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Catalytic reduction of water contaminants using palladium (Pd)-based catalysts and hydrogen gas as a reductant has been extensively studied at the bench-scale, but due to technical challenges it has only been limitedly applied at the field-scale. To motivate research that can overcome these technical challenges, this review critically analyzes the published research in the area of Pd-based catalytic reduction of priority drinking water contaminants (i.e., halogenated organics, oxyanions, and nitrosamines), and identifies key research areas that should be addressed. Specifically, the review summarizes the state of knowledge related to (1) proposed reaction pathways for important classes of contaminants, (2) rates of contaminant reduction with different catalyst formulations, (3) long-term sustainability of catalyst activity with respect to natural water foulants and regeneration strategies, and (4) technology applications. Critical barriers hindering implementation of the technology are related to catalyst activity (for some contaminants), stability, fouling, and regeneration. New developments overcoming these limitations will be needed for more extensive field-scale application of this technology.

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 min 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 g(Ni)(-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 NDMA reduction are not significantly affected by changing pH, and the presence of high concentrations of many common water constituents (Na+, Ca2+, Mg2+, Cl-, SO4(2-), HCO(3-), 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.

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.

There is considerable need for the rapid destruction of N-nitrosodimethylamine (NDMA) in water because current alternative treatment methods are relatively inefficient. Powdered metal catalysts in conjunction with hydrogen gas showed notable potential for rapid destruction of N-nitrosodimethylamine (NDMA) in water. Palladium, copper-enhanced palladium, and nickel catalysts showed significant efficacy for NDMA reduction, with observed half-lives on the order of hours using 10 mg L(-1) catalyst metal. Other catalysts were screened because of their well-documented efficacy for reduction of halogenated hydrocarbons, including zerovalent iron, nickel-enhanced iron, nickel, and manganese. Starting with 100 microg L(-1) NDMA, a level observed at multiple field sites, pseudo-first-order kinetics were observed for all catalysts tested. No reaction intermediates were observed in any experiment; the amine group of NDMA was cleaved and reduced to dimethylamine with carbon balance in excess of 97%. Reductive catalysis may prove an efficient technology for mitigating the health risk posed by NDMA; this study provides the foundation for mechanistic and longevity research.

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]

A response is presented from the authors of the article “Critical Review of Pd-Based Catalytic Treatment of Priority Contaminants in Water” from volume 46, 2012 of “Environmental Science and Technology” to comments in the issue by F. D. Kopinke on possible calculation errors in their report. Topics include external mass transfer coefficients, internal mass transfer limitation, and the incorporation of porous shell glass beads into lead catalysts. Several corrections are also offered to the original article for statements such as the effect of pH, cyclohexanone and cyclohexanol observation, and bond cleavage in halogenated alkanes.