersive X-ray spectroscopy, yttrium could be detected only at the core part of the particle, while silicon and oxygen could be detected at both the shell and core parts. Under ultraviolet excitation, the ideal core shell particles of Y₂Si₂O₇:Eu showed photoluminescent characteristics. Consequently, it could be concluded that Y₂Si₂O₇:Eu/SiO₂ core shell phosphor particles were successfully synthesized by flame spray pyrolysis.     

Morphology and formation mechanism of ceria nanoparticles by spray pyrolysis

Ceria-based materials are used in industrial applications such as catalyst supports, carbon monoxide reduction catalysts, and solid oxide fuel cell electrolytes. Various applications require different morphological particles. The ceria particles with various morphologies from the precursors of cerium(III) acetate hydrate, cerium(IV) nitrate hydrate, and cerium(IV) ammonium nitrate were prepared by spray pyrolysis (SP) because SP has the potential for simple and continuous process. The precursor behaviors and the particle morphologies were characterized by thermogravimetric analysis and by transmission electron microscopy. Four main morphologies of solid spherical, hollow spherical with a single pore, hollow concave, and hollow spherical with multiple pores were observed. The experimental results suggest that the morphological formation mechanism is highly correlated with the factors of precursor solubilities, solvent evaporation rates (droplet diameters), and precursor melting temperatures. In addition, total concentrations of cerium(III) in the ceria particles from various precursors were examined using X-ray photoelectron spectroscopy.