Milling Chemicals with no Solvents
Traditionally new chemicals are made within a solvent solution. This aids in the active chemicals reaching one another. Solvents are flammable and often pose other hazards, For the first time, scientists have studied a milling reaction in real time, using highly penetrating X-rays to observe the surprisingly rapid transformations as the mill mixed, ground, and transformed simple ingredients into a complex product. This research, reported Dec. 2 in Nature Chemistry, promises to advance scientists' understanding of processes central to the pharmaceutical, metallurgical, cement and mineral industries — and could open new opportunities in green chemistry and environmentally friendly chemical synthesis.
Mechanochemistry is the coupling of the mechanical and the chemical phenomena on a molecular scale and includes mechanical breakage, chemical behaviour of mechanically-stressed solids (e.g., stress-corrosion cracking), tribology, polymer degradation under shear, cavitation-related phenomena (e.g., sonochemistry and sonoluminescence), shock wave chemistry and physics, and even the burgeoning field of molecular machines. Mechanochemistry can be seen as an interface between chemistry and mechanical engineering. It is possible to synthesize chemical products by using only mechanical action.
Mechanochemical phenomena have been utilized since time immemorial, for example in making fire. The oldest method of making fire is to rub pieces of wood against each other, creating friction and hence heat, allowing the wood to undergo combustion at a high temperature.
While mechanical action can break chemical bonds—for example, in the wear and tear of textile fibers—mechanical force can also be used to synthesize new chemical compounds and materials. In recent years, ball milling has become increasingly popular in the production of highly complex chemical structures. In such synthesis, steel balls are shaken with the reactants and catalysts in a rapidly vibrating jar. Chemical transformations take place at the sites of ball collision, where impact causes instant hot spots of localized heat and pressure.
"When we set out to study these reactions, the challenge was to observe the entire reaction without disturbing it, in particular the short-lived intermediates that appear and disappear under continuous impact in less than a minute", says Friščić, an assistant professor in McGill's Department of Chemistry.
The team of scientists chose to study mechanochemical production of the metal-organic framework ZIF-8 from the simplest and non-toxic components. Materials such as ZIF-8 are rapidly gaining popularity for their ability to capture large amounts of CO2; if manufactured cheaply and sustainably, they could become widely used for carbon capture and storage, catalysis and even hydrogen storage.
"The team came to the ESRF because of our high-energy X-rays capable of penetrating 3 mm thick walls of a rapidly moving reaction jar made of steel, aluminium or plastic. The X-ray beam must get inside the jar to probe the mechanochemical formation of ZIF-8, and then out again to detect the changes as they happened", says Simon Kimber, a scientist at the European Synchrotron Radiation Facility (ESRF) in Grenoble, who is a member of the team.
This unprecedented methodology enabled the real-time observation of reaction kinetics, reaction intermediates and the development of their respective nanoparticles. In principle, this technique could be used to study all types of chemical reactions in a ball mill, and optimize them for processing in a range of industries. "That would translate into good news for the environment, for industry—and for consumers," Friščić says.
For further information see Mechanochemistry.
The experimental setup by T. Fričić.