Na 2 S was prepared from stoichiometric Na (Acros Organics, rod, 99.8%, mechanically cleaned prior to use) and S (see main text) in separate alumina crucibles (Almath) in an evacuated silica ampoule. The reactants were heated at 1°C min −1 to 300°C for 48 h and cooled ambiently to room temperature. The ground product was a fine powder of a slightly tan-color. The product was determined to be phase pure by XRD.

The control of solid state reaction pathways will enable the design and discovery of new functional inorganic materials. A range of synthetic approaches have been used to shift solid state chemistry away from thermodynamic control, in which the most energetically favorable product forms, toward a regime of kinetic control, so that metastable materials can be controllably produced. In this Perspective, we focus on the kinetic control of solid state metathesis reactions to alter solid state reaction pathways and products. We provide insight into the necessary components of a kinetically controlled solid state reaction and illustrate the utility of studying reactions in situ in order to observe the various intermediates and kinetic pathways that may extend synthetic solid state chemistry toward a paradigm of reaction-by-design.

Solid-state diffusion is often the primary limitation in the synthesis of crystalline inorganic materials and prevents the potential discovery and isolation of new materials that may not be the most stable with respect to the reaction conditions. Synthetic approaches that circumvent diffusion in solid-state reactions are rare and often allow the formation of metastable products. To this end, we present an in situ study of the solid-state metathesis reactions MCl2 + Na2S2 → MS2 + 2 NaCl (M = Fe, Co, Ni) using synchrotron powder X-ray diffraction and differential scanning calorimetry. Depending on the preparation method of the reaction, either combining the reactants in an air-free environment or grinding homogeneously in air before annealing, the barrier to product formation, and therefore reaction pathway, can be altered. In the air-free reactions, the product formation appears to be diffusion limited, with a number of intermediate phases observed before formation of the MS2 product. However, grinding the reactants in air allows NaCl to form directly without annealing and displaces the corresponding metal and sulfide ions into an amorphous matrix, as confirmed by pair distribution function analysis. Heating this mixture yields direct nucleation of the MS2 phase and avoids all crystalline binary intermediates. Grinding in air also dissipates a large amount of lattice energy via the formation of NaCl, and the crystallization of the metal sulfide is a much less exothermic process. This approach has the potential to allow formation of a range of binary, ternary, or higher-ordered compounds to be synthesized in the bulk, while avoiding the formation of many binary intermediates that may otherwise form in a diffusion-limited reaction.

Next-generation batteries based on divalent working ions have the potential to both reduce the cost of energy storage devices and increase performance. Examples of promising divalent systems include those based on Mg 2+ , Ca 2+ , and Zn 2+ working ions. Development of such technologies is slow, however, in part due to the difficulty associated with divalent cation conduction in the solid state. Divalent ion conduction is especially challenging in insulating materials that would be useful as solid-state electrolytes or protecting layers on the surfaces of metal anodes. Furthermore, there are no reports of divalent cation conduction in insulating, inorganic materials at reasonable temperatures, prohibiting the development of structure− property relationships. Here, we report Zn 2+ conduction in insulating ZnPS 3 , demonstrating divalent ionic conductivity in an ordered, inorganic lattice near room temperature. Importantly, the activation energy associated with the bulk conductivity is low, 351 ± 99 meV, comparable to some Li + conductors such as LTTO, although not as low as the superionic Li + conductors. First-principles calculations suggest that the barrier corresponds to vacancy-mediated diffusion. Assessment of the structural distortions observed along the ion diffusion pathways suggests that an increase in the P−P−S bond angle in the [P 2 S 6 ] 4− moiety accommodates the Zn 2+ as it passes through the high-energy intermediate coordination environments. ZnPS 3 now represents a baseline material family to begin developing the structure−property relationships that control divalent ion diffusion and conduction in insulating solid-state hosts.

Rational preparation of materials by design is a major goal of inorganic, solid-state, and materials chemists alike. Oftentimes, the use of nonmetallurgical reactions (e.g., chalcogenide fluxes, hydrothermal syntheses, and in this case solid-state metathesis) alters the thermodynamic driving force of the reaction and allows new, refractory, or otherwise energetically unfavorable materials to form under softer conditions. Taking this a step further, alteration of a metathesis reaction pathway can result in either the formation of the equilibrium marcasite polymorph (by stringent exclusion of air) or the kinetically controlled formation of the high-pressure pyrite polymorph of CuSe2 (by exposure to air). From analysis of the reaction coordinate with in situ synchrotron X-ray diffraction and pair distribution function analysis as well as differential scanning calorimetry, it is clear that the air-exposed reaction proceeds via slight, endothermic rearrangements of crystalline intermediates to form pyrite, which is attributed to partial solvation of the reaction from atmospheric humidity. In contrast, the air-free reaction proceeds via a significant exothermic process to form marcasite. Decoupling the formation of NaCl from the formation of CuSe2 enables kinetic control to be exercised over the resulting polymorph of these superconducting metal dichalcogenides.