Self-aggregated colloids can be used for the preparation of materials, and we studied long rod-like aggregates formed on the evaporation of water from dispersed particles of colloidal hydrochar. The monodispersed hydrochar particles (100–200 nm) were synthesized by the hydrothermal carbonization ofglucose and purified through dialysis. During the synthesis they formed colloidal dispersions which wereelectrostatically stable at intermediate to high pH and at low ion strengths. On the evaporation of water,macroscopically large rods formed from the dispersions at intermediate pH conditions. The rods formedat the solid-water interface orthogonally oriented with respect to the drying direction. Pyrolysis renderedthe rods highly porous without qualitatively affecting their shape. A Cu-Si alloy was reactively infiltratedinto the in-situ pyrolyzed hydrochars and composites of tricopper silicide (Cu3Si)-silicon carbide(SiC)/carbon formed. During this process, the Si atoms reacted with the C atoms, which in turned causedthe alloy to wet and further react with the carbon. The shape of the underlying carbon template wasmaintained during the reactions, and the formed composite preparation was subsequently calcined intoa Cu3Si-SiC-based replica of the rod-like assemblies of carbon-based colloidal particles. Transmission andscanning electron microscopy, and X-ray diffraction were used to study the shape, composition, andstructure of the formed solids. Further studies of materials prepared with reactive infiltration of alloysinto self-aggregated and carbon-based solids can be justified from a perspective of colloidal science, aswell as the explorative use of hydrochar prepared from real biomass, exploration of the compositionalspace in relation to the reactive infiltration, and applications of the materials in catalysis. 

Amorphous calcium carbonate (ACC), with the highest reported specific surface area of all current forms of calcium carbonate (over 350 m(2) g(-1)), was synthesized using a surfactant-free, one-pot method. Electron microscopy, helium pycnometry, and nitrogen sorption analysis revealed that this highly mesoporous ACC, with a pore volume of similar to 0.86 cm(3) g(-1) and a pore-size distribution centered at 8-9 nm, is constructed from aggregated ACC nanoparticles with an estimated average diameter of 7.3 nm. The porous ACC remained amorphous and retained its high porosity for over 3 weeks under semi-air-tight storage conditions. Powder X-ray diffraction, large-angle X-ray scattering, infrared spectroscopy, and electron diffraction exposed that the porous ACC did not resemble any of the known CaCO3 structures. The atomic order of porous ACC diminished at interatomic distances over 8 angstrom. Porous ACC was evaluated as a potential drug carrier of poorly soluble substances in vitro. Itraconazole and celecoxib remained stable in their amorphous forms within the pores of the material. Drug release rates were significantly enhanced for both drugs (up to 65 times the dissolution rates for the crystalline forms), and supersaturation release of celecoxib was also demonstrated. Citric acid was used to enhance the stability of the ACC nanoparticles within the aggregates, which increased the surface area of the material to over 600 m(2) g(-1). This porous ACC has potential for use in various applications where surface area is important, including adsorption, catalysis, medication, and bone regeneration.

Amine-CO2 chemistry is important for a range of different chemical processes, including carbon dioxide capture. Here, we studied how aspects of this chemistry could be used to prepare calcium carbonates. Chemically crosslinked organogels were first prepared by reacting hyperbranched polyethylene imine (PEI) dissolved in DMSO with carbon dioxide. The crosslinks of the organogel consisted of ammonium-carbamate ion pairs as was shown by IR spectroscopy. These carbamate-rich organogels were subsequently subjected to aqueous solutions of calcium acetate, and amorphous calcium carbonate (ACC) precipitated. The ACC did not crystalize during the mixing for up to 20 h, as was shown by a combination of IR spectroscopy, X-ray diffraction, scanning electron microscopy, and thermal analysis. Some PEI had been included or adsorbed on the ACC particles. Traces of calcite were observed in one sample that had been subjected to water in a work-up procedure.