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Title of Journal: J Solid State Electrochem

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Abbravation: Journal of Solid State Electrochemistry

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Springer-Verlag

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DOI

10.1007/bf00479564

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1433-0768

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A new method for electrocrystallization of AgTCNQF

Authors: Thanh H Le Anthony P O’Mullane Lisandra L Martin Alan M Bond
Publish Date: 2011/07/12
Volume: 15, Issue: 11-12, Pages: 2293-2304
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Abstract

Semiconducting AgTCNQF4 TCNQF4 = 2356tetrafluoro7788tetracyanoquinodimethane has been electrocrystallized from an acetonitrile 01 M Bu4NPF6 solution containing TCNQF4 and AgMeCN 4 + Reduction of TCNQF4 to the TCNQF 4 1− anion followed by reaction with AgMeCN 4 + forms crystalline AgTCNQF4 on the electrode surface Electrochemical synthesis is simplified by the reduction of TCNQF4 prior to AgMeCN 4 + compared with the analogous reaction of the parent TCNQ to form AgTCNQ where these two processes are coincident Cyclic voltammetry and surface plasmon resonance studies reveal that the electrocrystallization process is slow on the voltammetric time scale scan rate = 20 mV s−1 for AgTCNQF4 as it requires its solubility product to be exceeded The solubility of AgTCNQF4 is higher in the presence of 01 M Bu4NPF6 supporting electrolyte than in pure solvent Cyclic voltammetry illustrates a dependence of the reduction peak potential of AgMeCN 4 + to metallic Ag on the electrode material with the ease of reduction following the order Au  Pt  GC  ITO Ultravioletvisible Fourier transform infrared and Raman spectra confirmed the formation of reduced TCNQF 4 1− and optical microscopy showed needleshaped morphology for the electrocrystallized AgTCNQF4 AgTCNQF4 also can be formed by solid–solid transformation at a TCNQF4modified electrode in contact with aqueous media containing Ag+ ions Chemically and electrochemically synthesized AgTCNQF4 are spectroscopically identical Electrocrystallization of Ag2TCNQF4 was also investigated however this was found to be thermodynamically unstable and readily decomposed to form AgTCNQF4 and metallic Ag as does chemically synthesized Ag2TCNQF4Financial support from the Australian Research Council is greatly appreciated T H L gratefully acknowledges graduate scholarship funding from Danang City in Vietnam and the award of a Monash University Faculty of Science Dean’s International Postgraduate Research Scholarship

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