Modified thermodynamics in ionic liquids for controlled electrocrystallization of nanocubes, nanowires, and crystalline thin films of silver-tetracyanoquinodimethane.

Electrocrystallization of nanocubes, nanorods, nanowires, and crystalline thin films of silver-tetracyanoquinodimethane (AgTCNQ) onto glassy carbon, indium tin oxide, and platinum electrodes can be achieved from ionic liquids containing dissolved TCNQ and Ag(I) salts. In conventional molecular organic solvents, such as acetonitrile, the reduction of TCNQ and Ag(+) occurs at almost the same potential. In contrast, the different thermodynamics that apply to the room temperature ionic liquid, 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF(4)), give rise to a large potential separation in the two processes, which enables electrocrystallization of AgTCNQ to be undertaken via two distinctly different, potential-dependent mechanisms. Cyclic and microelectrode voltammetric, chronoamperometric, together with microscopic and spectroscopic techniques reveal that AgTCNQ nanostuctures of controlled morphology, size, density, and uniformity can be achieved by tuning the electrocrystallization parameters such as potential, stoichiometric ratio of Ag(+) and TCNQ, and their concentrations, time, and ionic liquid viscosity by altering the water content. In the potential range of -0.1 to 0.3 V vs Fc(0/+) (Fc = ferrocene), electrocrystallization occurs when Ag is deposited at electrode defect sites via a progressive nucleation and 3-D growth mechanism followed by reaction with TCNQ to produce structures ranging from nanocubes to nanowires. At higher stoichiometric concentrations of Ag(+) and more negative potentials (<-0.1 V vs Fc(0/+)), extremely thin crystalline films could be obtained via overpotential deposition. Infrared and Raman spectroscopy, elemental analysis, together with X-ray diffraction and scanning electron microscopy all confirm the formation of highly pure AgTCNQ nanomaterials, which exhibit differences in morphology but not phase. The study highlights the capability of the electrocrystallization method to precisely control the morphology of nanomaterials, and also the unprecedented opportunities provided by using ionic liquids as the medium for preparation of technologically important metal-TCNQ charge transfer complexes.