Lecture 12 Electrocatalysis and Electrochemical Synthesis II.pptVIP

B. Cathodic oxidation a. Function groups convertion 77% 80% 93% A. Conventional synthesis methods for adiponitrile a. With cyclohexane b. With butene CH2=CH-CH2-CH3 —? -H2 Cat. CH2=CH-CH=CH2 —? HCN Cat. (CH2CH2CN)2 B. Electrosynthesis cathode：2CH2=CH-CN + 2H+ + 2e —?(CH2-CH2CN)2 anode：H2O —? ? O2 + 2H+ + 2e CH2=CH-CH3 ——? NH3+O2 Cat. CH2=CH-CN —? electrolysis (CH2CH2CN)2 Side reaction: CH2=CH-CN + 2H+ + 2e —? CH3CH2CN CH2=CH-CN —? OH- HO-CH2-CH(CN)- —? H+ HO-CH2-CH2CN —? OH- -O-CH2-CH2CN O-CH2-CH2CN ? CH2-CH(CN)- ————? CH2CHCN —? H+ O-CH2-CH2CN ? CH2-CH2(CN) Proposed mechanism C. Electrolysis methods a. Electrolyte (moisture, low concentration of hyamine) CH2=CHCN + (CH2CH2CN)2 32% H2O 28% (C2H5)4N+ C2H5OSO3- 40% b. Electrolysis cell c. Producing process Tetraalkyl lead A. principle RCl + Mg ——?RMgCl eth RMgCl ——?R- + MgCl+ eth Pb anode： 4R- + Pb ——? R4Pb + 4e Steel cathode：4MgCl+ + 4e ——? 2Mg + 2MgCl2 Saccharin(糖精) A. Convenient chemical methods a. Dissolvation of raw material b. oxidation c. Balancing out Saccharin d. dissolved B. electrosynthesis Anode： Mn+ ——? M(n+1)+ + e chemical：M(n+1)+ + R ——? 2Mn+ + P indirect electro-oxidation EC mechanism The oxygen carrier is Cr6+ 2Cr3+ + 8H2O ??2CrO42- + 16H+ + 6e or 2Cr3+ + 7H2O ??2Cr2O72- + 14H+ + 6e The overall reaction is Milton J. Allen, Platinum Metals Rev., 1959, 3, 131-135 Electrochemical process for the production of saccharin Hydroquinone A typical example of electrosynthesis with two electrodes Anode oxidation(20% H2SO4、stirring)： Cathode reduced very purified and the yield is over 80%, direct current electrical power cost: 15000kW h h-1 Organic electrochemical fluorination 1949, Simons point out that the organic compounds can solvated in non-hydrous fluoride acid and formed a conductive solution. After power on, the organic compounds can be full