In Situ Electrochemical SFG/DFG Study of CN− and Nitrile Adsorption at Au from 1-Butyl-1-methyl-pyrrolidinium Bis(trifluoromethylsulfonyl) Amide Ionic Liquid ([BMP][TFSA]) Containing 4-{2-[1-(2-Cyanoethyl)-1,2,3,4-tetrahydroquinolin-6-yl]diazenyl} Benzonitrile (CTDB) and K[Au(CN)2]

Abstract

In this paper we report an in situ electrochemical Sum-/Difference Frequency Generation (SFG/DFG) spectroscopy investigation of the adsorption of nitrile and CN− from the ionic liquid 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl) amide ([BMP][TFSA]) containing 4-{2-[1-(2-cyanoethyl)-1,2,3,4-tetrahydroquinolin-6-yl]- diazenyl}benzonitrile (CTDB) at Au electrodes in the absence and in the presence of the Au-electrodeposition process from K[Au(CN)2]. The adsorption of nitrile and its coadsorption with CN− resulting either from the cathodic decomposition of the dye or from ligand release from the Au(I) cyanocomplex yield potential-dependent single or double SFG bands in the range 2,125–2,140 cm−1, exhibiting Stark tuning values of ca. 3 and 1 cm−1 V−1 in the absence and presence of electrodeposition, respectively. The low Stark tuning found during electrodeposition correlates with the cathodic inhibiting effect of CTDB, giving rise to its levelling properties. The essential insensitivity of the other DFG parameters to the electrodeposition process is due to the growth of smooth Au.

Perspective: Chemical reactions in ionic liquids monitored through the gas (vacuum)/liquid interface

“…[67][68][69][70][71][72] We also exclude studies where the reaction was not carried out in situ, that is, spectra were not recorded while the reaction proceeded, or the sample was moved to a different site in the XPS setup or was even removed from the XPS setup in order to carry out the reaction. [73][74][75][76][77] We also do not address studies that incorporate electrochemical sample manipulation, 66,67,[69][70][71][78][79][80][81][82][83][84][85][86] electrodeposition of metal or organic layers from ILs, [87][88][89][90][91] and IL decomposition 84,[92][93][94][95][96][97][98][99][100][101][102] or nanoparticle formation in ILs. 62,75,103 Each of these topics was studied extensively and would justify a separate review.…”