Titanium dioxide is one of the most intensely studied oxides due to its interesting electrochemical and photocatalytic properties and it is widely applied, for example in photocatalysis, electrochemical energy storage, in white pigments, as support in catalysis, etc. Common synthesis methods of titanium dioxide typically require a high temperature step to crystallize the amorphous material into one of the polymorphs of titania, e.g. anatase, brookite and rutile, thus resulting in larger particles and mostly non-porous materials. Only recently, low temperature solution-based protocols gave access to crystalline titania with higher degree of control over the formed polymorph and its intra- or interparticle porosity. The present work critically reviews the formation of crystalline nanoscale titania particles via solution-based approaches without thermal treatment, with special focus on the resulting polymorphs, crystal morphology, surface area, and particle dimensions. Special emphasis is given to sol-gel processes via glycolated precursor molecules as well as the miniemulsion technique. The functional properties of these materials and the differences to chemically identical, non-porous materials are illustrated using heterogeneous catalysis and electrochemical energy storage (battery materials) as example.

An extremely facile approach to produce close‐packed colloidal monolayers over large areas using direct assembly at the air–water interface is presented. The influence of small amounts of sodium dodecyl sulfate (SDS) as well as the influence of the pH value of the subphase on the quality of the resulting monolayer is investigated. It is found that small amounts of SDS at the interface influence capillary forces and form a soft barrier that facilitates the crystallization process. Increased electrostatic repulsion arising from a higher pH of the subphase induced a higher order using carboxylic acid functionalized particles. The deposited close‐packed monolayers were subjected to plasma treatment in order to shrink the colloids and produce non‐close packed monolayers with lattice spacing and symmetry reflecting the order of the initial close‐packed monolayer. A detailed examination of etching conditions and their influence on the shrinkage of the particles was performed, including effects of plasma power, composition, flow rates as well as polymeric‐ and substrate material. The monolayers exhibit vivid coloration, which is determined by their size and packing density. UV–Vis–NIR spectroscopy was used to investigate the change of monolayer color during the size reduction of the individual particles. A simple theoretical model was elaborated to explain the optical properties. Finally, the non‐close‐packed monolayers were used as masks to produce gold nanostructures to exemplify the versatility of the monolayer architectures in nanosphere lithography.

Colloidal monolayers with high order and increased complexity beyond plain hexagonal packing geometries are useful for 2D templating of surface nanostructures and lithographic applications. Here, binary colloidal monolayers featuring a close‐packed monolayer of large spheres (L) with a superlattice of small particles (S) are prepared in a single step using a Langmuir trough. Adjustment of the stoichiometry of the two particle types at the air–water interface leads to a high degree of control over the occupation of the interstitial sites in the close‐packed layer of large spheres by the small colloids. Thus, large areas of binary 2D crystals with LS2, LS6, and LS9 structures are fabricated in a controlled way. The process allows the formation of binary crystals over a wide range of particle size ratios from 0.19 to 0.40. The pH value of the subphase can be used to enhance the crystallization process by changing the contact angle of the particles at the interface. An interfacial polymerization of butyl cyanoacrylate is used to directly image the contact angle of the colloids at the interface. Transfer to solid substrates is achieved by a surface lowering technique. A variety of substrates with arbitrary topographies can thus be decorated with colloidal monolayers. Applied to a lithographic process, such monolayer architectures allow the generation of complex patterns, not accessible with conventional close‐packed monolayers.

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