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].
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.
Department of Innovation Engineering, University of Salento, Via Monteroni, 73100 Lecce, Italy. benedetto.bozzini@unisalento.it
Benedetto
B
Bozzini
Bertrand
B
Busson
Audrey
A
Gayral
Christophe
C
Humbert
Claudio
C
Mele
Catherine
C
Six
Abderrahmane
A
Tadjeddine
D000327:Adsorption; D001391:Azo Compounds / Q000737:chemistry*; D003460:Crystallization; D055664:Electrochemical Techniques / Q000379:methods*; D004566:Electrodes; D004573:Electrolytes / Q000737:chemistry; D004595:Electroplating; D006046:Gold / Q000737:chemistry*; D017612:Gold Compounds / Q000737:chemistry*; D052578:Ionic Liquids / Q000737:chemistry*; D009570:Nitriles / Q000737:chemistry*; D011758:Pyrroles / Q000737:chemistry*; D011759:Pyrrolidines; D011804:Quinolines / Q000737:chemistry*; D012996:Solutions; D013057:Spectrum Analysis
C521242:1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide; D001391:Azo Compounds; D004573:Electrolytes; D017612:Gold Compounds; D052578:Ionic Liquids; D009570:Nitriles; D011758:Pyrroles; D011759:Pyrrolidines; D011804:Quinolines; D012996:Solutions; D006046:Gold; C014356:benzonitrile