Mapping the redox chemistry of common solvents in solvothermal synthesis through in situ X-ray diffraction

Solvothermal technology shows great promise in “green” materials synthesis, processing, and recycling. The outcome of a specific solvothermal reaction depends strongly on the solvent properties, and the versatility of solvothermal synthesis hinges on the very large changes in solvent properties as a function of temperature and pressure. Here, six simple 3d transition metal nitrate salts (Cu(II), Ni(II), Co(II), Fe(III), Mn(II), Cr(III)) were dissolved in five common solvents (water, ethanol, ethylene glycol, glycerol, and 10% hydrogen peroxide solution) and heated stepwise up to 450 °C at a pressure of 250 bar using an in situ reactor while X-ray scattering data was recorded. A range of crystalline phases were observed in the form of metallic phases, metal oxides, and other ionic compounds. These data by themselves provide simple recipes for synthesis of many technologically important 3d transition metal nanomaterials. However, more generally the oxidation states of the metals in the synthesized materials can be used to map the solvent redox properties under solvothermal conditions. It is found that glycerol and ethylene glycol are strongly reducing, ethanol is moderately reducing, while water is weakly oxidizing. The behavior of the hydrogen peroxide solution is more complex including both oxidization and reduction. Furthermore, it is observed that the reducing powers of ethanol, ethylene glycol, and glycerol are enhanced with increasing temperature. The mapping of the redox properties of these common solvents provides a method for tailoring a given reaction through choice of solvent and reaction temperature. Solvothermal processes represent an environmentally benign alternative to the use of toxic reducing agents in chemical reactions, and quantification of the redox chemistry is a first step in rational materials design