Directed aerosol writing of ordered silica nanostructures on arbitrary surfaces with self-assembling inks.

This paper reports the fabrication of micro- and macropatterns of ordered mesostructured silica on arbitrary flat and curved surfaces using a facile robot-directed aerosol printing process. Starting with a homogenous solution of soluble silica, ethanol, water, and surfactant as a self-assembling ink, a columnated stream of aerosol droplets is directed to the substrate surface. For deposition at room temperature droplet coalescence on the substrates and attendant solvent evaporation result in continuous, highly ordered mesophases. The pattern profiles are varied by changing any number of printing parameters such as material deposition rate, printing speed, and aerosol-head temperature. Increasing the aerosol temperature results in a decrease of the mesostructure ordering, since faster solvent evaporation and enhanced silica condensation at higher temperatures kinetically impede the molecular assembly process. This facile technique provides powerful control of the printed materials at both the nanoscale and microscale through chemical self-assembly and robotic engineering, respectively.

Mesoporous carbon/silica nanocomposite through multi-component assembly.

Ordered mesoporous carbon/silica nanocomposites were synthesized through a novel multi-component molecular assembly and show promising potential as corrosion-resisted electrocatalyst supports.

Thermochromatism and structural evolution of metastable polydiacetylenic crystals.

Topochemically polymerized sodium 10,12-pentacosadiynoate (PCDA-Na) microcrystals show an irreversible red-to-blue chromatic transition accompanied by a distinct structural evolution upon initial thermal treatment, and show a subsequent completely reversible blue-to-red chromatic transition upon further thermal stimuli. Visible absorption spectroscopy, X-ray diffraction (XRD), and differential scanning calorimetry (DSC) are used to investigate the thermochromatic transition behavior of the polydiacetylenic microcrystals. Brief quantum mechanical geometry optimization is employed to explain the lattice dimensional change during the irreversible red-to-blue chromatic transition of the metastable polydiacetylenic crystals.

Mesoscopically ordered organosilica and carbon-silica hybrids with uniform morphology by surfactant-assisted self-assembly of organo bis-silanetriols.

Long-range molecularly ordered organosilica and carbon-silica hybrids with uniform morphology have been synthesized by surfactant-assisted hydrolysis and self-assembly of biphenyl bridged organosilane, followed by thermal polycondensation and carbonization.

A general approach towards hierarchical porous carbon particles.

A general, aerosol-based, one-step approach was explored to synthesize microporous and mesoporous spherical carbon particles with highly porous foam-like structures from aqueous sucrose solutions containing colloidal silica particles and/or silicate cluster templates.

Mesoporous silica with Ia3d cubic structure and good thermal stability.

Ia3d cubic mesoporous silica with unusual thermal stability has been synthesized using cetyltrimethylammonium bromide (CTAB) and sugar surfactant dodecyl-beta-D-maltoside (DM) as co-templates.

Synthesis of highly-ordered mesoporous carbon/silica nanocomposites and derivative hierarchically mesoporous carbon from a phenyl-bridged organosiloxane.

Mesoporous carbon/silica nanocomposites and derivative hierarchically mesoporous carbon have been prepared using 1,4-bis(triethoxysilyl)benzene (BTEB) as a precursor for a carbon/silica network and Pluronic P123 (HO(CH(2)CH(2)O)(20)(CH(2)CH(CH(3))O)(70)(CH(2)CH(2)O)(20)H) as a template for highly-ordered hexagonal pores. Co-assembly of BTEB and P123 and subsequent carbonization results in a mesoporous carbon/silica nanocomposite with hexagonally oriented pores. Removal of the silica component in the carbon/silica network creates a second porosity in the network and results in hierarchically mesoporous carbon. The mesostructure of these materials was characterized by transmission electron microscopy (TEM), field-emission scanning electron microscopy (FE-SEM), powder X-ray diffraction (PXRD), and N(2) sorption.

Surfactant templating effects on the encapsulation of iron oxide nanoparticles within silica microspheres.

Hollow silica microspheres encapsulating ferromagnetic iron oxide nanoparticles were synthesized by a surfactant-aided aerosol process and subsequent treatment. The cationic surfactant cetyltrimethyl ammonium bromide (CTAB) played an essential role in directing the structure of the composite. Translation from mesoporous silica particles to hollow particles was a consequence of increased loading of ferric species in the precursor solution and the competitive partitioning of CTAB between silicate and ferric colloids. The hypothesis was that CTAB preferentially adsorbed onto more positively charged ferric colloids under acidic conditions. At a critical Fe/Si ratio, most of the CTAB was adsorbed onto ferric colloids and coagulated the colloids to form larger clusters. During the aerosol process, a silica shell was first formed due to the preferred silicate condensation on the gas-liquid interface of the aerosol droplet. Subsequent drying concentrated the ferric clusters inside the silica shell and resulted in a silica shell/ferric core particle. Thermal treatment of the core shell particle led to encapsulation of a single iron oxide nanoparticle inside each silica hollow microsphere.

Responsive periodic mesoporous polydiacetylene/silica nanocomposites.

Responsive PMO materials have been synthesized through co-assembly of bridged diacetylenic silsesquioxane and surfactant. The spatially defined polydiacetylenic component, mesoporous network, and the covalent proximity of polydiacetylene to silica endow the PMO with mechanical robustness, reversible chromatic responses, improved thermal stability, and faster responses to chemical stimuli. This research also provides an efficient molecular design and assembly paradigm to fabricate a family of conjugated optoelectronic materials, creating novel platforms for sensors, actuators, and other device applications.

Polydiacetylene/silica nanocomposites with tunable mesostructure and thermochromatism from diacetylenic assembling molecules.

Conjugated polydiacetylene (PDA)/silica nanocomposites with tunable mesostructures and reversible thermochromatism were synthesized through self-directed assembly of diacetylenic silanes. In contrast to the previous studies, where the PDA side chains interacted weakly through noncovalent interactions, the side chains in the present nanocomposites are covalently connected to the inorganic silica frameworks, providing control over the molecular alignment, stability, and electronic properties. Furthermore, tuning the molecular architecture (e.g., the shape and side-chain length) allows control over the mesostructure (e.g., cubic and lamellar) and chromatic response of the nanocomposites (from irreversible to partially reversible and then to completely reversible). As a result of the covalent interactions, the nanocomposites also demonstrate higher reversible chromatic transition temperatures. This work not only provides responsive robust chromatic materials toward practically reusable PDA sensors but also is of great fundamental value for the design of supramolecular assembly and the understanding of the chromatic mechanism of PDA.