Catalytic oxidation of CO over Pt/Fe3O4 catalysts: Tuning O2 activation and CO adsorption

• Strong metal-support interaction exists on Pt/Fe₃O₄ catalysts. • Pt metal particles facilitate the formation of oxygen vacancies on Fe₃O₄. • Fe₃O₄ supports enhance the strength of CO adsorption on Pt metal particles. The self-inhibition behavior due to CO poisoning on Pt metal particles strongly impairs the performance of CO oxidation. It is an effective method to use reducible metal oxides for supporting Pt metal particles to avoid self-inhibition and to improve catalytic performance. In this work, we used in situ reductions of chloroplatinic acid on commercial Fe₃O₄ powder to prepare heterogeneous-structured Pt/Fe₃O₄ catalysts in the solution of ethylene glycol. The heterogeneous Pt/Fe₃O₄ catalysts achieved a better catalytic performance of CO oxidation compared with the Fe₃O₄ powder. The temperatures of 50% and 90% CO conversion were achieved above 260°C and 290°C at Pt/Fe₃O₄, respectively. However, they are accomplished on Fe₃O₄ at temperatures higher than 310°C. XRD, XPS, and H₂-TPR results confirmed that the metallic Pt atoms have a strong synergistic interaction with the Fe₃O₄ supports. TGA results and transient DRIFTS results proved that the Pt metal particles facilitate the release of lattice oxygen and the formation of oxygen vacancies on Fe₃O₄. The combined results of O₂-TPD and DRIFTS indicated that the activation step of oxygen molecules at surface oxygen vacancies could potentially be the rate-determining step of the catalytic CO oxidation at Pt/Fe₃O₄ catalysts. The reaction pathway involves a Pt-assisted Mars-van Krevelen (MvK) mechanism.     

In situ formation of bimetallic FeNi nanoparticles on sand through green technology: Application for tetracycline removal

• In situ preparation of FeNi nanoparticles on the sand via green synthesis approach. • Removal of tetracycline using GS-FeNi in batch and column study. • Both reductive degradation and sorption played crucial role the process. • Reusability of GS-FeNi showed about 77.39±4.3% removal on 4th cycle. • TC by-products after interaction showed less toxic as compared with TC. In this study, FeNi nanoparticles were green synthesized using Punica granatum (pomegranate) peel extract, and these nanoparticles were also formed in situ over quartz sand (GS-FeNi) for removal of tetracycline (TC). Under the optimized operating conditions, (GS-FeNi concentration: 1.5% w/v; concentration of TC: 20 mg/L; interaction period: 180 min), 99±0.2% TC removal was achieved in the batch reactor. The removal capacity was 181±1 mg/g. A detailed characterization of the sorbent and the solution before and after the interaction revealed that the removal mechanism(s) involved both the sorption and degradation of TC. The reusability of reactant was assessed for four cycles of operation, and 77±4% of TC removal was obtained in the cycle. To judge the environmental sustainability of the process, residual toxicity assay of the interacted TC solution was performed with indicator bacteria (Bacillus and Pseudomonas) and algae (Chlorella sp.), which confirmed a substantial decrease in the toxicity. The continuous column studies were undertaken in the packed bed reactors using GS-FeNi. Employing the optimized conditions, quite high removal efficiency (978±5 mg/g) was obtained in the columns. The application of GS-FeNi for antibiotic removal was further evaluated in lake water, tap water, and ground water spiked with TC, and the removal capacity achieved was found to be 781±5, 712±5, and 687±3 mg/g, respectively. This work can pave the way for treatment of antibiotics and other pollutants in the reactors using novel green composites prepared from fruit wastes.     

Biogenic palladium prepared by activated sludge microbes for the hexavalent chromium catalytic reduction: Impact of relative biomass

• Pd nanoparticles could be reduced and supported by activated sludge microbes. • The effect of biomass on Pd adsorption by microbes is greater than Pd reduction. • More biomass reduces Pd particle size, which is more dispersed on the cell surface. • When the biomass/Pd add to 6, the catalytic reduction rate of Cr(VI) reaches stable. Palladium, a kind of platinum group metal, owns catalytic capacity for a variety of hydrogenations. In this study, Pd nanoparticles (PdNPs) were generated through enzymatic recovery by microbes of activated sludge at various biomass/Pd, and further used for the Cr(VI) reduction. The results show that biomass had a strong adsorption capacity for Pd(II), which was 17.25 mg Pd/g sludge. The XRD and TEM-EDX results confirmed the existence of PdNPs associated with microbes (bio-Pd). The increase of biomass had little effect on the reduction rate of Pd(II), but it could cause decreasing particle size and shifting location of Pd(0) with the better dispersion degree on the cell surface. In the Cr(VI) reduction experiments, Cr(VI) was first adsorbed on bio-Pd with hydrogen and then reduced using active hydrogen as electron donor. Biomass improved the catalytic activity of PdNPs. When the biomass/Pd (w/w) ratio increased to six or higher, Cr(VI) reduction achieved maximum rate that 50 mg/L of Cr(VI) could be rapidly reduced in one minute.     

Ecotoxicity of nanoparticles of CuO and ZnO in natural water

The acute toxicity of CuO and ZnO nanoparticles in artificial freshwater (AFW) and in natural waters to crustaceans Daphnia magna and Thamnocephalus platyurus and protozoan Tetrahymena thermophila was compared. The L(E)C₅₀ values of nanoCuO for both crustaceans in natural water ranged from 90 to 224 mg Cu/l and were about 10-fold lower than L(E)C₅₀ values of bulk CuO. In all test media, the L(E)C₅₀ values for both bulk and nanoZnO (1.1-16 mg Zn/l) were considerably lower than those of nanoCuO. The natural waters remarkably (up to 140-fold) decreased the toxicity of nanoCuO (but not that of nanoZnO) to crustaceans depending mainly on the concentration of dissolved organic carbon (DOC). The toxicity of both nanoCuO and nanoZnO was mostly due to the solubilised ions as determined by specific metal-sensing bacteria.     

Immobilization of non-point phosphorus using stabilized magnetite nanoparticles with enhanced transportability and reactivity in soils

Laboratory batch and column experiments were conducted to investigate the immobilization of phosphorus (P) in soils using synthetic magnetite nanoparticles stabilized with sodium carboxymethyl cellulose (CMC-NP). Although CMC-stabilized magnetite particles were at the nanoscale, phosphorus removal by the nanoparticles was less than that of microparticles (MP) without the stabilizer due to the reduced P reactivity caused by the coating. The P reactivity of CMC-NP was effectively recovered when cellulase was added to degrade the coating. For subsurface non-point P pollution control for a water pond, it is possible to inject CMC-NP to form an enclosed protection wall in the surrounding soils. Non-stabilized “nanomagnetite” could not pass through the soil column under gravity because it quickly agglomerated into microparticles. The immobilized P was 30% in the control soil column, 33% when treated by non-stabilized MP, 45% when treated by CMC-NP, and 73% when treated by both CMC-NP and cellulase.     

Zero-valent iron nanoparticles in treatment of acid mine water from in situ uranium leaching

Acid mine water from in situ chemical leaching of uranium (Straz pod Ralskem, Czech Republic) was treated in laboratory scale experiments by zero-valent iron nanoparticles (nZVI). For the first time, nZVI were applied for the treatment of the real acid water system containing the miscellaneous mixture of pollutants, where the various removal mechanisms occur simultaneously. Toxicity of the treated saline acid water is caused by major contaminants represented by aluminum and sulphates in a high concentration, as well as by microcontaminants like As, Be, Cd, Cr, Cu, Ni, U, V, and Zn. Laboratory batch experiments proved a significant decrease in concentrations of all the monitored pollutants due to an increase in pH and a decrease in oxidation-reduction potential related to an application of nZVI. The assumed mechanisms of contaminants removal include precipitation of cations in a lower oxidation state, precipitation caused by a simple pH increase and co-precipitation with the formed iron oxyhydroxides. The possibility to control the reaction kinetics through the nature of the surface stabilizing shell (polymer vs. FeO nanolayer) is discussed as an important practical aspect.     

Transport of copper as affected by titania nanoparticles in soil columns

The effects of TiO₂ nanoparticles on the transport of Cu through four different soil columns were studied. For two soils (HB and DX), TiO₂ nanoparticles acted as a Cu carrier and facilitated the transport of Cu. For a third soil (BJ) TiO₂ nanoparticles also facilitated Cu transport but to a much lesser degree, but for a fourth soil (HLJ) TiO₂ nanoparticles retarded the transport of Cu. Linear correlation analysis indicated that soil properties rather than sorption capacities for Cu primary governed whether TiO₂ nanoparticles-facilitated Cu transport. The TiO₂-associated Cu of outflow in the Cu-contaminated soil columns was significantly positively correlated with soil pH and negatively correlated with CEC and DOC. During passage through the soil columns 46.6-99.9% of Cu initially adsorbed onto TiO₂ could be “stripped” from nanoparticles depending on soil, where Cu desorption from TiO₂ nanoparticles increased with decreasing flow velocity and soil pH.     

Aggregation and ecotoxicity of CeO₂ nanoparticles in synthetic and natural waters with variable pH, organic matter concentration and ionic strength

The influence of pH (6.0-9.0), natural organic matter (NOM) (0-10 mg C/L) and ionic strength (IS) (1.7-40 mM) on 14 nm CeO₂ NP aggregation and ecotoxicity towards the alga Pseudokirchneriella subcapitata was assessed following a central composite design. Mean NP aggregate sizes ranged between 200 and 10000 nm. Increasing pH and IS enhanced aggregation, while increasing NOM decreased mean aggregate sizes. The 48 h-E_rC20s ranged between 4.7 and 395.8 mg CeO₂/L. An equation for predicting the 48 h-E_rC20 (48 h-E_rC20 = −1626.4 × (pH) + 109.45 × (pH)² + 116.49 × ([NOM]) − 14.317 × (pH) × ([NOM]) + 6007.2) was developed. In a validation study with natural waters the predicted 48 h-E_rC20 was a factor 1.08-2.57 lower compared to the experimental values.     

Responses of a soil bacterium, Pseudomonas chlororaphis O6 to commercial metal oxide nanoparticles compared with responses to metal ions

The toxicity of commercially-available CuO and ZnO nanoparticles (NPs) to pathogenic bacteria was compared for a beneficial rhizosphere isolate, Pseudomonas chlororaphis O6. The NPs aggregated, released ions to different extents under the conditions used for bacterial exposure, and associated with bacterial cell surface. Bacterial surface charge was neutralized by NPs, dependent on pH. The CuO NPs were more toxic than the ZnO NPs. The negative surface charge on colloids of extracellular polymeric substances (EPS) was reduced by Cu ions but not by CuO NPs; the EPS protected cells from CuO NPs-toxicity. CuO NPs-toxicity was eliminated by a Cu ion chelator, suggesting that ion release was involved. Neither NPs released alkaline phosphatase from the cells’ periplasm, indicating minimal outer membrane damage. Accumulation of intracellular reactive oxygen species was correlated with CuO NPs lethality. Environmental deposition of NPs could create niches for ion release, with impacts on susceptible soil microbes.     

XAFS study of starch-stabilized magnetite nanoparticles and surface speciation of arsenate

It has been shown that starch can effectively stabilize nanoscale magnetite particles, and starch-stabilized magnetite nanoparticles (SMNP) are promising for in situ remediation of arsenic-contaminated soils. However, a molecular level understanding has been lacking. Here, we carried out XAFS studies to bridge this knowledge gap. Fe K-edge XAFS spectra indicated that the Fe-O and Fe-Fe coordination numbers of SMNP were lower than those for bare magnetite particles, and these coordination numbers decreased with increasing starch concentration. The decrease in the average coordination number at elevated stabilizer concentration was attributed to the increase in the surface-to-volume ratio. Arsenic K-edge XAFS spectra indicated that adsorbed arsenate on SMNP consisted primarily of binuclear bidentate (BB) complexes and monodentate mononuclear (MM) complexes. More BB complexes (energetically more favorable) were observed at higher starch concentrations, indicating that SMNP not only offered greater adsorption surface area, but also stronger adsorption affinity toward arsenate.