2.3. Amorphous Minerals 4354 3. Biological Routes to Controlling Morphology 4354 3.1. General Mechanisms 4356 3.1.1. Soluble and Insoluble Organic Molecules 4356 3.1.2. Control over Crystal Polymorph 4357 3.1.3. Control over Crystal Orientation 4359 3.2. Single-Crystal Biominerals 4359 3.2.1. Organic and Inorganic Soluble Additives 4360 3.2.2. Templating of Single-Crystal Morphologies 4361 3.3. Polycrystalline Biominerals 4366 3.3.1. Nacre Formation in Mollusks 4366 3.3.2. ForaminiferasA Biogenic Mesocrystal 4368 3.4. Amorphous Biominerals 4370 3.4.1. Silicification in Diatoms 4370 3.4.2. In Vitro Studies of Silicification in Diatoms 4371 4. Bioinspired Routes to Controlling Crystal Morphologies 4371

Controlling Mineral Morphologies and Structures in Biological and Synthetic Systems

Biogenic calcium carbonate forms the inorganic component of seashells, otoliths, and many marine skeletons, and its formation is directed by an ordered template of macromolecules. Classical nucleation theory considers crystal formation to occur from a critical nucleus formed by the assembly of ions from solution. Using cryotransmission electron microscopy, we found that template-directed calcium carbonate formation starts with the formation of prenucleation clusters. Their aggregation leads to the nucleation of amorphous nanoparticles in solution. These nanoparticles assemble at the template and, after reaching a critical size, develop dynamic crystalline domains, one of which is selectively stabilized by the template. Our findings have implications for template-directed mineral formation in biological as well as in synthetic systems.

The initial stages of template-controlled CaCO3 formation revealed by Cryo-TEM

Complex three-dimensional hierarchical structures assembled from well-defined low-dimensional nanosized building blocks are an interesting class of nanomaterials with a rich variety of tunable physicochemical properties. Tin dioxide (SnO2) is an important n-type wide-bandgap semiconductor with wide applications in transparent conductive films, gas sensors, lithium-ion batteries, and solar cells. In this review, we outline synthetic strategies of hierarchical SnO2 nanostructures in terms of the dimension and the facet control of their constituting building blocks, creation of porous and hollow structures, as well as their modification by doping and loading with other elements. The design of hierarchical SnO2 nanostructures with an improved performance in lithium-ion batteries, sensitized solar cells, and gas-sensing applications is reviewed.

Hierarchical SnO2 Nanostructures: Recent Advances in Design, Synthesis, and Applications

Flexible electronics have gained considerable research interest in the recent years because of their special features and potential applications in flexible displays, artificial skins, sensors, sustainable energy, etc. With unique geometry, outstanding electronic/optoelectronic properties, excellent mechanical flexibility and good transparency, inorganic nanowires (NWs) offer numerous insights and opportunities for flexible electronics. This article provides a comprehensive review of the inorganic NW based flexible electronics studied in the past decade, ranging from NWs synthesis and assembly to several important flexible device and energy applications, including transistors, sensors, display devices, memories and logic gates, as well as lithium ion batteries, supercapacitors, solar cells and generators. The integration of various flexible nanodevices into a self-powered system was also briefly discussed. Finally, several future research directions and opportunities of inorganic NW flexible and portable electronics are proposed.

Flexible electronics based on inorganic nanowires.

Two contrasting approaches, involving either polymer-mediated or fluoride-mediated self-transformation of amorphous solid particles, are described as general routes to the fabrication of hollow inorganic microspheres. Firstly, calcium carbonate and strontium tungstate hollow microspheres are fabricated in high yield using sodium poly(4-styrenesulfonate) as a stabilizing agent for the formation and subsequent transformation of amorphous primary particles. Transformation occurs with retention of the bulk morphology by localized Ostwald ripening, in which preferential dissolution of the particle interior is coupled to the deposition of a porous external shell of loosely packed nanocrystals. Secondly, the fabrication process is extended to relatively stable amorphous microspheres, such as TiO2 and SnO2, by increasing the surface reactivity of the solid precursor particles. For this, fluoride ions, in the form of NH4F and SnF2, are used to produce well-defined hollow spheroids of nanocrystalline TiO2 and SnO2, respectively. Our results suggest that the chemical self-transformation of precursor objects under morphologically invariant conditions could be of general applicability in the preparation of a wide range of nanoparticle-based hollow architectures for technological and biomedical applications.

Fabrication of Hollow Inorganic Microspheres by Chemically Induced Self‐Transformation

tion that is fundamental for understanding material properties. Still, a number of compounds have eluded such kinds of analysis because they are nanocrystalline, highly disordered, with strong pseudosymmetries or available only in small amounts in polyphasic or polymorphic systems. These materials are crystallographically intractable with conventional Xray or synchrotron radiation diffraction techniques. Single nanoparticles can be visualized by high-resolution transmission electron microscopy (HR-TEM) up to sub�ngstrom resolution, [2] but obtaining 3D information is still a difficult task, especially for highly beam-sensitive materials and crystal structures with long cell parameters. Electron diffraction (ED) delivers higher resolved data with a significant lower electron dose on the sample, but is biased by a substantial number of missing reflections and the occurrence of dynamic scattering that affects reflection intensities. [3] Therefore, ED is mainly used in combination with Xray powder diffraction and high-resolution electron microscopy. [4]

Ab Initio Structure Determination of Vaterite by Automated Electron Diffraction

Scale formation, the deposition of certain minerals such as CaCO3, MgCO3, and CaSO4·2H2O in industrial facilities and household devices, leads to reduced efficiency or severe damage. Therefore, incrustation is a major problem in everyday life. In recent years, double hydrophilic block copolymers (DHBCs) have been the focus of interest in academia with regard to their antiscaling potential. In this work, we synthesized well-defined blocklike PAA-PAMPS copolymers consisting of acrylic acid (AA) and 2-acrylamido-2-methyl-propane sulfonate (AMPS) units in a one-step reaction by RAFT polymerization. The derived copolymers had dispersities of 1.3 and below. The copolymers have then been investigated in detail regarding their impact on the different stages of the crystallization process of CaCO3. Ca2+ complexation, the first step of a precipitation process, and polyelectrolyte stability in aqueous solution have been investigated by potentiometric measurements, isothermal titration calorimetry (ITC), and dynamic ...

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PAA-PAMPS copolymers as an efficient tool to control CaCO3 scale formation.

Phase selection of calcium carbonate through the chirality of adsorbed amino acids.

It is well known that the formation of biominerals by living organisms is governed by the cooperation of soluble and insoluble macromolecules with peculiar interfacial properties. To date, most of the studies on mineralization processes involve model systems that account only for the existence of one organic matrix and thus disregard the interaction between the soluble and insoluble organic components that is crucial for a better understanding of the processes taking place at the inorganic-organic interface. We have set up a model system composed of a matrix surface, which is composed of a self-assembled monolayer (SAM) and a soluble component, poly(aspartic acid). It could be demonstrated that the phase selection of calcium carbonate and the morphology of the resulting particles are determined by the stabilization of amorphous precursor particles by the polymer and the interaction between polymer and SAM. The morphology of the hollow vaterite microspheres are reminiscent to a 3D analogue of the so-called "coffee-stain effect", where the transformation from a voluminous hydrated, amorphous material to a more dense crystalline material leads to the formation of hollow spheres from massive spherical microparticles.

Probing cooperative interactions of tailor-made nucleation surfaces and macromolecules: a bioinspired route to hollow micrometer-sized calcium carbonate particles.

Reaction pathways to SnO2 nanomaterials through the hydrolysis of hydrated tin tetrachloride precursors were investigated. The products were prepared solvothermally starting from hydrated tin tetrachloride and various (e.g., alkali) hydroxides. The influence of the precursor base on the final morphology of the nanomaterials was studied. X-ray powder diffraction (XRD) data indicated the formation of rutile-type SnO2. Transmission electron microscopy (TEM) studies revealed different morphologies that were formed with different precursor base cations. Data from molecular dynamics (MD) simulations provide theoretical evidence that the adsorption of the cations of the precursor base to the faces of the growing SnO2 nanocrystals is crucial for the morphology of the nanostructures.

Niklas Loges

Papers

Ab Initio Structure Determination of Vaterite by Automated Electron Diffraction

PAA-PAMPS copolymers as an efficient tool to control CaCO3 scale formation.

Phase selection of calcium carbonate through the chirality of adsorbed amino acids.

Probing cooperative interactions of tailor-made nucleation surfaces and macromolecules: a bioinspired route to hollow micrometer-sized calcium carbonate particles.

Interaction of Alkaline Metal Cations with Oxidic Surfaces: Effect on the Morphology of SnO2 Nanoparticles