Fast One-Step Fabrication of Highly Regular Microscrolls with Controllable Surface Morphology.

Although rolling origami technology has provided convenient access to three-dimensional (3D) microstructure systems, the high yield and scalable construction of complex rolling structures with well-defined geometry without impeding functionality has remained challenging. The straightforward, one-step fabrication that uses external mechanical stress to scroll micrometer thick, flexible planar films with centimeter lateral dimensions into tubular or spiral geometry within a few seconds is demonstrated. The method allows controlling the scrolls' diameter, number of windings and nanostructured surface morphology, and is applicable to a wide range of functional materials. The obtained 3D structures are highly promising for various applications including sensors, actuators, microrobotics, as well as energy storage and electronic devices.

Self-supporting V2O5 nanofiber-based electrodes for magnesium-lithium-ion hybrid batteries.

The increasing demand for high energy, sustainable and safer rechargeable electrochemical storage systems for portable devices and electric vehicles can be satisfied by the use of hybrid batteries. Hybrid batteries, such as magnesium-lithium-ion batteries (MLIBs), using a dual-salt electrolyte take advantage of both the fast Li+ intercalation kinetics of lithium-ion batteries (LIBs) and the dendrite-free anode reactions. Here we report the utilization of a binder-free and self-supporting V2O5 nanofiber-based cathode for MLIBs. The V2O5 cathode has a high operating voltage of ∼1.5 V vs. Mg/Mg2+ and achieves storage capacities of up to 386 mA h g-1, accompanied by an energy density of 280 W h kg-1. Additionally, a good cycling stability at 200 mA g-1 over 500 cycles is reached. The structural integrity of the V2O5 cathode is preserved upon cycling. This work demonstrates the suitability of the V2O5 cathode for MLIBs to overcome the limitations of LIBs and MIBs and to meet the future demands of advanced electrochemical storage systems.

Highly Porous Free-Standing rGO/SnO2 Pseudocapacitive Cathodes for High-Rate and Long-Cycling Al-Ion Batteries.

Establishing energy storage systems beyond conventional lithium ion batteries requires the development of novel types of electrode materials. Such materials should be capable of accommodating ion species other than Li+, and ideally, these ion species should be of multivalent nature, such as Al3+. Along this line, we introduce a highly porous aerogel cathode composed of reduced graphene oxide, which is loaded with nanostructured SnO2. This binder-free hybrid not only exhibits an outstanding mechanical performance, but also unites the pseudocapacity of the reduced graphene oxide and the electrochemical storage capacity of the SnO2 nanoplatelets. Moreover, the combination of both materials gives rise to additional intercalation sites at their interface, further contributing to the total capacity of up to 16 mAh cm-3 at a charging rate of 2 C. The high porosity (99.9%) of the hybrid and the synergy of its components yield a cathode material for high-rate (up to 20 C) aluminum ion batteries, which exhibit an excellent cycling stability over 10,000 tested cycles. The electrode design proposed here has a great potential to meet future energy and power density demands for advanced energy storage devices.

Fast-Growing Bacterial Cellulose with Outstanding Mechanical Properties via Cross-Linking by Multivalent Ions.

Bacterial cellulose is an organic product of certain bacterias' metabolism. It differs from plant cellulose by exhibiting a high strength and purity, making it especially interesting for flexible electronics, membranes for water purification, tissue engineering for humans or even as artificial skin and ligaments for robotic devices. However, bacterial cellulose's naturally slow growth rate has limited its large-scale applicability to date. Titanium (IV) bis-(ammonium lactato) dihydroxide is shown to be a powerful tool to boost the growth rate of bacterial cellulose production by more than one order of magnitude and that it simultaneously serves as a precursor for the Ti4+-coordinated cross-linking of the fibers during membrane formation. The latter results in an almost two-fold increase in Young's modulus (~18.59 GPa), a more than three-fold increase in tensile strength (~436.70 MPa) and even a four-fold increase in toughness (~6.81 MJ m-³), as compared to the pure bacterial cellulose membranes.

Binder-Free V2O5 Cathode for High Energy Density Rechargeable Aluminum-Ion Batteries.

Nowadays, research on electrochemical storage systems moves into the direction of post-lithium-ion batteries, such as aluminum-ion batteries, and the exploration of suitable materials for such batteries. Vanadium pentoxide (V2O5) is one of the most promising host materials for the intercalation of multivalent ions. Here, we report on the fabrication of a binder-free and self-supporting V2O5 micrometer-thick paper-like electrode material and its use as the cathode for rechargeable aluminum-ion batteries. The electrical conductivity of the cathode was significantly improved by a novel in-situ and self-limiting copper migration approach into the V2O5 structure. This process takes advantage of the dissolution of Cu by the ionic liquid-based electrolyte, as well as the presence of two different accommodation sites in the nanostructured V2O5 available for aluminum-ions and the migrated Cu. Furthermore, the advanced nanostructured cathode delivered a specific discharge capacity of up to ~170 mAh g-1 and the reversible intercalation of Al3+ for more than 500 cycles with a high Coulomb efficiency reaching nearly 100%. The binder-free concept results in an energy density of 74 Wh kg-1, which shows improved energy density in comparison to the so far published V2O5-based cathodes. Our results provide valuable insights for the future design and development of novel binder-free and self-supporting electrodes for rechargeable multivalent metal-ion batteries associating a high energy density, cycling stability, safety and low cost.

Bioinspired synthesis of SnO crosses as backbone in artificial sponges.

The distinct electronic properties, including p-type semiconducting and a wide optical band gap, renders SnO suitable for applications such as microelectronic devices, gas sensors and electrodes. However, the synthesis of SnO is rather challenging due to the instability of the oxide, which is usually obtained as a by-product of SnO2 fabrication. In this work, we developed a bioinspired synthesis, based on a hydrothermal approach, for the direct production of SnO nanoparticles. The amount of mineralizer, inducing the precipitation, was identified, which supports a template-free formation of the nanosized SnO particles at low temperature and mild chemical conditions. Moreover, the SnO nanoparticles exhibit a shape of unique three-dimensional crosses similar to the calcite crosses present in the calcareous sponges. We demonstrated that SnO crosses are evenly distributed and embedded in an organic scaffold by an ice-templating approach, in this way closely mimicking the structure of calcareous sponges. Such scaffolds, reinforced by an active material, here SnO, could be used as filters, sensors or electrodes, where a high surface area and good accessibility are essential. This article is part of the theme issue 'Bioinspired materials and surfaces for green science and technology (part 2)'.

Peptide Controlled Shaping of Biomineralized Tin(II) Oxide into Flower-Like Particles.

The size and morphology of metal oxide particles have a large impact on the physicochemical properties of these materials, e.g., the aspect ratio of particles affects their catalytic activity. Bioinspired synthesis routes give the opportunity to control precisely the structure and aspect ratio of the metal oxide particles by bioorganic molecules, such as peptides. This study focusses on the identification of tin(II) oxide (tin monoxide, SnO) binding peptides, and their effect on the synthesis of crystalline SnO microstructures. The phage display technique was used to identify the 7-mer peptide SnBP01 (LPPWKLK), which shows a high binding affinity towards crystalline SnO. It was found that the derivatives of the SnBP01 peptide, varying in peptide length and thus in their interaction, significantly affect the aspect ratio and the size dimension of mineralized SnO particles, resulting in flower-like morphology. Furthermore, the important role of the N-terminal leucine residue in the peptide for the strong organic⁻inorganic interaction was revealed by FTIR investigations. This bioinspired approach shows a facile procedure for the detailed investigation of peptide-to-metal oxide interactions, as well as an easy method for the controlled synthesis of tin(II) oxide particles with different morphologies.

Genetically Induced In Situ-Poling for Piezo-Active Biohybrid Nanowires.

Polycrystalline piezo-active materials only exhibit a high macroscopic piezoresponse if they consist of particles with oriented crystal directions and aligned intrinsic dipole moments. For ferroelectric materials, the postsynthesis alignment of the dipoles is generally achieved by electric poling procedures. However, there are numerous technically interesting non-ferroelectric piezo-active materials like zinc oxide (ZnO). These materials demand the alignment of their intrinsic dipoles during the fabrication process. Therefore, in situ-poling techniques have to be developed. This study utilizes genetically modified M13 phage templates for the generation of force fields, which directly control the ZnO dipole poling. By genetic modification of M13 phage template, the piezoelectric response of the ZnO/M13 phage hybrid nanowire is doubled compared to the hybrid nanowire based on unmodified M13 wild type (wt) phage templates. Thus, the formation of piezo-active domains consisting of oriented ZnO nanocrystals is directly induced by the genetic modification. By the combination of the fiber-like structure of individual M13 phages with the bioenhanced electromechanical properties of ZnO, hybrid nanowires with a length of ≈1.1 µm and a thickness of ≈63.5 nm are fabricated with a high piezoelectric coefficient of up to d33 = 7.8 pm V-1 for genetically modified M13 phage templates.

Free-standing nanostructured vanadium pentoxide films for metal-ion batteries.

Owing to their unique layer structure, high aspect ratio and intercalation capability, vanadium pentoxide (V2O5) nanofibers are close-to-ideal building blocks for high performance electrodes for metal-ion batteries. However, thus far investigated electrodes composed of V2O5 nanofibers mostly contain binders and conductive agents, which reduce the electrodes' gravimetric capacity. Here we demonstrate self-supporting V2O5 nanofiber-based films that combine high mechanical flexibility and stability with good electrical conductivity. This has been achieved by suitable adjustment of the nanofiber length, in combination with a suitable humidity controlled post-treatment, to ensure an effective nanofiber interconnection and aging of the films. The optimization of these two parameters allows for an impressive 81%, 184%, and 281% enhancement in Young's modulus, tensile strength and toughness respectively, along with an increase of electrical conductivity by up to 165%. Such films can reach storage capacities of up to 150 mA h g-1 without the support of conductive agents and binders. Our findings provide fundamental design guidelines for advanced binder-free electrode materials, which unite high specific storage capacity, excellent mechanical stability and good intrinsic electrical conductivity - the key to technologically advanced battery performance and lifetime.

Ultrahigh Damping Capacities in Lightweight Structural Materials.

The demand to outperform current technologies pushes scientists to develop novel strategies, which enable the fabrication of materials with exceptional properties. Along this line, lightweight structural materials are of great interest due to their versatile applicability as sensors, catalysts, battery electrodes, and acoustic or mechanical dampers. Here, we report a strategy to design ultralight (ρ = 3 mg/cm3) and hierarchically structured ceramic scaffolds of macroscopic size. Such scaffolds exhibit mechanical reversibility comparable to that of microscopic metamaterials, leading to a macroscopically remarkable dynamic mechanical performance. Upon mechanical loading, these scaffolds show a deformation mechanism similar to polyurethane foams, and this resilience yields ultrahigh damping capacities, tan δ, of up to 0.47.

Mesocrystalline calcium silicate hydrate: A bioinspired route toward elastic concrete materials.

Calcium silicate hydrate (C-S-H) is the binder in concrete, the most used synthetic material in the world. The main weakness of concrete is the lack of elasticity and poor flexural strength considerably limiting its potential, making reinforcing steel constructions necessary. Although the properties of C-S-H could be significantly improved in organic hybrids, the full potential of this approach could not be reached because of the random C-S-H nanoplatelet structure. Taking inspiration from a sea urchin spine with highly ordered nanoparticles in the biomineral mesocrystal, we report a bioinspired route toward a C-S-H mesocrystal with highly aligned C-S-H nanoplatelets interspaced with a polymeric binder. A material with a bending strength similar to nacre is obtained, outperforming all C-S-H-based materials known to date. This strategy could greatly benefit future construction processes because fracture toughness and elasticity of brittle cementitious materials can be largely enhanced on the nanoscale.

Template-controlled piezoactivity of ZnO thin films grown via a bioinspired approach.

Biomaterials are used as model systems for the deposition of functional inorganic materials under mild reaction conditions where organic templates direct the deposition process. In this study, this principle was adapted for the formation of piezoelectric ZnO thin films. The influence of two different organic templates (namely, a carboxylate-terminated self-assembled monolayer and a sulfonate-terminated polyelectrolyte multilayer) on the deposition and therefore on the piezoelectric performance was investigated. While the low negative charge of the COOH-SAM is not able to support oriented attachment of the particles, the strongly negatively charged sulfonated polyelectrolyte leads to texturing of the ZnO film. This texture enables a piezoelectric performance of the material which was measured by piezoresponse force microscopy. This study shows that it is possible to tune the piezoelectric properties of ZnO by applying templates with different functionalities.

Cuttlebone-like V2O5 Nanofibre Scaffolds - Advances in Structuring Cellular Solids.

The synthesis of ceramic materials combining high porosity and permeability with good mechanical stability is challenging, as optimising the latter requires compromises regarding the first two properties. Nonetheless, significant progress can be made in this direction by taking advantage of the structural design principles evolved by nature. Natural cellular solids achieve good mechanical stability via a defined hierarchical organisation of the building blocks they are composed of. Here, we report the first synthetic, ceramic-based scaffold whose architecture closely mimics that of cuttlebone -a structural biomaterial whose porosity exceeds that of most other natural cellular solids, whilst preserving an excellent mechanical strength. The nanostructured, single-component scaffold, obtained by ice-templated assembly of V2O5 nanofibres, features a highly sophisticated and elaborate architecture of equally spaced lamellas, which are regularly connected by pillars as lamella support. It displays an unprecedented porosity of 99.8 %, complemented by an enhanced mechanical stability. This novel bioinspired, functional material not only displays mechanical characteristics similar to natural cuttlebone, but the multifunctionality of the V2O5 nanofibres also renders possible applications, including catalysts, sensors and electrodes for energy storage.

Strengthening of Ceramic-based Artificial Nacre via Synergistic Interactions of 1D Vanadium Pentoxide and 2D Graphene Oxide Building Blocks.

Nature has evolved hierarchical structures of hybrid materials with excellent mechanical properties. Inspired by nacre's architecture, a ternary nanostructured composite has been developed, wherein stacked lamellas of 1D vanadium pentoxide nanofibres, intercalated with water molecules, are complemented by 2D graphene oxide (GO) nanosheets. The components self-assemble at low temperature into hierarchically arranged, highly flexible ceramic-based papers. The papers' mechanical properties are found to be strongly influenced by the amount of the integrated GO phase. Nanoindentation tests reveal an out-of-plane decrease in Young's modulus with increasing GO content. Furthermore, nanotensile tests reveal that the ceramic-based papers with 0.5 wt% GO show superior in-plane mechanical performance, compared to papers with higher GO contents as well as to pristine V2O5 and GO papers. Remarkably, the performance is preserved even after stretching the composite material for 100 nanotensile test cycles. The good mechanical stability and unique combination of stiffness and flexibility enable this material to memorize its micro- and macroscopic shape after repeated mechanical deformations. These findings provide useful guidelines for the development of bioinspired, multifunctional systems whose hierarchical structure imparts tailored mechanical properties and cycling stability, which is essential for applications such as actuators or flexible electrodes for advanced energy storage.

Piezoelectric Templates - New Views on Biomineralization and Biomimetics.

Biomineralization in general is based on electrostatic interactions and molecular recognition of organic and inorganic phases. These principles of biomineralization have also been utilized and transferred to bio-inspired synthesis of functional materials during the past decades. Proteins involved in both, biomineralization and bio-inspired processes, are often piezoelectric due to their dipolar character hinting to the impact of a template's piezoelectricity on mineralization processes. However, the piezoelectric contribution on the mineralization process and especially the interaction of organic and inorganic phases is hardly considered so far. We herein report the successful use of the intrinsic piezoelectric properties of tobacco mosaic virus (TMV) to synthesize piezoelectric ZnO. Such films show a two-fold increase of the piezoelectric coefficient up to 7.2 pm V(-1) compared to films synthesized on non-piezoelectric templates. By utilizing the intrinsic piezoelectricity of a biotemplate, we thus established a novel synthesis pathway towards functional materials, which sheds light on the whole field of biomimetics. The obtained results are of even broader and general interest since they are providing a new, more comprehensive insight into the mechanisms involved into biomineralization in living nature.

Hydrogen-bond reinforced vanadia nanofiber paper of high stiffness.

Low-temperature, solution-based self-assembly of vanadia nanofibers yields a free-standing, ceramic paper with an outstanding combination of high strength, stiffness, and macroscopic flexibility. Its excellent mechanical performance results from a brick-and-mortar like architecture, which combines strong covalent bonding within the single-crystalline nanofibers with an intricate hydrogen bonding network between them.

Silicateins--a novel paradigm in bioinorganic chemistry: enzymatic synthesis of inorganic polymeric silica.

The inorganic matrix of the siliceous skeletal elements of sponges, that is, spicules, is formed of amorphous biosilica. Until a decade ago, it remained unclear how the hard biosilica monoliths of the spicules are formed in sponges that live in a silica-poor (<50 µM) aquatic environment. The following two discoveries caused a paradigm shift and allowed an elucidation of the processes underlying spicule formation; first the discovery that in the spicules only one major protein, silicatein, exists and second, that this protein displays a bio-catalytical, enzymatic function. These findings caused a paradigm shift, since silicatein is the first enzyme that catalyzes the formation of an inorganic polymer from an inorganic monomeric substrate. In the present review the successive steps, following the synthesis of the silicatein product, biosilica, and resulting in the formation of the hard monolithic spicules is given. The new insight is assumed to open new horizons in the field of biotechnology and also in biomedicine.

Fabrication and characterization of biocompatible nacre-like structures from α-zirconium hydrogen phosphate hydrate and chitosan.

Composite materials with an ordered layered structure resembling that of nacre were fabricated by layer-by-layer assembly making use of presynthesized α-zirconium hydrogenphosphate hydrate (ZrP) platelets and chitosan. These two biocompatible materials were chosen in view of possible applications in the biomedical field, e.g., as bone or joint replacement implants. The effect of different concentrations of the inorganic ZrP platelets and the organic components (chitosan) on the composite assembly and structure was investigated. A high concentration of chitosan (0.1 wt.%) resulted in a misalignment of the inorganic platelets, while at very low concentrations (0.001 wt.%), the substrate was not fully covered by the polymer, again leading to misalignment. Also, the concentration of the α-ZrP platelets affected the composite assembly and structure. The number of dipping cycles was varied between 70 and 220, yielding a maximum thickness of approximately 6 µm. The pH value of the chitosan solution was also varied to investigate its influence on the composite assembly. The mechanical properties of the composites were tested with a nanoindenter. For samples prepared with the same number of dipping cycles, higher values of Young's modulus and hardness were obtained with improved alignment of the platelets in the samples. For samples prepared with 220 dipping cycles, a Young's modulus of 2.6 GPa and a hardness of 70 MPa were observed. Important general relationships are recognized between the preparation parameters, the degree of order within the nacre-like films and the resulting mechanical properties.

Toughening through nature-adapted nanoscale design.

The extraordinary combination of strength and toughness attained by nature's highly sophisticated structural design in nacre has inspired the synthesis of novel nanocomposites. In this context, the organic-inorganic hierarchical design of nacre has been mimicked. However, two key features of nacre, namely the scaling of the structural components and the low content of the organic phase, have not been replicated yet. Here, we present thin nanocomposite films with properly adjusted thicknesses of the organic and inorganic layers, as well as a microstructure that closely resembles that of nacre. These films, which are obtained by the combination of low-temperature chemical bath deposition of titania with layer-by-layer assembly of polyelectrolytes, exhibit enhancement in a fracture toughness by a factor of 4, combined with notable increase in hardness, while the Young's modulus is largely preserved in comparison to the single titania layer. Our findings highlight the significance of the 10:1 inorganic/organic layer thickness ratio evolved by nature, and provide novel perspectives for the future development of efficient bioinspired thin films.

Bio-sintering processes in hexactinellid sponges: fusion of bio-silica in giant basal spicules from Monorhaphis chuni.

The two sponge classes, Hexactinellida and Demospongiae, comprise a skeleton that is composed of siliceous skeletal elements (spicules). Spicule growth proceeds by appositional layering of lamellae that consist of silica nanoparticles, which are synthesized via the sponge-specific enzyme silicatein. While in demosponges during maturation the lamellae consolidate to a solid rod, the lamellar organization of hexactinellid spicules largely persists. However, the innermost lamellae, near the spicule core, can also fuse to a solid axial cylinder. Similar to the fusion of siliceous nanoparticles and lamella, in several hexactinellid species individual spicules unify during sintering-like processes. Here, we study the different stages of a process that we termed bio-sintering, within the giant basal spicule (GBS) of Monorhaphis chuni. During this study, a major GBS protein component (27 kDa) was isolated and analyzed by MALDI-TOF-MS. The sequences were used to isolate and clone the encoding cDNA via degenerate primer PCR. Bioinformatic analyses revealed a significant sequence homology to silicatein. In addition, the native GBS protein was able to mediate bio-silica synthesis in vitro. We conclude that the syntheses of bio-silica in M. chuni, and the subsequent fusion of nanoparticles to lamellae, and finally to spicules, are enzymatically-driven by a silicatein-like protein. In addition, evidence is now presented that in hexactinellids those fusions involve sintering-like processes.