Sulfate radical-based advanced oxidation processes (SR-AOPs) employing heterogeneous catalysts to generate sulfate radical (SO4 −) from peroxymonosulfate (PMS) and persulfate (PS) have been extensively employed for organic contaminant removal in water. This article aims to provide a state–of–the–art review on the recent development in heterogeneous catalysts including single metal, mixed metal, and nonmetal carbon catalysts for organic contaminants removal, with particular focus on PMS activation. The hybrid heterogeneous catalyst/PMS systems integrated with other advanced oxidation technologies is also discussed. Several strategies for the identification of principal reactive radicals in SO4 −–oxidation systems are evaluated, namely (i) use of chemical probe or spin trapping agent coupled with analytical tools, and (ii) competitive kinetic approach using selective radical scavengers. The main challenges and mitigation strategies pertinent to the SR-AOPs are identified, which include (i) possible formation of oxyanions and disinfection byproducts, and (ii) dealing with sulfate produced and residual PMS. Potential future applications and research direction of SR-AOPs are proposed. These include (i) novel reactor design for heterogeneous catalytic system based on batch or continuous flow (e.g. completely mixed or plug flow) reactor configuration with catalyst recovery, and (ii) catalytic ceramic membrane incorporating SR-AOPs.

Generation of sulfate radical through heterogeneous catalysis for organic contaminants removal: Current development, challenges and prospects

We propose a H2–CO kinetic model which incorporates the recent thermodynamic, kinetic, and species transport updates relevant to high-temperature H2 and CO oxidation. Attention has been placed on obtaining a comprehensive and kinetically accurate model able to predict a wide variety of H2–CO combustion data. The model was subject to systematic optimization and validation tests against reliable H2–CO combustion data, from global combustion properties (shock-tube ignition delays, laminar flame speeds, and extinction strain rates) to detailed species profiles during H2 and CO oxidation in flow reactor and in laminar premixed flames.

An optimized kinetic model of H2/CO combustion

A high-efficient, low-cost, and eco-friendly catalyst is highly desired to activate peroxides for environmental remediation. Due to the potential synergistic effect between bimetallic oxides’ two different metal cations, these oxides exhibit superior performance in the catalytic activation of peroxymonosulfate (PMS). In this work, novel Mn1.8Fe1.2O4 nanospheres were synthesized and used to activate PMS for the degradation of bisphenol A (BPA), a typical refractory pollutant. The catalytic performance of the Mn1.8Fe1.2O4 nanospheres was substantially greater than that of the Mn/Fe monometallic oxides and remained efficient in a wide pH range from 4 to 10. More importantly, a synergistic effect between solid-state Mn and Fe was identified in control experiments with Mn3O4 and Fe3O4. Mn was inferred to be the primary active site in the surface of the Mn1.8Fe1.2O4 nanospheres, while Fe(III) was found to play a key role in the synergism with Mn by acting as the main adsorption site for the reaction substrates....

Degradation of Bisphenol A by Peroxymonosulfate Catalytically Activated with Mn1.8Fe1.2O4 Nanospheres: Synergism between Mn and Fe

Kinetics of elementary reactions in low-temperature autoignition chemistry

Chemical Science Division, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352; Department of Chemistry, ShelbyHall, University of Alabama, Box 870336, Tuscaloosa, Alabama 35487-0336; Notre Dame Radiation Laboratory, University of Notre Dame,Notre Dame, Indiana 46556; Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 0520-8107; Argonne NationalLaboratory, 9700 South Cass Avenue, Argonne, Illinois 60439; Department of Computer Science and Department of Physics, 2710 University Drive,Washington State University, Richland, Washington 99352-1671; Lawrence Berkeley National Laboratory, 1 Cyclotron Road Mailstop 1-0472,Berkeley, California 94720; Department of Chemistry and Biochemistry, University of Texas at Austin, 1 University Station A5300,Austin, Texas 78712; Office of Basic Energy Sciences, U.S. Department of Energy, SC-141/Germantown Building, 1000 Independence Avenue,S.W., Washington, D.C. 20585-1290; Department of Physics and Engineering Physics, Stevens Institute of Technology, Castle Point on Hudson,Hoboken, New Jersey 07030; Department of Chemistry, Johns Hopkins University, 34th and Charles Streets, Baltimore, Maryland 21218;Department of Chemistry, University of Southern California, Los Angeles, California 90089-1062; Department of Chemistry, The Ohio StateUniversity, 100 West 18th Avenue, Columbus, Ohio 43210-1185; Department of Chemistry, Columbia University, Box 3107, Havemeyer Hall,New York, New York 10027; Department of Chemistry, University of Pittsburgh, Parkman Avenue and University Drive,Pittsburgh, Pennsylvania 15260; Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973-5000; Department of Physics andAstronomy, Rutgers, The State University of New Jersey, 136 Frelinghuysen Road, Piscataway, New Jersey 08854-8019; Department of Chemistry,516 Rowland Hall, University of California, Irvine, Irvine, California 92697-2025; Stanford Synchrotron Radiation Laboratory, Stanford LinearAccelerator Center, 2575 Sand Hill Road, Mail Stop 69, Menlo Park, California 94025; School of Chemistry and Biochemistry, Georgia Institute ofTechnology, 770 State Street, Atlanta, Georgia 30332-0400; Geology Department, University of California, Davis, One Shields Avenue,Davis, California 95616-8605; Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue,Cambridge, Massachusetts 02139-4307; Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907-2084Received July 23, 2004

http://casey.brown.edu/chemistry/research/LSWang/publications/194.pdf

Role of water in electron-initiated processes and radical chemistry: issues and scientific advances.

Absolute rate constants for the reactions of the hydroxyl radical with benzene and toluene were measured within the temperature and pressure ranges 213 less than or equal to T less than or equal to 1150 K and 20 less than or equal to P less than or equal to 200 torr by using He, Ar, and SF/sub 6/ as diluent gases. To help elucidate the variations in reaction mechanism with temperature, we also studied OH reactions with deuterated benzene (C/sub 6/D/sub 6/) and with selectively deuterated toluenes (C/sub 6/H/sub 5/CD/sub 3/, C/sub 6/D/sub 5/CD/sub 3/, and C/sub 6/D/sub 5/CH/sub 3/). Three major reaction channels were characterized kinetically. At T less than or equal to 298 K, electrophilic addition of the OH radical to the aromatic ring is the dominant reactive pathway in all systems studied. At temperatures above 500 K, rapid decomposition of the thermalized adduct back to reactants diminishes the importance of the addition channel and leads to bimolecular reaction rate-constant values significantly lower than those measured near room temperature. At elevated temperatures, the ring hydrogen abstraction (for benzene) and side-chain hydrogen abstraction (for toluene) pathways are shown to be predominant. The measured bimolecular rate constants increase monotonically withmore » increases in temperature above 500 K, and kinetic separation of the two hydrogen abstraction modes for toluene is achieved.« less

Kinetics of the reactions of hydroxyl radical with benzene and toluene

Absolute rate coefficients for the reactions OH + H/sub 2/ ..-->.. H/sub 2/O + H (k/sub 1/) and OH + D/sub 2/ ..-->.. DHO + D (k/sub 2/) have been measured between 250 and 1050/sup 0/K by using the flash photolysis-resonance fluorescence technique. The adaptation of the flash photolysis-resonance fluorescence technique to high-temperature studies is described. The measured values of k/sub 1/ and k/sub 2/ exhibit non-Arrhenius behavior. k/sub 1/ and k/sub 2/ are best described by three-parameter functions, k/sub 1/(T) = (4.12 x 10/sup -19/)T/sup 2/ /sup 44/ exp(-1281/T) cm/sup 3/ molecule/sup -1/ s/sup -1/ and k/sub 2/(T) = (4.37 x 10/sup -15/)T/sup 1/ /sup 18/ exp(-2332/T) cm/sup 3/ molecule/sup -1/ s/sup -1/ over the entire temperature range 250 to 1050/sup 0/K. Alternatively, at low temperatures k/sub 1/ and k/sub 2/ can be described by Arrhenius expressions, k/sub 1/(T) = (4.9 +- 0.5) x 10/sup -12/ exp(-(1.99 +- 0.34) x 10/sup 3//T) cm/sup 3/ molecule/sup -1/ s/sup -1/ for 250 < T < 400/sup 0/K and k/sub 2/(T) = 1.21 +- 0.52) x 10/sup -11/ exp(-(2.67 +- 0.15) x 10/sup 3//T) cm/sup 3/ molecule/sup -1/ s/sup -1/ for 250 < T < 470/sup 0/K. The results are compared withmore » theoretical calculations based on an ab initio potential energy surface for reaction 1.« less

Kinetic study of the reaction of hydroxyl with hydrogen and deuterium from 250 to 1050 K

Measurements were made for the rate constant of OH + CO + He at 293 K, and OD + CO + M (M = He, Ar, N2, air, SF6) at 253−343 K. Results were also obtained for OH + CO in a shock tube at 1400−2600 K using OH and CO absorption. A two-channel RRKM model of these and other representative results was constructed, with five adjustable parameters. A systematic optimization method was then employed to produce the best fit of the data and provide predictive k(T,P,D/H) expressions for other conditions.

F. P. Tully

Papers

Kinetics of the reactions of hydroxyl radical with benzene and toluene

Kinetic study of the reaction of hydroxyl with hydrogen and deuterium from 250 to 1050 K

OH(OD) + CO: Measurements and an Optimized RRKM Fit