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RECENT ADVANCES IN THE APPLICATION OF ELECTRO-FENTON AND PHOTOELECTRO-FENTON PROCESS FOR REMOVAL OF SYNTHETIC DYES IN WASTEWATER TREATMENT
J.M. Peralta-Hernndez,1,* Carlos A. Martnez-Huitle,2 Jorge L. Guzmn-Mar1 and A. Hernndez-Ramrez1
Facultad de Ciencias Qumicas CELAES Universidad Autnoma de Nuevo Len San Nicols de los Garza, NL. C.P. 66400. Mxico 2 CCET Departamento de Qumica Universidade Federal do Rio Grande do Norte Lagoa Nova - CEP 59.072-970, RN, Brazil
1

Key Words: Azo dyes, AOPs, electro-Fenton, oxygen reduction, photoelectro-Fenton ABSTRACT In recent years, an increasing need and interest to preserve environment has arisen, mainly by eliminating chemical compounds produced by many human activities, such as textile industry discharges. In this context, electrochemical advance oxidation processes capable of destroying several organic compounds in wastewater are being developed. The basis for these methods is the production of free hydroxyl radicals (OH) as a primary oxidant. In these systems, the OH is generated by water discharge over the anode of a high oxygen overvoltage material, and by the electro-Fenton type reaction. This last creates a mixture of iron ions (Fe2+) and hydrogen peroxide (H2O2), electrochemically generated at the cathode by oxygen reduction via two electrons in acidic media. UVA irradiation improves the regeneration of Fe2+ ions, enhancing the OH production, generating the photolectro-Fenton process. The main objective of this paper is to summarize and analyze the results of a narrow selection of published researches about the increasing progress on these two emerging methods, which are very promising technologies for the removal of synthetic dyes in wastewater treatment in the near future. INTRODUCTION Water is an essential resource for all species on this planet. Its usage is not limited to the human consumption, on the contrary, it is used in the development of a great diversity of productive activities such as agriculture, cattle raising, tourism, health, and diverse industrial activities. The demand of drinking water in the world continues to increase, since 1900 the demand has grown six-fold. An important aspect to take into account is population growth, about 12,000 million inhabitants by the middle of the 21st [1]. In order to provide better living conditions for mankind, constant technological developments in several productive fields around the world are expanding, which in turn generate large amounts of new waste with final destination commonly to water bodies. In most cases, these wastes are difficult to degrade by
*Corresponding author Email: jperalta@fcq.uanl.mx

conventional treatment methods. Azo dyes compounds constitute about one half of the dyes that are used in the textile industry and consequently represent a serious environmental problem [2]. Azo dyes cause mainly aesthetic and visual concern, which modifies the natural water body colour and consequently affects aquatic life cycle balance [3]. The chemical structure of this group of compounds is characterized by the presence of the azo group (N=N) as chromophore, associated with aromatic systems and other groups, such as OH, SO3H, among others [4]. Regarding the composition of the dyes, the azo group can be present one or more times in the molecular structure of the compound. Chemical structure of some members of the azo dyes is presented in Table 1. To avoid the azo dye accumulation in the aquatic systems, new methods are being developed to promote

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Table 1. Some azo dyes use in the textile industry

Name Acidic Yellow 36
NH

Structure
SO3H N=N

Acidic Orange 5
NH N=N
COOH HO3S N=N HO N N

SO3H

Acidic Yellow 23

SO3H

Acidic Viloet 7
CH3CONH N=N HO3S

OH

NHCOCH 3

SO3H

Acidic Orange 10
N=N HO3S

HO

SO3H

Reactive Blue 109

SO3H N=N

NH2

OH N=N

SO3H

HO3S SO3H

SO3H N NH N Cl N

Cl

the destruction of these compounds from natural water bodies and wastewater. Biological and physicochemical methods have been used with a low efficiency [59]; the most promising alternative are the so called advanced oxidation processes (AOPs), which are based on the free hydroxyl radicals production (OH) as a strong oxidant for organic compounds [10]. AOPS AOPs are defined as a process that involves the use of the free OH in aqueous solution, produced by different means such as chemical, photochemical or electrochemical reactions, to promote the oxidation of organic compounds present in wastewater [11]. This species, is the strongest oxidant (E = 2.8 V vs. NHE) after Fluorine (E = 3.0 V vs. NHE), which is capable of mineralizing some of substrates (reducing it to CO2, H2O and inorganic ions) [12].

The most important AOP is the Fentons system, which consisting in the reaction of H2O2 and Fe2+ in an acidic solution to produce free OH, (Eq. 1) [11].
Fe 2+ + H 2 O 2 Fe 3+ + OH + OH

(1)

Hydrogen peroxide is a green chemical that leaves O2 and water as by-products, although it can be hazardous due to its comburent character. It is used as disinfectant in medical and industrial applications and as an oxidant in product synthesis and wastewater treatment. However, the direct remediation of wastewaters with H2O2 is limited by its low oxidation power, since it can only attack reduced sulphur compounds, cyanides, chloride ion and certain organics such as aldehydes, formic acid and some nitro-organic and sulpho-organic compounds [13]. For this reason, H2O2 is commonly activated in acidic effluents with Fe2+ ion as catalyst (Fentons reagent) to yield homogenous OH as a strong oxidant of organics - a tra-

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259

ditional Fenton method. On the other hand, the catalytic efficiency of Fe2+ ions is improved when the system is illuminated with UVA light ( = 320-400 nm). This approach, commonly known as the photo-Fenton or photoassisted Fenton process, is based on the fact that the ferric ions Fe3+ generated as a by-product of the reaction between Fe2+ and H2O2 (Eq. 1), are photochemically transformed back into ferrous ions as shown by Eq. 2 [11]:
Fe 3+ + H 2 O h Fe 2 + + H + + OH

+
Oxidation H2O Oxidation Fe3+
OH OH OH OH

H2O

hv
Fe2+

H2O2 2e-

(2)

O2

O2

The main disadvantage of these chemical techniques is the fast consumption of the Fentons reagent, causing partial mineralization of organic pollutants. This problem can be solved by emerging electrochemical AOPs such as electro-Fenton (EF) and photoelectroFenton (PEF) method ELECTROCHEMICAL AOPS In recent times, the electrochemical processes have generated great interest, because they offer effective means to solve environmental problems related to several industrial processes [14,15], such as wastewater contamination by synthetic dyes. The main advantage of these methods is their environmental compatibility. Their main reagent is the electron, which is an inherently clean species whose energy can be carefully controlled by means of an applied potential, thus avoiding parallel reactions. In traditional chemistry, secondary reactions often result in by-products which sometimes increase removal costs [11,16,17]. The principal electrochemical methods are the following: a) Direct electrochemical oxidation, where the organic compound degradation can occur directly over the anode trough the adsorbed OH, or chemisorbed active oxygen in the anode surface (often called anodic oxidation, direct oxidation or electrochemical incineration), by means of the following equation [14,15, 1820]:
M + H 2 O M ( OH) + H + + e

Fig. 1. Generation of free hydroxyl radicals (OH) by means of EF and PEF processes.

dium catalyzed with iron ions to produce the hydroxyl radical species. The relevant electrochemical reaction, described by Eq. 4, corresponds to the 2e- reduction of dissolved oxygen (O2) under slightly acidic conditions [27]:

O 2 + 2H + + 2e H 2 O 2

(4)

It results from a complex system involving the formation of the superoxide anionic species O and the hy2 droperoxide radical OH2. This selective reaction takes place on the surface of a variety of carbonaceous materials such as graphite, carbon cloth, reticulated vitreous carbon, oxygen diffusion cathodes [28] following the Damjanovic mechanism, as evidenced by rotating ring disk experiments [27]. In the EF process, the presence of iron ions, which are usually introduced to the system as FeSO4, accelerates the production of OH radicals [29,30-32], by Eq. 5:
Fe 2+ + H 2 O 2 Fe (OH) 2+ + OH

(5)

(3)

This catalytic reaction is propagated from Fe2+ regeneration, which mainly takes place by the reduction of Fe3+ ions with the H2O2.
2. PEF process

and b) indirect electrochemical oxidation, where the organic compounds are treated in the bulk solution by means of species generated in the electrode [12], such as OH, Cl2, hypochlorite, peroxodisulfate and ozone, as the most common electrochemically generated oxidants [14]. EF and PEF are the most promising methods for wastewater treatment, involving mainly the generation of free hydroxyl radicals.
1. EF process

When the EF process (5) is irradiated by means of UVA light, this can accelerate the degradation of organic compounds by two principal pathways: a) the photolysis of Fe3+ -oxidation products complexes, and b) improving the Fe2+ regeneration from the photoreduction of Fe3+ ions according to the equation [15,21,24,33,34]:
Fe(OH)2+ + h Fe 2+ + OH

The EF process involves the in-situ electrochemical generation of H2O2 [15,21-26] as previously mentioned, which readily decomposes in aqueous me-

(6)

Figure 1 summarizes the coupled EF and PEF processes.

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DEGRADATION OF SYNTHETIC DYES BY EF AND PEF PROCESSES

(a)
N N N (CH3) N(CH3)22

As a consequence of the ability of EF and PEF processes to produce OH radical with consequent oxidation of organic compounds, these processes have been efficiently used in wastewater treatment. In this perspective, many papers have reported the degradation of a great number of azo dyes by reaction with electrogenerated OH species, as recently reviewed in detail by Martnez-Huitle and Brillas [15]. However, we will take into consideration in this contribution the most relevant studies conducted in the last years referring to electrochemical methods for the removal of azo dyes. The study for the treatment of synthetic dyes started in 1998, when Brillas et al. [35], tested the aniline mineralization by means of AOPs, among them EF and PEF using Pt sheet as anode and O2-diffusion carbon-PTFE cathode. They carried the degradation of the model organic pollutant in the acidic medium (pH 3) under photocatalytic (photocatalysis with TiO2) and electrochemical (anodic oxidation, EF and PEF) conditions. In their study, they evaluated the efficiency for mineralization of 1000 mg L-1 of aniline in each system, measuring the total organic carbon (TOC) decay. Their results showed that the rate of TOC decay by anodic oxidation was very slow, while it was considerably increased when they added Fe2+ in the system (by EF) due to the homogeneous free hydroxyl radical generation (Eq. 5). However, the application of UVA radiation accelerated the rate by photodecomposition of intermediates (by PEF), allowing a 92% of TOC removal after 6 h of treatment at 100 mA of current intensity. By reverse-phase high performance liquid chromatography technique, they determined some organic intermediates of aniline oxidation, such as: benzoquinone, nitrobenzene, maleic acid and fumaric acid for EF assays, and phenol, hydroquinone, benzoquinone and 1,2,4-benzenetriol for PEF experiments. Guivarch et al. [36] in 2003 investigated the degradation of the three azo dyes: Azobenzene, p-Methyl Red and Methyl Orange, (Fig. 2), respectively, in aqueous solution (pH 2-3) at room temperature by EF under simultaneous reduction of oxygen and ferrous ions on the carbon felt electrode. They reported the EF process was efficient for azo dye degradation, with > 90% decolorization and > 80% chemical oxygen demand (COD) decay. In this study, they identified the principal by-products (hydroquinone, 1-4-benzoquinone, pyrocatechol, 1,3,5-trihydroxynitrobencene, p-nitrophenol), and proposed the degradation pathway, as seen in Fig. 2d. The kinetics of decolourisation and degradation was found to follow the pseudo-first order. Pseudo-first order rate constant (min-1) and half life time (min) values were Azobenzene (0.11, 6.5), Methyl Orange (0.25, 2.8) and p-Methyl Red (0.42,

(b)
C O

HO

N(CH33)2 N (CH)2

(c)
O HO S O

(d)

O2N N N
OH .OH O2

HO

NO2

OH .OH O2

.OH/O22 OH/O -NO3OH O2 -2H+

OH .OH/O2

O2N

O2N HO

OH

HO

OH

OH

.OH/O2 OH/O
2

-NO3-

HOOC .OH/O2 2 HOOC

COOH a n d / o r

H2O + CO2

COOH

Fig. 2. Chemical structures of azo dyes treated by means of EF process: (a) Azobenzene, (b) p-Methyl Red and (c) Methyl Orange and d) Proposed reaction pathway for mineralization azobenzene by EF process.

Wang et al. [37] in 2005 compared the use of two different cathodes: active carbon fiber (ACF) felt and graphite, in order to improve the H2O2 generation through oxygen reduction, on EF treatment of Acid Red 14 (AR14). They estimated the color and TOC removal for AR14 using ACF cathode about 70%. They reported the greater H2O2 production was achieved on ACF felt cathode (600 M at 0.50 A after 60 min of electrolysis). The ability for mineralization was considerably different; for the ACF, after 360 min of electrolysis it was 70%, comparably higher than the 40% obtained by the graphite cathode. On the other hand, Peralta-Hernndez et al. [38] in 2006 reported the design and construction of an annular tubular reactor for electrochemical and photoelectrochemical experiments: EF, PEF and photoelec-

1.4).

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261

(a)

120 100 TOC (mg dm-3) 80 60 40 20 0 0 2 4 6 8 Specific charge (Ah dm-3) 10 (a)

(b)

120 [oxalic acid] (mg dm-3) 100 80 60 40 20 0 60 (c) [oxalic acid] (mg dm-3) 50 40 30 20 10 0 0 120 240 360 480 Time (min) 600 720 840 (b)

Fig. 3. (a) Chemical structure of Direct Yellow 52 and (b) Diagram of the experimental photoelectrochemical batch-recycle reactor.

trocatalysis for the oxidation of Direct Yellow-52 (DY-52) (Fig. 3), in acidic media (pH 2). A carbon cloth cathode, a TiO2 nanocrystalline anode and a UVA lamp at 365 nm (Fig. 3) were used. Applying a cathode potential of -700 mV vs Hg/HgSO4, they showed the possibility of electrogenerating 50 ppm of H2O2, after 50 min of electrolysis, with a current efficiency close to 32%. To perform EF and PEF processes two different iron concentrations (0.25 and 0.50 mM) were added to oxidize 20 mg L-1 of DY-52. TOC and colour removals were evaluated to observe the DY-52 degradation. PEF process was more effective than EF process, achieving 74 and 31% of colour decay, respectively. With the usage of 0.50 mM of Fe2+ ions, TOC abatements were 57 and 66%, respectively. The influence of the anode on the oxidation power of EF in undivided cell has been performed by Flox et al. [39] who studied the treatment of 100 cm3 of acidic aqueous solutions containing up to 900 mg L-1 of indigo carmine with Pt/O2 and boron doped diamond (BDD)/O2 electrodes (Fig. 4). The use of EF with a Pt anode at 100 mA provided only 90% TOC removal of 100 mg L-1 of the dye with 1.0 mM Fe2+ at pH 3.0 in 9 h. In contrast, when the BDD electrode was used as anode, the same solution achieved 91% TOC reduction after the same treatment time and complete decontamination with the release of NH4+ after 13 h. Similar degradation rate was found in the pH range 2.0-4.0. A faster degradation was observed with increasing current density and initial dye content. Indigo Carmine followed a pseudo-zero-order decay and disappeared at the same time as its identified aromatic derivatives isatin 5-sulphonic acid, indigo and isatin. Kinetic results corroborated the destruction of the dye and its aromatic intermediates mainly by OH

Fig. 4. (a) Dependence of TOC on specific charge and evolution of the concentration of (b) oxalic and (c) oxamic acids during the mineralization of 100 cm3 of 220 mg L-1 Indigo Carmine solutions in 0.05 M Na2SO4 of pH 3.0 at 100 mA and 35 C using the Pt/O2 or BDD/O2 cell with electrodes of 3 cm2 area. ( ) EF with Pt and 1.0 mM Fe2+; ( ) PEF with Pt and 1.0 mM Fe2+; ( ) EF with BDD and 1.0 mM Fe2+ and ( ) PEF with Pt and 1.0 mM Fe2+ + 0.25 mM Cu2+. Adapted from ref. [39].

formed in the bulk from Fentons reaction (Fig. 5). Figures 4b and 4c show a slow reaction of some species with heterogeneous Pt(OH) and homogeneous OH generated in the Pt/O2 cell, whereas they are quickly destroyed with heterogeneous BDD(OH) in the BDD/cell up to total removal. The greater ability of BDD(OH) than Pt(OH) to oxidize final Fe3+ complexes explains the feasibility of achieving faster mineralization in EF with a BDD anode.

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H N -O3S O
.OH OH

O SO3N H

indigo carmine

.OH OH

-2SO42H N O

H N O -O3S O isatin 5-sulfonic acid

N O H

indigo
.

OH OH H

OH OH

N O O isatin
.OH

-SO42-

COOH COOH Fe3+ Fe3+ -oxalato complexes hv -Fe2+ . BDD(OH) CO2 Cu2+ Cu2+ -oxalato complexes
.OH

COOH CONH2 Fe3+ Fe3+ -oxalato complexes . BDD( OH) CO2 NH4+ NO3Cu2+ Cu2+ -oxalato complexes
.

OH

OH OH

Fig. 5. General reaction sequence proposed by Flox et al. [39] for the mineralization of indigo carmine in acid medium by EF and PEF degradations with a Pt or BDD anode under the catalytic action of Fe2+, Cu2+ and UVA light.

Anotai et al. [40] studied the kinetics of aniline degradation at pH 2 by means of Fenton and EF processes. They reported that aniline removal efficiency was improved in the presence of electrical current (EF system) as compared to the typical Fenton reaction. Electro-Fenton process was found to be superior to ordinary Fenton process with the current impacts of 1.2 to 3.1 for removal efficiency and 1.2 to 5.8 for degradation rate, depending on initial Fe2+ concentration. The authors suggested that aniline degradation may occur via pathways of nitrobenzene, phenol and benzoquinonimine decomposition. Another important parameter, the reactivity of homogeneous OH in EF, has been clarified by Oturan et al. [41-43] using an undivided tank reactor equipped with a small (4.5-5.5 cm2) Pt sheet or cylinder as anode, centered in the cell, and surrounded by a larger 60 cm2 carbon-felt cathode. A strong inhibition for the oxidation process of 500 cm3 of air-saturated 1.0 mM Direct Orange 61 solutions in 0.05 M Na2SO4 of pH 3 was found with raising Fe2+ concentration in

the above mentioned two-electrode cell, attributed to the concomitant loss in OH [42]. Increasing the Fe2+ concentration to 0.1. 0.2 and 0.5 mM decreased the TOC removal of 96, 63 and 55%, respectively, after 8 h of electrolysis at 100 mA. The fastest decay for Direct Orange 61 was achieved with 0.1 mM Fe2+ as catalyst for a 0.05 mM dye solution operating at 60 mA. Under these optimum conditions, the solution was decolorized in 50 min while the compound reacts with homogeneous OH following a pseudo-first-order kinetics. The production of a similar small, but very effective OH concentration has been corroborated by this group from the decay kinetics of Yellow Drimaren, Congo Red and Methylene Blue under comparable conditions in a three-electrode cell [41]. Lahkimi et al. [41] demonstrated that these azo dyes can be degraded efficiently by EF process. They reported that when applied 10,000 C of electrical charge an 89% of mineralization was achieved. In this context, they suggested that the EF process as an ecologically friendly water treatment, because the reagents to produce free hydroxyl radicals are electrochemically generated; considering a low value of energetic consumption of 2 10-3 kWh L-1 to treat 1 mM of synthetic dye. Oturan et al. has demonstrated that the EF treatment of 250 cm3 of 0.5 mM Malachite Green with 0.2 mM Fe3+ or Fe2+ as catalyst at pH 3.0 yielded total color removal in 22 min and overall mineralization in 9 h using the two-electrode cell at 200 mA [43]. The decay of this dye followed pseudo first-order kinetics and its k1 value increased from 1.7 10-3 to 4.0 10-3 s-1, when the current varied from 60 to 200 mA, as expected by the faster production of OH from Fentons reaction due to the enhancement of H2O2 electrogeneration. Hammami et al. [44] studied the degradation of Acidic Orange 7 (AO7) by means of EF process using Pt and BDD anode to produce the free hydroxyl radicals, and the working electrode was a carbon felt piece of 60 cm2. In this study, the degradation process for AO7 followed a pseudo-first order kinetic with a similar value that was independent of the anode used. The absolute rate constant of AO7 oxidation reaction was estimated as (1.10 0.04) 1010 M-1 s-1. TOC mineralization results showed a better performance of EF using a BDD anode in accordance with the its properties [45]. AO7 degradation by EF process occurs via aromatic intermediates which are oxidized to aliphatic carboxylic acids before the mineralization. The decolorization and destruction of Orange II azo dye in aqueous acidic medium (pH 3) was performed by Peralta-Hernndez et al. [46]. They compared several AOPs (photolysis, EF and PEF) for wastewater treatment containing Orange II azo dye (50 mg L-1 in 7 g L-1 Na2SO4) in a recycle-batch reactor. By producing OH radicals as an active oxidant, all of these processes removed the colour from the solution in a short time, but the PEF with the lower iron concentra-

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tion showed the best performance. It not only decolorized the solution in less than 5 min, but it also destroyed 80% of TOC in 60 min of treatment with a concentration of 0.2 mM Fe2+. While TOC removal efficiency was 63% for the EF system and only 31% for photolysis. Kusvuran et al. [47] compared the degradation of Reactive Black 5 (from 20 to 100 mg L-1) using UV/TiO2, wet-air oxidation (WAO), EF and PEF processes. Mineralization efficiency was observed as WAO > UV/TiO2 > PEF > EF. Among all applied AOPs processes, WAO process was found to be the most effective method for the decolorization and partial mineralization of Reactive Black 5 with 77% of TOC removal at 250 C after 180 min treatment. UV/TiO2 achieved 71% of TOC removal. Even though EF was effective on decolorization, only 20% of mineralization was obtained and 29% was achieved by PEF. They also studied the decolorization of Reactive Red 120 azo dye (from 20 to 100 mg L-1) in aqueous solution of pH 3 with the same AOPs [48]. WAO process again was found to be the most efficient technique for decolorization of Reactive Red 120 azo dye. On the other hand, 52% of TOC removal was achieved by UV/TiO2 process. Even with UV light, mineralization by EF process was observed to be very low. Xie and Li studied the oxidation of azo dye Orange-G (4.5 g L-1 in a solution of Na2SO4 as supporting electrolyte) by photocatalysis, EF, PEF and photoelectrocatalysis [49]. The total degradation ratio of the Orange-G was 83% after 60 min. The TOC value decreased to 3.3 mg L-1 after 300 min. Nevertheless, the working electrode (Reticulated Vitreous Carbon) was controlled at -0.71 V as cathode potential and the total iron ion concentration was 16.7 mg L-1, total degradation ratio reached 57% after 60 min. The TOC value decreased from 12.6 to 7.2 mg L-1 after 300 min.
CONCLUSIONS

ACKNOWLEDGMENTS

Financial support from PROMEP/103.5/08/3125 is gratefully acknowledged. JMPH also acknowledges Dr. Eduardo Gmez Maqueo and Dr. Laura Hinojosa Reyes for their help in the manuscript revision.
REFERENCES

This paper summarizes the most relevant investigations carried out on EF and PEF processes for oxidation of synthetic dye compounds. The efficiency of these electrochemical processes seems to strongly dependent on parameters such as iron concentration, level of hydrogen peroxide, synthetic dye concentration, pH, current intensity and electrode material. Another important contribution in this topic is the reactor design and construction to couple both oxidation processes with the objective to improve the efficiency of organic compound degradation. Additionally, many researchers have focused on the mechanism pathway reaction, establishing the most important routes that synthetic dyes follow under oxidation treatment. Finally, the EF and PEF processes have been shown to be viable alternative techniques for treatment of industrial wastewater containing synthetic dyes due to their efficiency and low operational cost.

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Discussions of this paper may appear in the discussion section of a future issue. All discussions should be submitted to the Editor-in-Chief within six months of publication. Manuscript Received: January 28, 2009 Revision Received: March 31, 2009 and Accepted: April 4, 2009