title: Efficient heterogeneous catalytic reduction of perchlorate in water.
abstract: A new heterogeneous catalyst that promotes the reduction by hydrogen of perchlorate ion in water under mild conditions has been developed. The catalyst is prepared by adsorption of a rhenium(VII) precursor (either ammonium perrhenate or methylrhenium trioxide) onto carbon powder containing 5% palladium by weight. Under standard batch conditions of room temperature, 1 bar of hydrogen, and 200 ppm perchlorate (as HClO4), reduction proceeded to less than 1 ppm in as little as 5 h. Extended reaction times led to residual perchlorate at low parts per billion levels. Chloride was the only observed product, with good material balance. Catalytic materials ranging from 3% to 13% Re showed (pseudo) first-order rates linearly dependent on the Re content. Representative normalized rate constants for catalysts with 5-9% Re were in the range 0.1-0.3 L h(-1) (g of cat.)(-1). Inhibition by chloride was not significant, with little change in perchlorate reduction rate in the presence of excess chloride to 1000 ppm. However, optimal activity occurred in acidic solutions (pH ca. 3), and both the rate and extent of reaction decreased at higher values of pH. In its current form the catalyst might be best applied to destroy perchlorate in the acidic regeneration stream from selective ion exchange columns.
authors.affiliation: Center of Advanced Materials for the Purification of Water with Systems and Department of Chemistry, University of Illinois at Urbana-Champaign 61801, USA.
authors.forename: Keith D
authors.initials: KD
authors.lastname: Hurley
authors.forename: John R
authors.initials: JR
authors.lastname: Shapley
mesh_terms: D002244:Carbon; D002384:Catalysis; D002852:Chromatography, Ion Exchange; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D013058:Mass Spectrometry; D010084:Oxidation-Reduction; D010165:Palladium; D010472:Perchlorates / Q000737:chemistry*; D012211:Rhenium; D013056:Spectrophotometry, Ultraviolet; D014867:Water / Q000737:chemistry*; D018508:Water Purification / Q000379:methods*
chemical_list: D010472:Perchlorates; D014867:Water; D010165:Palladium; D012211:Rhenium; D002244:Carbon; C494474:perchlorate