Inorganic Reactions Self‐organize Life‐like Microstructures Far from Equilibrium

Knoll, Pamela; Steinbock, Oliver

doi:10.1002/ijch.201700136

Cited by 26 publications

(30 citation statements)

References 62 publications

(188 reference statements)

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“…[ 1–4 ] This has inspired synthetic assembly strategies to produce highly complex 3D shapes using simple methods. [ 4–18 ] Unfortunately, in both cases the choice of chemical compositions is limited. Alternatively, a wide selection of compositions can be reached by nanoparticle synthesis, [ 16,19–27 ] but assembling these in arbitrary microscopic 3D shapes has remained challenging.…”

Section: Figurementioning

confidence: 99%

Shape‐Preserving Chemical Conversion of Architected Nanocomposites

et al. 2020

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microscopic 3D shapes has remained challenging. Synthesis inherently entangles shape and composition; hence, current assembly routes offer control over either 3D shape or composition, but not both. In principle, chemically converting existing 3D shapes to a specified composition allows control over both the chemical composition and 3D geometry. The viability of this strategy is indicated by naturally occurring geochemical fossilization processes, [1] and laboratory demonstrations of shape-preserving ion-exchange and oxidation/reduction reactions on individual and ensembles of nanocrystals, as well as biominerals. [5,23-28] Nevertheless, conversion of arbitrary microscopic architectures is still challenging as conversion is diffusion-limited and slow, and significant changes in the atomistic unit cells could yield uncontrollable dissolution/ recrystallization, large deformations, and even fracture failure. We recognize that successful conversion reactions require a paradoxical combination of reactivity and stability to enable: i) diffusion of reactants and products in the solid phase, ii) crystal lattice rearrangements and unit-cell volume changes, while iii) preserving the overall 3D shape. We thus hypothesize that nanocomposites consisting of nanocrystals in an amorphous matrix have excellent characteristics to overcome these issues. Traditionally, nanocomposites have mainly been studied for their excellent mechanical properties. [1,2,5,6,13,14] Importantly, coprecipitation of carbonate salts Forging customizable compounds into arbitrary shapes and structures has the potential to revolutionize functional materials, where independent control over shape and composition is essential. Current self-assembly strategies allow impressive levels of control over either shape or composition, but not both, as self-assembly inherently entangles shape and composition. Herein, independent control over shape and composition is achieved by chemical conversion reactions on nanocrystals, which are first self-assembled in nanocomposites with programmable microscopic shapes. The multiscale character of nanocomposites is crucial: nanocrystals (5-50 nm) offer enhanced chemical reactivity, while the composite layout accommodates volume changes of the nanocrystals (≈25%), which together leads to complete chemical conversion with full shape preservation. These reactions are surprisingly materials agnostic, allowing a large diversity of chemical pathways, and development of conversion pathways yielding a wide selection of shape-controlled transition metal chalcogenides (cadmium, manganese, iron, and nickel oxides and sulfides). Finally, the versatility and application potential of this strategy is demonstrated by assembling: 1) a scalable and highly reactive nickel catalyst for the dry reforming of butane, 2) an agile magnetic-controlled particle, and 3) an electron-beam-controlled reversible microactuator with sub-micrometer precision. Previously unimaginable customization of shape and composition is now achievable for assembling advance...

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Section: Figurementioning

confidence: 99%

Shape‐Preserving Chemical Conversion of Architected Nanocomposites

et al. 2020

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“…The morphogenesis of these structures has been described phenomenologically [75] but the underlying morphogenetical mechanisms are still debated [62,69,[76][77][78]. From the chemical point of view the phenomenon of biomorph formation is explained by a self-feeding mechanism triggered by the reverse solubility of silica and carbonate with respect to pH provoking a coupled co-precipitation at the growth front [79] (Fig.…”

Section: Silica/carbonate Biomorphsmentioning

confidence: 99%

Mineral self-organization on a lifeless planet

García‐Ruiz

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Bach

2020

Physics of Life Reviews

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It has been experimentally demonstrated that, under alkaline conditions, silica is able to induce the formation of mineral selfassembled inorganic-inorganic composite materials similar in morphology, texture and nanostructure to the hybrid biomineral structures that, millions of years later, life was able to self-organize. These mineral self-organized structures (MISOS) have been also shown to work as effective catalysts for prebiotic chemical reactions and to easily create compartmentalization within the solutions where they form. We reason that, during the very earliest history of this planet, there was a geochemical scenario that inevitably led to the existence of a large-scale factory of simple and complex organic compounds, many of which were relevant to prebiotic chemistry. The factory was built on a silica-rich high-pH ocean and powered by two main factors: a) a quasi-infinite source of simple carbon molecules synthesized abiotically from reactions associated with serpentinization, or transported from meteorites and produced from their impact on that alkaline ocean, and b) the formation of self-organized silica-metal mineral composites that catalyze the condensation of simple molecules in a methane-rich reduced atmosphere. We discuss the plausibility of this geochemical scenario, review the details of the formation of MISOS and its catalytic properties and the transition towards a slightly alkaline to neutral ocean.

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“…The rational design of such processes has remained beyond the reach of modern chemistry and progress continues to rely on a few classic model systems [10] and accidental discoveries [11] . In addition to Liesegang patterns and chemical gardens, [10] “biomorphs” have become one of these important models [12–14] . Biomorphs are inorganic polycrystalline assemblies that display a variety of micrometer‐scale shapes such as cardioid leaves, single and double helices, funnels, urns, and coral‐like structures (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

“…Biomorphs are inorganic polycrystalline assemblies that display a variety of micrometer‐scale shapes such as cardioid leaves, single and double helices, funnels, urns, and coral‐like structures (Figure 1). These structures form spontaneously when a basic solution containing silicate and Ba 2+ (or Sr 2+ or Ca 2+ ) [12–14] ions is exposed to a carbonate source (e. g. air). Recent studies strongly suggest that biomorph shapes result from dynamic instabilities of an underlying nonlinear reaction‐diffusion system [15–17] that is possibly related to a self‐propagating band of decreased pH ahead of the active growth zone [18,19] .…”

Section: Introductionmentioning

confidence: 99%

Fibrous Bundles in Biomorph Systems: Surface‐Specific Growth and Interaction with Microposts

et al. 2021

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Biomorphs are polycrystalline assemblies that form when barium, silicate, and carbonate ions react in basic solutions. Their micrometer‐scale morphologies include leaf‐like sheets, helices, and cones, while their nanoscale architecture is based on co‐aligned witherite nanorods. We report a biomorph shape that resembles hair strands that smoothly curl into spirals or twisting fiber ribbons. They can thicken through continuous fractal‐like branching or abrupt events in which fibers split simultaneously. Raman and energy dispersive X‐ray spectroscopy as well as optical polarization microscopy reveal that their composition is very similar to classical biomorphs. They are most abundant in the absence of glass substrates and at high pH values. However, if a glass surface is covered by a thin SU‐8 resin layer, their growth is observed and photolithographically produced SU‐8 posts serve as nucleation sites. The hair‐like structures can detach resin posts from the glass surface and reposition them due to continued growth at the hair‐resin interface. Collisions of growing biomorph sheets with SU‐8 posts result in overgrowth or a sheet‐to‐hair transition.

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Inorganic Reactions Self‐organize Life‐like Microstructures Far from Equilibrium

Cited by 26 publications

References 62 publications

Shape‐Preserving Chemical Conversion of Architected Nanocomposites

Shape‐Preserving Chemical Conversion of Architected Nanocomposites

Mineral self-organization on a lifeless planet

Fibrous Bundles in Biomorph Systems: Surface‐Specific Growth and Interaction with Microposts

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