Sequential Synthesis Methodology Yielding Well-Defined Porous 75%SrTiO3/25%NiFe2O4 Nanocomposite

In this research, we reported on the formation of highly porous foam SrTiO3/NiFe2O4 (100−xSTO/xNFO) heterostructure by joint solid-state and sol-gel auto-combustion techniques. The colloidal assembly process is discussed based on the weight ratio x (x = 0, 25, 50, 75, and 100 wt %) of NiFe2O4 in the 100−xSTO/xNFO system. We proposed a mechanism describing the highly porous framework formation involving the self-assembly of SrTiO3 due to the gelation process of the nickel ferrite. We used a series of spectrophotometric techniques, including powder X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), N2 adsorption isotherms method, UV-visible diffuse reflectance spectra (UV-Vis DRS), vibrating sample magnetometer (VSM), and dielectric measurements, to investigate the structural, morphological, optical, magnetic, and dielectric properties of the synthesized samples. As revealed by FE-SEM analysis and textural characteristics, SrTiO3-NiFe2O4 nanocomposite self-assembled into a porous foam with an internally well-defined porous structure. HRTEM characterization certifies the distinctive crystalline phases obtained and reveals that SrTiO3 and NiFe2O4 nanoparticles were closely connected. The specific magnetization, coercivity, and permittivity values are higher in the 75STO/25NFO heterostructure and do not decrease proportionally to the amount of non-magnetic SrTiO3 present in the composition of samples.

Self-regulated co-assembly of soft and hard nanoparticles

Controlled self-assembly of colloidal particles into predetermined organization facilitates the bottom-up manufacture of artificial materials with designated hierarchies and synergistically integrated functionalities. However, it remains a major challenge to assemble individual nanoparticles with minimal building instructions in a programmable fashion due to the lack of directional interactions. Here, we develop a general paradigm for controlled co-assembly of soft block copolymer micelles and simple unvarnished hard nanoparticles through variable noncovalent interactions, including hydrogen bonding and coordination interactions. Upon association, the hairy micelle corona binds with the hard nanoparticles with a specific valence depending exactly on their relative size and feeding ratio. This permits the integration of block copolymer micelles with a diverse array of hard nanoparticles with tunable chemistry into multidimensional colloidal molecules and polymers. Secondary co-assembly of the resulting colloidal molecules further leads to the formation of more complex hierarchical colloidal superstructures. Notably, such colloidal assembly is processible on surface either through initiating the alternating co-assembly from a micelle immobilized on a substrate or directly grafting a colloidal oligomer onto the micellar anchor.

Microscopic origins of the crystallographically preferred growth in evaporation-induced colloidal crystals

Unlike crystalline atomic and ionic solids, texture development due to crystallographically preferred growth in colloidal crystals is less studied. Here we investigate the underlying mechanisms of the texture evolution in an evaporation-induced colloidal assembly process through experiments, modeling, and theoretical analysis. In this widely used approach to obtain large-area colloidal crystals, the colloidal particles are driven to the meniscus via the evaporation of a solvent or matrix precursor solution where they close-pack to form a face-centered cubic colloidal assembly. Via two-dimensional large-area crystallographic mapping, we show that the initial crystal orientation is dominated by the interaction of particles with the meniscus, resulting in the expected coalignment of the close-packed direction with the local meniscus geometry. By combining with crystal structure analysis at a single-particle level, we further reveal that, at the later stage of self-assembly, however, the colloidal crystal undergoes a gradual rotation facilitated by geometrically necessary dislocations (GNDs) and achieves a large-area uniform crystallographic orientation with the close-packed direction perpendicular to the meniscus and parallel to the growth direction. Classical slip analysis, finite element-based mechanical simulation, computational colloidal assembly modeling, and continuum theory unequivocally show that these GNDs result from the tensile stress field along the meniscus direction due to the constrained shrinkage of the colloidal crystal during drying. The generation of GNDs with specific slip systems within individual grains leads to crystallographic rotation to accommodate the mechanical stress. The mechanistic understanding reported here can be utilized to control crystallographic features of colloidal assemblies, and may provide further insights into crystallographically preferred growth in synthetic, biological, and geological crystals.

Tunable thermo-reversible bicontinuous nanoparticle gel driven by the binary solvent segregation

Bicontinuous porous structures through colloidal assembly realized by non-equilibrium process is crucial to various applications, including water treatment, catalysis and energy storage. However, as non-equilibrium structures are process-dependent, it is very challenging to simultaneously achieve reversibility, reproducibility, scalability, and tunability over material structures and properties. Here, a novel solvent segregation driven gel (SeedGel) is proposed and demonstrated to arrest bicontinuous structures with excellent thermal structural reversibility and reproducibility, tunable domain size, adjustable gel transition temperature, and amazing optical properties. It is achieved by trapping nanoparticles into one of the solvent domains upon the phase separation of the binary solvent. Due to the universality of the solvent driven particle phase separation, SeedGel is thus potentially a generic method for a wide range of colloidal systems.

Colloidal assembly by directional ice templating

We investigate directional ice templating of dilute aqueous colloidal particle dispersions and examine the nature of the assemblies that result.