Journal of Electroanalytical Chemistry, Vol.448, No.1, 5-15, 1998
In situ FTIR spectroscopic studies of electrooxidation of C-4 alcohols on platinum electrodes in acid solutions - Part II. reaction mechanism of 1,3-butanediol oxidation
The electrooxidation of 1,3-butanediol (1,3-BD) on platinum electrodes in perchloric and sulphuric acid solutions was studied by using cyclic voltammetry and in situ FTIR spectroscopy. The determination of intermediates and products involved in 1,3-BD oxidation was carried out in solutions prepared using either millipore water or deuterated water as solvent. The in situ FTIRS data acquired from experiments of single potential alteration and time-resolved determination demonstrated that the oxidation of 1,3-BD on the Pt electrode is a complex process and may obey a dual path reaction mechanism. Three pathways were determined in 1,3-BD oxidation. The first one is the dissociative adsorption of 1,3-BD, which yields CH3CHOHCH3 and poison species COad. The second one is the dehydration of 1,3-BD, which produces intermediates of CH3CH=CHCH2OH and CH2 =CHCH2CH2OH. The last one is the direct oxidation of 1,3-BD at potentials above 0.30 V(SCE) on a Pt surface free of COad, which produces intermediates of CH3CHOHCH2COOH and CH3COCH2CH2OH. These intermediates are characterised by IR bands appearing near 2045 (COad), 1600 (> C=C <), 1720 cm(-1) (> C=O) and a series of IR bands locating in the fingerprint region and around 3000 cm(-1). Ah the above intermediates can be oxidised further to acid compounds, among them acetoacetic acid which is characterised by the double carbonyl bands at 1724 and 1712 cm(-1) and has been determined as the majority species. As the acid compounds can be oxidised to CO2 which yields IR absorption at 2345 cm(-1) via a C-C bond breaking process at relatively high electrode potentials, they have been considered to play the role of both intermediate and product in 1,3-BD oxidation. The ultimate product of 1,3-BD oxidation at potentials above 0.30 V(SCE) is determined as CO2. The comparison of IR features of 1,3-BD oxidation with those of l-butanol oxidation reported in our previous paper [1] illustrated the effects of molecular structure in electrocatalysis of C-4 molecules.
Keywords:ELECTROCATALYTIC OXIDATION;ALIPHATIC DIOLS;INSITU FTIR;ADSORPTION;1;2-PROPANEDIOL;INTERFACE;BEHAVIOR;GOLD