Hybrid Biomimetic Materials from Silica/Carbonate Biomorphs

Opel, Julian; Unglaube, Niklas; Wörner, Melissa; Kellermeier, Matthias; Cölfen, Helmut; García‐Ruiz, Juan Manuel

doi:10.3390/cryst9030157

Cited by 10 publications

(7 citation statements)

References 34 publications

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“…The exquisite complexity and hierarchical structuring of biominerals offer an inexhaustible source of inspiration for the assembly of new materials with advanced functionalities. − In particular, bioinspired self-assembly can be exploited for hierarchical ordering of amorphous and crystalline substances in functional nanocomposites, while the inherent autonomous character of self-assembly is advantageous for straightforward upscaling. − Consequently, bioinspired nanocomposites have already been applied in fields such as robotics, sensing, and optics, ,− yet the full potential of self-assembly for advanced materials remains untapped.…”

Section: Introductionmentioning

confidence: 99%

Rational Design of Bioinspired Nanocomposites with Tunable Catalytic Activity

Hendrikse

Aguirre

Weijden

et al. 2021

Crystal Growth & Design

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Biological assembly processes offer inspiration for ordering building blocks across multiple length scales into advanced functional materials. Such bioinspired strategies are attractive for assembling supported catalysts, where shaping and structuring across length scales are essential for their performance but still remain tremendously difficult to achieve. Here, we present a simple bioinspired route toward supported catalysts with tunable activity and selectivity. We coprecipitate shape-controlled nanocomposites with large specific surface areas of barium carbonate nanocrystals that are uniformly embedded in a silica support. Subsequently, we exchange the barium carbonate to cobalt while preserving the nanoscopic layout and microscopic shape, and demonstrate their catalytic performances in the Fischer–Tropsch synthesis as a case study. Control over the crystal size between 10 and 17 nm offers tunable activity and selectivity for shorter (C 5 –C 11 ) and longer (C 20+ ) hydrocarbons, respectively. Hence, these results open simple, versatile, and scalable routes to tunable and highly reactive bioinspired catalysts.

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Section: Introductionmentioning

confidence: 99%

Rational Design of Bioinspired Nanocomposites with Tunable Catalytic Activity

Hendrikse

Aguirre

Weijden

et al. 2021

Crystal Growth & Design

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“…Already shape‐preserving ion‐exchange reactions have been developed toward a wide pallet of chemical compositions including perovskites, metals, and metal chalcogenides. [ 16–23 ] Therefore, the here‐demonstrated light‐controlled assembly strategies give unique independent control over shape and composition which directly impacts our access to user‐defined chemical compositions with desirable optic, catalytic, electronic, magnetic, and photovoltaic functionalities. The power of our strategy is that it enables full leveraging of the precision and control of photolithography techniques with the versatility and simplicity of bioinspired self‐assembly.…”

Section: Discussionmentioning

confidence: 99%

“…Already, post‐synthesis functionalization and ion‐exchange reactions of such architectures have enabled shape‐preserving conversion into chemical compositions with photovoltaic, magnetic, and catalytic performance. [ 16–23 ] Moreover, rudimental patterning and shaping of these composites has been demonstrated by modulating the reaction conditions either dynamically and globally, or statically and locally, leading to similar shapes, but not yet following exact user‐defined designs. Unlocking the full potential of this self‐assembly approach will require the ability to control chemical gradients both dynamically and locally—instead of statically and globally—for precisely guiding both nucleation and growth to guide assembly according to user‐defined designs.…”

Section: Introductionmentioning

confidence: 99%

Light‐Controlled Nucleation and Shaping of Self‐Assembling Nanocomposites

et al. 2021

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Controlling self‐assembly of nanocomposites is a fundamental challenge with exciting implications for next‐generation advanced functional materials. Precursors for composites can be generated photochemically, but limited insight in the underlying processes has hindered precise hands‐on guidance. In this study, light‐controlled nucleation and growth is demonstrated for self‐assembling composites according to precise user‐defined designs. Carbonate is generated photochemically with UV light to steer the precipitation of nanocomposites of barium carbonate nanocrystals and amorphous silica (BaCO3/SiO2). Using a custom‐built optical setup, the self‐assembly process is controlled by optimizing the photogeneration, diffusion, reaction, and precipitation of the carbonate species, using the radius and intensity of the UV‐light irradiated area and reaction temperature. Exploiting this control, nucleation is induced and the contours and individual features of the growing composite are sculpted according to micrometer‐defined light patterns. Moreover, moving light patterns are exploited to create a constant carbonate concentration at the growth front to draw lines of nanocomposites with constant width over millimeters with micrometer precision. Light‐directed generation of local gradients opens previously unimaginable opportunities for guiding self‐assembly into functional materials.

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“…shapes such as vases, stems, and helices, that can be further sculpted and chemically modified. [7][8][9][10][11][12][13][14][15][16][17][18] The structural layout of the helical composites has been studied in great detail: the rodshaped nanocrystals are elongated along their c-axes and align parallel to one another while precessing tangentially around the helical axis, [8][9][10][11][12][13][14][15][16][17][18] thus forming a chiral ensemble as shown in Figure 1.…”

Section: Introductionmentioning

confidence: 99%

Directed Emission from Self‐Assembled Microhelices

Helmbrecht

Tan

Röhrich

et al. 2019

Adv Funct Materials

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Bottom-up assembly can organize simple building blocks into complex architectures for light manipulation. The optical properties of self-assembled polycrystalline barium carbonate/silica double helices are studied using fluorescent Fourier and Mueller matrix microscopy. Helices doped with fluorescein direct light emission along the long axis of the structure. Furthermore, light transmission measured normal and parallel to the long axis exhibits twist sense-specific circular retardance (CR) and wave-guiding, respectively, albeit the measurements suffer from depolarization. The helices thus integrate highly directional emission with enantiomorphspecific polarization. This optical response emerges from the arrangement of nanoscopic mineral crystallites in the microscopic helix, and demonstrates how bottom-up assembly can achieve ordering across multiple length scales to form complex functional materials.Helical-shaped nanocomposites formed from barium carbonate (BaCO3) nanocrystals and amorphous silica (SiO2) can put these ideas to the test. These bioinspired nanocomposites have been observed to self-assemble into highly intricate, yet controllable, three-dimensional (3D) Received: ((will be filled in by the editorial staff)) Revised: ((will be filled in by the editorial staff))

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Hybrid Biomimetic Materials from Silica/Carbonate Biomorphs

Cited by 10 publications

References 34 publications

Rational Design of Bioinspired Nanocomposites with Tunable Catalytic Activity

Rational Design of Bioinspired Nanocomposites with Tunable Catalytic Activity

Light‐Controlled Nucleation and Shaping of Self‐Assembling Nanocomposites

Directed Emission from Self‐Assembled Microhelices

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