Treatment of selected Halogenated Organic Compounds in Water using Colloidal Silver Nanocatalysts under Reducing Borohydride Conditions
DOI:
https://doi.org/10.48039/mjtum.v4i2.95Keywords:
Colloidal silver nanocatalysts, Halogenated organic compounds, Reductive dehalogenation, Sodium borohydride, Water treatmentAbstract
Halogenated organic compounds (HOCs) are frequently encountered water contaminants. They are widely used as solvents or feed stocks in the production of paints, adhesives, lacquerers, pharmaceuticals and veterinary drugs, cosmetics, pesticides and herbicides. Most HOCs are recalcitrant, toxic and possible carcinogens. HOCs treatment in water may involve physical, biological and chemical processes. Chemical treatment via oxidation or reduction processes are preferred due to their ability to transform HOCs into environmental benign products. Compared to reduction, oxidation may produce toxic byproducts and thus for complete mineralization, huge amounts of redox equivalents are needed. Reductive dehalogenation is selective and more suited for HOCs treatment. It may employ electrocatalysts, metal catalysts and reagents. Nanoscale zero valent iron (nZVI) as an electron-releasing reagent is environmentally compatible but ineffective for transformation of saturated aliphatic HOCs containing < 2 Cl-atoms. Noble metals such as Pt, Rh and Pd are excellent hydrogenation catalysts for HOCs reduction but are expensive and susceptible to deactivation in water. Metallic Ag (Ag0) is a promising electrocatalyst for dechlorination of saturated aliphatic HOCs. Ag is relatively cheaper than the noble metals and is sparingly stable in water. Despite this potential, colloidal Ag0 catalysts have received less attention for HOCs treatment. In this study, optimal conditions were established for synthesis of colloidal Ag0 catalyst using sodium borohydride (NaBH4). Calculated Ag0 activities for reduction of dibromomethane, monobromomethane, perchloroethylene, trichloroethylene and vinylbromide were 86.92 ± 2.61, 3.45 ± 0.17, 2.38 ± 0.07, 1.16 ± 0.05 and 3.21 ± 0.10, respectively. The reduction of diclofenac and bromocresol blue by Ag0+NaBH4 was slow and incomplete due to catalyst deactivation. Thus, Ag0+NaBH4 is more appropriate for reduction of aliphatic and olefinic C—Cl and C—Br bonds.
References
Bajec, D., Grom, M., Lašič Jurković, D., Kostyniuk, A., Huš, M., Grilc, M., Likozar, B., & Pohar, A. (2020). A Review of Methane Activation Reactions by Halogenation: Catalysis, Mechanism, Kinetics, Modeling, and Reactors. Processes, 8(4). https://doi.org/10.3390/pr8040443
Bélteky, P., Rónavári, Andrea, Zakupszky, Dalma, Boka, Eszter, Igaz, Nóra, Szerencsés, Bettina, Pfeiffer ,Ilona, Vágvölgyi, Csaba, Kiricsi, Mónika, & Kónya, Z. (2021). Are Smaller Nanoparticles Always Better? Understanding the Biological Effect of Size-Dependent Silver Nanoparticle Aggregation Under Biorelevant Conditions. International Journal of Nanomedicine, 16(null): 3021–3040 https://doi.org/10.2147/IJN.S304138
Brumovský, M., Oborná, J., Micić, V., Malina, O., Kašlík, J., Tunega, D., Kolos, M., Hofmann, T., Karlický, F., & Filip, J. (2022). Iron Nitride Nanoparticles for Enhanced Reductive Dechlorination of Trichloroethylene. Environmental Science & Technology, 56(7): 4425–4436 https://doi.org/10.1021/acs.est.1c08282
Chepchirchir, R., Mwalimu, R., Tanui, I., Kiprop, A., Krauss, M., Brack, W., & Kandie, F. (2024). Occurrence, removal and risk assessment of chemicals of emerging concern in selected rivers and wastewater treatment plants in western Kenya. Science of The Total Environment, 948: 174982. https://doi.org/10.1016/j.scitotenv.2024.174982
Gong, L., Zhang, Z., Xia, C., Zheng, J., Gu, Y., & He, F. (2022). A quantitative study of the effects of particle’ properties and environmental conditions on the electron efficiency of Pd and sulfidated nanoscale zero-valent irons. Science of The Total Environment, 853: 158469. https://doi.org/10.1016/j.scitotenv.2022.158469
Jameel, M.S., Aziz, A.A., Dheyab, M.A., Khaniabadi, P.M., Kareem, A.A., Alrosan, M., Ali, A.T., Rabeea, M.A., & Mehrdel, B. (2022). Mycosynthesis of ultrasonically-assisted uniform cubic silver nanoparticles by isolated phenols from Agaricus bisporus and its antibacterial activity. Surfaces and Interfaces, 29: 101774. https://doi.org/10.1016/j.surfin.2022.101774
Jarosiewicz, M., Miłowska, K., Krokosz, A., & Bukowska, B. (2020). Evaluation of the Effect of Selected Brominated Flame Retardants on Human Serum Albumin and Human Erythrocyte Membrane Proteins. International Journal of Molecular Sciences, 21(11) https://doi.org/10.3390/ijms21113926
King, J.F., & Mitch, W.A. (2022). Electrochemical Reduction of Halogenated Alkanes and Alkenes Using Activated Carbon-Based Cathodes. Environmental Science & Technology, 56(24): 17965–17976 https://doi.org/10.1021/acs.est.2c05608
Kodavanti, P.R.S., Costa, L.G., & Aschner, M. (2023). Chapter One—Perspective on halogenated organic compounds. In P. R. S. Kodavanti, M. Aschner, & L. G. Costa (eds.), Neurotoxicity of Halogenated Organic Compounds Vol. 10: 1–25 Academic Press. https://doi.org/10.1016/bs.ant.2023.06.001
Mackenzie, K. (2022). Metallic Copper as Dehalogenation Catalyst in the Treatment of Water and Wastewaters. In D. Fernández González & L. F. Verdeja González (eds.), Copper—From the Mineral to the Final Application. IntechOpen. https://doi.org/10.5772/intechopen.108147
Njoya, O., Pam, S., & Oyono, J.S.O. (2024). Suitability of cyclic voltammetry for the measurement of sodium borohydride (NaBH4) in a solution of Cr(VI)/organic compounds/NaBH4. Water Practice and Technology, 19(7): 2920–2928 https://doi.org/10.2166/wpt.2024.174
Pagire, S.K., Föll, T., & Reiser, O. (2020). Shining Visible Light on Vinyl Halides: Expanding the Horizons of Photocatalysis. Accounts of Chemical Research, 53(4): 782–791 https://doi.org/10.1021/acs.accounts.9b00615
Saini, B., Khamari, L., & Mukherjee, T.K. (2022). Kinetic and Mechanistic Insight into the Surfactant-Induced Aggregation of Gold Nanoparticles and Their Catalytic Efficacy: Importance of Surface Restructuring. The Journal of Physical Chemistry B, 126(10), 2130–2141. https://doi.org/10.1021/acs.jpcb.2c00702
Shee, A., Kopinke, F.D., & Mackenzie, K. (2022). Borohydride and metallic copper as a robust dehalogenation system: Selectivity assessment and system optimization. Science of The Total Environment, 810: 152065 https://doi.org/10.1016/j.scitotenv.2021.152065
Silva, M.K.L., & Cesarino, I. (2022). Electrochemical sensor based on Sb nanoparticles/reduced graphene oxide for heavy metal determination. International Journal of Environmental Analytical Chemistry, 102(13): 3109–3123. https://doi.org/10.1080/03067319.2020.1763973
Sørensen, L.K., Khrennikov, D.E., Gerasimov, V.S., Ershov, A.E., Polyutov, S.P., Karpov, S.V., & Ågren, H. (2022). Nature of the Anomalous Size Dependence of Resonance Red Shifts in Ultrafine Plasmonic Nanoparticles. The Journal of Physical Chemistry C, 126(39): 16804–16814. https://doi.org/10.1021/acs.jpcc.2c03738
Sun, C., Wen, R., Qin, Y., Wang, L., Wang, Y., Dou, M., & Wang, F. (2023). Origin of Pt Site Poisoning by Impurities for Oxygen Reduction Reaction Catalysis: Tailored Intrinsic Activity of Pt Sites. ACS Applied Energy Materials, 6(11): 5700–5709. https://doi.org/10.1021/acsaem.3c00027
Šutka, A., Bitina, S., Smits, K., Šutka, A., Bikse, L., Maiorov, M., Käämbre, T., Timusk, M., Laipniece, L., & Lazdovica, K. (2024). Rapid, high-yield aqueous synthesis of ultrafine magnetite nanoparticles from Fe(III) precursor at room temperature. Journal of Materials Science, 59(2): 447–457 https://doi.org/10.1007/s10853-023-09233-5
Szczyglewska, P., Feliczak-Guzik, A., & Nowak, I. (2023). Nanotechnology–General Aspects: A Chemical Reduction Approach to the Synthesis of Nanoparticles. Molecules, 28(13) https://doi.org/10.3390/molecules28134932
Tamilselvan, S., Soniya, R.M., Vasantharaja, R., Kannan, M., Supriya, S., Batvari, B.P.D., Ramesh, T., & Govindaraju, K. (2022). Silver nanoparticles based spectroscopic sensing of eight metal ions in aqueous solutions. Environmental Research, 212: 113585 https://doi.org/10.1016/j.envres.2022.113585
Vandana, Priyadarshanee, M., Mahto, U., & Das, S. (2022). Chapter 2—Mechanism of toxicity and adverse health effects of environmental pollutants. In S. Das & H. R. Dash (Eds.), Microbial Biodegradation and Bioremediation (Second Edition) (Second Edition, pp. 33–53). Elsevier. https://doi.org/10.1016/B978-0-323-85455-9.00024-2
Villaverde, Laurenti, M., Rubio-Retama, J., & Contreras-Cáceres, R. (2021). Reducing Agents in Colloidal Nanoparticle Synthesis – an Introduction. In S. Mourdikoudis (Ed.), Reducing Agents in Colloidal Nanoparticle Synthesis (p. 0). The Royal Society of Chemistry. https://doi.org/10.1039/9781839163623-00001
Weidlich, T. (2021). The influence of copper on halogenation/dehalogenation reactions of aromatic compounds and its role in the destruction of polyhalogenated aromatic contaminants. Catalysts, 11(3), 378.
Wu, H., Chen, L., Tang, C., Fan, X., Liu, Q., & Xu, Y. (2024). Silver nanoparticles catalyzed electrochemical hydrodechlorination of dichloromethane to methane in N,N-Dimethylformamide using water as hydrogen donor. Separation and Purification Technology, 331, 125647. https://doi.org/10.1016/j.seppur.2023.125647
Zein, R., Alghoraibi, I., Soukkarieh, C., Ismail, M. T., & Alahmad, A. (2022). Influence of Polyvinylpyrrolidone Concentration on Properties and Anti-Bacterial Activity of Green Synthesized Silver Nanoparticles. Micromachines, 13(5). https://doi.org/10.3390/mi13050777
Sun Y., Zheng K., Du X., Qin H., Guan X.rt (2024). Insights into the contrasting effects of sulfidation on dechlorination of chlorinated aliphatic hydrocarbons by zero-valent iron. Water Research, 255: 121494.https://doi.org/10.1016/j.watres.2024.121494
Zhou, F., Zhu, Y., Yang, L., Yang, D.Q., & Sacher, E. (2022). Ag NP catalysis of Cu ions in the preparation of AgCu NPs and the mechanism of their enhanced antibacterial efficacy. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 632: 127831. https://doi.org/10.1016/j.colsurfa.2021.127831
Downloads
Published
Issue
Section
License
Copyright (c) 2025 Tadicha Adan , Opondo Victor Wandera , Ogweno Aloice , Shee Ali

This work is licensed under a Creative Commons Attribution 4.0 International License.


