Detecting patchy nanoparticle assembly at the single-particle level

Patchy colloidal particles offer a unique platform to explore and investigate spatially inhomogeneous colloidal interactions. In the present work we provide direct, in situ experimental observation at the single particle level on the colloidal interaction driven formation of a heterodimer, consisting of a patchy nanorod and a sphere. The gold nanorods employed during the experiments feature positively charged tip regions, while the side of the rods is covered by surface grafted PEG. The driving force of the assembly is the electric double layer interaction between the nanorod and the nanosphere possessing opposite surface charge. The great advantage of using gold heterodimers is that their optical scattering spectrum characteristics are known to be very sensitive to the actual structure of the assembly due to plasmon hybridization. This was exploited to determine the structure of the heterodimer in situ upon formation in aqueous medium. The results indicate, that despite the attractive patches being located at the nanorod tips, for the given particle pairs the spheres readily bind to the side region of the nanorods in the aqueous medium during the assembly. Finite element simulations of the electric double layer interaction reveal that this is the energetically favorable configuration for the given heterodimer. This work demonstrates the potential of in situ experiments performed at single particle level for the characterization of self-assembling structures, which can contribute to the development of rationally designed nanoscale building blocks

Control Over Structure and Properties in Nanocrystal Aerogels at the Nano-, Micro-, and Macroscale

The assembly of individual colloidal nanocrystals into macroscopic solvogels and aerogels introduced a new exciting type of material into the class of porous architectures. In these so-called nanocrystal gels, the structure and properties can be controlled and fine-tuned to the smallest details. Recently it was shown that by employing nanocrystal building blocks for such gel materials, the interesting nanoscopic properties can be conserved or even expanded to properties that are available neither in the nanocrystals nor in their respective bulk materials. In general, the production of these materials features the wet-chemical synthesis of stable nanocrystal colloids followed by their carefully controlled destabilization to facilitate arrangement of the nanocrystals into highly porous, interconnected networks. By isolation of the synthesis of the discrete building blocks from the assembly process, the electronic structure, optical properties, and structural morphology can be tailored by the myriad of procedures developed in colloidal nanocrystal chemistry. Furthermore, knowledge and control over the structure-property correlation in the resulting gel structures opens up numerous new ways for extended and advanced applications. Consequently, the amount of different materials converted to nanocrystal-based gel structures is rising steadily. Meanwhile the number of methods for assembly initiation is likewise increasing, offering control over the overall network structure and porosity as well as the individual nanocrystal building block connection. The resulting networks can be dried by different methods to obtain highly porous air-filled networks (aerogels) or applied in their wet form (solvogels). By now a number of different applications profiting from the unique advantages of nanocrystal-based gel materials have been realized and exploited in the areas of photocatalysis, electrocatalysis, and sensing.In this Account, we aim to summarize the efforts undertaken in the structuring of nanocrystal-based network materials on different scales, fine-tuning of the individual building blocks on the nanoscale, the network connections on the microscale, and the macroscale structure and shape of the final construct. It is exemplarily demonstrated how cation exchange reactions (at the nanoscale), postgelation modifications on the nanocrystal networks (microscale), and the structuring of the gels via printing techniques (macroscale) endow the resulting nanocrystal gel networks with novel physicochemical, mechanical, and electrocatalytic properties. The methods applied in the more traditional sol-gel chemistry targeting micro- and macroscale structuring are also reviewed, showing their future potential promoting the field of nanocrystal-based aerogels and their applications. Copyright © 2020 American Chemical Society

Temperature and Composition Dependent Optical Properties of CdSe/CdS Dot/Rod-Based Aerogel Networks

Employing nanocrystals (NCs) as building blocks of porous aerogel network structures allows the conversion of NC materials into macroscopic solid structures while conserving their unique nanoscopic properties. Understanding the interplay of the network formation and its influence on these properties like size-dependent emission is a key to apply techniques for the fabrication of novel nanocrystal aerogels. In this work, CdSe/CdS dot/rod NCs possessing two different CdSe core sizes were synthesized and converted into porous aerogel network structures. Temperature-dependent steady-state and time-resolved photoluminescence measurements were performed to expand the understanding of the optical and electronic properties of these network structures generated from these two different building blocks and correlate their optical with the structural properties. These investigations reveal the influence of network formation and aerogel production on the network-forming nanocrystals. Based on the two investigated NC building blocks and their aerogel networks, mixed network structures with various ratios of the two building blocks were produced and likewise optically characterized. Since the different building blocks show diverse optical response, this technique presents a straightforward way to color-tune the resulting networks simply by choosing the building block ratio in connection with their quantum yield

Cryoaerogels and Cryohydrogels as Efficient Electrocatalysts

Additive-free cryoaerogel coatings from noble metal nanoparticles are prepared and electrochemically investigated. By using liquid nitrogen or isopentane as cooling medium, two different superstructures are created for each type of noble metal nanoparticle. These materials (made from the same amount of particles) have superior morphological and catalytic properties as compared to simply immobilized, densely packed nanoparticles. The morphology of all materials is investigated with scanning electron microscopy (SEM). Electrochemically active surface areas (ECSAs) are calculated from cyclic voltammetry measurements. The catalytic activity is studied for the ethanol oxidation reaction (EOR). Both are found to be increased for superstructured materials prepared by cryoaerogelation. Furthermore, cryoaerogels with cellular to dendritic structure that arise from freezing with isopentane show the best catalytic performance and highest ECSA. Moreover, as a new class of materials, cryohydrogels are created for the first time by thawing flash-frozen nanoparticle solutions. Structure and morphology of these materials match with the corresponding types of cryoaerogels and are confirmed via SEM. Even the catalytic activity in EOR is in accordance with the results from cryoaerogel coatings. As a proof of concept, this approach offers a novel platform towards the easier and faster production of cryogelated materials for wet-chemical applications

Noble-Metal Nanorod Cryoaerogels with Electrocatalytically Active Surface Sites

Noble-metal-based electrocatalysts usually contain small nanoparticle building blocks to ensure a high specific surface area as the scene for the surface processes. Here, we show that relatively large noble-metal nanorods are also promising candidates to build up functional macrostructures with prominent electrocatalytic activity. After optimizing and upscaling the syntheses of gold nanorods and gold bipyramid-templated silver nanorods, cryoaerogels are fabricated on a conductive substrate via flash freezing and subsequent freeze drying. The versatile cryoaerogelation technique allows the formation of macrostructures with dendritic, open-pore structure facilitating the increase of the accessible nanorod surfaces. It is demonstrated via electrochemical oxidation and stripping test experiments that noble-metal surface sites are electrochemically active in redox reactions. Furthermore, gold nanorod cryoaerogels offer a platform for redox sensing, ethanol oxidation reaction, as well as glucose sensing. Compared to their simply drop-cast and dried counterparts, the noble-metal nanorod cryoaerogels offer enhanced activity due to the open porosity of the fabricated nanostructure while maintaining structural stability