Abstract
The present study reports the synthesis and characterization of metallic nanoparticles (NPs) of Pd and bimetallic alloys of PdCu NPs for their application as catalysts to achieve the microbial reduction of p-nitrophenol (PNP). Addition of bimetallic alloys of PdCu NPs to methanogenic sludge incubations increased up to threefold the rate of reduction of PNP. Moreover, their presence promoted a more efficient and selective reduction of PNP to the desired product (p-aminophenol) with negligible accumulation of toxic intermediates (p-nitroso-phenol and p-hydroxylamine-phenol), which prevailed in sludge incubations lacking nanocatalysts. PdCu NPs synthesized by adding precursors H2PdCl4 and H2CuCl4 independently and simultaneously to the synthesis vessel showed superior catalytic properties as compared to those produced by mixing the same precursors prior addition to the synthesis vessel. The enhanced catalytic properties of bimetallic NPs could be explained by higher physical stability and interfacial arrangement within PdCu alloys promoting a more efficient transfer of reducing equivalents derived from lactate/ethanol fermentation towards the target nitro group in PNP. A wastewater treatment technology, combining the microbial activity of methanogenic consortia and the catalytic activity of bimetallic NPs, is proposed as an alternative for the removal of recalcitrant pollutants from wastewaters.
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Aber, S., Mahmoudikia, E., Karimi, A., & Mahdizadeh, F. (2016). Immobilization of glucose oxidase on Fe3O4 magnetic nanoparticles and its application in the removal of acid yellow 12. Water, Air, and Soil Pollution, 227, 93.
Alvarez, L. H., & Cervantes, F. J. (2011). (Bio)nanotechnologies to enhance environmental quality and energy production. Journal of Chemical Technology and Biotechnology, 86, 1354–1363.
Alvarez, L. H., & Cervantes, F. J. (2012). Assessing the impact of alumina nanoparticles in an anaerobic consortium: methanogenic and humus reducing activity. Applied Microbiology and Biotechnology, 95, 1323–1331.
Alvarez, L. H., Jimenez-Bermudez, L., Hernández-Montoya, V., & Cervantes, F. J. (2012). Enhanced dechlorination of carbon tetrachloride by immobilized fulvic acids on alumina particles. Water, Air, and Soil Pollution, 223, 1911–1920.
Ansari, F., Grigoriev, P., Libor, S., Tothill, I. E., & Ramsden, J. J. (2009). DBT degradation enhancement by decorating Rhodococcus erythopolis IGST8 with magnetic Fe3O4 nanoparticles. Biotechnology and Bioengineering, 102, 1505–1512.
De Corte, S., Hennebel, T., Fitts, J. P., Bliznuk, V., Verschuere, S., Sabbe, T., Verstraete, W., & Boon, N. (2011). Bio-supported bimetallic nanostructures of Pd and Au as catalysts for dechlorination of environmental contaminants. Environmental Science and Technology, 86, 8506–8513.
De Corte, S., Sabbe, T., Hennebel, T., Vanhaecke, L., De Gusseme, B., Verstraete, W., & Boon, N. (2012). Doping of biogenic Pd catalysts with Au enables dechlorination of diclofenac at environmental conditions. Water Research, 46, 2718–2726.
Dong, Z., Le, X., Liu, Y., Dong, C., & Ma, J. (2014). Metal organic framework derived magnetic porous carbon composite supported gold and palladium nanoparticles as highly efficient and recyclable catalysts for reduction of 4-nitrophenol and hydrodechlorination of 4-chlorophenol. Journal of Materials Chemistry A, 2, 18775–18785.
Forrez, I., Carballa, M., Fink, G., Wick, A., Hennebel, T., & Vanhaecke, L. (2011). Biogenic metals for the oxidative and reductive removal of pharmaceuticals, biocides and iodinated contrast media in a polishing membrane bioreactor. Water Research, 45, 1763–1773.
Gonzalez-Estrella, J., Puyol, D., Gallagher, S., Sierra-Alvarez, R., & Field, J. A. (2015). Elemental copper nanoparticle toxicity to different trophic groups involved in anaerobic and anoxic wastewater treatment process. Science of the Total Environment, 512–513, 308–315.
Guisbiers, G., Mendoza-Cruz, R., Bazán-Díaz, L., Velázquez-Salazar, J. J., Mendoza-Perez, R., Robledo-Torres, J. A., Rodríguez-López, J. L., Montejano- Carrizales, J. M., Whetten, R. L., & Yacamán, M. J. (2016). Electrum, the gold silver alloy, from the bulk scale to the nanoscale: synthesis, properties, and segregation rules. ACS Nano, 10, 188–198.
Hennebel, T., Simoen, H., Windt, W., Verloo, M., Boon, N., & Verstraete, W. (2009). Biocatalytic dechlorination of trichloroethylene with bio-palladium in a pilot-scale membrane reactor. Biotechnology and Bioengineering, 102, 995–1002.
Hennebel, T., Benner, J., Clauwaert, P., Vanhaecke, L., Aelterman, P., Callebaut, R., Boon, N., & Verstraete, W. (2011). Dehalogenation of environmental pollutants in microbial electrolysis cells with biogenic palladium nanoparticles. Biotechnology Letters, 33, 89–95.
Hosseinkhani, B., Søbjerg, L. S., Rotaru, A. E., Emtiazi, G., Skrydstrup, T., & Meyer, R. L. (2012). Microbially supported synthesis of catalytically active bimetallic Pd-Au nanoparticles. Biotechnology and Bioengineering, 109, 45–52.
Jiang, X., Shen, J., Han, Y., Lou, S., Han, W., Sun, X., Li, J., Mu, Y., & Wang, L. (2016). Efficient nitro reduction and dechlorination of 2,4-dinitrochlorobenzene through the integration of bioelectrochemical system into upflow anaerobic sludge blanket: a comprehensive study. Water Research, 88, 257–265.
Lee, J., Mahendra, S., & Alvarez, P. J. J. (2010). Nanomaterials in the construction industry: a review of their applications and environmental health and safety considerations. ACS Nano, 4(7), 3580–3590.
Lloyd, J. R., Byrne, J. M., & Coker, V. S. (2011). Biotechnological synthesis of functional nanomaterials. Current Opinion in Biotechnology, 22, 509–515.
Losert, S., von Goetz, N., Bekker, C., Fransman, W., Wijnhoven, S. W. P., Delmaar, C., Hungerbuhler, K., & Ulrich, A. (2014). Human exposure to conventional and nanoparticle-containing sprays—a critical review. Environmental Science and Technology, 48, 5366–5378.
Mao, Y., Park, T.-J., Zhang, F., Zhou, H., & Wong, S. S. (2007). Environmentally friendly methodologies of nanostructure synthesis. Small, 3, 1122–1139.
Otero-González, L., Field, J. A., & Sierra-Alvarez, R. (2014). Inhibition of anaerobic wastewater treatment after long-term exposure to low levels of CuO nanoparticles. Water Research, 58, 160–168.
Ou, C., Shen, J., Zhang, S., Mu, Y., Han, W., Sun, X., Li, J., & Wang, L. (2016). Coupling of iron shavings into the anaerobic system for enhanced 2,4-dinitroanisole reduction in wastewater. Water Research, 101, 457–466.
Pat-Espadas, A. M., Razo-Flores, E., Rangel-Mendez, J. R., & Cervantes, F. J. (2013). Reduction of palladium and production of nano-catalyst by Geobacter sulfurreducens. Applied Microbiology and Biotechnology, 97, 9553–9560.
Pat-Espadas, A. M., Razo-Flores, E., Rangel-Mendez, J. R., & Cervantes, F. J. (2014). Direct and quinone-mediated palladium reduction by Geobacter sulfurreducens: mechanisms and modeling. Environmental Science and Technology, 48, 2910–2919.
Pat-Espadas, A. M., Field, J. A., Razo-Flores, E., Cervantes, F. J., & Sierra-Alvarez, R. (2016a). Continuous removal and recovery of palladium in an upflow anaerobic granular sludge bed (UASB) reactor. Journal of Chemical Technology and Biotechnology, 91, 1183–1189.
Pat-Espadas, A. M., Razo-Flores, E., Rangel-Mendez, J. R., Ascacio-Valdes, J. A., Aguilar, C. N., & Cervantes, F. J. (2016b). Immobilization of biogenic Pd(0) in anaerobic granular sludge for the biotransformation of recalcitrant halogenated pollutants in UASB reactors. Applied Microbiology and Biotechnology, 100, 1427–1436.
Pereira, L., Mehboob, F., Stams, A. J. M., Mota, M. M., Rijnaarts, H. H. M., & Alves, M. M. (2015). Metallic nanoparticles: microbial synthesis and unique properties for biotechnological applications, bioavailability and biotransformation. Critical Reviews in Biotechnology, 35(1), 114–128.
Pozun, Z. D., Rodenbusch, S. E., Keller, E., Tran, K., Tang, W., Stevenson, K. J., & Henkelman, G. (2013). A systematic investigation of p-nitrophenol reduction by bimetallic dendrimer encapsulated nanoparticles. Journal of Physical Chemistry, 117, 7598–7604.
Reyes-Nava, J. A., Rodríguez-López, J. L., & Pal, U. (2009). General segregation and chemical ordering in bimetallic nanoclusters through atomistic view points. Physical Reviews B, 80, 161412.
Shen, J., Xu, X., Jiang, X., Hua, C., Zhang, L., Sun, X., Li, J., Mu, Y., & Wang, L. (2014). Coupling of a bioelectrochemical system for p-nitrophenol removal in an upflow anaerobic sludge blanket reactor. Water Research, 67, 11–18.
Suja, E., Nancharaiah, Y. V., & Venugopal, N. (2014). Biogenic nanopalladium production by self-immobilized granular biomass: application for contaminant remediation. Water Research, 65, 395–401.
Zhao, P., Feng, X., Huang, D., Yang, G., & Astruc, D. (2015). Basic concepts and recent advances in nitrophenol reduction by gold- and other metal nanoparticles. Coordination Chemistry Reviews, 287, 114–136.
Zhu, C., Zeng, J., Lu, P., Liu, J., Gu, Z., & Xia, Y. (2013). Aqueous-phase synthesis of single-crystal Pd sedes 3 nm in diameter and their use for the growth of Pd nanocrystals with different shapes. Chemistry A European Journal, 19, 5127–5133.
Acknowledgments
The research described in the present study was financially supported by the Council of Science and Technology of Mexico (Grants SEP-CONACYT-166565, 106437, and 216315), the Marcos Moshinsky Foundation, and by IPICYT. We also acknowledge financial support and use of SAXS-S1 beamline resources, grant 17043 by the Brazilian Synchrotron Light Laboratory (LNLS, Brazil D11A-SAXS1) at Campinas, Brazil, staff Dr. Florian Meneau and Tiago Araujo Kalile, as well as helpful discussions with Dr. José Luis Sánchez García and Dr. Sergio Díaz Castañon. Mariana Peña Martínez thanks to CONACYT for a Master fellowship. Authors also thank Héctor G. Silva Pereyra, Beatriz A. Rivera Escoto, Gladis J. Labrada Delgado, Ana Iris Peña Martínez, Ma. del Carmen Rocha Medina, Mireya E. Martínez Pérez, Karla A. López Varela, Dulce Partida Gutiérrez, Juan Pablo Rodas Ortíz, and Guillermo Vidriales for their technical support. Finally, we gently acknowledge the use of resources from the CONACYT National Laboratories LANBAMA and LINAN for the sample characterization and analysis.
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Cervantes, F.J., Rodríguez-López, J.L., Peña-Martínez, M. et al. Enhanced Reduction of p-Nitrophenol by a Methanogenic Consortium Promoted by Metallic Nanoparticles. Water Air Soil Pollut 227, 368 (2016). https://doi.org/10.1007/s11270-016-3058-x
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DOI: https://doi.org/10.1007/s11270-016-3058-x