Abstract
In this study, the kinetics of catalytic degradation of methyl red, an anionic azo dye, by hexacyanoferrate(III) ions in the presence of ultrafine Ir–Cu bimetallic nanoparticles has been investigated. The effect of various parameters, including the concentration of dye, oxidant, Ir–Cu bimetallic nanoparticles (BMNPs), and solution pH on the reaction rate was investigated by measuring the light absorption at a wavelength of 425 nm, corresponding to the maximum absorption of the dye. The results reveal that the reaction follows first-order kinetics with respect to the concentration of hexacyanoferrate(III), methyl red, and Ir–Cu BMNPs at an optimum pH of 8.0 and a constant temperature of 40 ± 0.1°C. In order to determine how electrolytes interact with the reaction rate, the impact of ionic strength on the degradation rate was also examined. The high catalytic activity of Ir–Cu BMNPs was demonstrated by a three to four-fold rise in the reaction rate with increasing concentration of Ir–Cu BMNPs (particle size ca. 0.98nm). Thermodynamic parameters including activation energy (Ea), enthalpy of activation (ΔH#), entropy of activation (ΔS#), and free energy of formation (ΔF#) of the reaction were calculated by analyzing the reaction rate at four different temperatures within the 40 to 55°C range. The low value of activation energy also suggests a high degradation rate. A reaction mechanism through complex formation was proposed based on the experimental findings which were supported by the analysis of the products formed. The formation of simpler and less hazardous products (1,5-pentanediol and benzoic acid) was verified by UV–Vis spectroscopy and liquid chromatography and mass spectroscopy (LC–MS). The assessment of turnover frequencies for each catalytic cycle also proved the stability and reusability of the catalyst. As a result, the discovery offers an innovative and highly cost-effective solution for environmental safety against dye contamination, with the potential for expansion to additional toxins.
REFERENCES
Azeez, F., Al-Hetlani, E., Arafa, M., Abdelmonem, Y., Nazeer, A.A., Amin, M.O., and Madkour, M., Sci. Rep., 2018, vol. 8, no. 1, p. 1.
Gautam, A., Kshirsagar, A., Biswas, R., Banerjee, S., and Khanna, P.K., RSC Adv., 2016, vol. 6, no. 4, p. 2746.
Dawood, S. and Sen, T., J. Chem. Proc. Eng., 2014, vol. 1, no. 104, p. 1.
Reza, K.M., Kurny, A.S.W., and Gulshan, F., Appl. Water Sci., 2017, vol. 7, no. 4, p. 1569.
Gähr, F., Hermanutz, F., and Oppermann, W., Water Sci. Technol., 1994, vol. 30, no. 3, p. 255.
Neamtu, M., Yediler, A., Siminiceanu, I., and Kettrup, A., J. Photochem. Photobiol. A: Chem., 2003, vol. 16, no. 1, p. 87.
Pelegrini, R., Peralta-Zamora, P., Andrade, A.R., Reyes, J., and Duran, N., Appl. Catal. B:Environ., 1999, vol. 22, p. 83.
Kariyajjanavar, P., Narayana, J., and Nayaka, Y.A., J. Environ. Chem. Eng., 2013, vol. 1, no. 4, p. 975.
Wawrzkiewicz, M., Solv. Extr. Ion Exch., 2012, vol. 30, no. 5, p. 507.
Sangjan, S., Sratongin, M., Kawpakpor, A., Ampha, P., Jamtanom, L., and Kaewbang, K., Int. Mater. Sci. Forum, 2016, vol. 860, p. 105.
Qi, W., Jincai, Z., Yanqing, C., and Yi, Z., Chin. J. Catal., 2011, vol. 32, no. 6, p. 1076.
Mishra, A., Newkome, G.R., Moorefield, C.N., and Godínez, L.A., Dyes Pigm., 2003, vol. 58, no. 3, p. 227.
Giwa, A.R.A., Bello, I.A., Olabintan, A.B., Bello, O.S., and Saleh, T.A., Heliyon, 2020, vol. 6, no. 8, p. 04454.
Kadirvelu, K., Kavipriya, M., Karthika, C., Radhika, M., Vennilamani, N., and Pattabhi, S., Bioresour. Technol., 2003, vol. 87, no. 1, p. 129.
Benkhaya, S., M’rabet, S., and El Harfi, A., Heliyon, 2020, vol. 6, p. 03271.
Lasyal, R. and Rajput, S., J. Water Environ. Nanotechnol., 2023, vol. 8, no. 2, p. 108.
Goel, A., Kinet. Catal., 2021, no. 2, p. 592.
Goel, A. and Pooja, Int. J. Nanoparticles, 2021, vol. 13, no. 1, p. 1.
Hassan, M.M. and Carr, C.M., Chemosphere, 2018, vol. 209, p. 201.
Wojnarovits, L. and Takacs, E., Radiat. Phys. Chem., 2008, vol. 77, no. 3, p. 225.
Gutierrez, M.C. and Crespi, M., Color. Technol., 1999, vol. 115, no. 11, p. 342.
Islam, M.N., Abbas, M., and Kim, C., Curr. Appl. Phys., 2013, vol. 13, no. 9, p. 2010.
Goel, A. and Rani, N., Open J. Inorg. Chem., 2012, vol. 2, no. 3, p. 67.
Ramyadevi, J., Jeyasubramanian, K., Marikani, A., Rajakumar, G., and Rahuman, A.A., Mater. Lett., 2012, vol. 71, p. 114.
Vinoda, B.M., Vinuth, M., Bodke, Y.D., and Manjanna, J., J. Environ. Anal. Toxicol., 2015, vol. 5, no. 336, p. 2161.
Goel, A. and Lasyal, R., Water Sci., Technol., 2016, vol. 74, p. 2551.
Goel, A. and Chaudhary, M., Bull. Mater. Sci., 2018, vol. 41, no. 3, p. 81.
Goel, A., Bhatt, R., and Lasyal, R., Int. J. Chem. Sci., 2014, vol. 12, no. 4, p. 1527.
Goel, A. and Lasyal, R., Desalin. Water Treat., 2016, vol. 57, no. 37, p. 17547.
Aragaw, T.A. and Angerasa, F.T., Heliyon, 2020, vol. 6, no. 9, p. 04975.
Nagar, N. and Devra, V., Heliyon, 2019, vol. 5, no. 3, p. 01356.
Singh, H.P., Gupta, N., Sharma, S.K., and Sharma, R.K., Colloids Surf. A: Physicochem. Eng., 2013, vol. 416, p. 43.
Alardhi, S.M., Albayati, T.M., and Alrubaye, J.M., Heliyon, 2020, vol. 6, no. 1, p. 03253.
Giwa, A.R.A., Bello, I.A., Olabintan, A.B., Bello, O.S., and Saleh, T.A., Heliyon, 2020, vol. 6, no. 8, p. 04454.
Aragaw, T.A. and Angerasa, F.T., Heliyon, 2020, vol. 6, no. 9, p. 04975.
Barathi, S., Karthik, C., Nadanasabapathi, S., and Padikasan, I.A., Toxicol. Rep., 2020, vol. 7, p. 16.
Rauf, M.A., Meetani, M.A., Khaleel, A., and Ahmed, A., Chem. Eng. Trans., 2010, vol. 157, nos. 2–3, p. 373.
ACKNOWLEDGMENTS
The authors acknowledge to Gurukul Kangri University for providing the basic facilities for this research work. The authors are also thankful to the Director of the Department of Institutional Instrumentation Centre (IIC), IIT Roorkee for providing all required Techniques for the analysis of this work.
Funding
This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors.
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
The authors of this work declare that they have no conflict of interest.
Additional information
Publisher’s Note.
Pleiades Publishing remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Abbreviations: Ir–Cu BMNPs—Ir–Cu bimetallic nanoparticles; MR—methyl red; HCF(III)—hexacyanoferrate(III); PVP—polyvinylpyrrolidone; EG—ethylene glycol; EA—ethyl acetate; OC—organic compounds; LC–MS—liquid chromatography and mass spectroscopy; Ea– activation energy; ΔH#—enthalpy of activation; ΔS#—entropy of activation; ΔF#—free energy of formation; TEM—transmission electron microscopy; SEM—scanning electron microscopy; EDX—energy-dispersive X-ray spectroscopy; TLC—thin layer chromatography; TOF—turnover frequency; (da/dt)—degradation rate of MR.
Rights and permissions
About this article
Cite this article
Pooja, Goel, A. & Lasyal, R. Degradation of Methyl Red Azo Dye by Hexacyanoferrate(III) Ions from Water using Ultrafine Ir–Cu Bimetallic Nanoparticles: a Kinetic Approach. Kinet Catal 65, 122–132 (2024). https://doi.org/10.1134/S0023158423600657
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0023158423600657