Beruflich Dokumente
Kultur Dokumente
DOI 10.1007/s10098-015-0993-y
ORIGINAL PAPER
Received: 24 February 2015 / Accepted: 6 June 2015 / Published online: 14 June 2015
Springer-Verlag Berlin Heidelberg 2015
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82 S. Mahdavi
high adsorption capacity, ease of modification, and diversity Preparation of organic compound (modifiers)
in surface functionalization (Mahdavi et al. 2013). Nano-
sized titanium oxide powders are now widely produced on HA stock solution (500 mg L-1) was prepared according to
an industrial basis, and the average grain size of commer- Mahdavi et al.’s (2015) method. Extractant of walnut shell
cialized nanopowders usually varies from 10 to 30 nm was obtained by rinsing walnut shell in 0.1 N HNO3 (at
(Baraton and Merhari 2004). The ability of TiO2-NPs to solid/solution = 1 g: 10 mL) for 24 h at 70 C to obtain the
remove heavy metals from water has also been reported active functional groups (Kim et al. 2001). 1,5 diphenyl-
(Engates and Shipley 2011; Mahdavi et al. 2013). They can carbazon (MW = 243.28,C6H5NHNHCONHNHC6H5), was
also be functionalized to increase affinity to metal ions and dissolved in 20 C methanol and was then diluted with
to improve selectivity in the removal of metal ions (Hua deionized water to make the concentration of 500 mg L-1 of
et al. 2012; Chen et al. 2012). In this research, humic acid Cabazon and was stored at 4 C before use (with native pH).
(HA) (Ti–H), extractant of walnut shell (Ti–W), and 1,5 The modification processes were done according to
diphenyl-carbazon (Ti–C) were immobilized on the surface Mahdavi et al.’s (2015) method with the above-mentioned
of nano-TiO2 and used as new solid-phase adsorbents to modifiers.
remove Cd?2, Cu?2, and Ni?2 from single and competitive
solutions. The new modified nanoparticles (MNPs) were Preparation of MNPs
characterized by SEM, XRD, and FT-IR analysis. The
removal of metal ions depends on pH, contact time, and 0.5 g of TiO2 NPs was suspended in 30 mL of modifier
metals concentration. Thus, the optimal conditions for solution (Mahdavi et al. 2015). Then, the suspension was
adsorption were established. With these conditions, the sonicated at 70 for 6 h followed by evaporation of the
adsorption isotherms were measured and the results were solvent, washed with deionized water, air-dried, and finally
fitted to Langmuir and Freundlich models. To interpret the stored in a closed bottle for subsequent use.
sorption mechanism better, SEM–EDX spectroscopic anal-
ysis was carried out. Finally, the stability of the MNPs Studies on point of zero charge (pHpzc) and zeta
adsorbents (with 0.01 M CaCl2) for heavy metals (desorp- potential
tion experiments) was also determined.
In pHpzc determination, 0.01 M NaCl was prepared and its
pH was adjusted in the range of 2–12 by adding NaOH or
Materials and methods HCl according to Gupta and Nayak’s (2012) method.
Zeta potential (f in mV) measurements are measures of
Chemicals and methods used for NPs the magnitude of charge expressed in the DDL at the plane
characterization of slippage. If we set f * w0 (given the very short distance
of the plane of slippage from the surface), then the rela-
All chemicals used in this investigation were of analytical tionship between f and the PZC can be simply represented
grade and used without further purification treatment. as follows:
Nanostructured TiO2 was purchased (purity, 99.5 %) from f W0 ¼ 59:2ðpH0 pHÞ; ð1Þ
Tecnan (www.tecnan-nanomat.es, Spain). The concentra-
tion of metal ions was determined by flame atomic where w0 is the surface electrostatic potential, pH0 = pH
absorption spectrometer (FAAS) (Varian Spectra AA 220). of the PZC, and pH = the pH of the bulk solution
Power X-ray diffraction (XRD) spectra were measured by (Chappell 2009).
means of a Misone diffractometer (38066 RIVA, d/g. Via
M. Misone, 11/D (T/N) ITALY) operating at 40 kV and Batch removal procedure
40 mA with Cu-Ka monochromatic radiation in the
Bragg’s angle range of 20–80. The nanostructures of The adsorption of Cd2?, Cu2?, Ni2? in single and com-
MNPs were observed by scanning electron microscopy– petitive solutions by modified nano-TiO2 was performed by
energy dispersive X-ray (SEM–EDX Cam Scan MV2300, a batch operation at room temperature. 25 mg of the
Philips XL30) to determine their morphology, size, and adsorbent was suspended in 25 mL solution containing
purity on the surfaces of three MNPs. Adsorption of 50 mg L-1 of Cd2?, Cu2?, and Ni2? in single and com-
organic species on TiO2 particles was studied by FT-IR petitive solutions. The solutions were not buffered to
spectroscopy (Perkin–ElmerFTIR Spectrum 1000) (KBr mimic potential industrial practice. The solutions were
pellets). The spectra obtained in the range of sonicated for 120 min and were then left in equilibrium for
400–4000 cm-1 were analyzed. A sonicator (Elmasonic, 22 h. After a time period of agitation, the suspensions were
S30H) was used for sonication. centrifuged at 5000 rpm for 5 min. The residual
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Nano-TiO2 modified with natural and chemical compounds as efficient adsorbents for the removal of… 83
concentration of the ions in the supernatant solutions was equilibrium parameter that is used to predict whether an
determined by FAAS. The percentage removal of Cd2?, adsorption system is ‘‘favorable’’ or ‘‘unfavorable.’’ RL is
Cu2?, Ni2? by the adsorbents was calculated according to defined by
the following equation: 1
RL ¼ ; ð5Þ
C0 Ce 1 þ bC0
% Removal ¼ 100; ð2Þ
C0
where C0 is the initial concentration of Cd2?, Cu2?, and
where C0 and Ce are the initial and final concentrations of Ni2? (mg L-1) and b is the Langmuir adsorption equilib-
heavy metals in the solution phase, respectively. All the rium constant (L mg-1). Based on the effect of separation
investigations were carried out in triplicate to avoid any factor on isotherm shape, the RL values are in the range of
discrepancy in experimental results with the repeatability 0–1, which indicates that the adsorption of Cd2?, Cu2?,
and the relative deviation of the order of ±3.5 %. and Ni2? on MNPs is favorable (Zhang et al. 2009).
Adsorption isotherm studies were carried out with dif-
ferent initial concentrations of Cd2?, Cu2? and Ni2? in The effect of pH
single and competitive solutions while maintaining the
sorbent’s dosage at constant level. The pH of primary The effects of pH on sorption of Cd2?, Cu2?, and Ni2? ions
solutions was adjusted for Cd2? and Ni2? ions at 7 and 8, were studied by varying the pH of heavy metal solution
respectively (according to the results of pH effect). But for from 3 to 8. These samples were sonicated for 120 min and
Cu2? ions solution, native pH was considered. In order to were then left in equilibrium for 22 h. Then, the aliquots
inspect any adsorption of Cd2?, Cu2?, and Ni2? on the were filtered and analyzed for Cd2?, Cu2?, Ni2? by FAAS,
container’s surface, control experiments were carried out as mentioned above. To determine the influence of pH, the
without the sorbent. It was found that no adsorption tests were performed in triplicate.
occurred on the container’s wall. The isotherms’ data were
fitted to the linear Freundlich and Langmuir adsorption The effect of contact time
models. The Freundlich model describes the logarithmic
decrease in adsorption energy with increasing surface Batch experimental procedures were conducted with dif-
coverage. This model assumes no combination or dissoci- ferent shaking times of 10, 20, 30, 40, 50, 60, 90, 120, and
ation of the absorbed molecules. Thus, equal concentration 180, 1440 min, while other conditions remained the same
of surface site and adsorption occur by means of physical as in Batch removal experiments.
rather than chemical adsorption. The linearised equation is
usually expressed as follows: Kinetics modeling study
Log qe ¼ Log KF þ 1=n Log Ce ; ð3Þ The adsorption kinetics of metal ions with MNPs was
where qe and Ce are equilibrium solid-phase (mg g-1) and investigated by 2 kinetic models: pseudo-first-order and
liquid-phase (mg L-1) concentrations, respectively. KF pseudo-second-order models for Eqs. (6) and (7),
(mg g-1) is the Freundlich constant related to the adsorp- respectively.
tion capacity of the adsorbent and n is the heterogeneity
factor indicating the adsorption intensity of the adsorbent. Pseudo-first-order model
(Mahdavi et al. 2012; Zha et al. 2014). lnðqe qt Þ = ln qe K1 t: ð6Þ
The Langmuir equation is based on the assumption of a
structurally homogeneous adsorbent and is described using
the following equation: Pseudo-second-order model
Ce Ce 1 1 1 t
¼ þ ; ð4Þ ¼ þ ; ð7Þ
qe qm qm b qt K2 q2e qe
where qm (mg g-1) is the maximum adsorption capacity where qt (mg g-1) is adsorption at time t (min); qe
corresponding to complete monolayer coverage and b (KL) (mg g-1) is adsorption capacity at adsorption equilib-
(L mg-1) is the Langmuir constant related to the energy of rium; and K1 (min-1) and K2 (g mg-1 min-1) are the
adsorption which quantitatively reflects the affinity of the kinetic rate constants for the pseudo-first-order and the
binding sites (Peng et al. 2012). RL is another essential pseudo-second-order models, respectively. The kinetic
feature of a Langmuir isotherm which can be expressed in adsorption data were fitted to Eqs. (6) and (7) (Azizian
terms of a dimensionless constant separation factor or 2004).
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84 S. Mahdavi
Fig. 1 XRD powder pattern of MNPs (TiO2, Ti–C, Ti–H, and Ti–W)
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Nano-TiO2 modified with natural and chemical compounds as efficient adsorbents for the removal of… 85
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86 S. Mahdavi
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Nano-TiO2 modified with natural and chemical compounds as efficient adsorbents for the removal of… 87
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88 S. Mahdavi
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Nano-TiO2 modified with natural and chemical compounds as efficient adsorbents for the removal of… 89
Cd2? 12.34 9 9 10-3 0.941 30.30 5 9 10-3 0.961 6.12 14 9 10-3 0.973
2? -3 -3
Cu 14.71 3 9 10 0.972 14.71 3 9 10 0.961 9.26 6 9 10-3 0.967
2? -2 -2 -2
Ni 5.00 6 9 10 0.992 4.71 -4 9 10 0.994 3.37 -38 9 10 0.941
Moreover, the monolayer maximum adsorption capacities adsorbents in previous studies (listed in Tables 4, 5, and 6),
of Cd2? (in single solution) were calculated from the it is apparent that Ti–C in this work has much higher
Langmuir isotherm to be 9.9, 25.7 .8, and 31.7 mg g-1 for adsorption capacities for Cd2?and Cu2?. Therefore, Ti–C is
Ti–H, Ti–W, and Ti–C, respectively. Compared with other very promising for the effective removal of Cd2? and Cu2?
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90 S. Mahdavi
Table 4 Comparison of adsorption capacity of the proposed with some sorbents reported for the adsorption of Cd2?
Adsorbent Capacity (mg g1-Cd2?) Capacity (mg g1-Cd2?) Reference
(single) (competitive)
from the environment in single solution while Ti-H adsorbs treatment with heavy metals in final equilibrium concen-
few Cd2? and Cu2? (Tables 4, 5 and 6). HA adsorption can tration of isotherms Tables 4, 5, and 6. In Ti–H NPs with
generally decrease and block the micropore surface area of Ni2? and single solution, the accumulation of heavy metals
nano-TiO2 which in turn decreases adsorption (Yang et al. (in white color) (Fig. 6) in surfaces was obvious. In Ti–C,
2009). This operation decreases the surface area of Ti–H in accumulation of Cd2? is very prominent (Fig. 6) and in Ti–
comparison with Ti–W and Ti–C. Ti–H has the highest H, Cu2? is more prominent (Fig. 6). For these images,
adsorption capacity for Ni2? in comparison with other EDX analysis showed the peaks of Cd2?, Cu2?, and Ni2?
adsorbents. In competitive solutions, the high concentration in single solutions. The EDX spectra provided a direct
of Cu2? can precipitate some of Cu2? ions. The values of evidence for Cd2?, Cu2?, and Ni2 adsorbed on MNPs.
KL, Qmax, RL, n, KF, and R2 for different MNPs and models Other studies also used EDX analysis to give a direct
are listed in Table 3. The best model was judged from the detection of the presence of elements on the adsorbents
higher correlation coefficients (R2) and the results indicated (Yuwei and Jialong, 2011; Sica et al. 2014).
that the adsorption process in Ni2? best fitted to Freundlich
model but in Cd2? and Cu2? Langmuir model better illus-
trated the adsorption phenomena. Desorption
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Nano-TiO2 modified with natural and chemical compounds as efficient adsorbents for the removal of… 91
Table 5 Comparison of adsorption capacity of the proposed with some sorbents reported for the adsorption of Cu2?
Adsorbent Capacity (mg g1-Cu2?) Capacity (mg g1-Cu2?) Reference
(single) (competitive)
Table 6 Comparison of adsorption capacity of the proposed with some sorbents reported for the adsorption of Ni2?
Adsorbent Capacity (mg g1-Ni2?) Capacity (mg g1-Ni2?) Reference
(single) (competitive)
sorbed via electrostatic mechanism and release them into the solutions, Cu2? metals have the highest average desorption
aquatic environment. The data in Fig. 7 show the desorption (9.2 mg g-1). Other data are represented in Fig. 7. In general,
amount of Cd2?, Cu2?, and Ni2? as a function of CaCl2 in single solutions, the sequence of mean desorption of 3
solution in different MNPs and solutions. It is apparent that MNPs for each metal was Ni2? (4.4 mg/g [ Cd2? (3.5 mg/
Ni2? metals in single solutions have the highest average g) [ Cu 2? (1.4 mg/g). This trend for competitive solutions
desorption (4.4 mg/g) in total MNPs and give the best des- was Cu 2? (9.2 mg/g) [ Cd2? (3.1 mg/g) [ Ni2? (1.2 mg/
orption result. These results can reveal that some of sorption g). Therefore, the modified TiO2 particles could be operated
of Ni2? in MNPs is electrostatic adsorption. In competitive as stable adsorbents particularly in single solutions.
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92 S. Mahdavi
Fig. 6 SEM–EDX images of Ti–H, Ti–C, and Ti–H NPs, after treatment with single Ni2?, Cd2?, and Cu2? solutions, respectively
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Nano-TiO2 modified with natural and chemical compounds as efficient adsorbents for the removal of… 93
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