A colloidoscope of colloid-based porous materials and their uses

Nature evolved a variety of hierarchical structures that produce sophisticated functions. Inspired by these natural materials, colloidal self-assembly provides a convenient way to produce structures from simple building blocks with a variety of complex functions beyond those found in nature. In particular, colloid-based porous materials (CBPM) can be made from a wide variety of materials. The internal structure of CBPM also has several key attributes, namely porosity on a sub-micrometer length scale, interconnectivity of these pores, and a controllable degree of order. The combination of structure and composition allow CBPM to attain properties important for modern applications such as photonic inks, colorimetric sensors, self-cleaning surfaces, water purification systems, or batteries. This review summarizes recent developments in the field of CBPM, including principles for their design, fabrication, and applications, with a particular focus on structural features and materials’ properties that enable these applications. We begin with a short introduction to the wide variety of patterns that can be generated by colloidal self-assembly and templating processes. We then discuss different applications of such structures, focusing on optics, wetting, sensing, catalysis, and electrodes. Different fields of applications require different properties, yet the modularity of the assembly process of CBPM provides a high degree of tunability and tailorability in composition and structure. We examine the significance of properties such as structure, composition, and degree of order on the materials’ functions and use, as well as trends in and future directions for the development of CBPM.Engineering and Applied Science

Raspberry Colloid Templated Catalysts Fabricated Using Spray Drying Method

The majority of industrial chemical processes—from production of organic and inorganic compounds to air and water treatment—rely on heterogeneous catalysts. The performance of these catalysts has improved over the past several decades; in parallel, many innovations have been presented in publications, demonstrating increasingly higher efficiency and selectivity. One common challenge to adopting novel materials in real-world applications is the need to develop robust and cost-effective synthetic procedures for their formation at scale. Herein, we focus on the scalable production of a promising new class of materials—raspberry-colloid-templated (RCT) catalysts—that have demonstrated exceptional thermal stability and high catalytic activity. The unique synthetic approach used for the fabrication of RCT catalysts enables great compositional flexibility, making these materials relevant to a wide range of applications. Through a series of studies, we identified stable formulations of RCT materials that can be utilized in the common industrial technique of spray drying. Using this approach, we demonstrate the production of highly porous Pt/Al2O3 microparticles with high catalytic activity toward complete oxidation of toluene as a model reaction

Nanocrystalline Precursors for the Co-Assembly of Crack-Free Metal Oxide Inverse Opals

Inorganic microstructured materials are ubiquitous in nature. However, their formation in artificial self‐assembly systems is challenging as it involves a complex interplay of competing forces during and after assembly. For example, colloidal assembly requires fine‐tuning of factors such as the size and surface charge of the particles and electrolyte strength of the solvent to enable successful self‐assembly and minimize crack formation. Co‐assembly of templating colloidal particles together with a sol–gel matrix precursor material helps to release stresses that accumulate during drying and solidification, as previously shown for the formation of high‐quality inverse opal (IO) films out of amorphous silica. Expanding this methodology to crystalline materials would result in microscale architectures with enhanced photonic, electronic, and catalytic properties. This work describes tailoring the crystallinity of metal oxide precursors that enable the formation of highly ordered, large‐area (mm2) crack‐free titania, zirconia, and alumina IO films. The same bioinspired approach can be applied to other crystalline materials as well as structures beyond IOs.Chemistry and Chemical Biolog

A colloidoscope of colloid-based porous materials and their uses

Nature evolved a variety of hierarchical structures that produce sophisticated functions. Inspired by these natural materials, colloidal self-assembly provides a convenient way to produce structures from simple building blocks with a variety of complex functions beyond those found in nature. In particular, colloid-based porous materials (CBPM) can be made from a wide variety of materials. The internal structure of CBPM also has several key attributes, namely porosity on a sub-micrometer length scale, interconnectivity of these pores, and a controllable degree of order. The combination of structure and composition allow CBPM to attain properties important for modern applications such as photonic inks, colorimetric sensors, self-cleaning surfaces, water purification systems, or batteries. This review summarizes recent developments in the field of CBPM, including principles for their design, fabrication, and applications, with a particular focus on structural features and materials' properties that enable these applications. We begin with a short introduction to the wide variety of patterns that can be generated by colloidal self-assembly and templating processes. We then discuss different applications of such structures, focusing on optics, wetting, sensing, catalysis, and electrodes. Different fields of applications require different properties, yet the modularity of the assembly process of CBPM provides a high degree of tunability and tailorability in composition and structure. We examine the significance of properties such as structure, composition, and degree of order on the materials' functions and use, as well as trends in and future directions for the development of CBPM

New Architectures for Designed Catalysts: Selective Oxidation using AgAu Nanoparticles on Colloid-Templated Silica

A highly modular synthesis of designed catalysts with controlled bimetallic nanoparticle size and composition and a well-defined structural hierarchy is demonstrated. Exemplary catalysts—bimetallic dilute Ag-in-Au nanoparticles partially embedded in a porous SiO2 matrix (SiO2-AgxAuy)—were synthesized by the decoration of polymeric colloids with the bimetallic nanoparticles followed by assembly into a colloidal crystal backfilled with the matrix precursor and subsequent removal of the polymeric template. We show that these new catalysts architectures are significantly better than nanoporous dilute AgAu alloy catalysts (nanoporous Ag0.03Au0.97) while retaining a clear predictive relationship between their surface reactivity with that of single crystal Au surfaces. This paves the way for broadening the range of new catalyst architectures required for translating the designed principles developed under controlled conditions to designed catalysts under operating conditions for highly selective coupling of alcohols to form esters. Excellent catalytic performance of the porous SiO2-AgxAuy structure for selective oxidation of both methanol and ethanol to produce esters with high conversion efficiency, selectivity, and stability was demonstrated, illustrating the ability to translate design principles developed for support-free materials to the colloid-templated structures. The synthetic methodology reported is customizable for the design of a wide range of robust catalytic systems inspired by design principles derived from model studies. Fine control over the composition, morphology, size, distribution and availability of the supported nanoparticles was demonstrated.Chemistry and Chemical Biolog

The Optical Janus Effect: Asymmetric Structural Color Reflection Materials

Structurally colored materials are often used for their resistance to photobleaching and their complex viewing direction-dependent optical properties. Frequently, absorption has been added to these types of materials in order to improve the color saturation by mitigating the effects of nonspecific scattering that is present in most samples due to imperfect manufacturing procedures. The combination of absorbing elements and structural coloration often yields emergent optical properties. Here, we introduce a new hybrid architecture that leads to an interesting, highly directional optical effect. By localizing absorption in a thin layer within a transparent, structurally colored multilayer material, we create an optical Janus effect, wherein the observed reflected color is different on one side of the sample than on the other. We perform a systematic characterization of the optical properties of these structures as a function of their geometry and composition. The experimental studies are coupled with a theoretical analysis that enables a precise, rational design of various optical Janus structures with highly controlled color, pattern and fabrication approaches. These asymmetrically colored materials will open applications in art, architecture, semitransparent solar cells and security features in anti- counterfeiting materials.Chemistry and Chemical Biolog

Self-Assembled Organic Nanocrystals with Strong Nonlinear Optical Response

Facile molecular self-assembly affords a new family of organic nanocrystals that, unintuitively, exhibit a significant nonlinear optical response (second harmonic generation, SHG) despite the relatively small molecular dipole moment of the constituent molecules. The nanocrystals are self-assembled in aqueous media from simple monosubstituted perylenediimide (PDI) molecular building blocks. Control over the crystal dimensions can be achieved via modification of the assembly conditions. The combination of a simple fabrication process with the ability to generate soluble SHG nanocrystals with tunable sizes may open new avenues in the area of organic SHG materials