Vladimir Kitaev

Catalytic Nanomotors: Self‐Propelled Sphere Dimers

Experimental and theoretical studies of the self-propelled motional dynamics of a new genre of catalytic sphere dimer, which comprises a non-catalytic silica sphere connected to a catalytic platinum sphere, are reported for the first time. Using aqueous hydrogen peroxide as the fuel to effect catalytic propulsion of the sphere dimers, both quasi-linear and quasi-circular trajectories are observed in the solution phase and analyzed for different dimensions of the platinum component. In addition, well-defined rotational motion of these sphere dimers is observed at the solution-substrate interface. The nature of the interaction between the sphere dimer and the substrate in the aqueous hydrogen peroxide phase is discussed. In computer simulations of the sphere dimer in solution and the solution-substrate interface, sphere-dimer dynamics are simulated using molecular-dynamics methods and solvent dynamics are modeled by mesoscopic multiparticle collision methods taking hydrodynamic interactions into account. The rotational and translational dynamics of the sphere dimer are found to be in good accord with the predictions of computer simulations.

Ultrathin Gold Nanoframes through Surfactant-Free Templating of Faceted Pentagonal Silver Nanoparticles

Ultrathin gold nanoframes (up to 1.6 nm) were prepared via templating upon well-defined faceted silver morphologies. Starting with silver decahedra, small quantities of gold (1-10 mol% relative to the amount of silver) were selectively deposited on the nanoparticle edges under optimized reducing conditions. Silver dissolution in hydrogen peroxide yielded well-defined gold frames that retained their structural integrity in the ultrathin nanowire regime below 2 nm. The frame formation protocol was also successfully applied to other silver nanoparticle shapes featuring pentagonal twinning and (111) facets (e.g., pentagonal faceted rods and icosahedra). The demonstrated approach can be applied in the controlled preparation of ultrathin metal nanowires complementary to lithography and in the production of ultrafine noble-metal nanostructures for catalytic applications.

Slow photons in the fast lane in chemistry

A driving force in the rapidly developing field of photonic crystals has been the photonic bandgap, a range of energies where the propagation of light is completely forbidden. The photonic bandgap allows the design of photonic lattices that localize, guide and bend light at sub-micron length scales, providing opportunities for the creation of miniature optical devices and integrated optical circuits to help drive the revolution in photonics. A less well known attribute of photonic crystals is their theoretical ability to slow light to a velocity of zero. This phenomenon can be achieved at the high and low energy edges of photonic stopgaps where the photonic bands are flat and light exists as a standing wave commensurate with the photonic lattice and travels at a group velocity of zero, referred to as “slow photons” herein. It has been shown theoretically that the probability of harvesting slow photons scales inversely with their group velocity. This means that a number of well known photon driven processes and devices in chemistry and physics can be enhanced by capturing this unique property of slow photons. In this paper we will look at slow photons mainly through the eye of chemistry and highlight some recent developments in this exciting and emerging field that demonstrate the potential of slow photons in materials chemistry and nanochemistry.

Chiral nanoscale building blocks—from understanding to applications

Recent advances in the area of chiral nano-building blocks are presented and discussed in the context of nanoscience and nanotechnology moving toward emerging functional applications of chiral nanomaterials, such as enantioselective catalysis, sensing and chirooptical devices. The emphasis is given to chiral nanoparticles and clusters. General perspectives of related helical and tubular chiral nanostructures are considered in terms of transferring chirality from the molecular level onto the nanoscale and reducing it to practical use.

Silver nanoparticles with planar twinned defects: effect of halides for precise tuning of plasmon resonance maxima from 400 to >900 nm

We studied effects of halides on morphology of planar twinned silver nanoparticles and demonstrated application of these effects to precisely tune silver surface plasmon resonance maxima in a broad vis-NIR range using a reliable two-stage modification protocol.

Monodisperse hexagonal silver nanoprisms: synthesis via thiolate-protected cluster precursors and chiral, ligand-imprinted self-assembly.

Silver nanoprisms of a predominantly hexagonal shape have been prepared using a ligand combination of a strongly binding thiol, captopril, and charge-stabilizing citrate together with hydrogen peroxide as an oxidative etching agent and a strong base that triggered nanoprism formation. The role of the reagents and their interplay in the nanoprism synthesis is discussed in detail. The beneficial role of chloride ions to attain a high degree of reproducibility and monodispersity of the nanoprisms is elucidated. Control over the nanoprism width, thickness, and, consequently, plasmon resonance in the system has been demonstrated. One of the crucial factors in the nanoprism synthesis was the slow, controlled aggregation of thiolate-stabilized silver nanoclusters as the intermediates. The resulting superior monodispersity (better than ca. 10% standard deviation in lateral size and ca. 15% standard deviation in thickness (<1 nm variation)) and charge stabilization of the produced silver nanoprisms enabled the exploration of the rich diversity of the self-assembled morphologies in the system. Regular columnar assemblies of the self-assembled nanoprisms spanning 2-3 μm in length have been observed. Notably, the helicity of the columnar phases was evident, which can be attributed to the chirality of the strongly binding thiol ligand. Finally, the enhancement of Raman scattering has been observed after oxidative removal of thiolate ligands from the AgNPR surface.

Direct structural transformation of silver platelets into right bipyramids and twinned cube nanoparticles: morphology governed by defects

Silver platelets can undergo quantitative conversion to right bipyramids and twinned cubes by regrowth with silver in conditions that preserve original 2-D structural defects in resulting 3-D morphologies.

On the nature and importance of the transition between molecules and nanocrystals: towards a chemistry of “nanoscale perfection”

This paper discusses the importance of the transition between molecular compounds and nanocrystals. The boundary between molecular and nanocrystals/nanoclusters can be defined by the emergence of the bulk phase; atoms in the core of the nanoclusters that are not bound to ligands. This transition in dimensions and structural organization is important because it overlaps with the boundary between atomically defined moieties (molecules can be isolated with increasing purity) and mixtures (nanocrystals have a distribution of sizes, shapes, and defects; they cannot be easily separated into batches of structurally identical species). Passing through this boundary, as the size of a structure increases beyond a few nanometres, the information about the position of each atom gradually disappears. This loss of structural information about a chemical structure fundamentally compromises our ability to use it as a part of a complex chemical system. If we are to engineer complex functions encoded in a chemical language, we will need pure batches of atomically defined (truly monodisperse) nanoscale compounds, and we will need to understand how to make them and preserve them over a broad range of length scales, compositions, and timeframes. In this review we survey most classes of monodisperse nanomaterials (mostly nanoclusters) and highlight the recent breakthroughs in this area which might be spearheading the development of a chemistry of nanoscale perfection.

Low-temperature synthesis of nanoscale silica multilayers – atomic layer deposition in a test tube

Herein we demonstrate a simplified, ‘poor-mans’ form of the Atomic Layer Deposition (ALD) technique to grow uniform silica multilayers onto hydrophilic surfaces at low temperatures, including room temperature (RT). Tetramethoxysilane vapor is used alternately with ammonia vapor as a catalyst, with very common benchtop lab equipment in an ambient environment. This deposition method could be applied in a wide range of fields for growing nanoscale layers of silica from an inexpensive vapor source, without the sophisticated vacuum systems or high temperatures that are generally required for ALD. Conditions for uniform deposition are demonstrated for 20-nm-thick silica shells grown around polymer spheres at RT, and in the interstitial space of a colloidal crystal film. This approach is shown to provide a controlled means of sintering the silica spheres and thereby is an easy way to modify the photonic and mechanical properties of the resulting material. We believe this method has an advantage compared to other more sophisticated methods of ALD and provides a simple technique for broad applications in MEMs, nanoporous structures, sintering of components, cell encapsulation, and organic/inorganic layered composites.

Colloidal photonic crystal cladded optical fibers: Towards a new type of photonic band gap fiber

A facile approach of fabricating a new type of hollow photonic band gap fibers is proposed. Templates for generating such fibers are demonstrated by a complete and uniform coating of a standard silica optical fiber (125 mum diameter) with a three-dimensional colloidal photonic crystal through isothermal heating evaporation induced self-assembly. The photonic crystal cylindrical annulus is characterized by optical and scanning electron microscopy, and is found to yield a 1.4-mum stop band by optical reflection and transmission spectroscopy. The results also demonstrate a practical means of enveloping macro- or micro-curved surfaces with three-dimensional photonic crystals, a task that is geometrically challenging by other photonic crystal fabrication methods.