Expanded Tunability of Intraparticle Frameworks in Spherical Heterostructured Nanoparticles through Substoichiometric Partial Cation Exchange.

Partial cation exchange reactions provide a synthetic pathway for rationally constructing heterostructured nanoparticles that incorporate different materials at precise locations. Multiple sequential partial cation exchange reactions can produce libraries of exceptionally complex heterostructured nanoparticles, but the first partial exchange reaction is responsible for defining the intraparticle frameworks that persist throughout and help to direct subsequent exchanges. Here, we studied the partial cation exchange behavior of spherical nanoparticles of roxbyite copper sulfide, Cu1.8S, with substoichiometric amounts of Zn2+. We observed the formation of ZnS-Cu1.8S-ZnS sandwich spheres, which are already well known in this system, as well as ZnS-Cu1.8S Janus spheres and Cu1.8S-ZnS-Cu1.8S central band spheres, which have not been observed previously as significant subpopulations of samples. Aliquots taken during the formation of the heterostructured nanoparticles suggest that substoichiometric amounts of Zn2+ limit the number of sites per particle where exchange initiates and/or propagates, thereby helping to define intraparticle frameworks that are different from those observed using excess amounts of exchanging cations. We applied these insights from mixed-population samples to the higher-yield synthesis of ZnS-Cu1.8S Janus spheres, as well as the higher-order derivatives ZnS-(CdS-Cu1.8S), ZnS-(CdS-ZnS), and ZnS-(CdS-CoS), which have unique features relative to previously reported analogues. These results demonstrate how the diversity of intraparticle frameworks in spherical nanoparticles can be expanded to produce a broader range of downstream heterostructured products.

Orthogonal reactivity and interface-driven selectivity during cation exchange of heterostructured metal sulfide nanorods.

We report predictive guidelines for the substoichiometric cation exchange of model two-component metal sulfide nanorods containing divalent cations of similar hardness. Unit cell volume changes, cation radii, solubility constants, and solid state interfaces influence selectivity during substoichiometric exchange of Cu+ when multiple products are possible.

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.

Phosphine-Induced Phase Transition in Copper Sulfide Nanoparticles Prior to Initiation of a Cation Exchange Reaction.

Cation exchange reactions of colloidal copper sulfide nanoparticles are widely used to produce derivative nanoparticles having unique compositions, metastable crystal structures, and complex heterostructures. The copper sulfide crystal structure plays a key role in the mechanism by which cation exchange occurs and the product that forms. Here, we show that digenite copper sulfide nanoparticles undergo a spontaneous phase transition to tetragonal chalcocite in situ, prior to the onset of cation exchange. Room-temperature sonication of digenite (Cu1.8S) in trioctylphosphine, a Lewis base that drives cation exchange, extracts sulfur to produce tetragonal chalcocite (Cu2S). The subtle structural differences between digenite and tetragonal chalcocite are believed to influence the accessibility of cation diffusion channels and concomitantly the mechanism of cation exchange. Structural relationships in nanocrystal cation exchange are therefore dynamic, and intermediates generated in situ must be considered.

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.

Multi-Step Topochemical Pathway to Metastable Mo2AlB2 and Related Two-Dimensional Nanosheet Heterostructures.

The rational synthesis of metastable inorganic solids, which is a grand challenge in solid-state chemistry, requires the development of kinetically controlled reaction pathways. Topotactic strategies can achieve this goal by chemically modifying reactive components of a parent structure under mild conditions to produce a closely related analogue that has otherwise inaccessible structures and/or compositions. Refractory materials, such as transition metal borides, are difficult to structurally manipulate at low temperatures because they generally are chemically inert and held together by strong covalent bonds. Here, we report a multistep low-temperature topotactic pathway to bulk-scale Mo2AlB2, which is a metastable phase that has been predicted to be the precursor needed to access a synthetically elusive family of 2-D metal boride (MBene) nanosheets. Room-temperature chemical deintercalation of Al from the stable compound MoAlB (synthesized as a bulk powder at 1400 °C) formed highly strained and destabilized MoAl1-xB, which was size-selectively precipitated to isolate the most reactive submicron grains and then annealed at 600 °C to deintercalate additional Al and crystallize Mo2AlB2. Further heating resulted in topotactic decomposition into bulk-scale Mo2AlB2-AlOx nanolaminates that contain Mo2AlB2 nanosheets with thickness of 1-3 nm interleaved by 1-3 nm of amorphous aluminum oxide. The combination of chemical destabilization, size-selective precipitation, and low-temperature annealing provides a potentially generalizable kinetic pathway to metastable variants of refractory compounds, including bulk Mo2AlB2 and Mo2AlB2-AlOx nanosheet heterostructures, and opens the door to other previously elusive 2-D materials such as 2-D MoB (MBene).

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.

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.

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.