Bimetallic nanorods are important colloidal nanoparticles for optical applications, sensing, and light-enhanced catalysis due to their versatile plasmonic properties. However, tuning the plasmonic resonances is challenging as it requires a simultaneous control over the particle shape, shell thickness, and morphology. Here, we show that we have full control over these parameters by performing metal overgrowth on gold nanorods within a mesoporous silica shell, resulting in Au–Ag, Au–Pd, and Au–Pt core–shell nanorods with precisely tunable plasmonic properties. The metal shell thickness was regulated via the precursor concentration and reaction time in the metal overgrowth. Control over the shell morphology was achieved via a thermal annealing, enabling a transition from rough nonepitaxial to smooth epitaxial Pd shells while retaining the anisotropic rod shape. The core–shell synthesis was successfully scaled up from micro- to milligrams, by controlling the kinetics of the metal overgrowth via the pH. By carefully tuning the structure, we optimized the plasmonic properties of the bimetallic core–shell nanorods for surface-enhanced Raman spectroscopy. The Raman signal was the most strongly enhanced by the Au core–Ag shell nanorods, which we explain using finite-difference time-domain calculations.

Nanoparticles of Co3O4 and CoO are of paramount importance because of their chemical properties propelling their applications in catalysis and battery materials, and because of their intriguing magnetic properties. Here...

Thermally induced structural transformation of 2D materials opens unique avenues for generating other 2D materials by physical methods. Imaging these transitions in real time provides insight into synthesis routes and property tuning. We have used in situ transmission electron microscopy (TEM) to follow thermally induced structural transformations in layered CoSe2. Three transformation processes are observed: orthorhombic to cubic-CoSe2, cubic-CoSe2 to hexagonal-CoSe, and hexagonal to tetragonal-CoSe. In particular, the unit-cell-thick orthorhombic structure of CoSe2 transforms into cubic-CoSe2 via rearrangement of lattice atoms. Cubic-CoSe2 transforms to hexagonal-CoSe at elevated temperatures through the removal of chalcogen atoms. All nanosheets transform to basal-plane-oriented hexagonal 2D CoSe. Finally, the hexagonal to tetragonal transformation in CoSe is a rapid process wherein the layered morphology of hexagonal-CoSe is broken and islands of tetragonal-CoSe are formed. Our results provide nanoscopic insights into the transformation processes of 2D CoSe2 which can be used to generate these intriguing 2D materials and to tune their properties by modifying their structures for electro-catalytic and electronic applications.

The recent development of liquid cell (scanning) transmission electron microscopy (LC-(S)TEM) has opened the unique possibility of studying the chemical behavior of nanomaterials down to the nanoscale in a liquid environment. Here, we show that the chemically induced etching of three different types of silica-based silica nanoparticles can be reliably studied at the single particle level using LC-(S)TEM with a negligible effect of the electron beam, and we demonstrate this method by successfully monitoring the formation of silica-based heterogeneous yolk–shell nanostructures. By scrutinizing the influence of electron beam irradiation, we show that the cumulative electron dose on the imaging area plays a crucial role in the observed damage and needs to be considered during experimental design. Monte-Carlo simulations of the electron trajectories during LC-(S)TEM experiments allowed us to relate the cumulative electron dose to the deposited energy on the particles, which was found to significantly alter the silica network under imaging conditions of nanoparticles. We used these optimized LC-(S)TEM imaging conditions to systematically characterize the wet etching of silica and metal(oxide)–silica core–shell nanoparticles with cores of gold and iron oxide, which are representative of many other core–silica–shell systems. The LC-(S)TEM method reliably reproduced the etching patterns of Stöber, water-in-oil reverse microemulsion (WORM), and amino acid-catalyzed silica particles that were reported before in the literature. Furthermore, we directly visualized the formation of yolk–shell structures from the wet etching of Au@Stöber silica and Fe 3 O 4 @WORM silica core–shell nanospheres.

Yolk-shell nanoparticles based on mesoporous SiO2 (mSiO2) coating of Au nanoparticles (Au NPs) hold great promise for many applications in e.g., catalysis, biomedicine, and sensing. Here, we present a single-step...