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 MoAl_1-B. Mild thermal treatment of submicrometer grains of this destabilized MoAl_1-B 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.