Role of the Deep Eutectic Solvent Reline in the Synthesis of Gold Nanoparticles.

This work presents a mechanistic understanding of the synthesis of small (<3 nm) gold nanoparticles in a nontoxic, eco-friendly, and biodegradable eutectic mixture of choline chloride and urea (reline) without the addition of external reducing or stabilization agents. Reline acts as a reducing agent by releasing ammonia (via urea hydrolysis), forming gold nanoparticles even at trace ammonia concentration levels. Reline also affects the speciation of the gold precursor forming gold chloro-complexes, stabilizing Au+ species, leading to an easier reduction and avoiding the otherwise fast disproportionation reaction. Such a capability is however lost in the presence of large amounts of water, where water replaces the chloride ligands in the precursor speciation. In addition, reline acts as a weak stabilizing agent, leading to small particles (<3 nm) and narrow distributions although agglomerates quickly form. Such properties are maintained in the presence of water, indicating that it is linked to the urea stabilization rather than the hydrogen-bonding network. This work has important implications in the field of green synthesis of nanoparticles with small sizes, especially for biomedical and health care applications, due to the nontoxic nature of the components of deep eutectic solvents in contrast to the conventional routes.

Morphological Control of Nanostructured V2O5 by Deep Eutectic Solvents.

Herein, we show a facile surfactant-free synthetic platform for the synthesis of nanostructured vanadium pentoxide (V2O5) using reline as a green and eco-friendly deep eutectic solvent. This new approach overcomes the dependence of the current synthetic methods on shape directing agents such as surfactants with potential detrimental effects on the final applications. Excellent morphological control is achieved by simply varying the water ratio in the reaction leading to the selective formation of V2O5 3D microbeads, 2D nanosheets, and 1D randomly arranged nanofleece. Using electrospray ionization mass spectroscopy (ESI-MS), we demonstrate that alkyl amine based ionic species are formed during the reline/water solvothermal treatment and that these play a key role in the resulting material morphology with templating and exfoliating properties. This work enables fundamental understanding of the activity-morphology relationship of vanadium oxide materials in catalysis, sensing applications, energy conversion, and energy storage as we prove the effect of surfactant-free V2O5 structuring on battery performance as cathode materials. Nanostructured V2O5 cathodes showed a faster charge-discharge response than the counterpart bulk-V2O5 electrode with V2O5 2D nanosheet presenting the highest improvement of the rate performance in galvanostatic charge-discharge tests.