Non-heme manganese catalysts for on-demand production of chlorine dioxide in water and under mild conditions.
Two non-heme manganese complexes are used in the catalytic formation of chlorine dioxide from chlorite under ambient temperature at pH 5.00. The catalysts afford up to 1000 turnovers per hour and remain highly active in subsequent additions of chlorite. Kinetic and spectroscopic studies revealed a Mn(III)(OH) species as the dominant form under catalytic conditions. A Mn(III)(μ-O)Mn(IV) dinuclear species was observed by EPR spectroscopy, supporting the involvement of a putative Mn(IV)(O) species. First-order kinetic dependence on the manganese catalyst precludes the dinuclear species as the active form of the catalyst. Quantitative kinetic modeling enabled the deduction of a mechanism that accounts for all experimental observations. The chlorine dioxide producing cycle involves formation of a putative Mn(IV)(O), which undergoes PCET (proton coupled electron-transfer) reaction with chlorite to afford chlorine dioxide. The ClO2 product can be efficiently removed from the aqueous reaction mixture via purging with an inert gas, allowing for the preparation of pure chlorine dioxide for on-site use and further production of chlorine dioxide.
Brown Laboratory, Negishi Brown Institute, and Department of Chemistry, Purdue University , 560 Oval Drive, West Lafayette, Indiana 47907, United States.
Scott D
SD
Hicks
Doyeon
D
Kim
Silei
S
Xiong
Grigori A
GA
Medvedev
James
J
Caruthers
Seungwoo
S
Hong
Wonwoo
W
Nam
Mahdi M
MM
Abu-Omar
D002384:Catalysis; D017606:Chlorine Compounds / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D008345:Manganese / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D010087:Oxides / Q000737:chemistry*; D013696:Temperature; D014867:Water / Q000737:chemistry*
D017606:Chlorine Compounds; D010087:Oxides; D014867:Water; D008345:Manganese; C025109:chlorine dioxide