Variable Mechanical Properties in Layered Copper Bromide Hybrid Solids Based on Configuration of Organic Cations.

Organic-inorganic organohalide hybrid solids have garnered significant attention due to their unique structural diversity, desirable electronic structures, and excellent optoelectronic properties. Here, we investigate the mechanical properties of a homologous series of 2D copper bromide hybrids (A2CuBr4, ACuBr4) through nanoindentation to analyze the contribution of organic interlayer interactions to bulk mechanical response. We identify a direct correlation between the identity of the organic spacer and the bulk mechanical response, where stronger bonding interactions in the organic interlayer resulted in increased hardness and elasticity. Additionally, we uncover a unique conformational dependence within the series of arylammonium spacers which was found to periodically modulate pi-pi interactions between neighboring molecules, leading to an alternating even-odd bulk material response.

Heterogeneous Ice Nucleation in Model Crystalline Porous Organic Polymers: Influence of Pore Size on Immersion Freezing.

Heterogeneous ice nucleation activity is affected by aerosol particle composition, crystallinity, pore size, and surface area. However, these surface properties are not well understood, regarding how they act to promote ice nucleation and growth to form ice clouds. Therefore, synthesized materials for which surface properties can be tuned were examined in immersion freezing mode in this study. To establish the relationship between particle surface properties and efficiency of ice nucleation, materials, here, covalent organic frameworks (COFs), with different pore diameters and degrees of crystallinity (ordering), were characterized. Results showed that out of all the highly crystalline COFs, the sample with a pore diameter between 2 and 3 nm exhibited the most efficient ice nucleation activity. We posit that the highly crystalline structures with ordered pores have an optimal pore diameter where the ice nucleation activity is maximized and that the not highly crystalline structures with nonordered pores have more sites for ice nucleation. The results were compared and discussed in the context of other synthesized porous particle systems. Such studies give insight into how material features impact ice nucleation activity.

Polycrystalline Covalent Organic Framework Films Act as Adsorbents, Not Membranes.

Covalent organic framework (COF) membranes are of great promise for energy-efficient separations. Thick, polycrystalline COF films have been reported to separate dyes, salts, bacteria, and nanoparticles on the basis of size-selective transport through ordered pores. Here, we show that these materials function as adsorbents, not as size-sieving membranes. Binding isotherms of several dyes typical of the COF membrane literature to three COF powder samples illustrate that COFs are high-capacity adsorbents with affinities that span a range of 3 orders of magnitude, trends which map onto previously reported separation behavior. Computational results suggest that observed differences in adsorption can be correlated to variable entropic gains driving the adsorption process. Polycrystalline COF pellets show volume-dependent and flow-rate dependent "rejection" of dyes, consistent with an adsorption-based removal mechanism. Previous reports of thick, polycrystalline COF membranes used low flow rates and small dye volumes to probe rejection capabilities, where membrane and adsorbent behavior is not distinguishable. A mixed dye separation experiment in flow shows affinity-dependent performance. These results necessitate a careful reexamination of the COF membrane literature, as separations based on differential transport through 2D COF pores remain an important yet unrealized frontier.

Made-to-Order Heterostructured Nanoparticle Libraries.

Nanoparticles that contain multiple materials connected through interfaces, often called heterostructured nanoparticles, are important constructs for many current and emerging applications. Such particles combine semiconductors, metals, insulators, catalysts, magnets, and other functional components that interact synergistically to enable applications in areas that include energy, nanomedicine, nanophotonics, photocatalysis, and active matter. To synthesize heterostructured nanoparticles, it is important to control all of the property-defining features of individual nanoparticles-size, shape, uniformity, crystal structure, composition, surface chemistry, and dispersibility-in addition to interfaces, asymmetry, and spatial organization, which facilitate communication among the constituent materials and enable their synergistic functions. While it is challenging to control all of these nanoscale features simultaneously, nanoparticle cation exchange reactions offer powerful capabilities that overcome many of the synthetic bottlenecks. In these reactions, which are often carried out on metal chalcogenide materials such as roxbyite copper sulfide (Cu1.8S) that have high cation mobilities and a high density of vacancies, cations from solution replace cations in the nanoparticle. Replacing only a fraction of the cations can produce phase-segregated products having internal interfaces, i.e., heterostructured nanoparticles. By the use of multiple partial cation exchange reactions, multicomponent heterostructured nanoparticles can be synthesized.In this Account, we discuss the use of multiple sequential partial cation exchange reactions to rationally construct complex heterostructured nanoparticles toward the goal of made-to-order synthesis. Sequential partial exchange of the Cu+ cations in roxbyite Cu1.8S spheres, rods, and plates produces a library of 47 derivatives that maintain the size, shape, and uniformity defined by the roxbyite templates while introducing various types of interfaces and different materials into the resulting heterostructured nanoparticles. When an excess of the metal salt reagent is used, the reaction time controls the extent of partial cation exchange. When a substoichiometric amount of metal salt reagent is used instead, the extent of partial cation exchange can be precisely controlled by the cation concentration. This approach allows significant control over the number, order, and location of partial cation exchange reactions. Up to seven sequential partial cation exchange reactions can be applied to roxbyite Cu1.8S nanorods to produce derivative heterostructured nanorods containing as many as six different materials, eight internal interfaces, and 11 segments, i.e. ZnS-CuInS2-CuGaS2-CoS-[CdS-(ZnS-CuInS2)]-Cu1.8S. We considered all possible injection sequences of five cations (Zn2+, Cd2+, Co2+, In3+, Ga3+) applied to all accessible Cu1.8S-derived nanorod precursors along with simple design criteria based on preferred cation exchange locations and crystal structure relationships. Using these guidelines, we mapped out synthetically feasible pathways to 65 520 distinct heterostructured nanorods, experimentally observed 113 members of this heterostructured nanorod megalibrary, and then made three of these in high yield and in isolatable quantities. By expansion of these capabilities into a broader scope of materials and identification of additional design guidelines, it should be possible to move beyond model systems and access functional targets rationally and retrosynthetically. Overall, the ability to access large libraries of complex heterostructured nanoparticles in a made-to-order manner is an important step toward bridging the gap between design and synthesis.

Structure-Selective Synthesis of Wurtzite and Zincblende ZnS, CdS, and CuInS2 Using Nanoparticle Cation Exchange Reactions.

For polymorphic solid-state systems containing multiple distinct crystal structures of the same composition, identifying rational pathways to selectively target one particular structure is an important synthetic capability. Cation exchange reactions can transform a growing library of metal chalcogenide nanocrystals into different phases by replacing the cation sublattice, often while retaining morphology and crystal structure. However, only a few examples have been demonstrated where multiple distinct phases in a polymorphic system could be selectively accessed using nanocrystal cation exchange reactions. Here, we show that roxbyite (hexagonal) and digenite (cubic) Cu2- xS nanoparticles transform upon cation exchange with Cd2+, Zn2+, and In3+ to wurtzite (hexagonal) and zincblende (cubic) CdS, ZnS, and CuInS2, respectively. These products retain the anion and cation sublattice features programmed into the copper sulfide template, and each phase forms to the exclusion of other known crystal structures. These results significantly expand the scope of structure-selective cation exchange reactions in polymorphic systems.

Exploiting Crystallographic Regioselectivity To Engineer Asymmetric Three-Component Colloidal Nanoparticle Isomers Using Partial Cation Exchange Reactions.

The precise placement of different materials in specific regions of a nanocrystal is important for many applications, but this remains difficult to achieve synthetically. Here we show that regioselectivity during partial cation exchange reactions of metal chalcogenide nanocrystals emerges from crystallographic relationships between the precursor and product phases. By maximizing the formation of low-strain interfaces, it is possible to rationally integrate three distinct materials within uniform spherical and rod-shaped colloidal nanoparticles to produce complex asymmetric heterostructured isomers. Through sequential partial exchange of Cu+ in Cu1.8S nanocrystals with Zn2+ and Cd2+, five distinct ZnS/CdS/Cu1.8S nanosphere and nanorod isomers are accessible.

Structure-Selective Cation Exchange in the Synthesis of Zincblende MnS and CoS Nanocrystals.

The ability to selectively form one crystal structure among several options in a polymorphic system is an important goal in solid-state synthesis. Nanocrystal cation exchange, which proceeds rapidly under mild conditions, can retain key structural features and yield otherwise inaccessible phases, but the extent to which crystal structure can be retained and therefore selectively targeted during such reactions has been limited. Here, we show that nanocrystals of digenite Cu2-x S transform to zincblende MnS and CoS upon cation exchange. Zincblende MnS and CoS, which are metastable in bulk, retain both the tetrahedral cation coordination and cubic close packed anion sublattice of digenite Cu2-x S. Comparison with wurtzite MnS and CoS, which have been accessed previously through analogous cation exchange of roxbyite Cu2-x S, demonstrates the selective formation of the related zincblende vs. wurtzite polymorphs by cation exchange of structurally distinct templates.

Sequential Anion and Cation Exchange Reactions for Complete Material Transformations of Nanoparticles with Morphological Retention.

Ion exchange reactions of colloidal nanocrystals provide access to complex products that are synthetically challenging using traditional hot-injection methods. However, such reactions typically achieve only partial material transformations by employing either cation or anion exchange processes. It is now shown that anion and cation exchange reactions can be coupled together and applied sequentially in one integrated pathway that leads to complete material transformations of nanocrystal templates. Although the product nanocrystals do not contain any of the original constituent elements, the original morphology is retained, thereby fully decoupling morphology and composition control. The sequential anion/cation exchange process was applied to pseudo-spherical CdO nanocrystals and ZnO tetrapods, producing fully transformed and shape-controlled nanocrystals of copper and silver sulfides and selenides. Furthermore, hollow core-shell tetrapod ZnS@CdS heterostructures were readily accessible.

Rational construction of a scalable heterostructured nanorod megalibrary.

Integrating multiple materials in arbitrary arrangements within nanoparticles is a prerequisite for advancing many applications. Strategies to synthesize heterostructured nanoparticles are emerging, but they are limited in complexity, scope, and scalability. We introduce two design guidelines, based on interfacial reactivity and crystal structure relations, that enable the rational synthesis of a heterostructured nanorod megalibrary. We define synthetically feasible pathways to 65,520 distinct multicomponent metal sulfide nanorods having as many as 6 materials, 8 segments, and 11 internal interfaces by applying up to seven sequential cation-exchange reactions to copper sulfide nanorod precursors. We experimentally observe 113 individual heterostructured nanorods and demonstrate the scalable production of three samples. Previously unimaginable complexity in heterostructured nanorods is now routinely achievable with simple benchtop chemistry and standard laboratory glassware.

Tunable intraparticle frameworks for creating complex heterostructured nanoparticle libraries.

Complex heterostructured nanoparticles with precisely defined materials and interfaces are important for many applications. However, rationally incorporating such features into nanoparticles with rigorous morphology control remains a synthetic bottleneck. We define a modular divergent synthesis strategy that progressively transforms simple nanoparticle synthons into increasingly sophisticated products. We introduce a series of tunable interfaces into zero-, one-, and two-dimensional copper sulfide nanoparticles using cation exchange reactions. Subsequent manipulation of these intraparticle frameworks yielded a library of 47 distinct heterostructured metal sulfide derivatives, including particles that contain asymmetric, patchy, porous, and sculpted nanoarchitectures. This generalizable mix-and-match strategy provides predictable retrosynthetic pathways to complex nanoparticle features that are otherwise inaccessible.

Colloidal ZnO and Zn(1-x)Co(x)O tetrapod nanocrystals with tunable arm lengths.

Tetrapod-shaped ZnO nanocrystals exhibit exceptional optoelectronic properties, including intense ultraviolet photoluminescence emission, that make them attractive for applications that include lasers, sensors, and photocatalysts. However, synthetic methods that produce ZnO tetrapods typically include high-temperature vapor-deposition approaches that do not readily achieve characteristic dimensions of less than 100 nm or colloidal methods that require added metal dopants, which modify the inherent properties of ZnO. Here, we report a robust, modified solution-phase synthetic protocol for generating colloidal ZnO tetrapods that does not require the use of metal dopants. The ZnO tetrapod arm lengths can be tuned from 10 to 25 nm by adjusting the amount of Zn reagent used in the reaction. Subsequent seeded-growth produced even larger colloidal ZnO tetrapods with 62 nm arms. Photoluminescence (PL) measurements confirm that the tetrapods are of high crystalline quality, and the ultraviolet PL emission wavelengths that are observed fall between those of previously reported metal-doped colloidal ZnO tetrapods, which exhibit dopant-induced red- or blue-shifts. Furthermore, the reaction strategy can be modified to produce cobalt-substituted ZnO, offering a chemical pathway to tetrapod-shaped Zn1-xCoxO nanocrystals.