Materials Science & Engineering B 245 (2019) 75–84

Contents lists available at ScienceDirect

Materials Science & Engineering B

journal homepage: www.elsevier.com/locate/mseb

Tartaric acid enhanced CuFe2O4-catalyzed heterogeneous photo-Fenton-like T

degradation of methylene blue
⁎
Xiaojun Guo , Kebai Wang, Yanan Xu
College of Chemistry & Chemical Engineering, Northwest Normal University, Lanzhou 730070, China

A R T I C LE I N FO A B S T R A C T

Keywords: CuFe2O4 particles were obtained by sol-gel process and characterized by XRD, SEM and EDS. The effects of
Tartaric acid tartaric acid (TA) on the degradation of methylene blue (MB) were studied in the presence of CuFe2O4 and H2O2
CuFe2O4 particles under light irradiation. The results showed that introducing TA enhanced MB decolorization rate from 52.0% to
Photo-Fenton-like 92.1% within 80 min. The contribution of superoxide anions (%O2−) was only 10% and the contribution of
Degradation
hydroxyl radical (%OH) was around 88%. For H2O2-CuFe2O4-photo system, in the presence (or absence) of TA,
Methylene blue
the dynamic change of %OH suggested that the addition of TA could promote the generation of hydroxyl radicals.
The enhanced effect of TA in TA-H2O2-CuFe2O4-photo system could be attributed to its own structure and the
dissolved metal ions of the catalyst surface. In addition, a reasonable mechanism for the complex system was
elucidated.

1. Introduction (e.g.Fe3O4 and γ-Fe2O3) and metal ions doped iron oxides (e.g.CuO-
Fe3O4) were selected as commonly heterogeneous catalysts [12–14].
Owing to people’s increasing pursuit for beautiful colors, the dye- However, many of those catalysts often need to introduce auxiliary
stuff was widely used in many fields, such as food, textile, service and energy (e.g. electricity, light, microwave, and ultrasound) due to weak
construction industries. Inevitably, serious environmental pollution catalytic activity [15–17]. Light irradiation is advocated because of
would come with its application. According to report, over 1 million easy acquisition and lower cost. Thus, it is crucial to choose appropriate
tons of organic dyes were produced annually, 5% of which were lost in photo-Fenton-like catalysts for greater use of solar energy [18]. As a
effluents during application and manufacturing, 5–15% of which were kind of spinel, copper ferrite (CuFe2O4) is not only one of the most
discharged into the environment [1,2]. Considering the effects of these important heterogeneous Fenton-like catalysts, but also an effective
toxic compositions on humans and other living organisms, water and photocatalytic functional material [19–21]. Sharma et al. [22] sys-
wastewater regulatory requirements have become stricter and more tematically studied magnetic spinel ferrites MFe2O4 (M = Cu, Zn, Ni
demanding [3]. Therefore, hazardous and toxic organic pollutants and Co) to activate different inorganic oxidants in photo-Fenton-like
(especially dyestuff) presenting in wastewater have to be removed or oxidation process, which disclose the degradation rate attained max-
transformed into secondary less toxic by-products. Many methods are imum when choosing H2O2 as oxidant and the reactivity followed the
available to remove organic pollutants from wastewaters, including order CuFe2O4 > ZnFe2O4 > NiFe2O4 > CoFe2O4. Cheng and co-
physical processes [4,5], biological processes [6] and chemical pro- worker [23] reported CuFe2O4 as a heterogeneous photo-Fenton-like
cesses [7–9]. Fenton technology is one of the most powerful and widely catalyst to degrade glycerol under with and without visible light irra-
used advanced oxidation processes (AOPs) for the treatment of organic diation. Results showed that the Fenton degradation of glycerol had
dyestuff [10]. However, traditional homogeneous Fenton process exist changed from below 4.0% to nearly 40.0% without visible light. Be-
some drawbacks, such as a narrow pH range and sludge containing sides, Flores et al [24] also proved that spinel copper ferrites as het-
metals generated at the end of the process. To overcome these erogeneous catalyst exhibited an eminently performance in photo-
shortages, heterogeneous Fenton-like process has been widely re- Fenton degradation of Rhodamine B. However, it is necessary to in-
searched [11]. crease further the catalytic ability of CuFe2O4 particles for the de-
Previous researches showed that catalysts played a very important gradation of organic dyestuff in photo-Fenton-like system.
role in heterogeneous Fenton-like process. In general, iron oxides According to previous reports, the situ addition of some chelating

⁎
Corresponding author at: College of Chemistry & Chemical Engineering, Northwest Normal University, 967 Anning East Road, Lanzhou 730070, China.
E-mail address: [email protected] (X. Guo).

https://doi.org/10.1016/j.mseb.2019.05.015
Received 17 April 2018; Received in revised form 27 March 2019; Accepted 17 May 2019
Available online 22 May 2019
0921-5107/ © 2019 Elsevier B.V. All rights reserved.
X. Guo, et al. Materials Science & Engineering B 245 (2019) 75–84

agents into the metal oxides dispersions can improve the catalytic ac- (FT-IR) spectroscope was used by the KBr disk technique with a
tivities of the metal oxides [25,26]. Rodríguez et al [27] found that the FTS3000FX spectrometer to detect whether other substances were ad-
addition of oxalic acid (0.2 mmol L−1) to UV-Fe3O4-H2O2 system in- sorbed on the surface of CuFe2O4 particles. UV–Vis diffuse reflectance
creased the removal of BPA from 55.4% to 92.3% in 120 min. Li et al. spectra (DRS) of the samples before and after using in different systems
[28–30] also reported that the beneficial effect of oxalate on the de- were analyzed using a UV-2550 UV–Vis spectrophotometer. The mass
gradation of organic pollutant over various iron oxides in the absence of percent and transient state of composition elements of CuFe2O4 parti-
H2O2. This is because the dissolved and adsorbed Fe-oxalate complex cles surface before and after using were discussed by X-ray photoelec-
exhibited strong ligand-to-metal charge transmitting bands in the near- tron spectroscopy (XPS) using a PHI-5702 system. The energies of the
UV and visible region, and accelerated the formation of H2O2 and active highest occupied molecular orbital (EHOMO) of tested organic acid were
radical species via a photo-Fenton-like process [25–30]. Furthermore, calculated by the software Materials Studio 5.5.
Wang et al. [31] also explored that ligand-to-metal charge transmitting
bands between colorless aromatic pollutants or hydroxycarboxylic acid 2.4. Catalytic degradation of MB
and nano-TiO2 could induce the photocatalytic oxidation of organic
substrates under visible light irradiation. Hence, choosing appropriate The enhanced catalytic property of TA was assessed by the MB
chelates could promote the rate of some special reaction, although some degradation in the presence of CuFe2O4 particles as heterogeneous
reports proved different ligand demonstrated an obvious different ac- catalyst and H2O2 as oxidant. Light irradiation was carried out using a
tion [32,33]. In this paper, CuFe2O4 nanoparticles had been synthesized UV-curing lamp (365–450 nm) that simulated sunlight. In a typical
by traditional sol-gel method and characterized via various methods. catalytic experiment, 20 mg catalyst was dispersed to 100 mL
Owing to its special structure, TA could form stable coordination 50 mg L−1 MB aqueous solution. The heterogeneous system was vig-
complex with metal ions with more than one chelate ring. Thus, we had orously stirred by magnetic force about 30 min to reach the adsorption-
chosen it as ligand and observed the effects of TA on the degradation of desorption equilibrium before starting the illumination. Subsequently,
MB in TA-H2O2-CuFe2O4-photo system. By leaching analysis of metal 0.1 mmol TA and 0.2 mL H2O2 were rapidly added into the hetero-
ions and the stability analysis of dissolved metal ions, the MB de- geneous system and the MB degradation was started. At the same time
gradation mechanism in TA-H2O2-CuFe2O4-photo system was reason- interval, portion (1 mL) of the degradation solution was sampled, then
ably speculated. magnetically separated to remove catalyst and mixed immediately with
5 mL deionized water for quenching the oxidation of MB and testing
2. Experimental purposes.

2.1. Chemicals and reagents 2.5. Analytical methods

Copper nitrate (Cu(NO3)2·3H2O) and benzoquinone (BQ) were of- The concentrations of remnant dye in the aforementioned samples
fered from Damao chemical reagent Co., Tianjin, China. Ferric nitrate were analyzed using a UV8453 UV–Vis spectrophotometer to measure
(Fe(NO3)3·9H2O) and MB were obtained from Guangfu fine chemical the absorbance of MB at 664 nm. The contents of hydroxyl radical in
inst., Tianjin, China. TA and H2O2 (ω = 30%) were prepared from different systems were evaluated using coumarin as a fluorescence
Baishi chemicals Co., Tianjin, China and Kaitong chemical reagent Co., probe, which attributes to hydroxyl radical easily reacting with cou-
Tianjin, China, respectively. Coumarin was purchased from Macklin marin to form highly fluorescent 7-hydroxycoumarin [35]. In detail, l
biochemical Co., Shanghai, China. Other chemicals were acquired from mL degradation solution was acquired at the same time interval, 1 mL
Chemical reagent Co., Shanghai, China. All chemicals were analytical 1.0 mmol L−1 coumarin solution was immediately added into the above
grade reagents and without further purification. Deionized water was samples. After fully shaking about 1 min, 5 mL deionized water were
used throughout the experiment. injected in the mixed solution. The fluorescent intensity of generated 7-
hydroxyoumarin was detected at an emission wavelength of 456 nm
2.2. Preparation of CuFe2O4 particles with the excitation wavelength of 346 nm on a F97 Pro spectro-
fluorophotometer. The concentrations of dissolved iron ion and copper
Spinel ferrites CuFe2O4 particles were prepared via a glycol-assisted ion derived from the heterogeneous catalyst in 10 mL final reaction
sol-gel technique [34]. In a typical procedure, 10 mmol Cu(NO3)2·3H2O degradation solution were detected using Z-200 flame atomic absorp-
and 20 mmol Fe(NO3)3·9H2O was orderly dissolved in 40 mL ethylene tion spectrometry.
glycol to produce a clear solution, which then heated at 353 K for 4 h
under magnetic stirring. The rufous sol was dried at 393 K for 8 h and 3. Results and discussion
the obtained xerogel was preheated at 673 K for 1.5 h to remove organic
compounds and acid radical. Subsequently, the remaining powders 3.1. Characterization of CuFe2O4 particles
were calcined at 1073 K for 4 h before quenching to room temperature.
Finally, the as-prepared sample was washed with deionized water and XRD pattern of the as-prepared sample was shown in Fig. 1a. The
absolute ethanol several times and dried at 353 K for 2 h. diffraction for the obtained sample had major eight well-defined peaks
occurring at 2θ = 29.9°, 34.7°, 35.9°, 37.1°, 43.8°, 57.8°, 62.2°, 63.6°,
2.3. Characterization methods corresponding to lattice plane (1 1 2), (1 0 3), (2 1 1), (2 0 2), (2 2 0),
(3 2 1), (2 2 4) and (4 0 0), respectively. The major crystal phase of the
CuFe2O4 particles were characterized by power X-ray diffraction sample was in a good agreement with the JCPDS card 34-0425, which is
(XRD) on a Rigaku D/max-2400 diffractometer between 10° and 80° indexed as the tetragonal phase [space group: I41/amd (141)] of copper
with a 0.02° s−1 steps using Cu Ka radiation (λ = 0.154 nm) as the X- ferrite. The average crystallite size of CuFe2O4 particles was calculated
ray source. The structure parameters and unit cell model of CuFe2O4 from X-ray line broadening using Scherer’s equation
samples were obtained by Inorganic Crystal Structure Data and (D = 0.89λ(βcosθ)−1), where λ is the wavelength of the X-ray radia-
Diamond 3.2 software, respectively. The morphology of the sample was tion, θ is the diffraction angle, and β is the full-width at half-maximum
observed by scanning electron microscope (SEM) using ULTRA plus at (FWHM) intensity of (2 1 1) XRD line, works out to be 48.6 nm.
accelerating voltages of 5 kV, together with the energy-dispersive X-ray Fig. 1b shows the simulative crystal structure of tetragonal CuFe2O4
spectrum (EDS) was obtained from an Aztec-X-80 energy-dispersive sample. Tetragonal CuFe2O4 was proved to have a spinel structure with
spectrometer by point scanning analysis. Fourier transform infrared virtually complete inversion. In this structure, Cu2+ mainly occupies

76
X. Guo, et al. Materials Science & Engineering B 245 (2019) 75–84

Fig. 1. XRD patterns of CuFe2O4 samples calcined at 1073 K (a), the unit cell model of CuFe2O4 samples (b), the SEM image of CuFe2O4 samples calcined at 1073 K
(c), the EDS spectrum of CuFe2O4 samples calcined at 1073 K (d).

the octahedral center (B-sites), while Fe3+ evenly locates both on the degradation rate achieved 95.4% (curve 1 in Fig. 2a). The pseudo first
tetrahedral center (A-sites) and B-sites [10]. The structure parameters order model was applied to analyze the kinetics of the degradation
of CuFe2O4 were listed in Table S1 (Supporting Information). The dis- processes in different conditions. The relationship between ln(c0/c) and
tance between A-sites and four nearest oxygen sites was about 1.7419 Å time (t) in Fig. S1 (Supporting Information) is approximately linear and
for tetrahedral structure. By contrast, the distance between B-sites and the slope was known as the apparent rate constant k. Results showed
two vertex oxygen sites was 2.1596 Å for octahedral structure, and the that pseudo first order model was fit for these systems and the apparent
distance between B-sites and four plane oxygen sites was 2.1335 Å. rate constant k increased with the following order: TA-photo < TA-
Thus, A-sites have higher binding energy, and the metal ions in B-sites CuFe2O4-photo < CuFe2O4-photo < TA-H2O2-CuFe2O4 < H2O2-
are more unstable in lattice structure. photo < TA-H2O2-photo < H2O2-CuFe2O4-photo < TA-H2O2-
SEM analysis was used to observe the morphology of CuFe2O4 CuFe2O4-photo. Although the values of c/c0 basically remain constant
particles. As shown in Fig. 1c, the CuFe2O4 particles possess irregular with prolonging time for TA-CuFe2O4-photo and TA-photo system, the
morphology. The EDS spectrum (Fig. 1d) shows that the catalyst was addition of TA effectively enhances the catalytic ability of H2O2-
mainly composed of Cu, Fe and O. Assuming that the Cu content was 1, CuFe2O4-photo system in the degradation of MB.
the specific value of Fe and O was 2.2 and 3.7, respectively. The However, the enhanced effect of chelating agents is quite different
characterization results are consistent with the mole ratio of CuFe2O4 for Fenton or photo-Fenton systems. For example, Wang et al. [25]
molecular formula. found that the removal rate of Bisphenol A changed from 20.4% to
91.2% in reaction time of 120 min after adding EDTA into H2O2-BiFeO3
3.2. TA enhanced degradation of MB system at initial pH and 303 K. When introducing TA into this system,
the Bisphenol A removal rate increased slightly within 120 min. Simi-
Fig. 2a illustrates the degradation of MB in different systems at in- larly, Xue et al. [36] obtained the same conclusion in the degradation of
itial pH and 298 K. It is easily seen that MB can be slowly degraded on pentachlorophenol using H2O2-Fe3O4 system. Although the increase is
the surface of CuFe2O4 in the presence of light irradiation and H2O2, the modest, the addition of indeed enhanced the catalytic ability of the
decolorization rate was 52.0% within 80 min, and the decolorization above systems. This is quite different from our experimental results.
rate reached to 78.1% in 120 min (curve 3 in Fig. 2a). In other systems, Therefore, it is valuable to reveal the role of TA on the degradation of
no major removing of MB was observed except for TA-H2O2-CuFe2O4- MB in H2O2-CuFe2O4-photo system.
photo system (curve 2, 4, 5, 6, 7 and 8 in Fig. 2a). After TA
(1.0 mmol L−1) was introduced into H2O2-CuFe2O4-photo system, the
degradation of MB was observably promoted, resulting in a MB removal
of 92.1% within 80 min. Continuously increasing reaction time, the

77
X. Guo, et al. Materials Science & Engineering B 245 (2019) 75–84

Fig. 2. Degradation of MB in the systems of (1) TA-H2O2-CuFe2O4-photo, (2) TA-H2O2-CuFe2O4, (3) H2O2-CuFe2O4-photo, (4) TA-CuFe2O4-photo, (5) TA-H2O2-
photo, (6) CuFe2O4-photo, (7) H2O2-photo and (8) TA-photo at the conditions of [CuFe2O4] = 0.2 g L−1, [H2O2] = 0.02 mol L−1, [TA] = 1.0 mmol L−1, light ir-
radiation, temperature 298 K and initial pH ∼ 5.0 (a). Effect of added scavenger (benzoquinone (b) or isopropyl alcohol (c)) on the degradation of MB in TA-H2O2-
CuFe2O4-photo system. Changes of fluorescent intensity of the solution with reaction time in the systems of (1) CuFe2O4-photo, (2) H2O2-CuFe2O4-photo, (3) TA-
H2O2-CuFe2O4, (4) TA-CuFe2O4-photo, (5) TA-H2O2-photo and (6) TA-H2O2-CuFe2O4-photo (d).

3.3. Analysis of active species in TA-H2O2-CuFe2O4-photo system of MB. As illustrated in Fig. 2c, the degradation rate of MB decreased
from 92.1% to 11.3% in 120 min when the addition of IPA increased
As we known, Fenton and Fenton-like process, regardless of from 0 to 6.0 mL. The result indicated that hydroxyl radical was major
homogeneous or heterogeneous, possibly generated active species (i.e. responsible oxidant in the degradation process. Therefore, it was
superoxide anions, hydroxyl radicals), which possess strong oxidizing meaningful to study the dynamic change of the amount of %OH in de-
ability for target molecule [10,17]. Some authors already noticed that gradation process by reacting with coumarin. In different systems, the
molecular oxygen played an indispensable role in Fenton and Fenton- fluorescent spectra of sample solutions at excitation wavelength of
like process [14,17]. But molecular oxygen is not active enough for 346 nm were displayed in Fig. S2 (Supporting Information). The re-
organic compound oxidation at ambient condition because of spin re- lationship between the fluorescent intensity values at emission wave-
strictions [14]. Molecular oxygen is activated only when it accepts one length of 456 nm and degradation time (t) was shown in Fig. 2d. In
electron to form the superoxide anions and subsequently the organic detail, the fluorescent intensity hardly changed in CuFe2O4-photo
contaminant could be decomposed by active oxygen species generated. system within 120 min, indicating that the amounts of hydroxyl radical
Benzoquinone has the potential to trap %O2− by an electron transfer maintained a low value and relatively stable state (Curve 1 in Fig. 2d).
mechanism that BQ reacts with superoxide anions and generates mo- The fluorescent intensity of liquid samples sustainably increased in
lecular oxygen. Hence, BQ was selected to trap superoxide anions in the H2O2-CuFe2O4-photo and TA-H2O2-CuFe2O4 systems (Curve 2, 3 in
experimental process and the results were shown in Fig. 2b. Obviously, Fig. 2d). For TA-CuFe2O4-photo system, the fluorescent intensity at-
the degradation rate of MB reduced slightly within 120 min with the tained firstly the peak value, then gradually decreased to minimum and
addition of BQ changing from 0 to 100 mg. Therefore, superoxide an- kept constant (Curve 4 in Fig. 2d). In TA-H2O2-photo system, the
ions are not the main active species in TA-H2O2-CuFe2O4-photo system. fluorescent intensity showed a similar changing trend (Curve 5 in
To deeply understand whether %OH participated in the removal of Fig. 2d). For TA-H2O2-CuFe2O4-photo system, the fluorescent intensity
MB in TA-H2O2-CuFe2O4-photo system, isopropyl alcohol (IPA) was fluctuated within 120 min (Curve 6 in Fig. 2d). In addition, the fluor-
chosen as a model radical scavenger to study the degradation behavior escent intensity of TA-H2O2-CuFe2O4-photo system was about two

78
X. Guo, et al. Materials Science & Engineering B 245 (2019) 75–84

times more than other systems, proving that much of hydroxyl radical different ligands. The relationship between ln(c0/c) and time (t) was
was generated by adding TA into H2O2-CuFe2O4-photo system. fitted in Fig. S3 (Supporting Information) and the apparent rate con-
To clearly explain the result, the formation of hydroxyl radicals was stant k and degree of fitting with different ligands were listed in
analyzed as follows. In general, though light irradiation was added, the Table 1. On the one hand, the effect of the main chain length of organic
metal ions on the surface of CuFe2O4 hardly reacted with free H2O2 to acids was studied by selecting different ligands (Curve 2, 3, 4, 5, 6 and 7
generate hydroxyl radical according to Eq. (1). By comparing the in Fig. 3a). Obviously, the addition of oxalic acid, malonic acid and
fluorescent intensity, it was easily seen that introducing H2O2 into succinic acid could enhance the degradation of MB. And the apparent
CuFe2O4-photo system could smoothly increase the amount of hydroxyl rate constant k increased with the following order: azelaic acid <
radicals. As illustrated in Eq. (2), ferric ions (^Fe3+) (^ represented octanedioic acid < adipic acid < blank < succinic acid < malonic
the element on the surface of solid catalysts) interact with adsorbed acid < oxalic acid. The MB degradation rate decreased with the in-
hydrogen peroxide ((H2O2)s) to form peroxide hydroxyl radicals (% crease of the main chain length of organic acids. On the other hand, the
OOH) on the surface of catalyst. Generated ferrous ions (^Fe2+) in Eq. effect of hydroxyl number in main chain was also explored (curve 1, 4,
(3) sequentially react with (H2O2)s to produce hydroxyl radicals, which 8 in Fig. 3a). With 2,3-dihydroxy succinic acid as reference, the MB
greatly increased the amount of hydroxyl radicals in MB degradation degradation rate decreased because of reduced hydroxyl number in
[25]. Almost at the same time, %OOH react with hydrogen peroxide in main chain of succinic acid. Generally speaking, increasing the main
aqueous solution to produce hydroxyl radicals. Similarly, Cu2+ can also chain length of organic acids and decreasing the amount of hydroxyl
undergo Fenton-like reaction according to Eqs. (4) and (5) [37]. Com- groups could reduce the acid dissociation constants (Ka) of organic li-
paring with Fe2+/Fe3+ redox pair, Cu+/Cu2+ redox pair has faster gands aqueous solution. But the Ka of oxalic acid is considerably larger
reaction rate. Hence, higher activity of CuFe2O4 was attributed to the than that of TA, which is not consistent with the MB degradation in
presence of Cu+/Cu2+ redox pair on its surface. ligand-H2O2-CuFe2O4-photo system. Therefore, the MB degradation
hv was irrelevant to the content of hydrogen ions produced by ionization
≡ Mn+ + H2 O2 → ≡ M(n−1) + + ·OH + H+ (1) of organic ligands and was relevant to the ionized ligands in H2O2-
CuFe2O4-photo system with different ligands.
≡ Fe3 + + (H2 O2)s → ≡ Fe2 + + ·OOH + H+ (0.02M−1s−1 for Fe3 +) (2)
In the previous reports [25–30], the beneficial effect of organic
≡ Fe2 + + (H2 O2)s → ≡ Fe3 + + ·OH + OH− (76M−1s−1 for Fe2 +) (3) acids on the catalytic ability of catalysts was ascribed to the interaction
between a small number of organic acids and the catalyst dispersions. A
≡ Cu2 + + (H2 O2)s → ≡ Cu+ + ·OOH + H+ (1.15 × 10−6M−1s−1 for Cu2 +) charge-transfer-complex (CTC) pathway was formed by the catalyst
(4) dispersions and organic acids, which were sensitive under light irra-
≡ Cu+ + (H2 O2)s → ≡ Cu2 + + ·OH + OH− (1 × 10 4M−1s−1 for Cu+) (5) diation and induced the photo-oxidation of organic acids. A higher
energy of the highest occupied molecular orbital (EHOMO) of organic
≡ Mn+ − L+ (H2 O2)s → ≡ M(n−1) + − L+ ·OOH + H+ ( L= ligand) (6) acids is favorable to electron transfer within catalyst-organic acid
complexes [31,32,40,41]. Therefore, it is necessary to judge whether
≡ M(n−1) + − L+ (H2 O2)s → ≡ Mn + − L+ ·OH + OH− (7) TA-H2O2-CuFe2O4-photo system conformed to CTC pathway. As shown
H2 O2 + hv → 2·OH (8) in Table 1, the calculated EHOMO increased in the order of oxalic
acid < malonic acid < D/L-hydroxybutanedioic acid < tartaric
H2 O2 + ·OH → ·OOH + H2 O (9) acid < succinic acid < adipic acid < adipic acid < octanedioic
acid < azelaic acid. This showed that EHOMO of organic acids increased
·OOH + H2 O2 → ·OH + H2 O+ O2 (10)
with the increase of the main chain length and had no obvious reg-
Particularly, dicarboxylic acids and α-hydroxyl carboxylic acid may ularity with the change of hydroxyl number in main chain. It is also
strongly bind on the catalyst surface via ester linkages or a bidentate found from Fig. 3b that there is a proximate linear correlation between
coordinate bond [38]. After adding TA, the organic ligand chelated the apparent rate constant k of MB degradation and EHOMO of organic
with the metal ions (^Mn+) (M represented Fe or Cu) on the surface of acids. The obtained regression equation is k = -0.12–0.61EHOMO
CuFe2O4 (^Mn+-L) to absorb the visible region of the solar spectrum (R2 = 0.88). The result indicated a lower EHOMO of organic acids was
and generate active radical attacking to the target molecules depending favorable to the oxidative degradation of MB, which ran counter to the
on Eqs. (6) and (7). In addition, ^Mn+-L complexes photolysis can mechanism of CTC pathway. In order to further verify the conclusion,
produce higher quantum yield than M(OH)(n−1)+ ions, which is a ad- additional experiments were carried out. The same amount of CuFe2O4
vantage of organic complexes of Fe3+ and Cu2+ in the photocatalytic was dipped about 4 h in MB solution, TA solution and the mixed solu-
application. Comparing TA-H2O2-CuFe2O4 system with TA-H2O2- tion of MB and TA, respectively. FT-IR spectra of the above samples
CuFe2O4-photo system (Curve 3, 6 in Fig. 2d), the degradation rate of were displayed in Fig. S4 (Supporting Information), which demon-
photo-Fenton-like reaction was higher than that of Fenton-like reaction. strated that some substances were adsorbed on the surface of the cat-
The possible reason is that light irradiation not only greatly increases alyst under three different situations. Later, the interaction between
the transition of Mn+–M(n−1)+, but also generates more hydroxyl ra- organic acids and CuFe2O4 surface was examined by UV–Vis absor-
dicals on exposure to light as shown in Eqs. (8)–(10). bance spectroscopy. As shown in Fig. S5 (Supporting Information), the
In the MB degradation process, the OH radical plays a significant organic substances on the surface of catalyst can sensitize the surface of
role. For TA-H2O2-CuFe2O4-photo system, the formed hydroxyl radicals catalyst, but the effect is very weak. Lower MB degradation rate in TA-
were from different reaction processes and went through different CuFe2O4-photo system (Curve 4 in Fig. 2a) supports the conclusion
changes. Besides, both TA and MB can also react with hydroxyl radicals from another point of view. Consequently, the CTC pathway is not
in the process [39]. The consumption and generation of hydroxyl ra- major process in TA-H2O2-CuFe2O4-photo system.
dicals are in an unbalanced state. Therefore, the concentration of hy-
droxyl radicals presents a fluctuating tendency. 3.5. Analysis of stability in heterogeneous and homogeneous system

3.4. Effect of chemical structure of TA in degradation system As shown in Fig. S6 (Supporting Information), XPS spectra of
CuFe2O4 were recorded before and after the degradation of MB in dif-
In order to analyze the role of TA, the influence of the structure of ferent systems. Peaks of 2p orbit for iron and copper were clearly seen
ligands (small molecular organic acids) was also researched. Fig. 3a at 938.5 ± 0.5 eV and 719.9 ± 0.5 eV, respectively. The position of
showed the MB degradation in H2O2-CuFe2O4-photo system with peaks moved to the lower binding energy in different system comparing

79
X. Guo, et al. Materials Science & Engineering B 245 (2019) 75–84

Fig. 3. Degradation of MB in the systems of ligand-H2O2-CuFe2O4-photo under different ligand: (1) tartaric acid, (2) oxalic acid, (3) malonic acid, (4) succinic acid,
(5) adipic acid, (6) octanedioic acid, (7) azelaic acid and (8) D/L-Hydroxybutanedioic acid at the conditions of [CuFe2O4] = 0.2 g L−1, [H2O2] = 0.02 mol L−1,
[ligand] = 1.0 mmol L−1, light irradiation, temperature 298 K and initial pH ∼ 5.0 (a). Relationship between the apparent rate constant k and EHOMO of the organic
acids, Numbers 1 to 8 represent tartaric acid, oxalic acid, malonic acid, succinic acid, adipic acid, octanedioic acid, azelaic acid and D/L-Hydroxybutanedioic acid (b).

Table 1
Comparisons between EHOMO of small molecular organic acids (SOAs) and apparent rate constant k in photo-Fenton-like reaction within 120 min in the presence of
1.0 mmol L−1 SOAs at initial pH ∼ 5.0.
Properties of SOAs k (min−1) R2

Name Structure EHOMO (a.u)

Oxalic acid O O −0.2516 0.0333 0.95

C C
HO OH
Malonic acid O H O −0.2415 0.0275 0.95
C C C
HO H OH
Succinic acid O H H O −0.2258 0.0215 0.95
C C C C
HO H H OH
Adipic acid O O −0.2198 0.0130 0.94
C CH2 C
4
HO OH
Octanedioic acid O O −0.2119 0.0102 0.95
C CH2 C
6
HO OH
Azelaic acid O O −0.2062 0.0074 0.93
C CH2 C
7
HO OH
D/L-Hydroxybutanedioic acid H OH −0.2390 0.0241 0.94
O O
C C C C
HO H H OH
Tartaric acid O H OH O −0.2350 0.0352 0.97
C C C C
HO OHH OH

with the fresh CuFe2O4, which indicated the obvious transformation of the surface of the catalyst after 120 min.
Cu2+–Cu+ and Fe3+–Fe2+ after reaction. Similarly, the peaks of C 1s Table 2 showed the changes of element content for fresh and used
(285.1 ± 0.5 eV) and O 1s (532.9 ± 0.5 eV) for the used CuFe2O4 CuFe2O4. For the fresh catalyst, the mass percent of Cu, Fe and O were
slightly shift lower binding energy value. Because MB or its by-products 8.95%, 27.46% and 63.59%, respectively. After using in H2O2-CuFe2O4-
may be adsorbed on the surface of CuFe2O4, the peak of N 1s photo system, the mass percent of Cu, Fe and O were 3.07%, 9.78% and
(402.2 ± 0.2 eV) was observed. But the peak of N 1s was not found in 87.15%, respectively, which indicated the maximum leaching ions
XPS spectra of fresh catalyst. As shown in Fig. S7 (Supporting comparing with the fresh CuFe2O4 and the CuFe2O4 in other systems.
Information), FT-IR analysis of samples before and after using in dif- When tartaric acid was introduced into H2O2-CuFe2O4-photo system,
ferent system indicated that some organic substances were adsorbed on the percent content of Cu, Fe and O in the catalyst was 4.12%, 12.42%

80
X. Guo, et al. Materials Science & Engineering B 245 (2019) 75–84

Table 2 of ^Fe3+ and ^Cu2+ on the surface of fresh catalyst hardly happen.
The content and chemical state for CuFe2O4 before and after using in following After reacting in CuFe2O4-photo system, the percent content of ^Fe3+
system: (1) fresh CuFe2O4, (2) CuFe2O4-photo, (3) H2O2-CuFe2O4-photo, (4) and ^Cu2+ reduced to 80.53% and 86.18%, respectively. Simulta-
H2O2-TA-CuFe2O4-photo and (5) H2O2-TA-CuFe2O4. neously, the percent content of Fe2+ and Cu+ increased to 19.47% and
system Content Chemical State 13.82%, respectively. With the addition of hydrogen peroxide, the re-
duction reaction of ^Cu2+/^Cu+ almost no changed, but the percent
Cu (%) Fe (%) O (%) Cu2+ (%) Cu+ (%) Fe3+ (%) Fe2+ (%) content of ^Fe2+ increased from 19.47% to 25.65%, showing that
1 8.95 27.46 63.59 99.99 0.01 97.58 2.42 H2O2 could improve the transformation of ^Fe3+ to ^Fe2+ in the
2 6.46 20.90 72.65 86.18 13.82 80.53 19.47 surface of CuFe2O4. This is because the adsorbed hydrogen peroxide can
3 3.07 9.78 87.15 86.67 13.33 74.35 25.65 easily react with iron ions to promote the generation of ferrous ions.
4 4.12 12.42 83.46 82.69 17.31 84.33 15.67 When TA was introduced into H2O2-CuFe2O4-photo system, XPS spectra
5 6.31 22.88 70.80 70.51 19.49 87.52 12.48
clearly displayed that the percent content of ^Cu+ greatly enhanced in
catalytic process. On the contrary, the transformations of ^Fe3+ to
and 83.46%, respectively. The result indicated that tartaric acid had an ^Fe2+ dramatically decreased. The phenomena could be explained by
obvious inhibiting effect for the metal ions leaching from the surface of the mechanism that TA reacted with copper ions on the catalyst surface
CuFe2O4. In addition, supposed the mass percent of Cu and Fe was to form copper complex (^Cu2+-L) and increase the transformation of
standard for the fresh CuFe2O4, the leaching ratio of iron and copper ^Cu2+ to ^Cu+ in the presence of hydrogen peroxide. Compared with
were approximatively identical in the same system. This is due to oc- iron ions (^Fe3+), copper complexes (^Cu2+-L) is more likely to react
tahedral sites containing the same amounts of copper and iron exposed with hydrogen peroxide in the competitive process, leading to the de-
on the surface of catalyst and decided the catalytic activity of catalyst. crease of amount of ^Fe2+ in the presence of tartaric acid. However,
Fig. 4a showed XPS spectra of Fe 2p core level regions. All the Fe 2p without light irradiation, the transformation of ^Cu2+ to ^Cu+ was
spectra display a main peak at around 710.4 ± 0.5 eV and a shakeup improved again because of little leaching of metal ions and easily re-
satellite at around 718.0 ± 0.5 eV, suggesting the presence of ^Fe3+ acting with hydrogen peroxide.
cations. XPS spectra of Fe 2p regions can be fitted into four contribu- In general, most heterogeneous Fenton-like catalysts easy leach
tions. The high-resolution spectra of the peaks at 710.2 and 711.5 eV some metal ions into the aqueous phase and build homogeneous
are indicative of the presence of ^Fe2+ and ^Fe3+. Fig. 4b gave XPS Fenton-like reaction. This situation raises a question that the active sites
spectra of Cu 2p core level regions. XPS spectra of Cu 2p3/2 regions can of Fenton-like reaction is the metal ions on the solid phase or the
be also fitted into four contributions in the range from 929 to 946 eV. leaching metal ion species dissolved in the aqueous phase. First, XPS
The main peak at binding energy of 933.6 eV is assigned to ^Cu2+ on analysis results indicate that CuFe2O4 particles could leach metal ions
octahedral sites. And the satellite peaks at 940.8 and 943.2 eV are ba- into liquid phase. The dissolution of CuFe2O4 carries out according to
sically similar to that of dominated ^Cu2+ oxide species [42,43]. For Eqs. (11)–(15) [44]. Solid copper ferrite dissolves to produce CuFeO2
the fresh catalyst, it is clear that the transformation of ^Fe3+ to ^Fe2+ (delafossite), Fe2O3 and a part of metal ions in acidic conditions. Then
and ^Cu2+ to ^Cu+ and the reduction of ^Fe3+ and ^Cu2+ on the CuFeO2 and Fe2O3 dissolve to form Cu2+ and Fe3+ in acidic conditions
surface of fresh catalyst hardly happen. The peaks of Fe 2p3/2 [45,46]. Subsequently, dissolved iron ions undergo Fenton’s and Haber-
(711.5 eV) and Cu 2p3/2 (933.9 eV) for the used CuFe2O4 slightly Weiss reactions as Eqs. (16) and (17). Copper ions would also undergo
transferred to lower binding energy values, which indicated the obvious the similar reactions as Eqs. (18) and (19). Thus, for heterogeneous TA-
transformation of ^Fe3+ to ^Fe2+ and ^Cu2+ to ^Cu+ after reac- H2O2-CuFe2O4-photo system, it is very necessary to study its possible
tion [10]. homogeneous Fenton-like process.
The change of chemical state of each element in CuFe2O4 before and
4H+ (aq) + CuFe2 O4 (s) ↔ Fe3 + (aq) + CuFeO2 (s) + 4H2 O(aq) + 3e− (aq)
after using in catalytic process was also listed in Table 2. The trans-
formation of ^Fe3+ to ^Fe2+ and ^Cu2+ to ^Cu+ and the reduction (11)

Fig. 4. XPS spectra of Fe 2p core level regions (a) and Cu 2p core level regions (b) for CuFe2O4 before and after using in different systems: (1) fresh CuFe2O4, (2)
CuFe2O4-photo, (3) H2O2-CuFe2O4-photo, (4) H2O2-TA- CuFe2O4-photo and (5) H2O2-TA-CuFe2O4.

81
X. Guo, et al. Materials Science & Engineering B 245 (2019) 75–84

Fig. 5. The contents of Fe (a) and Cu (b) in degradation solution under the systems of (1) CuFe2O4-photo, (2) H2O2-CuFe2O4-photo, (3) TA-H2O2-CuFe2O4, (4) TA-
CuFe2O4-photo and (5) TA-H2O2-CuFe2O4-photo at the conditions of [CuFe2O4] = 0.2 g L−1, [H2O2] = 0.02 mol L−1, [TA] = 1.0 mmol L−1, light irradiation, tem-
perature 298 K and initial pH ∼ 5.0.

2H+ (aq) + CuFe2 O4 (s) ↔ Cu2 + (aq) + Fe2 O3 (s) + H2 O(aq) (12) two carboxylic acid groups or the oxygen atoms of hydroxyl groups.
Fe3+ coordinates strongly with TA to form a monomeric complex Fe
4H+ (aq) + CuFeO2 (s) ↔ Cu+ (aq) + Fe3 + (aq) + 2H2 O(aq) (13) (L2−)+ in acidic conditions. Similarly, Cu2+ also interacted with TA to
form stable metal ions-TA complexes. These behaviors effectively pre-
Fe2 O3 (s) ↔ Fe2 + (aq) + 4e− (aq) + 1.5O2 (aq) (14)
vented the formation of precipitation. Besides, literature [25] reported
Fe2 O3 (s) + 6H+ (aq) ↔ 2Fe3 + (aq) + 3H2 O(aq) (15) that the formation of metal ions-TA complexes was a key factor for
improving degradation rate. Hydroxyl radicals (%OH) and other oxi-
Fe2 + (aq) + H2 O2 (aq) ↔ Fe3 + (aq) + ·OH(aq) + OH− (aq) (16) dizing radicals could be generated through a ligand-to-metal-charge-
transfer (LMCT) pathway, these active species were responsible for the
Fe3 + (aq) + ·OOH(aq) ↔ Fe2 + (aq) + O2 (g) + H+ (aq) (17) degradation efficiency of MB under light irradiation, which is consistent
with our experimental results.
Cu+ (aq) + H2 O2 (aq) ↔ Cu2 + (aq) + ·OH(aq) + OH− (aq) (18)
It was reported that Fe3+ can strongly catalyze the degradation of
Cu2 + (aq) + ·OOH(aq) ↔ Cu+ (aq) + O2 (g) + H+ (aq) (19) MO by adding citric acid under weakly acidic conditions because of the
formation of Fe3+-citrate complexes, which is of high catalytic activity
Fig. 5 shows the change of content of metal ions in the process. to produce hydroxyl radicals through a photo-Fenton-like reaction
Clearly, the contents of iron and copper were 1.4 mg L−1 and system [49,50]. Similarly, Fe3+ and Cu2+ reacted with TA to form
3.0 mg L−1 in TA-H2O2-CuFe2O4-photo system after reacting 120 min, complexes and reached a lower oxidation state Fe2+(TA) and Cu+(TA)
respectively (Curve 5 in Fig. 5a and b). The contents of iron and copper under light irradiation according to Eqs. (20) and (21). The Fe2+/Cu+-
were 0.24 mg L−1 and 0.36 mg L−1 in the absence of TA, respectively TA complexes produced Fe2+/Cu+ and TA radicals according to Eq.
(Curve 2 in Fig. 5a and b). Similar phenomena could be found in (22) [51]. In addition, the presence of molecular oxygen and hydrogen
CuFe2O4-photo system with (or without) the addition of TA (Curve 1, 4 peroxide also accelerated the transformation of chemical state of metal
in Fig. 5a and b). In order to confirm the existence of homogeneous ions according to Eqs. (23)–(25) [52].
Fenton-like reaction, additional experiments were carried out. First, to
prepare the following solutions: 3.0 mg L−1 copper solution, 3.0 mg L−1 Fe3 +/Cu2 + + TA → Fe3 + (TA)/Cu2 + (TA) (20)
iron solution, mixed solution of 1.5 mg L−1 copper and 1.5 mg L−1 iron
in 100 mL 50 mg L−1 methylene blue solution; then, to degrade target hv
Fe3 + (TA)/Cu2 + (TA) → Fe 2 + (TA)·/Cu+ (TA)· (21)
molecules under the conditions of Fenton-like, photo-Fenton-like and
TA-photo-Fenton-like. The result was shown in Fig. S8 (Supporting
Information), indicating copper ions could build Fenton-like reaction, Fe 2 + (TA)·/Cu+ (TA)·→Fe 2 +/Cu+ + (TA)· (22)
but oxidation efficiency is slightly lower than iron ions. Light irradia-
tion and the addition of TA improve the degradation efficiency of MB. Fe 2 + (TA)·/Cu+ (TA)·+O2 → Fe3 + (TA)/ Cu+ (TA) + O2−· (23)
The change of content of metal ions in the above-mentioned process
was depicted in Fig. S9 (Supporting Information). Clearly, the content HOO·/O2- · + Fe2 + / Cu + → Fe3 + /Cu2 + + H2 O2 (24)
of metal ions showed a decreasing trend and the content of iron reduced
much. Comparing with other systems, the addition of TA enhanced the H2 O2 + Fe 2 +/Cu+ → Fe3 + /Cu2 + + ·OH + OH− (25)
content of metal ions in degradation solution.
In detail, the hydrolysis constant Kh of iron ions is much greater Therefore, the dissolved metal ions reacted with TA to form pho-
than that of copper ions, which leads to easy precipitation in aqueous tosensitive metal ions-TA complexes which could improve the de-
solution. In a aqueous solution of TA, there are (CHOH)2(COOH)2, gradation of MB [53]. The effect of ligand on the catalytic ability of
(CHOH)2-C2O4H− and (CHOH)2-C2O42− and their relative proportions iron-bearing powders was mainly attributed to the formed soluble iron
depend upon the pH [47,48]. TA interacts with metal ions through its complexes that accelerated the regeneration of Fe2+.

82
X. Guo, et al. Materials Science & Engineering B 245 (2019) 75–84

Fig. 6. The schematic diagrams of metal-ligand-electron-transfer pathway in TA-H2O2-CuFe2O4 -photo system for MB degradation.

3.6. A mechanism on TA enhanced oxidative degradation of MB absorbed organic substances. Thus, the degradation efficiency of MB is
inferior in the absence of H2O2. In the presence of H2O2, light irradia-
On the basis of the above discussions, a possible mechanism on TA tion played an important role for MB degradation. Moreover, it is also
enhanced degradation of MB is proposed as illustrated in Fig. 6. The reported that the complexes of M(n−1)+/Mn+ with ligand decreased the
decomposition of H2O2 involved in the initial adsorption of H2O2 to M(n−1)+/Mn+ redox potential and enhanced the thermodynamic
CuFe2O4 surface binding metal ions (^Mn+) that located in octahedral driving force for the Fenton-like reaction [25]. In short, leaching metal
sites of catalyst surface. The process would produce ^M(n−1)+ and % ions promoted the formation of homogeneous catalysis system in the
O2−/%OOH radicals. The generated ^M(n−1)+ could react with ad- presence of H2O2 and improved the degradation rate of MB. The ad-
sorbed H2O2 to produce %OH radicals, whereas the %OOH radicals dition of TA inhibits the metal ions leaching from CuFe2O4 surface and
might further reduce ^Mn+ to ^M(n−1)+. As for the slow reaction enhances homogeneous photo-Fenton-like system by preventing the
between ^Mn+ and H2O2, %OOH radicals might be mainly consumed in hydrolysis of metal ions.
the effective reduction of ^Mn+. Besides, homogeneous Fenton-like
reaction via dissolved metal ions was also implemented in the presence
4. Conclusions
of H2O2. When TA was introduced into H2O2-CuFe2O4-photo system, it
could be easily adsorbed on the surface ^Mn+ sites, which may affect
In this study, CuFe2O4 particles were obtained by sol-gel process,
the catalytic activity of CuFe2O4 in the following possible ways: (1) to
and the effects of TA on MB degradation were investigated by using
prevent the dissolution of metal ions from the surface of CuFe2O4; (2) to
CuFe2O4 particles as heterogeneous catalyst and H2O2 as oxidant. It was
enhance homogeneous photo-Fenton-like reactions in solution; (3) to
found that CuFe2O4 particles had weak photocatalytic ability in the
attract water-soluble methylene blue depending on electrostatic at-
oxidation of MB. When introducing 0.02 mol L−1 H2O2 into CuFe2O4-
traction; (4) to sensitize the surface of CuFe2O4; (5) to change the redox
photo system, the degradation rate of MB was 52.0% within 80 min.
properties of the metal ions [25].
After adding 1.0 mmol L−1 TA into H2O2-CuFe2O4-photo system, the
The adsorbed TA prevents hydrogen ions from interacting with the
MB degradation rate changed from 52.0% to 92.1% within 80 min. In
metal ions of CuFe2O4 surface and slows down the dissolution rate of
the MB degradation process, %OH contributed more significantly, and
metal ions from the catalyst surface. Hydrolysis of the dissolved metal
the addition of TA could promote the generation of hydroxyl radicals.
ions coming from catalyst surface is a key factor to affect the catalytic
The enhanced degradation efficiency of MB was related to special
effect of homogeneous Fenton-like reactions. The adsorbed TA would
structure of TA and the dissolved metal ions coming from the catalyst
dissolve into the degradation solution again and react with the dis-
surface. A possible TA enhanced mechanism for the MB degradation is
solved metal ions to form stable metal ions-tartaric acid complexes.
proposed on the basis of the experimental results. This study suggests
This prevents hydrolysis of metal ions in acidic condition and inhibits
that TA-H2O2-CuFe2O4-photo system is capable of removing MB from
the generation of iron mud, resulting in an enhancing catalytic activity.
the contaminated water and provides valuable information on the po-
Because TA contains a high density of functional groups, it could im-
tential application of this process.
prove the dissolution of iron and copper by forming soluble metal ions
complexes, thus the generated homogeneous Fenton reactions increase
the production of hydroxyl radicals and other oxidizing radicals Acknowledgements
through a LMCT pathway. In addition, metal ions-TA complexes could
increase the reduction rate of ^Mn+ and Mn+ with %O2−/%OOH ra- The work was financially supported by the Fundamental Research
dicals. Due to electrostatic interactions, the carboxyl groups of TA Funds for the Universities of Gansu Province and Key Laboratory of
would effectively attract the molecule of water-soluble methylene blue. Polymer Materials of Gansu Province.
Simultaneously, according to UV–Vis absorbance spectroscopy of sam-
ples in additional experiment, the adsorbed TA enhanced light ab-
Appendix A. Supplementary data
sorption by producing photoelectron in the degradation process.
Because of its lower band gap, CuFe2O4 would lead to greater re-
Supplementary data to this article can be found online at https://
combination of e-/h+ pairs and weaker photosensitization effect of the
doi.org/10.1016/j.mseb.2019.05.015.

83
X. Guo, et al. Materials Science & Engineering B 245 (2019) 75–84

References [27] E. Rodríguez, G. Fernández, B. Ledesma, P. Alvarez, F. Beltrán, Photocatalytic de-

gradation of organics in water in the presence of iron oxides: influence of carboxylic
acids, Appl. Catal., B 92 (2009) 240–249.
[1] S. Hisaindee, M.A. Meetani, M.A. Rauf, Application of LC-MS to the analysis of [28] F.B. Li, X.Z. Li, X.M. Li, T.X. Liu, J. Dong, Heterogeneous photodegradation of bi-
advanced oxidation process (AOP) degradation of dye products and reaction me- sphenol A with iron oxides and oxalate in aqueous solution, J. Colloid Interface Sci.
chanisms, Trends Anal. Chem. 49 (2013) 31–44. 311 (2007) 481–490.
[2] R.R. Jitta, R. Gundeboina, N.K. Veldurthi, R. Guje, V. Muga, Defect pyrochlore [29] F.B. Li, X.Z. Li, C.S. Liu, X.M. Li, T.X. Liu, Effect of oxalate on photodegradation of
oxides: as photocatalyst materials for environmental and energy applications-a re- bisphenol A at the interface of different Iron oxides, Ind. Eng. Chem. Res. 46 (2007)
view, J. Chem. Technol. Biotechnol. 90 (2015) 1937–1948. 781–787.
[3] S. Gligorovski, R. Strekowski, S. Barbati, D. Vione, Environmental implications of [30] F.B. Li, J. Chen, C.S. Liu, J. Dong, T.X. Liu, Effect of iron oxides and carboxylic acids
hydroxyl radicals (•OH), Chem. Rev. 115 (2015) 54–62. on photochemical degradation of bisphenol A, Biol. Fertil. Soils 42 (2006) 409–417.
[4] M. Asgher, H.N. Bhatti, Removal of reactive blue 19 and reactive blue 49 textile [31] N. Wang, L.H. Zhu, K.J. Deng, Y.B. She, Y.M. Yu, H.Q. Tang, Visible light photo-
dyes by citrus waste biomass from aqueous solution: equilibrium and kinetic study, catalytic reduction of Cr(VI) on TiO2 in situ modified with small molecular weight
Can. J. Chem. Eng. 90 (2012) 412–419. organic acids, Appl. Catal., B 95 (2010) 400–407.
[5] N. Nasuha, B.H. Hameed, A.T.M. Din, Rejected tea as a potential low-cost adsorbent [32] N. Wang, L.H. Zhu, Y.P. Huang, Y.B. She, Y.M. Yu, H.Q. Tang, Drastically enhanced
for the removal of methylene blue, J. Hazard. Mater. 175 (2010) 126–132. visible-light photocatalytic degradation of colorless aromatic pollutants over TiO2
[6] F. Jamal, T. Qidwai, D. Singh, P.K. Pandey, Biocatalytic activity of immobilized via a charge-transfer-complex path: a correlation between chemical structure and
pointed gourd (Trichosanthes dioica) peroxidase–concanavalin a complex on calcium degradation rate of the pollutants, J. Catal. 266 (2009) 199–206.
alginate pectin gel, J. Mol. Catal. B: Enzym. 74 (2012) 125–131. [33] Y. Baba, T. Yatagai, T. Harada, Y. Kawase, Hydroxyl radical generation in the
[7] C.A. Basha, J. Sendhil, K.V. Selvakumar, P.K.A. Muniswaran, W.L. Chang, photo-Fenton process: effects of carboxylic acids on iron redox cycling, Chem. Eng.
Electrochemical degradation of textile dyeing industry effluent in batch and flow J. 277 (2015) 229–241.
reactor systems, Desalination 285 (2012) 188–197. [34] L. Li, X. Wang, L. Yan, G. Wen, S.L. Zhang, Synthesis, photocatalytic and electro-
[8] E. Tsantaki, T. Velegraki, A. Katsaounis, D. Mantzavinos, Anodic oxidation of textile catalytic activities of wormlike GdFeO3 nanoparticles by a glycol-assisted sol-gel
dyehouse effluents on boron-doped diamond electrode, J. Hazard. Mater. 207–208 process, Ind. Eng. Chem. Res. 52 (2013) 9130–9136.
(2011) 91–96. [35] T. Maezono, M. Tokumura, M. Sekine, Y. Kawase, Hydroxyl radical concentration
[9] L. Hua, H. Ma, L. Zhang, Degradation process analysis of the azo dyes by catalytic profile in photo-Fenton oxidation process: generation and consumption of hydroxyl
wet air oxidation with catalyst CuO/γ-Al2O3, Chemosphere 90 (2013) 143–149. radicals during the discoloration of azo-dye Orange II, Chemosphere 82 (2011)
[10] Y.B. Wang, H.Y. Zhao, M.F. Li, J.Q. Fan, G.H. Zhao, Magnetic ordered mesoporous 1422–1430.
copper ferrite as a heterogeneous Fenton catalyst for the degradation of imidaclo- [36] X.F. Xue, K. Hanna, C. Despas, F. Wu, N. Deng, Effect of chelating agent on the
prid, Appl. Catal., B 147 (2014) 534–545. oxidation rate of PCP in the magnetite/H2O2 system at neutral pH, J. Mol. Catal. A:
[11] Y. Zhang, J. Deng, C. He, S. Huang, S. Tian, Y. Xiong, Application of Fe2V4O13 as a Chem 311 (2009) 29–35.
new multi-metal heterogeneous Fenton-like catalyst for the degradation of organic [37] L.L. Zhang, Y.L. Nie, C. Hu, J.H. Qu, Enhanced Fenton degradation of Rhodamine B
pollutants, Environ. Technol. 31 (2010) 145–154. over nanoscaled Cu-doped LaTiO3 perovskite, Appl. Catal., B 125 (2012) 418–424.
[12] L. Xu, J. Wang, Fenton-like degradation of 2,4-dichlorophenol using Fe3O4 mag- [38] K.D. Donbson, A.J. Mcquillan, In situ infrared spectroscopic analysis of the ad-
netic nanoparticles, Appl. Catal., B 123–124 (2012) 117–126. sorption of aliphatic carboxylic acids to TiO2, ZrO2, Al2O3, and Ta2O5 from aqueous
[13] L. Hou, Q. Zhang, F. Jérǒme, D. Duprez, H. Zhang, S. Royer, Shape-controlled na- solutions, Spectrochim. Acta, Part A 55 (1999) 1395–1405.
nostructured magnetite-type materials as highly efficient Fenton catalysts, Appl. [39] K. Hanna, S. Chiron, M.A. Oturan, Coupling enhanced water solubilization with
Catal., B 144 (2014) 739–749. cyclodextrin to indirect electrochemical treatment for pentachlorophenol con-
[14] Y. Lei, C.S. Chen, Y.J. Tu, Y.H. Huang, H. Zhang, Heterogeneous degradation of taminated soil remediation, Water Res. 39 (2005) 2763–2773.
organic pollutants by persulfate activated by CuO-Fe3O4: mechanism, stability, and [40] A.G. Agrios, K.A. Gray, E. Weitz, Photocatalytic transformation of 2,4,5-tri-
effects of pH and bicarbonate ions, Environ. Sci. Technol. 49 (2015) 6838–6845. chlorophenol on TiO2 under sub-band-gap illumination, Langmuir 19 (2003)
[15] W. Luo, L. Zhu, N. Wang, H. Tang, M. Cao, Y. She, Efficient removal of organic 1402–1409.
pollutants with magnetic nanoscaled BiFeO3 as a reusable heterogeneous Fenton- [41] A.G. Agrios, K.A. Gray, E. Weitz, Narrow-band irradiation of a homologous series of
like catalyst, Environ. Sci. Technol. 44 (2010) 1786–1791. chlorophenols on TiO2: charge-transfer complex formation and reactivity, Langmuir
[16] L. Xu, J. Wang, Magnetic nanoscaled Fe3O4/CeO2 composite as an efficient Fenton- 20 (2004) 5911–5917.
like heterogeneous catalyst for degradation of 4-chlorophenol, Environ. Sci. [42] J.H. Deng, J.Y. Jiang, Y.Y. Zhang, X.P. Lin, C.M. Du, Y. Xiong, FeVO4 as a highly
Technol. 46 (2012) 10145–10153. active heterogeneous Fenton-like catalyst towards the degradation of Orange II,
[17] X. Liu, S. An, W. Shi, Q. Yang, L. Zhang, Microwave-induced catalytic oxidation of Appl. Catal., B 84 (2008) 468–473.
malachite green under magnetic Cu-ferrites: new insight into the degradation me- [43] F. Ji, C.L. Li, J.H. Zhang, L. Deng, Heterogeneous photo-Fenton decolorization of
chanism and pathway, J. Mol. Catal. A: Chem 395 (2014) 243–250. methylene blue over LiFe(WO4)2 catalyst, J. Hazard. Mater. 186 (2011) 1979–1984.
[18] A.N. Soon, B.H. Hameed, Degradation of Acid Blue 29 in visible light radiation [44] C.C. Kuan, S.Y. Chang, S.L.M. Schroeder, Fenton-like oxidation of 4-chlorophenol:
using iron modified mesoporous silica as heterogeneous photo-Fenton catalyst, App. homogeneous or heterogeneous, Ind. Eng. Chem. Res. 54 (2015) 8122–8129.
Catal., A 450 (2013) 96–105. [45] X.Y. Zhang, Y.B. Ding, H.Q. Tang, X.Y. Han, L.H. Zhu, N. Wang, Degradation of
[19] G.A. Bagheri, V. Ashayeri, Photocatalytic efficiency of CuFe2O4 by supporting on bisphenol A by hydrogen peroxide activated with CuFeO2 microparticles as a het-
clinoptilolite in the decolorization of acid red 206 aqueous solutions, Iran. J. Catal. erogeneous Fenton-like catalyst: efficiency, stability and mechanism, Chem. Eng. J.
2 (2012) 135–140. 236 (2014) 251–262.
[20] Y. Shen, Y.B. Wu, H.F. Xu, J. Fu, X.Y. Li, Q.D. Zhao, Y. Hou, Facile preparation of [46] Y. Wang, Y.K. Sun, W.G. Li, W.D. Tian, A. Irini, High performance of nanoscaled
sphere-like copper ferrite nanostructures and their enhanced visible-light-induced Fe2O3 catalyzing UV-Fenton under neutral condition with a low stoichiometry of
photocatalytic conversion of benzene, Mater. Res. Bull. 48 (2013) 4216–4222. H2O2: kinetic study and mechanism, Chem. Eng. J. 267 (2015) 1–8.
[21] A. Nasiri, M. Nasiri, S. Nouhi, S. Khodadadian, Nanocrystalline copper ferrite: [47] J.K. Sircar, K.L. Yadava, Ionophoretic studies in copper (II)-, nickel (II)-, cobalt (II)-,
synthesis of different shapes through a new method and its photocatalyst applica- uranyl (II)-, and thorium (IV)-tartaric acid systems, J. Chem. Eng. Data 27 (1982)
tion, J. Mater. Sci. Mater. Electron. (2016), https://doi.org/10.1007/s10854-016- 231–233.
5810-9. [48] J.C. Danilewicz, Role of tartaric and malic acids in wine oxidation, J. Agric. Food
[22] R. Sharma, V. Kumar, S. Bansal, S. Singhala, Assortment of magnetic nanospinels for Chem. 62 (2014) 5149–5155.
activation of distinct inorganic oxidants in photo-Fenton’s process, J. Mol. Catal. A: [49] N.S. Deng, F. Wu, F. Luo, M. Xiao, Ferric-citrate induced photodegradation of dyes
Chem. 402 (2015) 53–63. in aqueous solutions, Chemosphere 36 (1998) 3101–3112.
[23] C.K. Cheng, Z.Y. Kong, M.R. Khan, Photocatalytic-Fenton degradation of glycerol [50] J. Guo, Y.Y. Du, Y.Q. Lan, J.D. Mao, Photodegradation mechanism and kinetics of
solution over visible light-responsive CuFe2O4, Water Air Soil Pollut. 226 (2015) methyl orange catalyzed by Fe (III) and citric acid, J. Hazard. Mater. 186 (2011)
1–12. 2083–2088.
[24] A. Flores, K. Nesprias, P. Vitale, J. Tasca, A. Lavat, N. Eyler, A.A. Caňizo, [51] S.Q. Wei, L. Liu, H.B. Li, J. Shi, Y. Liu, Z.C. Shao, Photodecolourization of orange II
Heterogeneous photocatalytic discoloration/degradation of Rhodamine B with with iron corrosion products and oxalic acid in aqueous solution, Appl. Catal., A
H2O2 and spinel copper ferrite magnetic nanoparticles, Aust. J. Chem. 67 (2014) 417–418 (2012) 253–258.
609–614. [52] J. Guo, X. Chen, Y. Shi, Y. Lan, C. Qin, Rapid photodegradation of methyl orange
[25] N. Wang, L. Zhu, M. Lei, Y. She, M. Cao, H. Tang, Ligand-induced drastic en- (MO) assisted with Cu (II) and tartaric acid, PLoS One 10 (2015) 1–12.
hancement of catalytic activity of nano-BiFeO3 for oxidative degradation of bi- [53] D.R. Manenti, P.A. Soares, A.N. Módenes, F.R. Espinoza-Quiǹones,
sphenol A, ACS Catal. 1 (2011) 1193–1202. R.A.R. Boaventura, R. Bergamasco, V.J.P. Vilar, Insights into solar photo-Fenton
[26] S.Q. Liu, L.R. Feng, N. Xu, Z.G. Chen, X.M. Wang, Magnetic nickel ferrite as a process using iron (III)-organic ligand complexes applied to real textile wastewater
heterogeneous photo-Fenton catalyst for the degradation of Rhodamine B in the treatment, Chem. Eng. J. 266 (2015) 203–212.
presence of oxalic acid, Chem. Eng. J. 203 (2012) 432–439.

84