Study On Theredox Mechanism Of Aromatic P-nitro Compounds By In FT-IR Spectroelectrochemistry

In this dissertation, experimental technique and achievements of electrochemical studies of nitro compounds and aromatic nitro compounds were reviewed firstly. Secondly, cyclic voltammetry (CV), IR spectroelectrochemistry cyclic voltabsorpto-metry (CVA), derivative cyclic voltabsorptometry (DCVA) technique and reconstructed i-E curves were used to investigate the electrochemical reduction of Dinitrodurene (PND) and Dinitrodurene (DNT) in aprotic media. In addition, a low temperature in-situ infrared reflected absorbance spectroelecrochemical (LT IRRAS) cell was designed to study the electrochemical reduction of Dinitrodurene (DNT) at a low temperature. The main researching contents are concluded as follows:1.Cyclic voltammetry (CV), IR spectroelectrochemistry cyclic voltabsorptometry (CVA), Derivative cyclic voltabsorpt-ometry (DCVA) technique and reconstructed i-E curves were used to investigate the electrochemical reduction process of4-Nitrotoluene (PNT) in aprotic media. The results show that only one coupled redox waves appear in the CV of4-Nitrotoluene, suggesting that4-Nitrotoluene was reversibly reduced in one-step one-electron transfer. A series of IR absorption bands at1349;1518;1226and1056cm-1tracing to PNT and PNT-were observed clearly in the3D IR spectra. What is more, the electrochemical reduction mechanism was given intuitively though analyzing cyclic voltabsorptometry, derivative cyclic voltabsorptom-etry and reconstructed i-E curves. The mechanism can be expressed as:PNT+e(?)PNT-.2. The electrochemical behavior of DNT was studied in aprotic media. The results show that electrochemical reduction of DNT was provided with the characteristics of two-electron two-step reaction. However, the CV of DNT showed only one CV wave. A series of IR absorption bands at1541;1330and1195,1025cm-1tracing to DNT and DNT-were observed. In addition, a series of IR absorption bands at1541;1330;1025;1195and1433,1133cm-1, tracing to DNT; DNT-and DNT2-were observed clearly in the3D spectra. What is more, the electrochemical reduction mechanism was given Intuively though analying cyclic voltabsorptometry, derivative cyclic voltabsorptom. The mechanism can be expressed as:DNT(?)DNT-(?)DNT2-.3. To study the low-temperature electrochemical reaction, a novel low temperature in-situ infrared reflected absorbance spectroelectrochemical cell was designed. Cyclic voltammetry, in-situ FT-IR spectroscopy, cyclic voltabsorptometry (CVA), and derivative cyclic voltabsorptometry(DCVA) were used to characterize this cell. The experiment results of Potassium hexacyanoferrate and BQ(benzoquinone) show good performances of the cell. The results indicate that the novel low temperature spectroelectrochemical cell could be used under low temperature electrochemical experiments.