Mechanism of silver particle formation during photoreduction using in situ time-resolved SAXS analysis

Formation mechanisms of silver (Ag) particles in an aqueous ethanol solution of poly(N-vinyl-2-pyrrolidone) (PVP) by the photoreduction of AgClO(4) were investigated by means of in situ small-angle X-ray scattering (SAXS) measurements. The kinetics of association process (nucleation, growth, and coalescence) of Ag(0) atoms to produce Ag particles was successfully revealed by the quantitative SAXS analysis for the number-average of radius (R(0)), number of particles (n(Ag)), reduced standard deviation (σ(R)/R(0)), and volume fraction (?(Ag)) of Ag particles produced by the photoreduction. The rate of nucleation and growth process during Ag particle formation strongly depend on the initial metal concentration. The time evolution of radius and number of Ag particles indicates that a mechanism of Ag particle formation is composed of different three processes, that is, reduction-nucleation, Ostwald ripening, and particle coalescence. In a rapid reduction-nucleation process, small nuclei or particles (average radius ～2.5 nm) are produced by an autocatalytic reduction. After the formation of small nuclei or particles proceeds, Ostwald ripening and particle coalescence, predicted by the Lifshitz-Slyozov-Wagner theory (LSW theory), subsequently occur, resulting in the particle growth (average radius ～11.5 nm).     

“非保护型”金属胶体纳米簇形成机理研究

碱-乙二醇法制备的"非保护型"金属及合金纳米簇由表面吸附的溶剂分子和简单离子实现稳定化,它们被广泛用于制备高性能复相催化剂和研究复相催化剂中的尺寸、组成、载体表面基团以及修饰剂对催化性能的影响。关于此类非保护金属纳米簇的形成过程及机理的认识尚有待进一步深化。本文采用原位快速扫描X射线吸收精细结构谱(QXAFS)、原位紫外-可见(UV-Vis)吸收光谱、透射电子显微镜和动态光散射技术研究了碱-乙二醇法合成中非保护型金属胶体纳米簇的形成过程与机理。结果表明,在碱-乙二醇法合成非保护型Pt金属纳米簇的过程中,室温下即有部分Pt(IV)被还原至Pt(II)。随着反应温度的升高,OH-逐渐取代与Pt离子配位的Cl-,在Pt―Pt键形成之前,反应体系的UV-Vis吸收光谱中可观察到明显的纳米粒子的散射信号,原位QXAFS分析表明Pt纳米簇是由Pt氧化物纳米粒子还原所形成的;在Ru金属纳米簇的形成过程中,OH-首先取代了Ru Cl_3中的Cl~-,形成羟基配合物Ru(OH) _6~(3-),后者进一步缩合形成氧化钌纳米粒子,最终Ru金属纳米簇由乙二醇还原氧化钌纳米粒子形成。由于先形成了氧化物纳米粒子,后续的还原反应被限制在氧化物纳米粒子内,使最终得到的非保护型金属纳米簇具有尺寸小、分布窄的特点。本工作所获得的知识对发展高性能能源转化催化剂、精细化学合成催化剂、传感器等功能体系具有重要意义。     

Dissolution kinetics of titanium dioxide nanoparticles: the observation of an unusual kinetic size effect

Different types of industrially produced titanium dioxide nanoparticles and a precipitated titanium dioxide have been dissolved in aqueous NaCl solutions at temperatures of 25 and 37 degrees C. The titanium concentration in solution with regard to dependence on time has been determined up to 3000 h after starting the dissolution experiment. The effect of particle size, pH value, temperature, background electrolyte concentration, and mass concentration of titanium dioxide exposed to the liquid phase has been studied. The nanoparticles have been characterized by N2 physisorption measurements and XRD. The total dissolved titanium in solution has been determined by adsorptive stripping voltammetry (AdSV) and inductively coupled plasma mass spectrometry (ICP-MS). A new kinetic size effect has been observed. It turns out that this effect can be explained by applying an already existing phenomenological thermodynamic and kinetic model. The model describes all possible phenomena in a colloidal dispersion, nucleation, growth of particles, Ostwald ripening, and dissolution of particles using a uniform concept.     

Surface chemical states of gold nanoparticles prepared using the solution-plasma method in a CsCl aqueous solution

In this study, gold nanoparticles (AuNPs) prepared in a 5 mM CsCl aqueous solution using the solution-plasma method are characterized via transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy with synchrotron radiation (SR-XPS). The particle diameter is measured over the process time via TEM. During the solution-plasma process, small particles of 2.1 to 2.2-nm diameter are generated in the CsCl aqueous solution; these particles then enlarge via Ostwald ripening over time until they reach an equilibrium size of ~13 nm after 36 days. In addition, the surface chemical states of the AuNPs are characterized at different depths via SR-XPS. The SR-XPS measurements obtained using incident X-ray energy (hν) of 945.0 eV revealed that Cs─Au, Cl─Au, and Cs─Cl─Au bonds are present 1.2 nm below the surface. The measurements obtained at an incident X-ray energy of 2515.0 eV showed that Cs─Cl─Au bonding is also present 2.5 nm below the surface, indicating that Cs and Cl strongly interact with Au. The TEM and SR-XPS measurements revealed that 2 processes occur cyclically during the growth process via Ostwald ripening: (i) the Cs and Cl in the aqueous solution adsorb on the AuNP surface and (ii) Au atoms subsequently bond to the AuNPs surface.     

Nucleation reaction dynamics of Pt nanoparticles observed by the heterodyne transient grating method

The nucleation reaction dynamics of platinum nanoparticles in the photoreduction process of H(2)Pt(IV)Cl(6) solution were investigated by the heterodyne transient grating (HD-TG) method. The formation mechanism of platinum nanoparticles was considered, supported by information obtained from UV/VIS absorption spectroscopy during the reaction and SEM images of the generated nanoparticles. In particular, the roles of poly(N-vinyl-2-pyrrolidone) (PVP) as a protective polymer and ethanol as a solvent were studied. The chemical species involved in the reaction can be identified from the diffusion coefficients obtained from HD-TG measurements; the species observed by UV pulse irradiation were assigned to H(2)Pt(IV)Cl(6) as a reactant species and H(2)Pt(II)Cl(4) and Pt nuclei as product species. It was observed that the amounts of the reactant and product species increased, and many homogeneous nanoparticles were generated, by an increase in PVP concentration. The addition of ethanol to the solvent showed a larger effect on the enhancement of the reduction of H(2)Pt(IV)Cl(6) than that of PVP; however, it did not lead to Pt nuclei formation in the order of seconds. Nevertheless, because nanoparticle formation was confirmed by UV/VIS absorption spectroscopy and SEM images, the formation of nanoparticles following nuclei formation must have proceeded via a slow reaction. Therefore, nucleation and nanoparticle formation are considered to occur on a longer time scale than 10 s in water/ethanol solvent.     

Dissolution kinetics of oxidic nanoparticles: The observation of an unusual behaviour

The solubility of nanoparticles was measured in aqueous solution as a function of time, and oxides of aluminium, silicon, titanium, and zirconium were investigated. Our solubility results show a maximum at the beginning of the dissolution process, whereas over time, the solubility levels are shown to decrease. Depending on the special conditions the solubility maximum may exceed the long-time solubility of the nanoparticles by several orders of magnitude. This behaviour is called as kinetic size effect. The extent of the effect depends on the size, surface tension and mass of the particles exposed to dissolution. It will always be of practical interest if a larger quantity of nanoparticles is brought into contact with a solvent, even when the equilibrium solubility data appears negligible. A rigorous thermodynamic and kinetic analysis of a colloidal system, which includes nucleation, particle growth, Ostwald ripening, and dissolution of particles, shows at least a qualitative agreement between all the experimental results and model calculations.     

Silver nanoparticles capped by oleylamine: formation, growth, and self-organization

Nearly monodisperse silver nanoparticles have been prepared in a simple oleylamine-liquid paraffin system. Intensive study has found that the formation process of silver nanoparticles could be divided into three stages: growth, incubation, and Ostwald ripening stages. Ultraviolet-visible spectroscopy, transmission electron microscopy (TEM), and high-resolution TEM have all demonstrated the occurrence of Ostwald ripening, which could result in better control over the size and size distribution of silver nanoparticles. SAXS (small-angle X-ray scattering) results show that the as-obtained silver nanoparticles can self-assemble into ordered arrays. The possible reduction mechanism of silver ions by oleylamine is related to the Ag+-mediated conversion of primary amines to nitriles.     

In situ optical microspectroscopy approach for the study of metal transport in dielectrics via temperature- and time-dependent plasmonics: Ag nanoparticles in SiO2 films

This study proposes in situ optical microspectroscopy as a means for the investigation of particle growth and metal transport in nanocomposite systems based on the temperature- and time-dependent optical response of the material. The technique has been successfully employed for the real-time monitoring of the growth of Ag nanoparticles (NPs) in SiO(2) films deposited on soda-lime glass during thermal processing in nitrogen atmosphere. By fitting the surface plasmon resonance (SPR) profiles with spectra calculated by Mie theory in the quasi-static regime, the time variation in effective Ag particle size was determined and subsequently analyzed in the context of crystal growth theory. The Ag NPs were indicated to grow first through a diffusion-based process and subsequently via Ostwald ripening. The experimental determination of the activation energies associated with each one of the particle growth mechanisms was carried out based on the time evolution of the SPR of Ag NPs. Arrhenius-type analyses of a set of time-dependent isotherms allowed for estimating the activation energies at 2.3 eV for the diffusion-based growth and 2.8 eV for the ripening stage.     

In situ time-resolved XAFS study on the structural transformation and phase separation of Pt3Sn and PtSn alloy nanoparticles on carbon in the oxidation process

The dynamic behavior and kinetics of the structural transformation of supported bimetallic nanoparticle catalysts with synergistic functions in the oxidation process are fundamental issues to understand their unique catalytic properties as well as to regulate the catalytic capability of alloy nanoparticles. The phase separation and structural transformation of Pt(3)Sn/C and PtSn/C catalysts during the oxidation process were characterized by in situ time-resolved energy-dispersive XAFS (DXAFS) and quick XAFS (QXAFS) techniques, which are element-selective spectroscopies, at the Pt L(III)-edge and the Sn K-edge. The time-resolved XAFS techniques provided the kinetics of the change in structures and oxidation states of the bimetallic nanoparticles on carbon surfaces. The kinetic parameters and mechanisms for the oxidation of the Pt(3)Sn/C and PtSn/C catalysts were determined by time-resolved XAFS techniques. The oxidation of Pt to PtO in Pt(3)Sn/C proceeded via two successive processes, while the oxidation of Sn to SnO(2) in Pt(3)Sn/C proceeded as a one step process. The rate constant for the fast Pt oxidation, which was completed in 3 s at 573 K, was the same as that for the Sn oxidation, and the following slow Pt oxidation rate was one fifth of that for the first Pt oxidation process. The rate constant and activation energy for the Sn oxidation in PtSn/C were similar to those for the Sn oxidation in Pt(3)Sn/C. In the PtSn/C, however, it was hard for Pt oxidation to PtO to proceed at 573 K, where Pt oxidation was strongly affected by the quantity of Sn in the alloy nanoparticles due to swift segregation of SnO(2) nanoparticles/layers on the Pt nanoparticles. The mechanisms for the phase separation and structure transformation in the Pt(3)Sn/C and PtSn/C catalysts are also discussed on the basis of the structural kinetics of the catalysts themselves determined by the in situ time-resolved DXAFS and QXAFS.     

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.     

Numerical analysis of Ostwald ripening in two-dimensional systems

This work addresses theory of Ostwald ripening based on the continuum second order kinetic equation for the size distribution of embryos over sizes. Numerical studies are performed with two-dimensional condensing systems having different growth laws of islands, using different forms of kinetic equation. The material influx into the system is terminated to enable the Ostwald ripening process. We obtain numerical solutions for the size distributions with and without fluctuation effects described by the second derivative in the kinetic equation. We show that fluctuations lead to a considerable broadening of size distribution at the early Ostwald ripening step in the diffusion limited growth of islands. Comparison of our numerical distributions with the deterministic Lifshitz-Slezov shape shows that the latter in principle withstands fluctuations. However, the correspondence between the numerical large time asymptotes and the Lifshitz-Slezov spectra is not perfect, particularly in the diffusion-induced growth regime, and becomes worse when the fluctuations are included.     

Mechanism of YF3 nanoparticle formation in reverse micelles

This article reports an investigation of the mechanism of YF(3) nanoparticle formation in two variants of the reverse microemulsion precipitation method. These two variants involve the addition of F(-), either as a microemulsion or directly as an aqueous solution, to Y(3+) dispersed in nonionic reverse micelles. The two methods yield amorphous and single-crystal nanoparticles, respectively. The kinetics of reagent mixing are studied by (19)F NMR and colorimetric model reactions, and the particle growth is monitored by TEM. Mixing and nucleation are shown to occur within seconds to minutes whereas particle growth continues for 4 to 48 h, depending on the particle type. Moreover, the growth rate remains constant during most of the growth period, indicating that Ostwald ripening is the most probable growth mechanism. The single-emulsion method also produces a minority amorphous population that exhibits significantly different growth kinetics, attributed to a coagulation mechanism. Secondary growth experiments, involving the addition of precursor ions to mature particles, have been conducted to evaluate the relative importance of nucleation and the competitive growth of existing particle populations. The key differences between the two methods reside in the nucleation step. In the case of the classical method, nucleation occurs upon intermicellar collisions and under conditions of comparable concentrations of Y(3+) and F(-). This method generates more numerous stable nuclei and smaller particles. In the single-microemulsion method, nucleation occurs in the presence of excess F(-) through the interaction of Y(3+)-containing micelles with microdroplets of aqueous F(-). These conditions lead to the formation of crystalline particles and a wider size distribution of unstable nuclei.     

A kinetic model to describe nanocrystal growth by the oriented attachment mechanism.

The classical model of particle coagulation on colloids is revisited to evaluate its applicability on the oriented attachment of nanoparticles. The proposed model describes well the growth behavior of dispersed nanoparticles during the initial stages of nanoparticle synthesis and during growth induced by hydrothermal treatments. Moreover, a general model, which combines coarsening (i.e., Ostwald ripening) and oriented attachment effects, is proposed as an alternative to explain deviations between experimental results and existing theoretical models.     

Heterogeneous Au-Pt nanostructures with enhanced catalytic activity toward oxygen reduction

Heterogeneous Au-Pt nanostructures have been synthesized using a sacrificial template-based approach. Typically, monodispersed Au nanoparticles are prepared first, followed by Ag coating to form core-shell Au-Ag nanoparticles. Next, the galvanic replacement reaction between Ag shells and an aqueous H(2)PtCl(6) solution, whose chemical reaction can be described as 4Ag + PtCl(6)(2-)→ Pt + 4AgCl + 2Cl(-), is carried out at room temperature. Pure Ag shell is transformed into a shell made of Ag/Pt alloy by galvanic replacement. The AgCl formed simultaneously roughens the surface of alloy Ag-Pt shells, which can be manipulated to create a porous Pt surface for oxygen reduction reaction. Finally, Ag and AgCl are removed from core-shell Au-Ag/Pt nanoparticles using bis(p-sulfonatophenyl)phenylphosphane dihydrate dipotassium salt to produce heterogeneous Au-Pt nanostructures. The heterogeneous Au-Pt nanostructures have displayed superior catalytic activity towards oxygen reduction in direct methanol fuel cells because of the electronic coupling effect between the inner-placed Au core and the Pt shell.     

Growth kinetics of platinum nanocrystals prepared by two different methods: role of the surface

In order to examine the applicability of the diffusion-limited Ostwald ripening model to the growth kinetics of nanocrystals, platinum nanocrystals prepared by two different methods have been investigated by a combined use of small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). One of the methods of synthesis involved the reduction of chloroplatinic acid by sodium citrate while in the other method reduction was carried out in the presence of polyvinylpyrrolidone (PVP) as a capping agent. The growth of platinum nanocrystals prepared by citrate reduction in the absence of any capping agent follows a Ostwald ripening growth with a D(3) dependence. In the presence of PVP, the growth of platinum nanocrystals does not completely follow the Ostwald ripening model, making it necessary to include a surface reaction term in the growth equation. Thus, the growth of platinum nanocrystals in the presence of PVP has contributions both from diffusion and surface reaction, exhibiting a D(3)+D(2) type behavior.     

Two-step growth of goethite from ferrihydrite

Goethite (alpha-FeOOH) is an antiferromagnetic iron oxyhydroxide that is often synthesized by precipitation from homogeneous, aqueous solution followed by aging. This paper addresses goethite growth by phase transformation of six-line ferrihydrite nanoparticles to goethite followed by oriented aggregation of the goethite primary particles. Data tracking goethite nanocrystal growth as a function of pH, temperature, and time is presented. In general, goethite growth by oriented aggregation is faster at higher pH and at higher temperature even as growth by coarsening becomes increasingly important as pH increases. In addition, particle size measurements demonstrate that the primary nanoparticles grow by Ostwald ripening even as they are being consumed by oriented aggregation. Finally, the use of a microwave anneal step in the preparation of the precursor six-line ferrihydrite nanoparticles substantially improves the homogeneity of the final goethite product. Final goethite nanoparticles are unaggregated, acicular crystals in the tens of nanometers size range. These particles may be ideal for mineral liquid crystal and magnetic-recording media applications.     

Size control in the synthesis of 1-6 nm gold nanoparticles via solvent-controlled nucleation

We report a facile synthetic route for size-controlled preparation of gold nanoparticles. Nearly monodisperse gold nanoparticles with core diameters of 1-6 nm were obtained by reducing AuP(Phenyl)(3)Cl with tert-butylamine borane in the presence of dodecanethiol in the solvent mixture of benzene and CHCl(3). Mechanism studies have shown that the size control is achieved by the solvent-controlled nucleation in which the nuclei concentration increases with increasing the fraction of CHCl(3), leading to smaller particles. It was also found that, following the solvent-controlled nucleation, particle growth occurs via ligand replacement of PPh(3) on the nuclei by Au(I)thiolate generated by the digestive etching of small particles. This synthetic strategy was successfully demonstrated with other alkanethiols of different chain length with which size-controlled, monodisperse gold nanoparticles were prepared in remarkable yield without requiring any postsynthesis treatments.     

以聚电解质多层膜为纳米反应器制备Au@Pt核壳纳米粒子

以聚二烯丙基二甲基氯化铵和聚苯乙烯磺酸钠为构筑单元,通过静电层层自组装制备了多层膜,利用薄膜中存在的抗衡阴离子,选择AuCl-4和PtCl2-6作为Au和Pt的前驱体,通过连续的阴离子交换/还原,原位制备了Au-Pt双金属纳米粒子。 紫外-可见分光光度法、透射电子显微镜和能量色散X射线能谱数据表明,在聚电解质多层薄膜中成功地制备了具有核壳结构的Au@Pt双金属纳米粒子。 这种纳米粒子在电化学催化、燃料电池方面具有潜在的应用价值。     

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.     

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。