Progress in Mesocrystal Formation

Brunner, Julian; Cölfen, Helmut

doi:10.1021/bk-2020-1358.ch004

Cited by 7 publications

(4 citation statements)

References 147 publications

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“…Although their TEM images could also be interpreted as primary, disorderly aggregated (nanocrystalline) subunits ( e.g. , Wolthers et al 112 and Brunner & Cölfen 113 ), their TEM images clearly show a transition from aggregates, consisting of ca. 5–10 nm-sized subunits, to a clearly crystalline euhedral phase.…”

Section: Resultsmentioning

confidence: 99%

Asymmetrical Dependence of {Ba²⁺}:{SO₄^2–} on BaSO₄Crystal Nucleation and Growth in Aqueous Solutions: A Dynamic Light Scattering Study

2023

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The impact of solution stoichiometry, upon formation of BaSO4 crystals in 0.02 M NaCl suspensions, on the development of particle size was investigated using dynamic light scattering (DLS). Measurements were performed on a set of suspensions prepared with predefined initial supersaturation, based on the quotient of the constituent ion activity product {Ba2+}{SO4 2–} over the solubility product K sp (Ωbarite = {Ba2+}{SO4 2–}/K sp = 100, 500, or 1000–11,000 in steps of 1000), and ion activity solution stoichiometries (r aq = {Ba2+}:{SO4 2–} = 0.01, 0.1, 1, 10 and 100), at circumneutral pH of 5.5–6.0, and ambient temperature and pressure. DLS showed that for batch experiments, crystal formation with varying r aq was best investigated at an initial Ωbarite of 1000 and using the forward detection angle. At this Ωbarite and set of r aq, the average apparent hydrodynamic particle size of the largest population present in all suspensions increased from ∼200 to ∼700 nm within 10–15 min and was independently confirmed by transmission electron microscopy (TEM) imaging. Additional DLS measurements conducted at the same conditions in flow confirmed that the BaSO4 formation kinetics were very fast for our specifically chosen conditions. The DLS flow measurements, monitoring the first minute of BaSO4 formation, showed strong signs of aggregation of prenucleation clusters forming particles with a size in the range of 200–300 nm for every r aq. The estimated initial bulk growth rates from batch DLS results show that BaSO4 crystals formed fastest at near-stoichiometric conditions and more slowly at nonstoichiometric conditions. Moreover, at extreme SO4-limiting conditions, barite formation was slower compared to Ba-limiting conditions. Our results show that DLS can be used to investigate nucleation and growth at carefully selected experimental and analytical conditions. The combined DLS and TEM results imply that BaSO4 formation is influenced by solution stoichiometry and may aid to optimize antiscalant efficiency and regulate BaSO4 (scale) formation processes.

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Section: Resultsmentioning

confidence: 99%

Asymmetrical Dependence of {Ba²⁺}:{SO₄^2–} on BaSO₄Crystal Nucleation and Growth in Aqueous Solutions: A Dynamic Light Scattering Study

2023

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“…For instance, cryotransmission electron microscopy (Cryo-TEM) observations show the crystallization of magnetite through the formation and aggregation of primary nanoparticles . The formed nanoparticles may also agglomerate and transform to mesocrystal in the growth process . In fact, the precursors widely exist during mineralization of natural biological productions such as teeth, mammalian odonthyalus, vertebrate bone, crustacean skeleton, and so on. − Thus, nonclassical nucleation and growth models have been proposed to describe these special phenomena, where precursors are considered as building units for the crystallization…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Nonclassical Crystallization: Fundamentals, Applications, and Challenges

Gao

Zhang

et al. 2021

Crystal Growth & Design

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Ubiquitous crystals play an important role in our daily lives. Recent studies on the properties and formation of crystals have proven the attachment of particles ranging from ion pairs to well-crystallized nanocrystals for crystallization. Compared with the monomer-by-monomer (i.e., atoms, ions, or molecules) addition described in long-standing classical theories, so-called nonclassical crystallization pathways are more complex due to the influence of nonspecific interactions influenced by the variation in system free energy and reaction kinetics. In view of the fact that detailed insights into nonclassical crystallization pathways have broadened the scope of research across various disciplines such as geological events, biomineralization mechanisms, environmental remediation, and the development of functional materials, this paper reviews the current state of the art in nonclassical nucleation (the prenucleation clusters pathway, aggregation pathway, etc.) and growth pathways (oriented attachment and random attachment) based on several highlights. In addition, the observed specific phenomena on crystallization in the last 10 years as well as recent advancements and achievements on the synthesis of mesocrystals are also elucidated. With implications and perspectives of nonclassical crystallization research proposed in this paper, this review aims to summarize research advancements regarding crystallizing systems. Emphasis will be placed on novel insights into nonclassical crystallization of materials, which are expected to provide completely new perspectives on the underlying crystallization mechanisms.

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“…Nanoparticles offer many exciting opportunities for creating materials with unique structures and properties. − These opportunities arise because the properties of nanoparticles often strongly differ from the physical and chemical properties of the corresponding bulk material . Furthermore, the tendency of nanoparticles for aggregation and self-assembly also represents an excellent chance for the bottom-up generation of extraordinarily nanostructured materials. ,− Such an assembly process, which belongs to nonclassical crystallization, is especially important for the formation of mesocrystals from nanocrystals. − Within the mesocrystalline structure, the nanoparticles not only keep their nanoparticle properties, but their crystallographic alignment may lead to emergent properties, including amplification of electric or magnetic dipoles. By definition, mesocrystals must consist of nanocrystals and must show their preferable crystallographic orientation.…”

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confidence: 99%

“…Literature suggests that these mesocrystals form in dispersion by a homogeneous nucleation event that precedes the mesocrystals’ growth and then eventually drop on a silicon substrate. , However, this statement is debatable for the systems where the formation of mesocrystals occurs in the presence of a substrate and with low driving forces of the crystallization process. Beyond the fundamental research, nowadays studies on mesocrystals also focus on using mesocrystals for specific applications such as microswimmers, ,, conductors, gas sensors, , and photocatalysis . Such applications often demand highly ordered, faceted mesocrystals with large and/or defined sizes.…”

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confidence: 99%

Self-Assembled Faceted Mesocrystals: Advances in Optimization of Growth Conditions

Brunner

Maier

Kirner

et al. 2021

Crystal Growth & Design

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One aspect of the research on mesocrystals nowadays focuses on applications, whereby such applications demand mesocrystals with a tunable size. To achieve this task, more effort needs to be undertaken to understand how mesocrystals form, which parameters influence mesocrystal formation, and which kind of structure results from the nanoparticle assembly. Within this communication, we demonstrate for faceted mesocrystals assembled from iron oxide nanocubes stabilized by oleic acid that the proper choice of crystallization conditions in the gas phase diffusion setup is essential to achieve this task. The appropriate choice of substrate, dispersion and destabilizing agents, additive, nanocrystal concentration, crystallization kinetics, and duration allows growing faceted iron oxide mesocrystals with sizes ranging from a few micrometers up to almost a millimeter. By these findings supported by light and scanning electron microscopy, we show that in this system, heterogeneous nucleation is the predominant mechanism for mesocrystal formation on a solid substrate. Additionally, other surfactants than oleic acid can also act as molecular additives to support mesocrystal growth. These findings should be transferable to tune the size and quality of other self-assembled mesocrystals.

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Progress in Mesocrystal Formation

Cited by 7 publications

References 147 publications

Asymmetrical Dependence of {Ba²⁺}:{SO₄^2–} on BaSO₄Crystal Nucleation and Growth in Aqueous Solutions: A Dynamic Light Scattering Study

Asymmetrical Dependence of {Ba²⁺}:{SO₄^2–} on BaSO₄Crystal Nucleation and Growth in Aqueous Solutions: A Dynamic Light Scattering Study

Recent Advances in Nonclassical Crystallization: Fundamentals, Applications, and Challenges

Self-Assembled Faceted Mesocrystals: Advances in Optimization of Growth Conditions

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Progress in Mesocrystal Formation

Cited by 7 publications

References 147 publications

Asymmetrical Dependence of {Ba2+}:{SO42–} on BaSO4Crystal Nucleation and Growth in Aqueous Solutions: A Dynamic Light Scattering Study

Asymmetrical Dependence of {Ba2+}:{SO42–} on BaSO4Crystal Nucleation and Growth in Aqueous Solutions: A Dynamic Light Scattering Study

Recent Advances in Nonclassical Crystallization: Fundamentals, Applications, and Challenges

Self-Assembled Faceted Mesocrystals: Advances in Optimization of Growth Conditions

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Asymmetrical Dependence of {Ba²⁺}:{SO₄^2–} on BaSO₄Crystal Nucleation and Growth in Aqueous Solutions: A Dynamic Light Scattering Study

Asymmetrical Dependence of {Ba²⁺}:{SO₄^2–} on BaSO₄Crystal Nucleation and Growth in Aqueous Solutions: A Dynamic Light Scattering Study