Journal of Environmental Management 193 (2017) 146e153

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Journal of Environmental Management

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Research article

Electroplating sludge derived zinc-ferrite catalyst for the efcient

photo-Fenton degradation of dye
Zhenbang Cao, Jia Zhang, Jizhi Zhou, Xiuxiu Ruan, Dan Chen, Jianyong Liu, Qiang Liu,
Guangren Qian*
School of Environmental and Chemical Engineering, Shanghai University, No. 333 Nanchen Rd, Shanghai 200444, PR China

a r t i c l e i n f o a b s t r a c t

Article history: A zinc-dominant ferrite catalyst for efcient degradation of organic dye was prepared by the calcination
Received 7 August 2016 of electroplating sludge (ES). Characterizations indicated that zinc ferrite (ZnFe2O4) coexisted with Fe2O3
Received in revised form structure was the predominant phase in the calcined electroplating sludge (CES). CES displayed a high
14 November 2016
decolorization ratio (88.3%) of methylene blue (MB) in the presence of H2O2 combined with UV irradi-
Accepted 17 November 2016
ation. The high efciency could be ascribed to the photocatalytic process induced by ZnFe2O4 and the
photo-Fenton dye degradation by ferrous content, and a small amount of Al and Mg in the sludge might
also contribute to the catalysis. Moreover, the degradation capability of dye by CES was supported by the
Keywords:
Electroplating sludge
synthetic ZnFe2O4 with different Zn to Fe molar ratio (n(Zn): n(Fe)), as 84.81%e86.83% of dye was
Zinc ferrite removed with n(Zn): n(Fe) ranged from 1:0.5 to 1:3. All synthetic ferrite samples in the simulation
Photocatalysis achieved adjacent equilibrium decolorization ratio, the exible proportioning of divalent metal ions
Fenton (M2) to trivalent metal ions (M3) applied in the synthesis indicated that the catalyst has a high
availability. Therefore, an efcacious catalyst for the degradation of dye can potentially be derived from
heavy metal-containing ES, it's a novel approach for the reutilization of ES.
2016 Elsevier Ltd. All rights reserved.

1. Introduction catalysts only relied on its adsorption capability. The exploitation

Electroplating sludge (ES) is a hazardous waste that contains
various heavy metals (e.g., Cr, Zn,Pb, Ni and Fe) (Chung et al., 2014).
Currently, the prevailing treatments for ES are landlling (Li et al.,
2015b) and brick-making (Tang et al., 2014). Unfortunately, insuf-
cient immobilized ability of landll may lead to the heavy metal
leaching, and contaminate soil and underground water (Li et al.,
2014). And brick-making is usually accompanied by high risk of
heavy metal volatilization at high temperature (Zhang et al., 2014).
Consequently, the appropriate reutilization of ES is becoming more
urgent.
Recently, the sludge-derived catalytic system, such as sewage
sludge and paper mill sludge, emerged as a potential way of sludge
reutilization (Bandosz and Block, 2006; Wen et al., 2012). And the
sludge-derived products have already been proved effective in the
removal of organic pollutants (Gu et al., 2013; Marques et al., 2011;
Zhou et al., 2015). However, a large number of sludge-based
* Corresponding author.
E-mail address: grqian@shu.edu.cn (G. Qian).
of specic element and its function lacks enough emphasis.
As an iron-rich heavy metal-containing sludge, ES can be ex-
pected to build a novel catalytic system. Our previous results
demonstrated that ES could be explored as one of the raw materials
in ferrite synthesis owed to its distinctive multi-metal elements
(Chen et al., 2010). Typical formula of ferrite can be expressed as
MeFe2O4 (AB2O4), where Me2 (A sites) can be a divalent ion (Mg2,
Fe2, Mn2, Ni2, Co2, or Zn2) or their combinations, and Fe3 is
the main component in B sites but can be substituted by trivalent
ions (Al3, Co3 and Cr3). Ferrite can be formed once ions simul-
taneously occupied the position Me2 (A) or the Fe3 (B) (Feng
et al., 2015). As a matter of fact, the catalytic properties of ferrites
are strongly dependent on the nature and amount of the transition
metals on the octahedral or tetrahedral sites, as the substitution of
transition metals (Co, Ni, Cu, and Zn) in spinel ferrites could modify
its redox activity (Hammiche-Bellal et al., 2013; Khan et al., 2008;
Liu et al., 2016; Meshkani and Rezaei, 2015; Tu et al., 2012).
Moreover, in ferrites as NiFe2O4, CoFe2O4 and ZnFe2O4 etc., that are
responsive to external illumination (Goldman, 2006), the adsorp-
tion energies at the catalytic sites can be also modied by the metal
dopants (Cai et al., 2015; Liu et al., 2016). One of the successful

http://dx.doi.org/10.1016/j.jenvman.2016.11.039
0301-4797/ 2016 Elsevier Ltd. All rights reserved.
 Z. Cao et al. / Journal of Environmental Management 193 (2017) 146e153
applications is ZnFe2O4 (Dom et al., 2015), it has been widely
studied in the decomposition of organic contaminants such as
Rhodamine B (Guo et al., 2014; Liu et al., 2012; Nan et al., 2013),
methyl orange (Bhukal et al., 2014b; Fan et al., 2009; Kulkarni et al.,
2016), and methylene blue (Fei et al., 2013; Feng et al., 2015;
Sharma and Singhal, 2013; Shen et al., 2008; Soltani and Entezari,
2013). More importantly, the Fenton-like process can be induced
by the ferrous content (Casbeer et al., 2012; Jauhar et al., 2014;
Martirosyan and Luss, 2007; Reddy and Lee, 2013).
Therefore, the aim of the current study is to 1) prepare Zn-
dominant ferrite catalyst from selected ES; 2) conduct the photo-
Fenton degradation of MB by calcined electroplating sludge (CES);
3) Synthesize ferrites with variable Zn/Fe molar ratio, and to vali-
date the feasibility of the reutilization of ES; and 4) Verify the
environmental security of sludge-derived catalyst application. To
the best of our knowledge, it is the rst time to report on a novel
approach to reuse heavy metal-containing ES to form Zn-dominant
ferrite-based catalytic system.
2. Materials and methods
2.1. Materials
Raw ES was directly collected from Shanghai Hazardous Waste
Management Centre. The water was freshly distilled and deionized
before used. All the reagents are analytical grade and procured from
Sino-pharm Group Chemical Reagent Co. Ltd., China.
2.2. Preparation of calcined electroplating sludge
CES samples were prepared as Fig. 1. Dry ES was grinned and
sieved through a 0.15 mm mesh, samples were calcined in mufe
furnace (SX-G12123 Ruipu Co., China). The temperature was
increased to 300  C, 500  C and 700  C with 5  C/min, and then kept
constant for 6 h. The electroplating sludge calcined at different
temperatures was marked as CES300, CES500 and CES700,
respectively.
2.3. Synthesis of ZnFe2O4
Pure ferrite was prepared by zinc nitrate(Guin et al., 2005).
Stoichiometric amounts of Zn(NO3)2 and Fe(NO3)3$9H2O are dis-
solved in water. The pH of the solution was adjusted to 8 by slow
addition of ammonia solution. The reaction mixture was stirred for
Fig. 1. The preparation of CES samples.
147
1 h before transferring the contents to 1000 mL stainless steel
autoclave. The temperature of the autoclave was maintained at
230  C for half an hour and then the reaction mixture was allowed
to cool to room temperature. The product formed was washed
several times, ltered and dried at 100  C for 8 h. The synthesized
ferrites were employed as control to in the MB degradation.
2.4. Adsorption and degradation experiments
The degradation was conducted in the apparatus as Fig. 2. In
general, 0.5 g CES samples were added into 500 mL of MB solution
(initial concentration of MB is 10 mg/L). The initial pH was
controlled at 3 and the initial H2O2 concentration was 2.5 mmol/L,
according to the optimal reaction conditions study (data not
shown). A 75 W Hg lamp (Toshiba SHL-100 UVQ-2) was employed
as the UV source. For the kinetics, a proper amount of liquid sam-
ples were extracted from the system at 0, 10, 30, 60, 90 and 120 min
and separated by centrifuge for 10 min before spectrophotometric
measurements. The concentration of dye was determined at
664 nm for MB using an ultravioletevisible (UVeVis) spectropho-
tometer (U-3010, Hitachi Co., Japan), The decolorization capacity of
MB was calculated by the following equation:
C0  C
W  100% (1)
C0
where W stands for the decolorization rate (%), C0 and Ce are the
initial and equilibrium concentrations of MB (mg/L), respectively.
2.5. Leaching test
In this study, the US Environmental Protection Agency (US EPA)
Toxicity Characteristic Leaching Procedure (TCLP) (1311) was fol-
lowed to determine the chemical stability of the prepared catalyst.
According to the standard procedure and the reaction condition,
distilled water with pH adjusted to 4.93 0.05 was chosen as the
extraction uid, and the volume ratio of solid to liquid was 1:20.
The mixed samples were shaken at the rate of 302 rpm for 18 h,
and then were ltered to collect the ltrate. Finally, the leached
metal concentrations in the ltrate were determined with induc-
tively coupled plasma optical emission spectrometer (ICP-OES,
Leeman Co., USA).
Fig. 2. The experimental set-up for MB degradation, a. Toshiba SHL-100 UVQ-2 UV
light source, b. Cool down water pump, c. Cool down water, d, UV lamp, e. MB solution,
and f. stirrer.
148 Z. Cao et al. / Journal of Environmental Management 193 (2017) 146e153

2.6. Materials characterization

X-ray diffractometer (XRD, Model XD-3A, Shimazu Co., Japan)

was employed to record the XRD patterns of as-obtained ferrites
and various other materials. The XRD patterns were recorded on a
Dmax/RB diffractometer (Rigaku Co.) with Cu Ka radiation
(l 0.15418 nm) at a rate of 3 per min in 2q 10e80 . Fourier
Transform Infrared (FTIR) spectra were collected on Nicolet 380
FTIR (Thermo Fisher Scientic, Inc., USA) after 32 scans within
4000e400 cm1 at a resolution of 4 cm1 by measuring the IR
absorbance of KBr disc containing 1e2 wt % of sample. The metal
compositions were analyzed by ICP-OES after suitable treatment.
Scanning electron microscope (SEM) images were obtained using a
Nova NanoSEM 430 scanning electron microscope (operating
voltage 10 kV).

Fig. 3. XRD patterns of (a) CES700, (b) CES500, (c) CES300, and (d) raw ES.
3. Results and discussion

3.1. Characterization of sludge derived ferrite

The variance of metal content among ES and CES was negligible

according to Table 1. However, Zn and Fe content in the latter two
samples were 2.2% and 2.7% higher than the raw ES, respectively.
The variance might be relative to the dehydration of metals hy-
droxide portion in the sample at high temperature (>300  C). The
Zn to Fe molar ratios (n(Zn): n(Fe)) among all samples were
approximately 1:3. Since Fe can be converted into ferrite matrix,
the occupation of Zn on the tetrahedral sites in the structure might
thereby generate ZnFe2O4. Noticed that a small amount of other
metals such Al and Mg was also contained. These components
might lead to the metal substitution in multiple ways.
The XRD patterns of ES and CES are shown in Fig. 3. The peaks of
raw ES were weak but already with weak characteristics of
ZnFe2O4, this could be attributed to the heating process in desic-
cation, in which a small amount of ZnFe2O4 was yielded. Diffraction
peaks in CES300 were stronger than the former, indicated the for-
mation of a larger amount of ZnFe2O4 yet still with poor crystal-
linity. Peaks of ZnFe2O4 in CES500 and CES700 were evident, as the
content and crystallinity of ZnFe2O4 were both improved as calci-
nation temperature rose. CES700 also showed identical peaks of
Fe2O3, referred to the formation of Fe2O3 structure. It may be
explained as more Zn replaced Fe on the tetrahedral sites, and a
larger amount of Fe2 transited to octahedral sites due to higher
temperature treatment in CES500 and CES700. Fig. 4. The XRD diffraction pattern of synthetic ZnFe2O4, (a) CES700, (b) n(Zn):
n(Fe) 1:3, (c) n(Zn): n(Fe) 1:2, (d) n(Zn): n(Fe) 1:1 and (e) n(Zn): n(Fe) 1:0.5.
In comparison, XRD patterns of synthetic ferrite with different
Zn to Fe molar ratios were shown in Fig. 4. The crystal size were
calculated from the XRD patterns according to the Scherrer equa- contribute to the difference. As its indeed observed evident crys-
tion and listed in Table 2. The crystal sizes of CES-derived ferrite and tallized peaks of Fe2O3 in Fig. 4a and b. Moreover, the diffraction
synthetic ferrite (Zn:Fe 1:3) are 166 and 171 , respectively. The patterns well reected a cubic ZnFe2O4 structure, and the lattice
similar size indicated the ferrite is the predominant phase among parameter (a) of synthetic ferrite (n(Zn): n(Fe) 1:2) and CES700
all three phases. It's also noticed that both CES700 and synthetic are both 8.43 . These values are in good accordance with the
ferrite (n(Zn): n(Fe) 1:3) had a larger value than synthetic ferrite standard ZnFe2O4 (Franklinite) value of 8.44 (JCPDS No. 22-1012).
with n(Zn): n(Fe) 1:2, this difference may by assigned to the Samples were also characterized by Fourier Transform Infrared
coexistence of Fe2O3. The impurities such as Mg and Al may also (FT-IR) spectrum as in Fig. 5. None obvious band was observed in
the raw ES sample. In the CES samples, the adsorption band at
Table 1 1635 cm1 is assigned to HeOeH vibration (y0H2O), indicating the
Main metal contents in ES and CES. adsorption of water in the sample. Interestingly, in CES samples,
two prominent absorption bands were spotted in the range of
Metal contents in ES and CES (mg g1)
400e600 cm1 and no bands above 700e1600 cm1. Vibrations
Fe Al Zn Mg with such features might refer to two sub-lattices of the single
ES 459.7 13.4 41.1 2.54 173.3 4.27 10.1 0.45 phase spinel structure, the high frequency band y1 was due to the
CES300 459.7 9.55 40.2 5.21 173.3 9.34 9.9 2.21 stretching vibrations of the tetrahedral metal-oxygen bond (ZneO)
CES500 470.5 21.8 41.0 10.2 177.7 18.3 9.8 3.29
whereas the low frequency band y2 was caused by the metal-
CES700 476.7 22.9 40.7 7.98 178.2 15.2 10.6 1.97
 Z. Cao et al. / Journal of Environmental Management 193 (2017) 146e153 149

Table 2 duplicates were beneath 2%. The minute removal of MB might be

Cell parameter of synthetic ferrite and CES700. attributed to the adsorption on the CES surface and weak catalytic
Sample a () Crystallite size ()a respond of ZnFe2O4 induced by visible light (Kulkarni et al., 2016).
CES700 8.43 166
Generally, the isolated utilization of CES in the solution caused no
Synthetic ferrite, 1:0.5 8.43 213 signicant decolorization of MB with current conditions.
n(Zn):n(Fe) 1:1 8.45 208 However, by the specic metal constitutions of ES, it occurred to
1:2 8.43 162 us that the ferrous content in the CES can be exploited as a reliable
1:3 8.44 171
iron source to form Fenton system (Dantas et al., 2006; Ling et al.,
a
Crystallite size was estimated by following Scherrer equation according to lat- 2014). In addition, the Fenton catalytic process can be greatly
tice parameter a in XRD patterns of samples.
accelerated by the presence of UV irradiation (Cai et al., 2016),
Demonstrated by the UVeVis adsorption spectrum of CES, it's
calculated that the band gap is approximately 2.9 eV, indicated a
response to UV radiation. Therefore, the degradation of MB by
photo-Fenton system formed with CES and H2O2 has been studied
in this section.
The decolorization of MB by UV/CES/H2O2 system was shown in
Fig. 7. In the presence of H2O2 without UV irradiation, no CES
sample demonstrated adequate MB degradation capability. The MB
decolorization ratios with H2O2-assisted CES catalyst were only
approximately 3% (Fig. 7a.), indicated a rather low efciency. In
contrast, the enhancement induced by UV irradiation was signi-
cant. All duplicates with UV irradiation displayed decolorization
ratio over 70% (Fig. 7b.), among which the CES700/H2O2/UV system
achieved 88.27% ratio, probably due to the higher crystallinity
(Bhukal et al., 2014a; Deraz, 2010) (Fig. 4). According to the band
shift in Fig. 5 and Table 3, a larger amount of Zn participated in the
Fe substitution than CES300 and CES500, suggested larger amount of
ZnFe2O4 might be contained in the CES700.
Besides, the independent utilization of H2O2 with UV irradiation
had only 53% decolorization ratio, as hydroxyl radicals (OH) can be
yielded while H2O2 was irradiated by UV(Liao et al., 2016). Obvi-
ously, the generation of OH might be accelerated in the combina-
Fig. 5. FT-IR spectra of (a) raw ES, (b) CES300, (c) CES500, and (d) CES700. tion with CES than using H2O2 exclusively. Above experiments
disclosed that in the CES-based Fenton system, UV activation was
indispensable for the effective dye degradation with the CES-
oxygen vibrations (FeeO) in octahedral sites (Shahbaz Tehrani derived Ferrite. To trace the degradation process of MB with
et al., 2012; Vidyadhar et al., 2013). As the calcination tempera- CES700, the change of characteristic peaks in MB was recorded by
ture increased, considerable shifts of y1 and y2 were observed as UVeVis absorption spectra.
listed in Table 3. The photocatalytic activity was evaluated by measuring the
The band shift might be attributed to the decrease in the unit
cell dimension led by the metal substitution. The Zn2 ions have a
strong tendency to replace the Fe3 ions in the tetrahedral sites.
The vibration frequency of tetrahedral sites declined since Zn has a
greater atomic weight and larger radius. The Fe3 ions migrated
into the octahedral sites thereby increased the octahedral vibration
frequency (Kurian and Nair, 2015). Apparently both procedures
were fortied at higher temperature. The result of FTIR analysis
supported the generation of ZnFe2O4 phase in the calcined ES
samples.

3.2. Degradation of MB by CES-derived catalyst

The MB degradations by ES and CES were carried out. The results

were shown in Fig. 6. The raw ES displayed poor degradation ef-
ciency, so as the calcined ES samples. The decolorization ratios of all

Table 3
FT-IR absorption band frequencies of CES samples.

FT-IR frequency bands (cm1)

A-site (tet) y1 B-site (oct) y2

CES300 554.95 418.63

Fig. 6. The decolorization rate of MB by (a) ES, (b) CES300, (c) CES500, and (d) CES700;
CES500 552.11 420.42
The initial MB concentration is 10 mg/L, and the dosage of solid is 0.5 g, and the initial
CES700 546.63 427.72
pH is 3.
150 Z. Cao et al. / Journal of Environmental Management 193 (2017) 146e153

Fig. 7. The decolorization rate of MB by (a) CES H2O2 without UV irradiation and (b) with UV irradiation; The initial MB concentration is 10 mg/L, and the dosage of solid 0.5 g, the
initial pH is 3, the initial H2O2 concentration is 2.5 mmol/L and A 75 W Hg lamp (Toshiba SHL-100 UVQ-2) was employed as the UV source.

degradation procedures of MB. Fig. 8 showed the changes in the sludge-derived catalyst. The photocatalytic process of ZnFe2O4 and
absorbance proles of MB solution in the CES700/H2O2/UV system. preponderances over pure ferrite Fe3O4 can be understood as
The reaction started with the MB concentration of 50 mg/L. Four follow.
characteristic peaks (246, 291, 615, 664 nm) were observed, which When irradiated with UV, photo-generated electrons (e CB) and
was in accordance with the reported. Absorption bands of MB at holes (h
VB) were excited in ZnFe2O4, and the photo-reactions were
648e655 nm, 620e634 nm, and 608e612 nm were for Azure A, B proceeded as Eqs. (2)e(6) (Daneshvar et al., 2007; Su et al., 2012).
and C, respectively (Zhang et al., 2001). As bands at 291 and 246 nm
were referred to phenothiazine species. All peaks reduced rapidly ZnFe2O4 (CES) hy/ ZnFe2O4 (CES) (e
CB hVB) (2)
along with the time increasing, it also could be observed from Fig. 7
that approximately 60% of the MB was removed during the rst h
VB dye / oxidation of dye (3)
20 min. The eventual disappearance of the original absorptions
suggested the almost complete degradation of MB (Zhang et al., h
VB H2O / H OH
 (4)
2006).
h 
VB OH / OH H

(5)
3.3. Preponderances of CES-derived ferrite in catalytic application
OH dye / degradation of dye (6)
ZnFe2O4 coexistent with Fe2O3 were predominant phases of
As Fe presented different oxidation states in all samples, a
photo-Fenton process could be initiated in the H2O2/UV system as
Eqs. (7)e(11)(Garrido-Ramrez et al., 2010; Kim and Kan, 2015; Li
et al., 2015a; Navalon et al., 2010).

Fe2 H2O2/ Fe3 OH OH (7)

Fe3 H2O2/ Fe2 OOH H (8)

Fe(OH)2 hy/ Fe2 OH (9)

H2O2 e 
CB/ OH OH
 (10)

Fe3 e
CB / Fe
2
(11)

Compared to typical photo-Fenton procedures, more e

Fig. 8. The variance in the absorbance of the photodegradation by CES700 in the UV/
H2O2 system.
CB/hVB
pairs can be yielded in the solution by the photo-activated ZnFe2O4,
hence reaction Eq. (9) could be conducted more effectively,
although Eq. (9) was normally considered as a limitation in the
 Z. Cao et al. / Journal of Environmental Management 193 (2017) 146e153 151

catalyst within the system contributed to the degradation rather

than the photo-sensitized MB.
According to the chemical stoichiometry dosed in the synthesis,
the resultant (a, b, c, and d) can be dened as a ferrite solid solution
with different expected maximum mass ratio of ZnFe2O4, the value
of which in a, b, c and d are approximately 49.79%, 74.84%, 100%, and
75.70%, respectively. The most effective degradation among syn-
thetic ferrite occurred in the sample c (86.83%), which might be
attributed to the highest ZnFe2O4 content. It can also be seen that
the efciency of sample a slightly lower than others, as sample a
had a much smaller content of ZnFe2O4 (49.79% of ZnFe2O4
compared to 75e100% in other samples). Moreover, CES700 (e) has
analogous n(Zn): n(Fe) with sample d in composition, in contrast,
the former not only showed the highest decolorization ratio of
88.27%, but also achieved 60% efciency in the rst 20min, which
was signicantly more efcient than synthetic ferrites (Fig. 9). On
the basis of composition variance, a small amount of Al and Mg
might account for the preponderance in the catalytic application.
Fig. 9. The MB decolorization in the UV/H2O2 system by synthetic ferrite (a) n(Zn): Kinetic models are also established to compare the perfor-
n(Fe) 1:0.5, (b) n(Zn): n(Fe) 1:1, (c) n(Zn): n(Fe) 1:2, (d) n(Zn): n(Fe) 1:3 and
(e) CES700.
mance. As adsorption is considered critical in the heterogeneous
photocatalytic oxidation process, the LangmuireHinshelwood
model was used to describe the photocatalytic kinetics of dyes by a
Fenton process(Kim and Kan, 2015). The synergistic effect of photo- few previous researchers. This treatment is subject to the as-
activated ZnFe2O4 and Fenton process not only diminished the h VB sumptions that sorption of both the oxidant and the reductant is a
and e CB recombination effectively but also led to the larger scale of rapid equilibrium process and that the rate-determining step of the
OH generation (Cai et al., 2016; Su et al., 2012), these reasons might reaction involves both species present in a monolayer at the sol-
contribute to the highly efcient degradation of MB. ideliquid interface (Daneshvar et al., 2007). Kinetic parameters are
To elucidate the preponderance of sludge-derived Zn-dominant listed in Fig. S5 and Table 4. Both CES and synthetic ferrite tted
ferrite in the MB degradation, Zn-ferrite samples with different well with the kinetic model, and the CES700 has the highest reaction
initial Zn/Fe molar ratios were synthesized to simulate the MB constant (k 0.019).
catalytic degradation. The n(Zn): n(Fe) were adjusted to 1:0.5, 1:1, As mentioned above, regarding the difference on the structural
1:2 and 1:3, respectively (Fig. 4). The MB decolorization curves by parameter, other than the existence of Fe2O3, the incorporation of
synthetic ZnFe2O4 were shown in Fig. 9. Meanwhile, the decolor- Mg and Al ions into tetrahedral A sites and octahedral B sites may
ization of MB in UV in the absence of both H2O2 and CES are pre- also led to a variance.
sented in Fig. S3, the less than 0.4% decolorization indicated the It has been well established that metal substitutions in ferrite
were able to not only change the structure such as the lattice
parameter and surface area, but also modify the band gap energy.
Table 4 For instance, in the Mg doped ZnFe2O4, the band gap energy was
Concentration of heavy metals leached from CES-derived catalyst. narrowed from 2.15 eV (ZnFe2O4) to 1.42 eV (Zn0.2Mg0.8Fe2O4),
n(Zn):n(Fe) CES700 photocatalytic performance was enhanced due to the alteration of
band gap energy (Liu et al., 2016; Manikandan et al., 2013). The Al
1:0.5 1:1 1:2 1:3
substituted ZnFe2O4 (ZnFexAl1xO4, 0 < x < 2) also presented better
k 0.0183 0.0182 0.0179 0.0174 0.0192 catalytic performance than pure ZnFe2O4 in dye degradation under
R2 0.99134 0.98985 0.99468 0.99109 0.97347
UV light, due to the smaller crystal size and also the dosage of Al3

Fig. 10. Proposed processing of UV/CES/H2O2 system.

152 Z. Cao et al. / Journal of Environmental Management 193 (2017) 146e153
Table 5
Concentration of heavy metals leached from CES-derived catalyst.
Sample Metal concentrations (mg L1)
Fe Al Zn
CES700 0.07 0.35 0.38
restrained the recombination of h 
VB and eCB (Borhan et al., 2014).
Since the CES-derived ferrite was a MgeAl co-doped zinc ferrite as
[Zn(1x)Mgx][Fe(2y)Aly]O4$zFe3O4, it can be expected that these
metal dopants could strengthen the effectiveness in the heteroge-
neous photocatalytic system formed by CES-derived ferrite. This
hypothesis was also supported by the aggregation of small particle
of CES700 along with well distribution of Mg/Al/Fe/Zn, compared to
that of ES (Fig. S6). Therefore, the catalytic process by CES-derived
ferrite was proposed as Fig. 10.
Evidently, in spite of the evident divergence of ZnFe2O4 content
in the composition, all samples in simulation reached adjacent
equilibrium MB decolorization ratio (84.81%e88.27%), which might
suggest that the different n(Zn): n(Fe) ratios didn't cause signicant
variance in the decolorization capability. Hence the Zn and Fe
proportioning required to ensure the catalytic efciency can be
highly exible. Meanwhile, as ES is a Fe-rich substance contained
various heavy metals, it can be deduced that in the CES-derived
catalyst, the proportions of divalent metal ions (M2) and triva-
lent metal ions (M3) were also adjustable, which indicated the
CES-derived catalyst has a high availability.
3.4. TCLP leaching of CES-derived catalyst
Application of heterogeneous catalysts in the purication of
waste water required that they be stable toward metal ion leaching
from the catalyst to the liquid phase under the operating con-
ditions(Kurian and Nair, 2015). Table 5 gives the result of leaching
test.
TCLP analysis indicated that the heavy metals leaching from the
ferrite products during the catalysis is very limited, meeting the
requirements of US EPA standard. Hence the heterogeneous cata-
lytic system remained safe after the application.
The recyclability of CES700 after leaching test was also tested;
result was listed in Fig. 11. The decolorization rate after 5 times still
maintained over 90%, this indicated a great potential for the
Fig. 11. Recycle efciency of CES on MB degradation.
continuous utilization of CES-derived catalyst.
4. Conclusions
Mg
In conclusion, a Zn-dominant Ferrite has been derived through
0.67
ES calcination, and ZnFe2O4 coexisted with Fe2O3 structure were
the predominant phases in the resultant. When the initial MB
concentration is 10 mg/L, and the dosage of solid 0.5 g, the initial pH
is 3, and the initial H2O2 concentration is 2.5 mmol/L, the CES-
derived catalyst presented excellent MB decolorization efciency
(88.27%) in UV/H2O2 system. The photocatalytic process induced by
activated ZnFe2O4 and photo-Fenton process by ferrous content
accounted for the high effectiveness, and Coexistent Mg/Al in the
sludge contributed to the preponderance compared to synthetic
ferrites. In addition, the exibility of metal proportions in raw ES
indicated the high availability of sludge-derived catalysts.
Acknowledgement
This project is supported by National Nature Science Foundation
of China Nos. 21477071, 20907029 and 51174132.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jenvman.2016.11.039.
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