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Triastuti Sulistyaningsih1,2,*, Sri Juari Santosa2, Dwi Siswanta2, and Bambang Rusdiarso2
1
Department of Chemistry, Semarang State University, Sekaran, Gunungpati
Semarang, Central Java 50229, Indonesia
2
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada
Sekip Utara PO BOX BLS 21 Yogyakarta 55281, Indonesia
ABSTRACT
It has been examined the application of Mg/Al-NO3 hydrotalcite-magnetite synthesized mechanically (MHT) and
ultrasonically (UMHT) by co-precipitation method as adsorbents for [AuCl4] from aqueous solution. Two techniques
of synthesis were conducted to determine the effect on the increase of adsorption ability of the [AuCl4] . Magnetite
and Mg/Al-NO3 hydrotalcite-magnetite synthesized by co-precipitation with modifications hydrothermal treatment at
120 C for 5 h. The adsorbents were characterized by Fourier Transform Infrared (FTIR) spectroscopy, X-ray
diffraction (XRD), Scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) and Vibrating sample
magnetometer (VSM). Adsorption studies were done by getting the optimum pH, optimum contact time and the
optimum concentration. A result of the adsorption study of [AuCl4] on both adsorbents was optimum at pH 3 and
fitted well to Langmuir isotherm and pseudo second-order kinetic models. The adsorption capacity of UMHT
-1 -1
(ultrasonic technique) was 66.67 mg g and it was higher than that of MHT (mechanic technique), i.e. 31.25 mg g .
This shows that the ultrasonic radiation technique can increase the adsorption capacity of the [AuCl4] . Based on the
-1
desorption using 0.5 mol L NaOH solution, more [AuCl4] was eluted from MHT, indicating that [AuCl4] was weakly
bound on MHT than UMHT.
Keywords: [AuCl4] ; magnetite; hydrotalcite; ultrasonic assisted; adsorption
ABSTRAK
Telah diuji aplikasi Mg/Al-NO3 hidrotalsit-magnetit yang disintesis secara mekanik dan ultrasonik dengan
metode ko-presipitasi sebagai adsorben [AuCl4] dalam larutan. Dua teknik sintesis digunakan untuk mengetahui
efek pada peningkatan kemampuan adsorpsi terhadap [AuCl4] . Magnetit dan Mg/Al-NO3 hidrotalsit-magnetit
disintesis secara ko-presipitasi dengan modifikasi perlakuan hidrotermal pada suhu 120 C selama 5 jam. Adsorben
dikarakterisasi menggunakan by Fourier Transform Infared (FTIR) spectroscopy, X-ray diffraction (XRD), Scanning
electron microscopy (SEM), Brunauer-Emmett-Teller (BET) dan Vibrating sample magnetometer (VSM). Kajian
adsorpsi dilakukan untuk mendapatkan pH optimum, waktu kontak optimum dan konsentrasi optimum. Hasil kajian
adsorpsi [AuCl4] pada kedua adsorben menunjukkan optimum adsorpsi terjadi pada pH 3 dan sesuai dengan
isoterm Langmuir serta model kinetika orde dua semu. Kapasitas adsorpsi UMHT (teknik ultrasonik) terhadap
-1 -1
[AuCl4] adalah 66,67 mg g dan lebih tinggi daripada MHT (teknik mekanik), yaitu 31,25 mg g . Hal ini
menunjukkan bahwa teknik radiasi ultrasonik dapat meningkatkan kapasitas adsorpsi [AuCl4] . Berdasarkan kajian
-1
desorpsi menggunakan larutan NaOH 0,5 mol L , [AuCl4] yang terelusi dari MHT lebih banyak, menunjukkan
bahwa [AuCl4] terikat lebih lemah pada MHT daripada UMHT.
Kata Kunci: [AuCl4] ; magnetit; hidrotalsit; ultrasonik; adsorpsi
magnetite (UMHT). For synthesis under mechanical concentration at optimum pH. Into every [AuCl4]
stirring technique (MHT), the procedure was similar to solution, 10 mg of MHT (or UMHT) was poured and
the above mentioned procedure except prolonging the then shaken for optimum contact time. After separated
aging time to 12 h and removing the ultrasonic by external magnet, concentrations of [AuCl4] in the
irradiation. filtrate were analyzed using AAS.
Fig 1. FTIR spectra (A) and XRD patterns (B) of the magnetites and Mg/Al-NO3-HT magnetite before and after
[AuCl4] adsorption
Fig 3. SEM image of (A) the MM, (B) UM, (C) MHT and (D) UMHT
Fig 5. Effect of pH on the adsorption of [AuCl4] on
-1
Fig 4. Stability curve magnetites in Mg/Al-NO3 HT MHT and UMHT (initial [AuCl4] concentration 25 mg L ;
solution volume 10 mL; adsorbent dose 0.01 g)
resistance of Fe dissolved from Mg/Al-NO3 hydrotalcite pH < 3 is attributed to the MHT or UMHT materials may
relatively high from pH 3 to 8, but at pH 2.5 magnetite be partly dissolved. At pH < 3 or high media acidity, the
was not stable (Fig. 4). In this study, the influence of hydroxide groups in the MHT or UMHT are protonated,
solution pH on the adsorption of [AuCl4] was their bonds to Mg and Al or both of them are broken
investigated in the pH range in which magnetite was and, therefore, occur the dissolution of metal cations
stable. The adsorption of [AuCl4] on both of MHT and [22]. A maximum [AuCl4] adsorption is achieved at pH
UMHT tends to increase with the increasing of media 3.
acidity from pH 2.5 to 3 and then decrease rapidly from
pH 3 to 8 (Fig. 5). The observed decrease at the [AuCl4] Effect of Contact Time on [AuCl4] Adsorption
adsorption at higher pH > 3 is attributed to the increase
of competitive effect of OH anions in alkaline condition, Fig. 6 shows the variation of the adsorption of
while the decrease of the [AuCl4] adsorption at lower [AuCl4] during the adsorption process at various
contact times. It is seen that the [AuCl4] adsorption is Pseudo second-order model is represented as
increased greatly as the contact time is increased from 0 [24]:
to 60 min, and then tends to be constant when the t 1 1
t (2)
contact time is longer than 60 min indicating an qt k 2 qe2 qe
equilibrium state. Hence, the equilibrium time of 60 min where qe and qt have the same meaning as mentioned
was applied for study of adsorption isotherms of both previously and k2 is the rate constant for the pseudo
MHT and UMHT. Fig. 6 demonstrates that the second-order kinetics. The plots of t/qt versus t are
adsorption capacity of [AuCl4] on MHT is larger than shown in Fig. 7b and the k2 and qe calculated from the
UMHT.
Adsorption Kinetics
Fig 7. Plot of kinetics model for (a) pseudo first-order, (b) pseudo second-order, (c) first order and (d) second order
Table 1. Kinetic parameters of the pseudo first-order, pseudo second-order, first-order and second-order model for
adsorption [AuCl4] on both of MHT and UMHT
Model Parameter MHT UMHT
2
Lagergrens pseudo first-order R 0.757 0.971
-1 -5 -5
ln qe -qt =lnqe -k1t qe (mol g )
-1
1.47x10 2.42x10
k1 (min ) 0.028 0.093
2
Hos pseudo second-order R 0.999 0.997
-1 -5 -5
t 1 1 qe (mol g ) 5.16x10 2.83x10
= + t -1 -1
k2 (g mol min ) 2.87x10
4
7.37x10
4
qt k 2 qe2 qe
2
Santosa's first-order R 0.666 0.694
-1 -1
1 Ca Ca0 -Cae ks (L mol min ) 0.615 0.592
ln =k s t
Cae Ca0 Ca -Cae
2
Hos second-order R 0.442 0.587
-1 -1
1 1 k2 (g mol min ) 0.029 0.055
=k 2 t+
Ct C0
Table 2. Parameter of Langmuir and Freundlich isotherm model for adsorption [AuCl4] on both MHT and UMHT
Model Parameter MHT-H UMHT-H
2
Langmuir R 0.965 0.949
-1
C e Ce 1 qm (mg g ) 31.250 66.667
= + -1
KL (L mg ) 0.120 0.066
qe qm K L qm -1
G (KJ mol ) 26.662 25.169
2
Freundlich R 0.898 0.947
-1 -1 n
1 Kf ((mg g )/ (mg L ) ) 2.842 2.353
lnqe =lnK f + lnCe n 1.7 1.2
n
Fig 9. Effect of the concentration of NaOH solution (a) and desorption time (b) on the desorption of [AuCl4]
-1 -1
(adsorbent dose 0.01 g, solution volume 10 mL, initial concentration of [AuCl4] 2.16 mg g (MHT) and 1.36 mg g
(UMHT)
from MHT increased with increasing elution time to 1.5h 7. Akita, S., Yang, L., and Takeuchi, H., 1996,
and abruptly decreased above the elution time 1.5h. On Hydrometallurgy, 43 (1-3), 3746.
the other hand, the maximum elution of [AuCl4] for 8. Ranjbar, R., Naderi, M., Omidvar, H., and
UMHT was reached at elution time 1h (Fig. 9b). Amoabediny, G., 2014, Hydrometallurgy, 143, 54
59.
CONCLUSION 9. Rabiega, M.P., and Trochimczuk, A.W., 2014,
Hydrometallurgy, 146, 111118.
Magnetite nanoparticles and Mg/Al-NO3 HT- 10. Chen, D., Li, Y., Zhang, J., Zhou, J., Guo, Y., and
magnetite (MHT) as magnetic adsorbents were Liu, H., 2012, Chem. Eng. J., 185-186, 120126.
successfully prepared through co-precipitation method 11. Li, S.K., Huang, F.Z., Wang, Y., Shen, Y.H., Qiu,
with the involvement of ultrasonic radiation, the L.G., Xie, A.J., and Xu, S.J., 2011, J. Mater.
preparation time for the prepared material (UMHT) Chem., 21, 74597466.
became much shorter. Adsorption of [AuCl4] on MHT 12. Shen, Y.F., Tang, J., Nie, Z.H., Wang, Y.D., Ren,
and UMHT was affected by pH and contact time. It was Y., and Zuo, L., 2009, Sep. Purif. Technol., 68 (3),
found that the optimum pH was 3 and by the 312319.
-5
employment of 10 mL of 7.35 x 10 mol/L [AuCl4] 13. Chen, C., Gunawan, P., and Xu, R., 2011, J. Mater.
solution and 0.01 g adsorbent, the adsorption equilibrium Chem., 21, 12181225.
was reached at contact time 60 min for both of MHT and 14. Chen, D., Li, Y., Zhang, J., Li, W., Zhou, J., Shao,
UMHT. The kinetics of adsorption of [AuCl4] on both L., and Qian, G., 2012, J. Hazard. Mater., 243,
MHT and UMHT was well described by the pseudo 152160.
second-order kinetic. The adsorption capacity of [AuCl4] 15. Petcharoen, K., and Sirivat, A., 2012, Mater. Sci.
on UMHT was higher than MHT, while percentage Eng., B, 177 (5), 421427.
desorption of [AuCl4] on UMHT was lower than MHT. In 16. Meng, J.H., Yang, G.Q., Yan, L.M., and Wang,
addition to speed up preparation time, ultrasonic X.Y., 2005, Dyes Pigm., 66 (2), 109113.
radiation technique can reduce the size of the adsorbent 17. Lu, W., Shen, Y., Xie, A., and Zhang, W., 2010, J.
thereby increasing the adsorption capacity of the Magn. Magn. Mater., 322 (13), 18281833.
adsorbent to [AuCl4] in the aqueous solution. 18. Olanrewaju, J., Newalkar, B.L., Mancino, C., and
Komarneni, S., 2000, Mater. Lett., 45 (6), 307310.
ACKNOWLEDGEMENT 19. Frost, R.L., Spratt, H.J., and Palmer, S.J., 2009,
Spectrochim. Acta, Part A, 72 (5), 984988.
The authors would like to thank Directorate 20. Xiao, L., Ma, W., Han, M., and Cheng, Z., 2010, J.
General of Higher Education (DGHE), Ministry of Hazard. Mater., 186 (1), 690698.
National Education Republic Indonesia for providing the 21. Chang, Q., Zhu, L., Luo, Z., Lei, M., Zhang, S., and
financial support through doctoral dissertation research Tang, H., 2011, Ultrason. Sonochem., 18 (2), 553
grant, contract number DIPA-023.04.1.673453/2015. 561.
22. Heraldy, E., Triyono, Wijaya, K., and Santosa, S.J.,
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