Nine accurate experimental data sets on amorphous calcium carbonate (ACC) formation in dilute solution were collected varying temperature and pH. The entire precipitation process is described using a complete thermodynamic-kinetic model. The thermodynamic model includes two new complex chemical interactions whereas the kinetic model is based on the discretized population balance approach. Saturation, primary particles size distribution, average secondary particles size, nucleation, and growth rates, as well as a number of additional parameters on the ACC precipitation reaction, are reported. The excellent agreement among experiments, calculated results, and literature data demonstrates that a complete thermodynamic-kinetic model can significantly contribute toward the understanding of a plausible pathway for precipitating systems. In this case study, the classical nucleation theory, which includes homogeneous nucleation, “true” secondary nucleation, and diffusion limited growth events, is able to completely describe the entire precipitation process. The calculated surface (γ) and cohesion (β) energies range from 28 to 35 and 30 to 42 mJ m–2, respectively, as a function of pH and temperature. Clusters or prenucleation entities act as spectators and are not directly involved in the solid formation pathway. The general methodological approach presented can be readily applied to other solid phase formation processes.
An overarching computational framework unifying several optical theories to describe the temporal evolution of gold nanoparticles (GNPs) during a seeded growth process is presented. To achieve this, we used the inexpensive and widely available optical extinction spectroscopy, to obtain quantitative kinetic data. In situ spectra collected over a wide set of experimental conditions were regressed using the physical model, calculating light extinction by ensembles of GNPs during the growth process. This model provides temporal information on the size, shape, and concentration of the particles, and any electromagnetic interactions between them. Consequently, we were able to describe the mechanism of GNP growth and divide the process into distinct genesis periods. We provide explanations for several longstanding mysteries, e.g., the phenomena responsible for the purple-greyish hue during the early stages of GNP growth, the complex interactions between nucleation, growth and aggregation events, and a clear distinction between agglomeration and electromagnetic interactions. The presented theoretical formalism has been developed in a generic fashion so that it can readily be adapted to other nanoparticulate formation scenarios such as the genesis of various metal nanoparticles. KeywordsGold nanoparticles, seeded growth, UV-Vis spectroscopy, computational modeling, kinetics and mechanism.reason, there is a great need for a general and easily adaptable theoretical framework that utilizes the practical application of OES in the study of nanomaterial formation.So far, several investigations have addressed the mechanistic aspects during the (seeded) growth of GNPs using various characterization techniques such as atomic force microscopy (AFM), 5,14,18 electrophoretic measurements, 19,20 redox potential/pH measurements, 18-20 dynamic light scattering (DLS), 14,19,21 ex situ TEM, 4,5,7,14,[19][20][21][22][23] in situ TEM, 4,5 , and X-ray scattering. 6,7,13,23,24 Many of these studies follow the process also using ex situ 5,[19][20][21][22] or in situ 14,23,24 UV-vis spectroscopy but the information is treated merely qualitatively.From the plethora of research, some of which was summarized above, we know that the processes of seeded growth is typically accompanied by nucleation of new particles. 5,25 This could either be in a homogeneous fashion, 25 or in the close vicinity of the already present seed surface 5 (so called true catalytic secondary nucleation 26 or, equivalently, near surface nucleation followed by particle mediated growth 5 ). Additional complications arise from the possibility of agglomeration/aggregation invoked in many studies to describe the transient enhanced extinction in the wavelength range 600-800 nm, namely, the temporary purple-greyish colour of the suspension. 7,[18][19][20]27 Biggs et al. 18 and Chow and Zukoski 19 explained this in the light of the reduced colloidal stability in the presence of Au(III) in solution. Later, Rodriguez-Gonzalez and co-workers noticed that a homogeneous Au(III)→Au(I...
A mesoscale pathway of calcium–silicate–hydrate precipitation, leading to nanocrystallites packing nematically in anisotropic particles is quantitatively described for the first time.
Calcium carbonate is a model system to investigate the mechanism of solid formation by precipitation from solutions, and it is often considered in the debated classical and nonclassical nucleation mechanism. Despite the great scientific relevance of calcium carbonate in different scientific areas, little is known about the early stage of its formation. Therefore, contactless devices are designed that are capable of providing informative investigations on the early stages of the precipitation pathway of calcium carbonate in supersaturated solutions using classical scattering methods such as wide‐angle X‐ray scattering (WAXS) and small‐angle X‐ray scattering (SAXS) techniques. In particular, SAXS is exploited for investigating the size of entities formed from supersaturated solutions before the critical conditions for amorphous calcium carbonate (ACC) nucleation are attained. The saturation level is controlled and kept constant by mixing four diluted solutions (i.e., NaOH, CaCl2, NaHCO3, H2O) at constant T and pH. The scattering data are collected on a liquid jet generated about 75 s after the mixing point. The data are modeled using parametric statistical models providing insight about the size distribution of denser matter in the liquid jet. Theoretical implications on the early stage of solid formation pathway are inferred.
Understanding and manipulating micelle morphology are key to exploiting surfactants in various applications. Recent studies have shown surfactant self-assembly in a variety of Deep Eutectic Solvents (DESs) where both the nature of surfactants and the interaction of the surfactant molecule with the solvent components influence the size, shape, and morphology of the micelles formed. So far, micelle formation has only been reported in type III DESs, consisting solely of organic species. In this work, we have explored the self-assembly of cationic surfactant dodecyl trimethylammonium nitrate/bromide (C12TANO3/C12TAB), anionic surfactant sodium dodecyl sulfate (SDS), and non-ionic surfactants hexaethylene glycol monododecyl ether (C12EO6) and octaethylene glycol monohexadecyl ether (C16EO8) in a type IV DES comprising metal salt, cerium (III) nitrate hexahydrate, and a hydrogen bond donor, urea, in the molar ratio 1:3.5. C12TANO3, C12TAB, C12EO6, and C16EO8 form spherical micelles in the DES with the micelle size dependent on both the surfactant alkyl chain length and the head group, whereas SDS forms cylindrical micelles. We hypothesize that the difference in the micelle shape can be explained by counterion stabilization of the SDS headgroup by polycations in the DES compared to the nitrate/bromide anion interaction in the case of cationic surfactants or molecular interaction of the urea and the salting out effect of (CeNO3)3 in the DES on the alkyl chains/polyethoxy headgroup for non-ionic surfactants. These studies deepen our understanding of amphiphile self-assembly in this novel, ionic, and hydrogen-bonding solvent, raising the opportunity to use these structures as liquid crystalline templates to generate porosity in metal oxides (ceria) that can be synthesized using these DESs.
In this article, we report the results of careful, room-temperature, high-pressure adsorption studies, in which simple complexes of copper and silver reversibly adsorb hydrogen when dispersed within nanoporous carbon. Whereas these complexes alone did not adsorb hydrogen, when they were nanoconfined within carbon, they adsorbed 1−3 mol of H 2 per metal center. As a figure of merit, nanoconfined cupric formate adsorbed ∼2.6 H 2 /Cu at 100 bar and 20 °C, much larger than any reported metal-containing adsorption medium. On carbon alone, the heat of hydrogen adsorption decreased with an increase in adsorption extent, limiting to insufficient levels of uptake. By contrast, when these metal salts were dispersed within the carbon, the heats of adsorption increased markedly in a linear manner, meaning that the thermodynamics has moved in the right direction and is not self-limiting. Such thermodynamic behavior is associated with side-on dihydrogen binding onto a metal center, the so-called Kubas binding. Such interaction, however, is generally observed with earlier transition metals and is therefore rather unexpected with coinage metals. Thus, we infer that there are cooperative interactions between hydrogen, the carbon pore, and the metal center, which may be exploited to enhance reversible hydrogen adsorption and to reach more practical levels.
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