Nanomaterials Research at a Primarily Undergraduate Institution: Transforming Nanorods, Undergraduate Research Communities, and Infrastructure.

Undergraduate research transforms student's conceptions of themselves as scientists and encourages participation and retention in science, technology, engineering, and mathematics (STEM) fields. Many barriers exist to carrying out scientifically impactful undergraduate research in nanomaterials at primarily undergraduate institutions (PUIs). Here, we share several practices and design principles that demonstrate pathways to overcome these barriers. Design of modular research projects with low entry barriers is essential. Postsynthetic transformation of nanoparticles is a field that enables such design and has been used successfully to advance nanoscience research while being achievable within undergraduate laboratories. Relatively large, inclusive research communities can be supported through the creation of opportunities with peer- and near-peer mentoring. We also share emerging strategies for enabling routine undergraduate access to transmission electron microscopy, which is one of the most mainstream characterization techniques in nanoscience yet is frequently absent from the infrastructure at undergraduate-focused institutions.

Solution Synthesis and Diffusion-Mediated Formation Pathway of NbTe4 Particles.

NbTe4 is an important material because of its fundamental low-temperature electronic behavior and its potential interest for thermoelectric, catalytic, and phase-change applications, especially as nano- and microscale particles. As a tellurium-rich group V transition metal telluride, bulk NbTe4 is typically synthesized through high-temperature solid-state or metal flux reactions and NbTe4 films can be made by sputtering and annealing, but NbTe4 is generally not amenable to the lower-temperature solution-based syntheses that yield small particles. Here, we demonstrate a solvothermal route to NbTe4 particles that is based on mainstream colloidal nanoparticle synthesis. We find that the reaction proceeds in situ through a multistep pathway that begins by first forming elemental tellurium needles. NbTe4 then deposits on the surface of the tellurium needles through a diffusion-based process. Time-point studies throughout the reaction reveal that crystallographic relationships between Te and NbTe4 define how the diffusion-based reaction proceeds and help to rationalize the morphology of the resulting NbTe4 particles. As synthesized, NbTe4 particles exhibit a surface consisting of predominantly Nb-Te and reduced NbOx species, but after storage, surface oxidation transforms these species to primarily Nb2O5 and TeO2, while the NbTe4 remains unchanged. These synthetic capabilities and reaction pathway insights for NbTe4, made using a solvothermal method, will help to advance future studies on the properties and applications of this and related tellurides.

Disentangling Competitive and Synergistic Chemical Reactivities During the Seeded Growth of High-Entropy Alloys on High-Entropy Metal Sulfide Nanoparticles.

The seeded growth of one type of nanoparticle on the surface of another is foundational to synthesizing many multifunctional nanostructures. High-entropy nanoparticles that randomly incorporate five or more elements offer enhanced properties due to synergistic interactions. Incorporating high-entropy nanoparticles into seeded growth platforms is essential for merging their unique properties with the functional enhancements that arise from particle-particle interactions. However, the complex compositions of high-entropy materials complicate the seeded growth process due to competing particle growth and chemical reactivity pathways. Here, we design and synthesize a 36-member nanoparticle library to identify and disentangle these competitive interactions, ultimately defining chemical characteristics that underpin the seeded growth of high-entropy alloys on high-entropy metal sulfide nanoparticles. As a model system, we focus on (Cu,Zn,Co,In,Ga)S-SnPdPtRhIr, which combines a high-entropy metal sulfide semiconductor with a high-entropy alloy catalyst. We study the seeded growth of all possible pairwise combinations of Sn, Pd, Pt, Rh, Ir, and SnPdPtRhIr on the metal sulfides Cu1.8S, ZnS, Co9S8, CuInS2, CuGaS2, and (Cu,Zn,Co,In,Ga)S, which have comparable morphologies and sizes. Through these studies, we uncover unexpected chemical reactivities, including cation exchange, redox reactions, and diffusion. Reaction temperature, threshold reduction potentials, metal/sulfide chemical reactivity, and the relative strengths of the various bonds that could be formed during particle growth emerge as the primary factors that underpin seeded growth. Finally, we disentangle these competitive and synergistic chemical reactivities to generate a reactivity map that provides practical guidelines for achieving seeded growth in compositionally complex systems.

Synthetic Roadmap to a Large Library of Colloidal High-Entropy Rare Earth Oxyhalide Nanoparticles Containing up to Thirteen Metals.

Nanoparticles of high-entropy materials that incorporate five or more elements randomized on a crystalline lattice often exhibit synergistic properties that can be influenced by both the identity and number of elements combined. These considerations are especially important for structurally and compositionally complex materials such as multimetal multianion compounds, where cation and anion mixing can influence properties in competitive and contradictory ways. Here, we demonstrate the synthesis of a large library of colloidal high-entropy rare earth oxyhalide (REOX) nanoparticles. We begin with the synthesis of (LaCePrNdSmEuGdDyHoErYbScY)OCl, which homogeneously incorporates 13 distinct rare earth elements. Through time point studies, we find that (LaNdSmGdDy)OCl, a 5-metal analogue, forms through in situ generation of compositionally segregated core@shell@shell intermediates that convert to homogeneously mixed products through apparent core-shell interdiffusion. Assuming that all possible combinations of 5 through 13 rare earth metals are synthetically accessible, we propose the existence of a 7099-member REOCl nanoparticle library, of which we synthesize and characterize 40 distinct members. We experimentally validate the incorporation of a large number of rare earth elements using energy dispersive X-ray spectra, despite closely spaced and overlapping X-ray energy lines, using several fingerprint matching strategies to uniquely correlate experimental and simulated spectra. We confirm homogeneous mixing by analyzing elemental distributions in high-entropy nanoparticles versus physical mixtures of their constituent compounds. Finally, we characterize the band gaps of the 5- and 13-metal REOCl nanoparticles and find a significantly narrowed band gap, relative to the constituent REOCl phases, in (LaCePrNdSmEuGdDyHoErYbScY)OCl but not in (LaNdSmGdDy)OCl.

Colloidal Nanoparticles of High Entropy Materials: Capabilities, Challenges, and Opportunities in Synthesis and Characterization.

Materials referred to as "high entropy" contain a large number of elements randomly distributed on the lattice sites of a crystalline solid, such that a high configurational entropy is presumed to contribute significantly to their formation and stability. High temperatures are typically required to achieve entropy stabilization, which can make it challenging to synthesize colloidal nanoparticles of high entropy materials. Nonetheless, strategies are emerging for the synthesis of colloidal high entropy nanoparticles, which are of interest for their synergistic properties and unique catalytic functions that arise from the large number of constituent elements and their interactions. In this Perspective, we highlight the classes of materials that have been made as colloidal high entropy nanoparticles as well as insights into the synthetic methods and the pathways by which they form. We then discuss the concept of "high entropy" within the context of colloidal materials synthesized at much lower temperatures than are typically required for entropy to drive their formation. Next, we identify and address challenges and opportunities in the field of high entropy nanoparticle synthesis. We emphasize aspects of materials characterization that are especially important to consider for nanoparticles of high entropy materials, including powder X-ray diffraction and elemental mapping with scanning transmission electron microscopy, which are among the most commonly used techniques in laboratory settings. Finally, we share perspectives on emerging opportunities and future directions involving colloidal nanoparticles of high entropy materials, with an emphasis on synthesis, characterization, and fundamental knowledge that is needed for anticipated advances in key application areas.

Soft Chemistry of Hard Materials: Low-Temperature Pathways to Bulk and Nanostructured Layered Metal Borides.

Conspectus"Synthesis by design" is often considered to be the primary goal of chemists who make molecules and materials. Synthetic chemists usually have in mind a target they want to make, and they want to be able to design a pathway that can get them to that target as quickly and efficiently as possible. Chemists who synthesize refractory solids, which have melting points above 1000 °C and are often chemically inert at these high temperatures, have access to only a small number of synthetic strategies due to the need to overcome solid-state diffusion, which is the rate-limiting step in such reactions. The use of extremely high temperatures to facilitate diffusion among two or more refractory solids, which precedes any chemical reaction that must occur, generally drives the system to form only the product that is the most thermodynamically stable-the global minimum on an energy landscape-for a certain combination of elements. When trying to target a different product in the same system, one generally cannot rely on thermally driven reactions. Lower-temperature reactions that side step this diffusion limitation can succeed where high temperatures fail by providing access to local minima on an energy landscape. These local minima represent metastable phases that are primed for synthesis, but only if an appropriate pathway and set of reactions can be identified. It is therefore important to develop and understand low-temperature, or "soft", chemical reactions in "hard" refractory systems. These reactions allow us to apply the retrosynthetic framework that molecular chemists rely on to systems where chemists have not previously had such control over reactions, reactivities, and metastable product formation.In this Account, we discuss the development of soft chemical reactions of hard materials in the context of a class of layered, refractory metal borides that are precursors to an emerging family of two-dimensional nanomaterials. Layered ternary metal boride phases such as MoAlB have layers of metal borides, which are chemically unreactive, interleaved with layers of aluminum, which are reactive. Some of the interlayer aluminum can be deintercalated at room temperature in dilute aqueous sodium hydroxide, transforming stable MoAlB into destabilized MoAl1-xB. Mild thermal treatment of submicrometer grains of this destabilized MoAl1-xB sample allows it to traverse the energy landscape and crystallize as Mo2AlB2, a metastable compound. Further thermal treatment transforms Mo2AlB2 into a Mo2AlB2-alumina nanolaminate and ultimately mesoporous MoB, all through continued traversing of the energy landscape using mild chemical and thermal treatments. Similar topochemical manipulations, which maintain structure but change composition, are emerging for other MAB phases and are opening the door to new types of metastable compounds and nanostructured materials in traditionally refractory systems.

Temperature-Dependent Selection of Reaction Pathways, Reactive Species, and Products during Postsynthetic Selenization of Copper Sulfide Nanoparticles.

Rational design of elaborate, multicomponent nanomaterials is important for the development of many technologies such as optoelectronic devices, photocatalysts, and ion batteries. Combination of metal chalcogenides with different anions, such as in CdS/CdSe structures, is particularly effective for creating heterojunctions with valence band offsets. Seeded growth, often coupled with cation exchange, is commonly used to create various core/shell, dot-in-rod, or multipod geometries. To augment this library of multichalcogenide structures with new geometries, we have developed a method for postsynthetic transformation of copper sulfide nanorods into several different classes of nanoheterostructures containing both copper sulfide and copper selenide. Two distinct temperature-dependent pathways allow us to select from several outcomes-rectangular, faceted Cu2-xS/Cu2-xSe core/shell structures, nanorhombuses with a Cu2-xS core, and triangular deposits of Cu2-xSe or Cu2-x(S,Se) solid solutions. These different outcomes arise due to the evolution of the molecular components in solution. At lower temperatures, slow Cu2-xS dissolution leads to concerted morphology change and Cu2-xSe deposition, while Se-anion exchange dominates at higher temperatures. We present detailed characterization of these Cu2-xS-Cu2-xSe nanoheterostructures by transmission electron microscopy (TEM), powder X-ray diffraction, energy-dispersive X-ray spectroscopy, and scanning TEM-energy-dispersive spectroscopy. Furthermore, we correlate the selenium species present in solution with the roles they play in the temperature dependence of nanoheterostructure formation by comparing the outcomes of the established reaction conditions to use of didecyl diselenide as a transformation precursor.

Thermally Induced Domain Migration and Interfacial Restructuring in Cation Exchanged ZnS-Cu1.8S Heterostructured Nanorods.

Partial cation exchange reactions can be used to rationally design and synthesize heterostructured nanoparticles that are useful targets for applications in photocatalysis, nanophotonics, thermoelectrics, and medicine. Such reactions introduce intraparticle frameworks that define the spatial arrangements of different materials within a heterostructured nanoparticle, as well as the orientations and locations of their interfaces. Here, we show that upon heating to temperatures relevant to their synthesis and applications, the ZnS regions and Cu1.8S/ZnS interfaces of heterostructured ZnS-Cu1.8S nanorods migrate and restructure. We first use partial cation exchange reactions to synthesize a library of seven distinct samples containing various patches, bands, and tips of ZnS embedded within Cu1.8S nanorods. Upon annealing in solution or in air, ex situ TEM analysis shows evidence that the ZnS domains migrate in different ways, depending upon their sizes and locations. Using differential scanning calorimetry, we correlate the threshold temperature for ZnS migration to the superionic transition temperature of Cu1.8S, which facilitates rapid diffusion throughout the nanorods. We then use in situ thermal TEM to study the evolution of individual ZnS-Cu1.8S nanorods upon heating. We find that ZnS domain migration occurs through a ripening process that minimizes small patches with higher-energy interfaces in favor of larger bands and tips having lower-energy interfaces, as well as through restructuring of higher-energy Cu1.8S/ZnS interfaces. Notably, Cu1.8S nanorods containing multiple patches of ZnS thermally transform into ZnS-Cu1.8S heterostructured nanorods having ZnS tips and/or central bands, which provides mechanistic insights into how these commonly observed products form during synthesis.

High Entropy Sulfide Nanoparticles as Lithium Polysulfide Redox Catalysts.

The polysulfide shuttle contributes to capacity loss in lithium-sulfur batteries, which limits their practical utilization. Materials that catalyze the complex redox reactions responsible for the polysulfide shuttle are emerging, but foundational knowledge that enables catalyst development remains limited with only a small number of catalysts identified. Here, we employ a rigorous electrochemical approach to show quantitatively that the lithium polysulfide redox reaction is catalyzed by nanoparticles of a high entropy sulfide material, Zn0.30Co0.31Cu0.19In0.13Ga0.06S. When 2% by weight of the high entropy sulfide is added to the lithium sulfur cathode composite, the capacity and Coulombic efficiency of the resulting battery are improved at both moderate (0.2 C) and high (1 C) charge/discharge rates. Surface analysis of the high entropy sulfide nanoparticles using X-ray photoelectron spectroscopy provides important insights into how the material evolves during the cycling process. The Zn0.30Co0.31Cu0.19In0.13Ga0.06S nanoparticle catalyst outperformed the constituent metal sulfides, pointing to the role that the high-entropy "cocktail effect" can play in the development of advanced electrocatalytic materials for improved lithium sulfur battery performance.

Topochemical Anionic Subunit Insertion Reaction for Constructing Nanoparticles of Layered Oxychalcogenide Intergrowth Structures.

Intergrowth compounds contain alternating layers of chemically distinct subunits that yield composition-tunable synergistic properties. Synthesizing nanoparticles of intergrowth structures requires atomic-level intermixing of the subunits rather than segregation into stable constituent phases. Here we introduce an anionic subunit insertion reaction for nanoparticles that installs metal chalcogenide layers between metal oxide sheets. Anionic [CuS]- subunits from solution replace interlayer chloride anions from LaOCl to form LaOCuS topochemically with retention of crystal structure and morphology. Sodium acetylacetonate helps extract Cl- concomitant with the insertion of S2- and Cu+ and is generalized to other oxychalcogenides. This topochemical reaction produces nanoparticles of ordered mixed-anion intergrowth compounds and expands nanoparticle ion exchange chemistry to anionic subunits.

Unexpected Multi-Step Transformation of AgCuS to AgAuS During Nanoparticle Cation Exchange.

Cation exchange reactions can modify the compositions of colloidal nanoparticles, providing easy access to compounds or nanoparticles that may not be accessible directly. The most common nanoparticle cation exchange reactions replace monovalent cations with divalent cations or vice versa, but some monovalent-to-monovalent exchanges have been reported. Here, we dissect the reaction of as-synthesized AgCuS nanocrystals with Au+ to form AgAuS, initially hypothesizing that Au+ could be selective for Cu+ (rather than for Ag+) based on a known Au+-for-Cu+ exchange and the stability of the targeted AgAuS product. Unexpectedly, we found this system and the putative cation exchange reaction to be much more complex than anticipated. First, the starting AgCuS nanoparticles, which match literature reports, are more accurately described as a hybrid of Ag and a variant of AgCuS that is structurally related to mckinstryite Ag5Cu3S4. Second, the initial reaction of Ag-AgCuS with Au+ results in a galvanic replacement to transform the Ag component to a AuyAg1-y alloy. Third, continued reaction with Au+ initiates cation exchange with Cu+ in AuyAg1-y-AgCuS to form AuyAg1-y-Ag3CuxAu1-xS2 and then AuyAg1-y-AgAuS, which is the final product. Crystal structure relationships among mckinstryite-type AgCuS, Ag3CuxAu1-xS2, and AgAuS help to rationalize the transformation pathway. These insights into the reaction of AgCuS with Au+ reveal the potential complexity of seemingly simple nanoparticle reactions and highlight the importance of thorough compositional, structural, and morphological characterization before, during, and after such reactions.

Temporal Evolution of Morphology, Composition, and Structure in the Formation of Colloidal High-Entropy Intermetallic Nanoparticles.

Morphology-controlled nanoparticles of high entropy intermetallic compounds are quickly becoming high-value targets for catalysis. Their ordered structures with multiple distinct crystallographic sites, coupled with the "cocktail effect" that emerges from randomly mixing a large number of elements, yield catalytic active sites capable of achieving advanced catalytic functions. Despite this growing interest, little is known about the pathways by which high entropy intermetallic nanoparticles form and grow in solution. As a result, controlling their morphology remains challenging. Here, we use the high entropy intermetallic compound (Pd,Rh,Ir,Pt)Sn, which adopts a NiAs-related crystal structure, as a model system for understanding how nanoparticle morphology, composition, and structure evolve during synthesis in solution using a slow-injection reaction. By performing a time-point study, we establish the initial formation of palladium-rich cube-like Pd-Sn seeds onto which the other metals deposit over time, concomitant with continued incorporation of tin. For (Pd,Rh,Ir,Pt)Sn, growth occurs on the corners, resulting in a sample having a mixture of flower-like and cube-like morphologies. We then synthesize and characterize a library of 14 distinct intermetallic nanoparticle systems that comprise all possible binary, ternary, and quaternary constituents of (Pd,Rh,Ir,Pt)Sn. From these studies, we correlated compositions, morphologies, and growth pathways with the constituent elements and their competitive reactivities, ultimately mapping out a framework that rationalizes the key features of the high entropy (Pd,Rh,Ir,Pt)Sn intermetallic nanoparticles based on those of their simpler constituents. We then validated these design guidelines by applying them to the synthesis of a morphologically pure variant of flowerlike (Pd,Rh,Ir,Pt)Sn particles as well as a series of (Pd,Rh,Ir,Pt)Sn particles with tunable morphologies based on control of composition.

Synthesis and Magnetic, Optical, and Electrocatalytic Properties of High-Entropy Mixed-Metal Tungsten and Molybdenum Oxides.

High-entropy oxides (HEOs) are of interest for their unique physical and chemical properties. Significant lattice distortions, strain, and tolerance for high-vacancy concentrations set HEOs apart from single-metal or mixed-metal oxides. Herein, we synthesized and characterized the structures and compositions, along with the optical, magnetic, and electrocatalytic properties, of two families of high-entropy mixed-metal tungsten and molybdenum oxides, AWO4 and B2Mo3O8, where A and B are 3d transition metals. The HEOs A6WO4 (A = Mn, Fe, Co, Ni, Cu, and Zn) and B25Mo3O8 (B = Mn, Fe, Co, Ni, and Zn), as well as all accessible single-metal AWO4 and B2Mo3O8 parent compounds, were synthesized using high-temperature solid-state methods. X-ray photoelectron spectroscopy analysis of the surfaces revealed that the HEOs largely had the metal oxidation states expected from the bulk chemical formulas, but in some cases they were different than in the parent compounds. A6WO4 exhibited antiferromagnetic (AFM) ordering with a Néel temperature of 30 K, which is less than the average of its AFM parent compounds, and had a narrow band gap of 0.24 eV, which is much lower than all of its parent compounds. B25Mo3O8 was paramagnetic, despite the existence of AFM and ferromagnetic ordering in several of its parent compounds and had no observable band gap, which is analogous to its parent compounds. Both A6WO4 and B25Mo3O8 exhibited superior catalytic activity relative to the parent compounds for the oxygen evolution reaction, the oxidation half reaction of overall water splitting, under alkaline conditions, based on the overpotential required to reach the benchmark surface area normalized current density. Consistent with literature predictions of OER durability for ternary tungsten and molybdenum oxides, A6WO4 and B25Mo3O8 also exhibited stable performance without significant dissolution during 10 h stability experiments at a constant current.

One-step topochemical transformation of MoAlB into metastable Mo2AlB2 using a metal chloride salt reaction.

Reacting MoAlB with ZnCl2 at 550 °C produces metastable Mo2AlB2 through a one-step topochemical transformation. This reaction showcases differences in reactivity between boride-based MAB phases and carbide-based MAX phases, which are solid-state precursors to an important family of 2-D materials.

Formation and Transformation of Cu2-xSe1-yTey Nanoparticles Synthesized by Tellurium Anion Exchange of Copper Selenide.

Ion exchange reactions of colloidal nanoparticles post-synthetically modify the composition while maintaining the morphology and crystal structure and therefore are important for tuning properties and producing otherwise inaccessible and/or metastable materials. Reactions involving anion exchange of metal chalcogenides are particularly interesting, as they involve the replacement of the sublattice that defines the structure while also requiring high temperatures that can be disruptive. Here, we show that the tellurium anion exchange of weissite Cu2-xSe nanoparticles using a trioctylphosphine-tellurium complex (TOP═Te) yields weissite Cu2-xSe1-yTey solid solutions, rather than complete exchange to weissite Cu2-xTe, with compositions that are tunable based on the amount of TOP═Te used. Upon storage at room temperature in either solvent or air, tellurium-rich Cu2-xSe1-yTey solid solution nanoparticles transform, over the span of several days, to a selenium-rich Cu2-xSe1-yTey composition. The tellurium that is expelled from the solid solution during this process migrates to the surface and forms a tellurium oxide shell, which correlates with the onset of particle agglomeration due to the change in surface chemistry. Collectively, this study demonstrates tunable composition during tellurium anion exchange of copper selenide nanoparticles along with unusual post-exchange reactivity that transforms the composition, surface chemistry, and colloidal dispersibility due to the apparent metastable nature of the solid solution product.