Synthesis of AgCu and Ag-Cu
2O Alloy Nanoparticles Using Process of Simultaneous Cations Reduction Mediated Polyol
Ali Kareem abbas1,Fadhel Y Khudheyer2 Abbas Matrood Bashi*3, Suhad Kareem abbas4, and Amal Jassim5
1Department of public health, faculty of applied medical sciences, University of Kerbala, Iraq
2Al-Zahrawi University College Department of Pharmacy karbala, Iraq
3Department of Anastasi, College of Altuff-iraq
4 Department of chemistry, Collage of science. University of Kerbala, Iraq
5Department of medical analysis laboratories, faculty of applied medical sciences, University of Kerbala, Iraq
E: [email protected] Abstract
The Ag –Cu core shell was synthesized by reducing the two mixed cations in the polyal solution containing the reducer agent and the stabilizer. By using the controlled silver-copper nanoparticles to form alloyed nanoparticles, the core Ag−Cu and Ag−Cu2O nanostructures can be obtained within a range of 25−59 nm. The results showed that synthesized silver/Cu core shell nanoparticles cause significant inhibition to bacterial cell when compared with controls at low concentration. Significant Higher anti-bacterial was observed at very low concentration (0.0125 µg/ ml). Whereas. The obtained morphology and composition of the nanostructures were analyzed using SEM, EDS, FTIR, and XRD. Particles sizes distributions was showed a maximum at 35nm and minimum particles sizes at 6 nm
Keywords: Silver- copper, nanoparticles, core shell, dry method
The size and shape properties of different synthesized nano metallic were taken into consideration when it was being examined. Silver nanostructures were the most attracted because of their extensive applications in various areas such as bio-labelling, electronics, and sensing (Tao et al 2015, Amirjani et al 2016, Loo et al 2016, Sutradhar and Saha 2016, Niknafs et al 2017, Abbas et al 2019). Besides, it is also due to the variety of sizes and shapes available for the silver nanostructures (Murphy 2002, Yang et al 2007, Amirjani et al 2015, Niknafs et al 2017) and they have metals that can be reduced such as the Pb, Cu, and Ni (Park et al 2007, Carroll et al 2011). Jeon et al (2014), and Gomez-Acosta et al (2015), observed different silver nanostructures can be prepared by adjusting the stoichiometry with the existence of short-chain polyvinyl pyrrolidone (PVP). Liu et al (2008), reported the synthesis of the mono-sized Au-Fe alloy nanoparticles along with the Au’s optical functionality and the steel’s magnetic properties. Additionally, several studies on the synthesis of various bimetallic nanostructures were discovered, such as the Ni-Pd (Maity and Eswaramoorthy 2016), Ni-Pt (Aijaz et al 2015), and Au-Ag (Kumari et al 2015). To prepare the core-shell nanostructures, the polyol approach was used as a new generation of nanostructured materials. The improvised chemical and physical properties, increment in the stability, and enhanced protection of the core materials were shown by the core shells/alloy nanostructures (Ghosh Chaudhuri and Paria 2012, Sevonkaev et al 2014). Carroll et al (2011), reported that the Cu-Ni nanoparticles were synthesized using the process of mixed caption reduction.
Meanwhile, the Ag-Cu alloy was applied to prepare Ag-Cu bimetallic nanostructures and observed that the particle size for Ag was 30.33 nm and for Cu was 16.93 nm. The reduction of Cu and Ag was difficult because of their specific redox potentials and the Cu’s volatility in the aqueous media. In this study, the copper and the silver nanoparticles had been successfully synthesized and regulated through a process of polyol hydrothermal.
MATERIALS AND METHODS
Copper nitrate pentahydrated (Cu(SO4)5H2O) and the silver nitrate (AgNO3) are the precursors. Ethylene glycol (EG) and polyvinylpyrrolidone (PVP) were utilized without being purified. The 0.42g of silver nitrate, ammonium hydroxide (2ml of 10%), PVP 1gm was dissolved in 20ml of distilled water with EG(0.2ml), Copper sulphate (2.9 gm), 0.42M of nitric acid (0.1ml), and 16.7ml of ethanol absolute were stirred for 1/2 hour. Sodium borohydride (1gm in 10ml) was added drop by drop using the string for ½ hour. The resulted solution was filled by Buchner funnel and the ppt was washed by distilled water for 4 times.
Then, the Acetone was added for drying and left to dry. Samples were taken for further analysis.
The size of synthesized silver and the copper nanoparticles were determined using the scanning electron microscope (SEM, Philips XL30, and 25 kV). By utilizing a Philips PW 1140 X-ray diffraction unit, the X-ray diffraction (XRD) patterns of prepared nanostructures can be achieved.
RESULTS AND DISCUSSIONS
Structural, morphological, and optical study: Based on the outcome obtained from the XRD, the structural study of the silver and Cupper nanoparticles was conducted (Fig. 1). The cupper nanoparticles’ were referred to the planes of the face-centered cubic (FCC) of 111, 200, 220 and 311. The Ag nanoparticles (JCPDS File No. 04-0783) were monitored. In addition, the characteristic of the silver’s peaks were obtained at 38.3, 44.4, 64.5, and 77.4 degrees. The diffractions resultant to the Cu2O nanoparticles were the planes 011, 111, 200, 220 and 311.
There was an improvement in the existence of silver in the core and the cupper in the shell.
There are 20, 38, 31, 12 and 6 percent of 20, 25, 31, 12, 37 and 6 % with 50 nm. This confirms the particles size of silver and the cupper are within this range of sizes.
Fig 1. X-ray diffractions (XRD) of Ag-CuO core shell appeared on different planes of Ag and Cu.
Fig 2. The EDX projections on three particles in the core shell of Ag -Cu Table 1. Energy Dispersive X-Ray Analysis (EDX) projections
Elt Line W% A% ZAF Pk/Bg Class LConf HConf
O Ka 19.27 32.76 0.2242 218.05 A 18.89 19.65 Cu Ka 22.42 9.60 0.8814 22.97 A 22.17 22.68 Ag La 32.18 8.11 0.8278 55.46 A 31.90 32.46
Fig 3. Scanning electronic microscope (SEM) image of the core shell Ag-Cu2O shows the distributions of particles size
Fig 4. Distributions of the particles sizes
Fourier-transform infrared spectroscopy (FTIR):
Synthesis of silver-copper oxide nanoparticles: The presence of synthesized absorption of functional groups at 600 cm-1 to indicate that the vibrations of the bonds related to ethylene glycol, which is an organic source: Fig 5. The absorption peaks at 3428 cm-1 refers to the vibration of N-H stretching, 2917 cm-1 refers to the vibration of C-H stretching, and 1652 cm-
1 -1
vibration of C–N stretching. Finally, the bands at 836 and 631 cm-1 were attributed to the groups of NO3-
, while the bands between 600-400 cm-1 were associated to the vibrations of Ag-O and Cu2O.
.
Fig 5. Absorptions different groups in FTIR
Cupper /Silver nanoparticles’ antibacterial activity
The evaluation of the antibacterial activity was conducted using the method of agar well diffusion onto the silver nanoparticles. It was conducted on five human pathogenic strains of Escherichia coli, Staphylococcus aureus, Proteus mirabilis, Enterococcus faecalis, and Acinetobacter baumannii. After the incubation period it indicated that the Silver nanoparticles had greater efficiency against the isolated bacterias Table 2.
A few past studies on the silver nanoparticles’ antibacterial activity had reported that the nanoparticles of the silver –Cupper core-shell have antibacterial activity against the pathogenic strains of E. coli and S. aureus that had been tested. It also has antibacterial activity towards other pathogenic bacteria.
Table 2. Silver nanoparticles’ Antibacterial activity on studied bacteria
Concentration of CuO-Ag
(mg/ml)
Bacterial isolate
E.coli Yersinia spp. S. aureus S. pyogenes
Inhibition zone rate (mm)
5 15
15
20 20
15 14
13 13
2.5 13
12
18 18
12 11.5
12 12
70 80 90 100 110 120
1000 2000
3000 4000
Ag+Cu
cm-1
Intensities
2 11 --
17 --
11 11
11 --
1.5 10
10
15 15
10 10
10 10
1 10
10
12 12
10 ---
10 10
0.5 10
---
11 11
10 10
10 10
0.25 9
9
10 10
9 9
9 9
0.1 9
9
9 9
9 9
9 9
0.01 0
0
0 0
0 0
0 0
0.001 0
0
0 0
0 0
0 0
Conclusion:
Core-shell Cu/Ag nanoparticles was successfully synthesized by using dry mechanical method. The product with considerable quantities, the steroichiometry was played an important role in the synthesis process, the synthesized nanoparticles showed a significant anti-bacterial activity against four types of bacteria (‘E.coli Yersinia spp., S. aureus, S.
pyogenes'). The SEM and XRD techniques have been shown a good distribution of the Cu/Ag nanoparticles. The distribution of particles sizes with maximum at 35nm and minimum particles sizes at 6nm, the synthesized nano hybrids. XRD showed the super posing diffractions planes of Cu within the spectrum pattern of the Ag diffractions.
REFERENCES:
1. Abbas, A. K., Abass, S. K., & Bashi, A. M. 2019. CuO nano particles synthesized via the mechanichanical method starting with solids state chemichal reactions. In IOP Conference Series: Materials Science and Engineering 71 (1): 012067.
A. Amirjani, P. Marashi, D. Fatmehsari 2014. Effect of Different Mediated Agents on Morphology and Crystallinity of Synthesized Silver Nanowires Prepared by Polyol Process, Colloids. Surf. 444:33−39.
2. Aijaz, A., Zhu, Q. L., Tsumori, N., Akita, T., & Xu, Q. 2015. Surfactant-free Pd nanoparticles immobilized to a metal–organic framework with size-and location- dependent catalytic selectivity. Chemical Communications, 51(13): 2577-2580.
3. Amirjani, A., Bagheri, M., Heydari, M., & Hesaraki, S. 2016. Label-free surface plasmon resonance detection of hydrogen peroxide; a bio-inspired approach. Sensors and Actuators B: Chemical, 227: 373-382.
4. Amirjani, A., Fatmehsari, D. H., & Marashi, P. 2015. Interactive effect of agitation rate and oxidative etching on growth mechanisms of silver nanowires during polyol process. Journal of Experimental Nanoscience, 10 (18): 1387-1400.
5. Carroll, K. J., Reveles, J. U., Shultz, M. D., Khanna, S. N., & Carpenter, E. E. 2011.
Preparation of elemental Cu and Ni nanoparticles by the polyol method: an experimental and theoretical approach. The Journal of Physical Chemistry C, 115(6):
2656-2664.
6. Gomez-Acosta, A., Manzano-Ramirez, A., López-Naranjo, E. J., Apatiga, L. M.,
on the stirring-time in a high-yield polyol synthesis using a short-chain PVP. Materials Letters, 138:167-170.
7. Ghosh Chaudhuri, R., & Paria, S. (2012). Core/shell nanoparticles: classes, properties, synthesis mechanisms, characterization, and applications. Chemical reviews, 112(4):
2373-2433.
8. H. L. Liu, J. H. Wu, J. H. Min, Y. K. Kim 2008. Synthesis of monosized magnetic- optical AuFe alloy nanoparticles, J. Appl. Phys 103: 529.
9. Jeon, S. J., Lee, J. H., & Thomas, E. L. 2014. Polyol synthesis of silver nanocubes via moderate control of the reaction atmosphere. Journal of colloid and interface science, 435: 105-111.
10. Loo, C. Y., Rohanizadeh, R., Young, P. M., Traini, D., Cavaliere, R., Whitchurch, C.
B., & Lee, W. H. 2016. Combination of silver nanoparticles and curcumin nanoparticles for enhanced anti-biofilm activities. Journal of Agricultural and Food Chemistry, 64(12): 2513-2522.
11. Kumari, M. M., Jacob, J., & Philip, D. 2015. Green synthesis and applications of Au–
Ag bimetallic nanoparticles. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 137:185-192. \
12. Maity, S., & Eswaramoorthy, M. 2016. Ni–Pd bimetallic catalysts for the direct synthesis of H2O2–unusual enhancement of Pd activity in the presence of Ni. Journal of Materials Chemistry A, 4(9): 3233-3237.
13. Murphy, C. J. 2002. Nanocubes and nanoboxes. Science, 298(5601): 2139-2141.
14. M. Tsuji, S. Hikino, R. Tanabe, M. Matsunaga, Y. Sano, Cryst 2010. Syntheses of Ag/Cu alloy and Ag/Cu alloy core Cu shell nanoparticles using a polyol method, Eng.
Comm, 12: 3900−3908.
15. M. M. Kumari, J. Jacob, D. Philip 2015. Green synthesis and applications of Au-Ag bimetallic nanoparticles. Spectrochim. Acta. A: Molecular and Biomolecular Spectroscopy, 137: 185−192.
16. M. Valodkar, S. Modi, A. Pal, S.Thakore, Mater. Res. Bull 2011. Sapota fruit latex mediated synthesis of Ag, Cu mono and bimetallic nanoparticles and their in vitro toxicity studies 46: 384−389.
17. Niknafs, Y., Amirjani, A., Marashi, P., & Fatmehsari, D. H. 2017. Synthesis of Ag- Cu and Ag-Cu2O alloy nanoparticles using a seed-mediated polyol process, thermodynamic and kinetic aspects. Materials Chemistry and Physics, 189: 44-49.
18. Park, B. K., Jeong, S., Kim, D., Moon, J., Lim, S., & Kim, J. S. (2007). Synthesis and size control of monodisperse copper nanoparticles by polyol method. Journal of Colloid and Interface Science, 311(2): 417-424.
19. Sevonkaev, I. V., Herein, D., Jeske, G., & Goia, D. V. (2014). Size control of noble metal clusters and metallic heterostructures through the reduction kinetics of metal precursors. Nanoscale, 6(16): 9614-9617.
20. Sutradhar, P., & Saha, M. 2016. Silver nanoparticles: synthesis and its nanocomposites for heterojunction polymer solar cells. The Journal of Physical Chemistry C, 120(16): 8941-8949.
21. S. Maity and M. Eswaramoorthy 2016. Ni–Pd bimetallic catalysts for the direct synthesis of H2O2 – unusual enhancement of Pd activity in the presence of Ni J.
Mater. Chem 4:3233−3237.
22. Tao, J., Zhao, P., Zheng, J., Wu, C., Shi, M., Li, J., Li, Y. & Yang, R. 2015.
Electrochemical detection of type 2 diabetes mellitus-related SNP via DNA-mediated
growth of silver nanoparticles on single walled carbon nanotubes. Chemical Communications, 51(86):15704-15707.
23. Yang, Y., Matsubara, S., Xiong, L., Hayakawa, T., & Nogami, M. 2007.
Solvothermal synthesis of multiple shapes of silver nanoparticles and their SERS properties. The Journal of Physical Chemistry C, 111(26): 9095-9104.
24. Rycenga, M., Cobley, C. M., Zeng, J., Li, W., Moran, C. H., Zhang, Q., & Xia, Y.
(2011). Controlling the synthesis and assembly of silver nanostructures for plasmonic applications. Chemical reviews, 111(6): 3669-3712.
25. B. Wiley, Y. Sun, B. Mayers, Y. Xia2005. Shape‐Controlled Synthesis of Metal Nanostructures: The Case of Silver, Chem. Eur. J 11: 454−463.
26. Lu, J., Moon, K.S., Xu, J. and Wong, C.P., 2006. Synthesis and dielectric properties of novel high-K polymer composites containing in-situ formed silver nanoparticles for embedded capacitor applications. Journal of Materials Chemistry, 16(16): 1543-1548.
27. Y. Wang, J. He, C. Liu, W. H. Chong, H. Chen 2015. Thermodynamics versus kinetics innanosynthesis. Angew. Chem. Int. Ed 54: 2022−205.
