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Recent work demonstrates reduction of aqueous perchlorate by hydrogen at ambient temperatures and pressures using a novel rhenium—palladium bimetal catalyst immobilized on activated carbon (Re/Pd-AC). This study examines the influence of Re speciation on catalyst activity and stability. Rates of perchlorate reduction are linearly dependent on Re content from 0-6 wt %, but no further increases are observed at higher Re contents. Surface-immobilized Re shows varying stability and speciation both in oxic versus H2-reducing environments and as a function of Re content. In oxic solutions, Re immobilization is dictated by sorption of the Re(VII) precursor, perrhenate (ReO4-), to activated carbon via electrostatic interactions. Under H2-reducing conditions, Re immobilization is significantly improved and leaching is minimized by ReO4- reduction to more reduced species on the catalyst surface. X-ray photoelectron spectroscopy shows two different Re binding energy states under H2-reducing conditions that correspond most closely to Re(V)/Re(IV) and Re(I) reference standards, respectively. The distribution of the two redox states varies with Re content, with the latter predominating at lower Re contents where catalyst activity is more strongly dependent on Re content. Results demonstrate that both lower Re contents and the maintenance of H2-reducing conditions are key elements in stabilizing the active Re surface species that are needed for sustained catalytic perchlorate treatment. [ABSTRACT FROM AUTHOR]

This study tested the stability, activity, and selectivity of an alumina-supported Pd–In bimetallic catalyst during repetitive sulfide fouling and oxidative regeneration conditions. Nitrate reduction with hydrogen was used as the probe reaction in a continuous-flow packed-bed reactor to assess changes in the catalyst structure as a result of the fouling and regeneration processes. Partial regeneration of a severely sulfide-fouled Pd–In catalyst was achieved with a NaOCl/NaHCO3 solution. However, the regenerated catalyst had a reduced activity for NO3 − reduction and increased selectivity towards NH3. Analysis of the catalyst bed after regeneration experiments using XPS, ICP-MS, and BET surface area revealed that bulk structural transformations of the Pd–In bimetallic catalyst occurred, as a result of preferential Pd dissolution near the column influent. The dissolved Pd showed limited mobility in the column, and was re-deposited on the catalyst, resulting in Pd enrichment on the catalyst surface and redistribution of Pd towards the end of the column. These changes along with residual sulfur content on the catalyst surface were likely responsible for the increased selectivity towards NH3. These results indicate the importance of limiting the exposure of reduced sulfur species to Pd-based catalysts, especially when treating contaminants like NO3 −, where product selectivity is a priority. [ABSTRACT FROM AUTHOR]

This study tested the selectivity and sustainability of an alumina-supported Pd–In bimetallic catalyst for nitrate reduction with H2 in a continuous-flow packed-bed reactor in the presence of: (i) dissolved oxygen (DO), an alternative electron acceptor to nitrate, (ii) variable NO3 −:H2 influent loadings, and (iii) the presence of a known foulant, sulfide. The sustainability of the catalyst was promising, as the catalyst was found to be stable under all conditions tested with respect to metal leaching. The presence of DO at concentrations typical of treatment conditions will increase H2 demand for NO3 − reduction, but has no negative impact on the selectivity of the catalyst. Under optimal conditions, i.e., a pH of 5.0 and a high NO3 −:H2 influent loading, low NH3 selectivity (5%) was achieved for extended periods (36 days), resulting in sustained levels of NH3 that approached the European legal limit. The biggest challenge to the sustainability of the catalyst was the addition of sulfide, that initially increased NH3 selectivity and ultimately resulted in complete deactivation of the catalyst. Further work is required to identify regeneration methods to restore sulfide-fouled catalyst activity and selectivity; however, the most effective use would be to remove sulfide prior to catalytic treatment. [ABSTRACT FROM AUTHOR]

There is a need for new technologies to rapidly and economically treatwater contaminated with N-nitrosodimethylamine (NDMA) and related compounds because of their high toxicity and recent detection in drinking water sources as a consequence of industrial releases and chlorine disinfection of wastewater effluent Treatment of N-nitrosamines with H2 in conjunction with a high surface area porous nickel material, a model nonprecious metal catalyst, has been evaluated. Experiments show that NDMA is reduced rapidly and catalytically to dimethylamine and N2 (e.g., t1/2 = 1.5 mm for 500 mg/L catalyst and PH2 = 1 atm), and kinetic trends are consistent with a surface-mediated mechanism involving scission of the N-nitrosamine N-N bond and subsequent reactions with adsorbed atomic hydrogen. The metal-loading-normalized pseudo-first-order rate constant (77.9 ± 13.1 L gNi-1 h-1) exceeds values reported for Pd-based catalysts. Several related N-nitrosamines react at rates similar to those of NDMA, indicating a weak dependence on structure. The reaction rates for NOMA reduction are not significantly affected by changing pH, and the presence of high concentrations of many common water constituents (Na+, Ca2+, Mg2+, Cl-, SO42-, HCO3-, and NOM) exerts only a small effect on reaction rates. Nitrate is also reduced by the Ni catalyst, and high nitrate concentrations competitively inhibit the reduction of NDMA. (Bi)sulfide poisons the catalyst by strong chemisorption to the Ni surface. Cost-normalized rate constants for the Ni catalyst are highly favorable compared to Pd-based catalysts, indicating that, with further development Ni-based catalysts may become attractive alternatives to precious metal catalysts. [ABSTRACT FROM AUTHOR]

Pd-based catalysts provide efficient and selective reduction of several drinking water contaminants, but their long-term application requires effective treatments for catalyst regeneration following fouling by constituents in natural waters. This study tested alumina-supported Pd-Cu and Pd-In bimetallic catalysts for nitrate reduction with H2 after sulfide fouling and oxidative regeneration procedures. Both catalysts were severely deactivated after treatment with μM levels of sulfide. Regeneration was attempted with dissolved oxygen, hydrogen peroxide, sodium hypochlorite, and heated air. Only sodium hypochlorite and heated air were effective regenerants, specifically restoring nitrate reduction rates for a Pd-In/γ-Al2O3 catalyst from 20% to between 39 and 60% of original levels. Results from ICP-MS revealed that sodium hypochlorite caused dissolution of Cu from the Pd-Cu catalyst but that the Pd-In catalyst was chemically stable over a range of sulfide fouling and oxidative regenerative conditions. Analysis by XPS indicated that PdS and In2S3 complexes form during sulfide fouling, where sulfur is present as S2-, and that regeneration with sodium hypochlorite converts a portion of the S2- to S6+, with a corresponding increase in reduction rates. These results indicate that Pd-In catalysts show exceptional promise for being robust under fouling and regeneration conditions that may occur when treating natural waters. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The molecular Re(V) complex, chlorobis(2-(2′-hydroxyphenyl)-2-oxazoline)-oxorhenium(V), Re(O)(hoz)2Cl, has been investigated as a suitable precursor, when combined with activated carbon powder containing 5 wt % Pd, to provide a heterogeneous catalyst for the reduction of aqueous perchlorate by hydrogen. Two general methods for catalyst preparation have been adopted: first, by a standard "incipient wetness" impregnation of the carbon powder with handling under largely aerobic conditions for convenience and, second, by a completely anaerobic procedure maintaining a hydrogen atmosphere during adsorption of the complex in water onto the powder. Both types of catalyst were efficient for the complete reduction of perchlorate to chloride within a few hours at room temperature over a range of initial concentrations (2-200 ppm) under 1 atm of H2 and acidic conditions (pH 2.7-3.7). The perchlorate reduction profiles displayed pseudo-first-order kinetics, and the rates were insensitive to excess chloride. Complete reduction of perchlorate was observed even at pH 5.9 in a phosphate buffer over the course of two weeks. Under comparable conditions, chlorate reduction proceeded ca. 10 times more quickly than perchlorate reduction. The impregnated catalyst was examined by STEM/EDS, which revealed a wide distribution in Pd nanoparticle sizes and also suggested that the Re complex did not aggregate preferentially on or near the Pd particles. XPS of this material provided evidence for reduced Pd after the reaction, but only a +7 oxidation state was seen for the Re sites both pre- and postreduction. Elemental analyses of the catalyst materials taken pre- and postreduction showed variable amounts of Re loss (0-50%) but relatively unchanged amounts of nitrogen. These results show the need to maintain a reducing atmosphere during the preparation and operation of the catalyst in order to achieve optimum activity and stability. [ABSTRACT FROM AUTHOR]