Malaysian Journal of Analytical Sciences Vol 25 No 6 (2021): 921 - 929

 

 

 

 

SYNTHESIS AND CHARACTERIZATION OF 4-CHLOROPHENOXYACETIC ACID HERBICIDE INTERCALATED INTO CALCIUM-ALUMINIUM LAYERED DOUBLE HYDROXIDE THROUGH CO-PRECIPITATION METHOD

 

(Sintesis dan Pencirian Herbisid Asid 4-Klorofenoksiasetik Diinterkalatkan dengan Kalsium-Aluminium Hidroksida Dua Lapisan Melalui Kaedah Pemendakan Bersama)

 

Farah Liyana Bohari¹, Muhammad Alinsan Kamil Mukamil Hamzah¹, Sheikh Ahmad Izaddin Sheikh Mohd Ghazali¹*, Nur Nadia Dzulkifli¹, Is Fatimah², Nurain Adam³

 

¹Material, Inorganic, and Oloechemistry (MaterInoleo) Research Group,

School of Chemistry and Environment, Faculty of Applied Sciences

Universiti Teknologi MARA Cawangan Negeri Sembilan Kampus Kuala Pilah, 72000, Negeri Sembilan, Malaysia

²Department of Chemistry, Faculty of Mathematics and Natural Sciences,

Universitas Islam Indonesia, Kampus Terpadu UII, J1. Kaliurang Km 14, Sleman, Yogyakarta, Indonesia

³Kontra Pharma (M) Sdn Bhd (90082-V)

Kotra Technology Centre (Block B) 1,2 &3, Industrial Estate,75250, Jalan Ttc 12, Malacca, Malaysia

 

*Corresponding author:  sheikhahmadizaddin@uitm.edu.my

 

 

Received: 15 September 2021; Accepted: 10 November 2021; Published:  27 December 2021

 

 

Abstract

Layered double hydroxide (LDH) or hydrotalcite-like compound is a material that can be used in agriculture as a support for controlled release formulations of herbicides such as 4-chlorophenoxyacetic acid (4-CPA). In this study, calcium-aluminium (Ca-Al) LDH host was prepared as a new herbicide delivery system by intercalating 4-CPA with Ca-Al LDH through a co-precipitation method. The synthesis was performed at pH 12 using different concentrations of Al(NO₃)₃.9H₂O, which were 0.025 M and 0.10 M. The successful intercalation was obtained using 0.025 M of Al(NO₃)₃.9H₂O and has been confirmed through several analyses. First, the results obtained from the powder X-ray diffraction (PXRD) pattern showed that the basal spacing for the 0.025M nanocomposites had increased from 8.54 Å to 9.98 Å, indicating the successful intercalation of 4-CPA into the Ca-Al LDH. Meanwhile, the basal spacing of the 0.1 M nanocomposite remains unchanged. This result was supported by the ATR-FTIR band, which showed that the nitrate peak disappeared and the carboxylate ion (COO^-) band was present at 1634 cm^-1 unlike the nitrate peak for the 0.10 M nanocomposite, which remained at 1365 cm^-1. The nanocomposite synthesized has shown mesoporous-type material with a H3 hysteresis loop in the Brunauer-Emmett-Teller (BET) analysis. This study has demonstrated the potential of Ca-Al LDH as a safer agent for agrochemicals by reducing the dosage of herbicide in the agriculture field and protecting the herbicide through leaching and runoff into the water system.

 

Keywords:  4-chlorophenoxyacetic acid, intercalation, co-precipitation, layered double hydroxide, nanoparticles

 

 

Abstrak

Hidroksida dua lapisan (LDH) atau sebatian seperti hidrotalsit ini adalah bahan yang boleh digunakan sebagai sokongan bagi formulasi pelepasan terkawal untuk racun herba seperti asid 4-klorofenoksiasetik (4-CPA) dalam pertanian. Dalam kajian ini, perumah kalsium-aluminium (Ca-AL) LDH telah dihasilkan sebagai sistem hantaran racun herba yang baharu dengan menginterkalat 4-CPA ke dalam Ca-Al LDH melalui kaedah pemendakan bersama. Sintesis ini telah dilakukan pada pH 12 dengan kepekatan yang berbeza untuk Al(NO₃)₃.9H₂O iaitu 0.025 M dan 0.10 M. Interkalasi yang berjaya telah diperolehi dengan menggunakan 0.025 M Al(NO₃)₃.9H₂O dan telah disahkan melalui beberapa analisis. Pertama, keputusan yang diperolehi daripada pola serbuk belauan sinar-X (PXRD) menunjukkan bahawa penjarakan asas untuk komposit nano 0.025 M telah meningkat daripada 8.54 Å kepada 9.98 Å, membuktikan kejayaan interkalasi 4-CPA ke dalam Ca-Al LDH. Manakala penjarakan asas bagi komposit nano 0.10 M kekal sama. Keputusan ini telah disokong oleh jalur ATR-FTIR menunjukkan kehilangan puncak nitrat dan kewujudan jalur ion karboksilat (COO^-) pada 1634 cm^-1 tidak seperti puncak nitrat pada 0.10 M yang kekal pada 1365.30 cm^-1. Komposit nano yang telah disintesis menunjukkan bahan jenis mesoliang dengan gelung hysteresis H3 dalam analisis Brunauer-Emmett-Teller (BET). Kajian ini telah membuktikan potensi Ca-Al LDH sebagai agen agrokimia yang lebih selamat dengan mengurangkan dos racun herba dalam bidang pertanian dan melindungi racun herba daripada melarut resap dan meleleh ke dalam sistem air.

 

Kata kunci:  4-klorofenoksiasetik, interkalasi, pemendakan bersama, hidroksida dua lapisan, zarah nano

 

References

1.      Prasad, C., Tang, H. and Liu, W. (2018). Magnetic Fe₃O₄ based layered double hydroxides (LDHs) nanocomposites (Fe₃O₄/LDHs): recent review of progress in synthesis, properties and applications. Journal of Nanostructure in Chemistry, 8(4): 393-412.

2.      Sarijo, S. H., Ghazali, S. A. I. S. M., Hussein, M. Z. and Ahmad, A. H. (2015). Intercalation,
physicochemical and controlled release studies of organic-inorganic–herbicide (2, 4, 5 tricholorphenoxy butyric acid) nanohybrid into hydrotalcite-like compounds. Materials Today: Proceedings, 2(1): 345-354.

3.      Valente, J. S., Tzompantzi, F., Prince, J., Cortez, J. G. and Gomez, R. (2009). Adsorption and photocatalytic degradation of phenol and 2, 4 dichlorophenoxiacetic acid by Mg-Zn-Al layered double hydroxides. Applied Catalysis B: Environmental, 90(3–4): 330-338.

4.      Matusinovic, Z., Lu, H., and Wilkie, C. A. (2012). The role of dispersion of LDH in fire retardancy: The effect of dispersion on fire retardant properties of polystyrene/Ca−Al layered double hydroxide nanocomposites. Polymer Degradation and Stability, 97(9): 1563-1568.

5.      Bernardo, M. P., Moreira, F. K. V., and Ribeiro, C. (2017). Synthesis and characterization of eco-friendly Ca-Al-LDH loaded with phosphate for agricultural applications. Applied Clay Science, 137: 143-150.

6.      Mills, S. J., Christy, G., Genin, J.-M. R., Kameda, T. and Colombo, F. (2012). Nomenclature of the hydrotalcite supergroup: natural layered double hydroxide. Mineralogical Magazine, 76(5): 1289-1336.

7.      Baikousi, M., Stamatis, A., Louloudi, M. and Karakassides, M. A. (2013). Thiamine pyrophosphate intercalation in layered double hydroxides (LDHs): An active bio-hybrid catalyst for pyruvate decarboxylation. Applied Clay Science, 75: 126-133.

8.      Jaśkaniec, S., Hobbs, C., Seral-Ascaso, A., Coelho, J., Browne, M. P., Tyndall, D. and Nicolosi, V. (2018). Low-temperature synthesis and investigation into the formation mechanism of high-quality Ni-Fe layered double hydroxides hexagonal platelets. Scientific Reports, 8(1): 4179.

9.      Bashi, A. M., Hussein, M Z., Zainal, Z., Rahmani, M. and Tichit, D. (2012). Simultaneous intercalation and release of 2,4-dichloro-and 4-chloro-phenoxyacetate into Zn/Al layered double hydroxide. Arabian Journal of Chemistry, 9: 1457-1463.

10.   Derylo-Marczewska, A., Blachnio, M., Marczewski, A. W., Swiatkowski, A. and Buczek, B. (2017). Adsorption of chlorophenoxy pesticides on activated carbon with gradually removed external particle layers. Chemical Engineering Journal, 308: 408-418.

11.   Baliyan, S. P., Rao, K. M., Baliyan, P. S. and Mahabile, M. (2013). The effects of 4-chlorophenoxy acetic acid plant growth regulator on the fruit set, yield and economic benefit of growing tomatoes in high temperatures. International. Journal Agriculture Science, 3(2): 29-36.

12.   Pirozzi, D., Sannino, F., Pietrangeli, B., Abagnale, M., Imparato, C., Zuccaro, G. and Aronne, A. (2017). Oxidative degradation of organic pollutants by a new hybrid titania-based gel-derived material with stable radical species. Chemical Engineering Transactions, 57: 769-774.

13.   Abdelhaleem, A. and Chu, W. (2017). Photodegradation of 4-chlorophenoxyacetic acid under visible LED activated N-doped TiO₂ and the mechanism of stepwise rate increment of the reused catalyst. Journal of Hazardous Materials, 338: 491-501.

14.   Songkhum, P., Wuttikhun, T., Chanlek, N., Khemthong, P. and Laohhasurayotin, K. (2018). Controlled release studies of boron and zinc from layered double hydroxides as the micronutrient hosts for agricultural application. Applied Clay Science, 152: 311-322.

15.   Ali, N. S. M., Hasanuddin, N. I., Azizan, N. A., Abdullah, A., Dzulkifli, N. N., Me, R., and Ghazali, S. M. (2017) Development of herbicide delivery system based on magnesium aluminium–4-chlorophenoxyacetic acid (MAC) nanocomposite. Journal of Engineering and Science Research, 1(2): 152-157.

16.   Ghazali, S. A. I. S. M., Hussein, M. Z. and Sarijo, S. H. (2013). 3,4-Dichlorophenoxyacetate interleaved into anionic clay for controlled release formulation of a new environmentally friendly agrochemical. Nanoscale Research Letters, 8: 362.

17.   Barahuie, F., Hussein, M. Z., Arulselvan, P., Fakurazi, S. and Zainal, Z. (2014). Drug delivery system for an anticancer agent, chlorogenate-Zn/Al-layered double hydroxide nanohybrid synthesised using direct co-precipitation and ion exchange methods. Journal of Solid State Chemistry, 217:31-41.

18.   Hussein, M. Z., Nazarudin, N. F. B., Sarijo, S. H. and Yarmo, M. A. (2012). Synthesis of a layered organic-inorganic nanohybrid of 4-chlorophenoxyacetate-zinc-layered hydroxide with sustained release properties. Journal of Nanomaterials, 5: 189-195.

19.   Megat, S., Mohsin, N., Hussein, M. Z., Sarijo, S. H., Fakurazi, S., Arulselvan, P. and Hin, T. Y. (2013). Synthesis of (cinnamate-zinc layered hydroxide) intercalation compound for sunscreen application. Chemistry Central Journal, 26(7): 1-12.