Attachment-driven morphology evolvement of rectangular ZnO nanowires

The rectangular cross-sectional ZnO nanowires were synthesized in a solution method. An attachment-driven growth mechanism was proposed for the morphology evolvement of ZnO nanocrystals from nanoparticles to nanoplates and eventually to nanowires. Due to the pileup attachment of the nanoplates to recrystallize into nanowires, unique one-dimensional (1D) ZnO nanowires with the rectangular cross section were obtained, which is different from those nanowires in the previous reports. It is the first time the evidence that "oriented attachment" can occur not only for nanoparticles but also for nanoplates was obtained, suggesting that "oriented attachment" is an intrinsic behavior for nanosized materials. According to the growth model proposed based on the direct TEM observations, ZnO nanocrystals can be easily controlled as nanoparticles, nanoplates, or nanowires by tuning the synthetic parameters.     

NaOH concentration effect on the oriented attachment growth kinetics of ZnS

In this work, the crystal growth kinetics of ZnS nanoparticles coarsened under 100 degrees C with NaOH concentration from 2 to 8 M was investigated, aiming to study the role of NaOH concentration on the oriented attachment growth kinetics. It reveals that 2 M NaOH is sufficient to lead to two-stage growth kinetics of ZnS nanoparticles, resulting in pure and multistep oriented attachment growth characteristics in the first stage. When the NaOH concentration increases, the rate of crystal growth by oriented attachment mechanism increases, while the time period for crystal growth at the pure oriented attachment stage was similar. We suggest that the concentration of solute is critical to enhance the oriented attachment growth rate and achieve exclusively oriented attachment growth of nanoparticles at a large size scale.     

Oriented attachment kinetics for ligand capped nanocrystals: coarsening of thiol-PbS nanoparticles

In this work, the growth kinetics of thiol-capped PbS nanoparticles was studied. Two-stage growth process was observed, which was controlled first by oriented attachment (OA) mechanism and then by the hybrid Ostwald ripening (OR) and OA mechanism. Different from the NaOH-ZnS system, where OA will occur between any two multilevel nanoparticles, an OA kinetic model only considering the attachment related to original particles was fitted well with the experimental results. Analysis reveals that this model may be a universal one to describe the OA crystal growth process of nanocrystals capped with easily destroyed ligands, such as thiol-ZnS in the previous report. The OA crystal growth characteristics determined by the surface agent were discussed and compared. We propose that with stronger surface capping, the OR growth of nanocrystals is hindered, which facilitates the size controlling via OA kinetics during nanosynthesis.     

Crystal Growth Kinetics of Nanocrystalline ZnS under Surface Adsorption

The crystal growth mechanism,kinetics,and microstructure development play a fundamental role in tailoring the materials with controllable size and morphology. In this study,by introducing the strong surface adsorption of the concentrated NaOH,two-stage crystal growth kinetics of ZnS nanoparticles was observed. In the first stage,the primary particles grow into a size over a hundred times of the original volume and the growth is controlled by the crystal-lographically specific oriented attachment. The first stage data were fitted by the "multistep OA kinetic model" built based on the molecular collision and reaction. In the second stage,following the dispersal of nanoparticles,an abrupt transition from asymptotic to parabola growth kinetics occurs,which can be fitted by a standard Ostwald ripening volume diffusion model. The presence of surface adsorption causes the two-stage growth kinetics and permits an almost exclusive OA-based growth to dominate in the first stage.     

A multistep oriented attachment kinetics: coarsening of ZnS nanoparticle in concentrated NaOH

Crystal growth of ZnS nanoparticles during hydrothermal coarsened in 4 M NaOH occurs via a two-stage process. In the first stage, the primary particles grow into a size over hundred times of the original volume. The initial growth rate can be fitted by an asymptotic curve. High-resolution transmission electron microscope (HRTEM) data indicate that in this stage, crystal growth mainly occurs via a multistep crystallographically specific oriented attachment (OA). The higher the coarsening temperature, the earlier the first stage ends. In the second stage, an abrupt transition from asymptotic to square parabola growth kinetics occurs. The crystal growth data can be fitted by a standard Ostwald ripening (OR) model consistent with growth controlled by dissolution/precipitation of ions in solution. HRTEM data indicate that a minor amount of OA-based growth also occurs in the early period of the second stage. A new multistep OA kinetics model analogous to the reaction between molecules was proposed to illustrate the asymptotic growth in the first stage of coarsening. The effect of concentrated NaOH was discussed and proved to be the key that hindered the OR process, attributing to the almost exclusive pure OA-based growth of ZnS particles in the first stage.     

Mechanism and modeling of nanorod formation from nanodots

A population balance model based on Smoluchowski aggregation kinetics is developed to explain the formation of nanorods from a colloidal suspension of spherical nanoparticles (nanodots). Our model shows that linear pearl-chain aggregates form by the oriented attachment (OA) of nanodots during the early stages of synthesis, since it occurs with a time scale smaller than the coalescence time scale of nanodots present within an aggregate. The slower coalescence step leads to the transformation of the linear pearl-chain aggregate into a smooth nanorod over a longer time scale of many hours, as observed in experiments. The attachment kinetics is modeled by a modified Brownian collision frequency, with the latter decreasing with nanorod length, leading to the experimentally observed slower growth in nanorod length at longer times. The collision frequency also includes the effects of attractive dipole-dipole and van der Waals interactions between nanodots, which are primarily responsible for OA. Our model predictions are general, and they compare favorably with available experimental data in the literature on the distribution of the aspect ratio (length to diameter) of ZnO and ZnS nanorods over different time scales.     

光催化合成金属Ag纳米颗粒的生长机制——晶核密度控制的生长模式转换

利用AgNO3水溶液,通过严格控制TiO2薄膜的化学活性,系统研究了在TiO2表面光催化合成金属Ag纳米颗粒的生长行为。研究发现,光催化合成金属Ag纳米颗粒存在着两个完全不同的生长机制,分别对应着金属Ag纳米颗粒的各向同性和各向异性生长。当溶液浓度较低时,Ostwald熟化(OR)机制主导着金属Ag纳米颗粒的长大过程;当溶液浓度较高时,取向附生(OA)机制决定着金属Ag纳米颗粒长大成纳米片。原位消光光谱分析表明,OR机制和OA机制生长的前期具有相近消光特征,决定金属Ag纳米颗粒生长模式的关键是AgNO3溶液的浓度,更准确地说是金属Ag初级晶核的局域密度。在此基础上提出了有关光催化合成金属Ag纳米颗粒的生长模型。     

A mathematical model for crystal growth by aggregation of precursor metastable nanoparticles

A mathematical model is developed to describe aggregative crystal growth, including oriented aggregation, from evolving pre-existing primary nanoparticles with composition and structure that are different from that of the final crystalline aggregate. The basic assumptions of the model are based on the ideas introduced in an earlier published report [Buyanov and Krivoruchko, Kinet. Katal. 1976, 17, 666-675] to describe the growth of low-solubility metal hydroxides (e.g., iron oxides) by oriented aggregation. It is assumed that primary particles can be described as pseudo-species A, B, and C, which have the following properties: (1) fresh primary particles (colloidally stable inert nanoparticles, denoted as A), (2) mature primary particles (partially transformed nanoparticles at an optimum stage of development for attachment to a growing crystal, denoted as B), and (3) nucleated primary particles (denoted as C1). The evolution of primary particles, A --> B --> C1, is treated as two first-order consecutive reactions. Crystal growth via crystal-crystal aggregation (Ci +) is described using the Smoluchowski equation. The new element of this model is the inclusion of an additional crystal growth mechanism via the addition of primary particles (B) to crystals (Ci): (B + ). Two distinct, but constant, kernels (K not equal K') are used. It is shown that, when K' = 0, a steplike crystal size distribution (CSD) is obtained. Within a range of K'/K values (e.g., K'/K = 10(3)), CSD with multiple peaks are obtained. Comparison with predictions of models that do not include the intermediate stage of primary particles (B) indicates pronounced differences. Despite its simplicity, the model is able to capture the qualitative features of CSD evolution that have been obtained from crystal growth experiments in hematite, which is a system that is believed to undergo oriented aggregation.     

Observation of rotated-oriented attachment during the growth of Ag2S nanorods under mediation of protein

In this study, protein-conjugated Ag2S nanorods were prepared in aqueous solution, and high-resolution transmission electron microscopy (HRTEM) was used to track the whole process of the nanorod growth. Our results showed that the final products were formed via two-step oriented attachment, that is, particle-particle and rod-rod oriented. More interestingly, before oriented attachment, the nanoparticles or nanorods attached without sharing the same lattice plane; they could then rotate to a perfect array and fuse together by eliminating the two high energy surfaces. On the basis of the calculation of surface energy, two-step attachments and rotations were brought forward, and the role of protein in the forming process of nanorods was discussed.     

An analytical expression for the van der Waals interaction in oriented-attachment growth: a spherical nanoparticle and a growing cylindrical nanorod

A mathematical derivation of an analytical expression is presented to evaluate the van der Waals interaction between a sphere and a cylindrical rod. This expression then is applied to study the growth of one-dimensional nanostructures, such as nanorods, using a common growth mechanism in colloidal chemistry, the oriented attachment growth mechanism. Parameters associated with the dimensions and the separation of nanoparticles and nanorods are varied in calculations to assess their influence on the magnitude of the van der Waals interaction.     

Oriented attachment mechanism in anisotropic nanocrystals: a "polymerization" approach.

The kinetic model of stepwise polymerization is revisited, with some adaptations for its application to the kinetics of oriented attachment of nanoparticles in colloidal suspensions, which results in the formation of anisotropic particles. A comparison with experimental data reported in the literature shows good agreement with the model and supports comparisons with other systems.     

Oriented attachment-based assembly of dendritic silver nanostructures at room temperature

How particles aggregate into an interesting dendritic structure has been the object of research for many years because of its importance in understanding physical processes involved and in designing novel materials. In this work, we for the first time describe an oriented attachment-based assembly mechanism for formation of different types of dendritic silver nanostructures at room temperature. It is found that the concentration of both AgNO(3) and p-aminoazobenzene (PA) molecules has a significant effect on the formation and growth of these novel nanostructures. Characterization by transmission electron microscopy (TEM) clearly shows that the dendritic silver nanostructures can be obtained through the preferential oriented growth along a crystallographically special direction. Interestingly, we observe that the oriented attachment at room temperature can also take place between relatively large single-crystalline silver particles with a diameter range from 20 to 60 nm, which may provide a new possibility for the design of novel metal nanostructures by using large metal nanoparticles as building blocks at room temperature. Moreover, a surface-enhanced Raman scattering (SERS) technique is used to investigate the role of PA molecules during the growth of the dendritic silver nanostructures.     

Roles of amorphous calcium phosphate and biological additives in the assembly of hydroxyapatite nanoparticles

Potential mechanisms for formation of highly organized biomineralized structures include oriented crystal growth on templates, the aggregation of nanocrystals by oriented attachment, and the assembly of inorganic nanoparticles mediated by organic molecules into aggregated structures. In the present study, the potential role of amorphous calcium phosphate (ACP) in facilitating the assembly of hydroxyapatite (HAP) nanoparticles into highly ordered structures was evaluated. The physical characteristics of HAP nanoparticles prepared by three different methods were analyzed after extended exposure to additives in solution. Higher order HAP architecture was detected only when the starting particles were aggregates of nanospheres with HAP cores and ACP shells. Enamel-like HAP architecture was produced when the biologic additive was 10 mM glycine or 1.25 microM amelogenin. Large platelike crystals of the type present in bone were induced when the additive was 10 mM glutamic acid. Surface ACP initially links the HAP nanoparticles in a way that allows parallel orientation of the HAP nanoparticles and then is incorporated into HAP by phase transformation to produce a more highly ordered architecture with features that are characteristic for HAP in biologic structures. These studies provide evidence for a new mechanism for assembly of biominerals in which ACP functions by linking HAP nanocrystals while they assume parallel orientations and then is incorporated by phase transformation into HAP molecules that rigidly link HAP nanocrystals in larger fused crystallites. Biologic molecules present during this process of biomineral assembly specifically regulate the assembly kinetics and determine the structural characteristics of the final HAP architecture.     

Highly efficient dye-sensitized solar cells with a titania thin-film electrode composed of a network structure of single-crystal-like TiO2 nanowires made by the "oriented attachment" mechanism

In this study, single-crystal-like anatase TiO(2) nanowires were formed in a network structure by surfactant-assisted self-assembling processes at low temperature. The crystal lattice planes of the nanowires and networks of such wires composed of many nanoparticles were almost perfectly aligned with each other due to the "oriented attachment" mechanism, resulting in the high rate of electron transfer through the TiO(2) nanonetwork with single-crystal-like anatase nanowires. The direction of crystal growth of oriented attachment was controlled by changing the mole ratio of acetylacetone to Ti, that is, regulating both the adsorption of surfactant molecules via control of the reaction rate and the surface energy. A single-crystalline anatase exposing mainly the [101] plane has been prepared, which adsorbed ruthenium dye over 4 times higher as compared to P-25. A high light-to-electricity conversion yield of 9.3% was achieved by applying the titania nanomaterials with network structure as the titania thin film of dye-sensitized solar cells.     

Design-Oriented Modelling of Different Quenching Solutions in Induction Plasma Synthesis of Copper Nanoparticles

The aim of this paper is to compare the effects of different mechanisms underlying the synthesis of copper nanoparticles using an atmospheric pressure radio-frequency induction thermal plasma. A design oriented modelling approach was used to parametrically investigate trends and impact of different parameters on the synthesis process through a thermo-fluid dynamic model coupled with electromagnetic field equations for describing the plasma behaviour and a moment method for describing nanoparticles nucleation, growth and transport. The effect of radiative losses from Cu vapour on the precursor evaporation efficiency is highlighted, with occurrence of loading effect even with low precursor feed rate due to the decrease in plasma temperature. A method to model nanoparticle deposition on a porous wall is proposed, in which a sticking coefficient is employed to model particle sticking on the porous wall used to carry a quench gas flow into the chamber. Two different reaction chamber designs combined with different quench gas injection strategies (injection through a porous wall for “active” quenching; injection of a shroud gas for “passive” quenching) are analysed in terms of process yield and size distribution of the synthetized nanoparticles. Conclusion can be drawn on the characteristics of each quenching strategy in terms of throughput and mean diameter of the synthesized nanoparticles.     

SnO2纳米棒的生长过程、发光性能及光催化活性

在柠檬酸的调控下,采用水热法合成SnO_2纳米棒。利用高分辨透射电子显微镜、X射线衍射、傅里叶变换红外光谱、Brunauer-Emmett-Teller氮吸附、紫外可见漫反射光谱和光致发光光谱研究了SnO_2样品在生长过程中的结构特征。结果表明,SnO_2纳米晶体的生长可进一步分为2个阶段:早期SnO_2纳米晶遵循定向附着模式生长,而后期采取Ostwald熟化模式沿[001]方向缓慢生长。SnO_2纳米粒子在不同阶段的光致发光性能和光催化活性显示:在晶体的生长过程中,这2种性能变化趋势几乎相似,即生长前期性能迅速增加,随后性能逐渐降低。     

Evolution of single crystalline dendrites from nanoparticles through oriented attachment

Single crystalline PbMoO4 dendrites were prepared by a simple hydrothermal method in the presence of surfactants. The formation and evolution of these dendrites was investigated by transmission electron microscopy, and the results clearly showed that the dendritic structure was achieved through oriented attachment of nanoparticles along crystallographically specific direction while the traditional Ostwald ripening mechanism also acted to form the initial particles before attachment and smooth the morphology of the dendrites after attachment.     

Selective Adsorption of Functionalized Nanoparticles to Patterned Polymer Brush Surfaces and Its Probing with an Optical Trap

The site‐specific attachment of nanoparticles is of interest for biomaterials or biosensor applications. Polymer brushes can be used to regulate this adsorption, so the conditions for selective adsorption of phosphonate‐functionalized nanoparticles onto micropatterned polymer brushes with different functional groups are optimized. By choosing the strong polyelectrolytes poly(3‐sulfopropyl methacrylate), poly(sulfobetaine methacrylate), and poly[2‐(methacryloyloxy)ethyl trimethylammonium chloride], it is possible to direct the adsorption of nanoparticles to specific regions of the patterned substrates. A pH‐dependent adsorption can be achieved by using the polycarboxylate brush poly(methacrylic acid) (PMAA) as substrate coating. On PMAA brushes, the nanoparticles switch from attachment to the brush regions to attachment to the grooves of a patterned substrate on changing the pH from 3 to 7. In this manner, patterned substrates are realized that assemble nanoparticles in pattern grooves, in polymer brush areas, or substrates that resist the deposition of the nanoparticles. The nanoparticle deposition can be directed in a pH‐dependent manner on a weak polyelectrolyte, or is solely charge‐dependent on strong polyelectrolytes. These results are correlated with surface potential measurements and show that an optical trap is a versatile method to directly probe interactions between nanoparticles and polymer brushes. A model for these interactions is proposed based on the optical trap measurements.     

In situ investigation of complex BaSO4 fiber generation in the presence of sodium polyacrylate. 2. Crystallization mechanisms

The formation mechanisms of complex BaSO(4) fiber bundles and cones in the presence of polyacrylate sodium salt via a bioinspired approach at ambient temperature in an aqueous environment are reported. These complex organic-inorganic hybrid structures assemble after heterogeneous nucleation of amorphous precursor particle aggregates on polar surfaces, and the crystallization area can be patterned. In contrast to earlier reports, three different mechanisms based on the oriented attachment of nanoparticles were revealed for the formation of typical fibrous superstructures depending on the supersaturation or on the number of precursor particles. (A) High supersaturation (S > 2): large amorphous aggregates stick to a polar surface, form fiber bundles after mesoscopic transformation and oriented attachment, and then form a narrow tip through polymer interaction. (B) Low supersaturation (S = 1.02-2): only a few fibers nucleate heterogeneously from a single nucleation spot, and amorphous particles stick to existing fibers, which results in the formation of a fiber bundle. (C) Vanishing supersaturation (S = 1-1.02): nucleation of a fiber bundle from a single nucleation spot with self-limiting repetitive growth as a result of the limited amount of building material. These growth processes are supported by time-resolved optical microscopy in solution, TEM, SEM, and DLS.     

Controlling oriented aggregation using increasing reagent concentrations and trihalo acetic acid surfactants

Zinc oxide particle growth from homogenous solutions prepared with isopropyl alcohol was monitored using in situ UV–vis spectroscopy, and results show that the rate of ZnO particle growth and the final ZnO nanoparticle size depend strongly upon the concentrations of precursors and the identity of surfactants used. In addition, particle size versus time data was fit using the coarsening model and the simultaneous oriented aggregation and coarsening model in order to evaluate the effect of changing synthetic variables on the mechanism of nanoparticle growth. In general, an increase in growth by oriented aggregation with increasing precursor concentrations was observed, a result that was consistent with results from high-resolution transmission electron microscopy (HRTEM) characterization. The increase in precursor concentrations resulted in an increase in the number concentration of ZnO nanoparticles, which resulted in a higher probability of particle–particle interactions and hence increased growth by oriented aggregation. Additionally, particle growth in solutions of trifluoro-, trichloro-, and tribromoacetate surfactants was studied, and growth by oriented aggregation followed the trend expected based on the number concentration of zinc oxide particles. Growth with trifluoroacetate was an exception, with growth by oriented aggregation substantially suppressed.