Mechanism of Dye Degradation during Electrochemical Treatment

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Mechanism of Dye Degradation during Electrochemical Treatment Seema Singh, Vimal Chandra Srivastava, and Indra Deo Mall J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/jp405289f • Publication Date (Web): 05 Jul 2013 Downloaded from http://pubs.acs.org on July 9, 2013

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The Journal of Physical Chemistry

Mechanism of Dye Degradation during Electrochemical Treatment Seema Singh, Vimal Chandra Srivastava*, Indra Deo Mall Department of Chemical Engineering, Indian Institute of Technology, Roorkee, Roorkee– 247667, Uttarakhand, India. Corresponding Author *Phone: +91–1332–285889; Fax: +91–1332–276535; E–mail: [email protected], [email protected] Abstract Studies were conducted for understanding the electrochemical (EC) degradation mechanism of a triphenylmethane dye namely basic green 4 (BG) commonly known as malachite green with aluminum electrode. At the optimum condition (current density=117.64 A m–2, initial dye concentration=125 mg L–1, pH=6.5, electrode gap=1 cm and NaCl concentration=1.5 g L–1), over 85% of BG degradation was observed within 50 min of treatment. UV–visible and Fourier transform infrared (FTIR) spectroscopy, high performance liquid chromatography (HPLC), gas chromatography–mass spectroscopy (GCMS) and high resolution mass spectroscopy (HRMS) analysis showed that the degradation occurred via the cleavage of conjugated structure and N–de–methylation. The intermediates products identified included hydroxymethylated intermediates during the N–de–methylation of the dye;

and

N,

N,

N’,

N’–tetramethyl–4,4'–diaminobenzophenone;

4,

4'–bis–

aminobenzophenone and N–methyl–para–aminophenol after cleavage of conjugated triphenylmethane ring. Zeta potential study indicated hard acid-base interaction between aluminum ions and hydroxide generated in situ during EC treatment process and –N(CH3)2 group of dye molecule. Generation of active species such as hydrogen peroxide, ozone and chlorinated oxidizing compounds was observed during the EC treatment process; and that the BG degradation occurred via •OH radical attack. Keywords: Dye degradation schemes; aluminum electrode; malachite green; zeta potential; N–de–methylation; triphenylmethane dye. 1 ACS Paragon Plus Environment


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INTRODUCTION Triphenylmethane is a colorless crystalline hydrocarbon containing three benzene rings with the formula (C6H5)3CH. Many synthetic dyes, also called as triarylmethane dyes are derived from triphenylmethane by substitution. Basic green 4 (BG), bromocresol green, methyl violet, crystal violet, victoria blue, brilliant green, ethyl violet, pararosaniline, cresol red, bromopheno1blue, methyl green, basic fuchsin, etc. are some of the most commonly used

triphenylmethane

or

triarylmethane

dyes.

BG

[(N,N,N',N'–tetramethyl–

4,4'diaminotriphenylcarbenium a tri–phenyl methane] dye is most widely used as a direct dye for coloring jute, wool, silk in textile industry.1–4 Other industries such as leather and paper also use this dye.5 Triphenylmethane dyes such as BG on photo–oxidation via nascent oxygen break into various N–de–alkylated primary and secondary amine derivatives which are similar to carcinogenic aromatic amines.6 BG is sometimes used as antiseptic and fungicide in aquatic and fisheries industry where it easily gets reduced to lipophilic leucomalachite green (LMG) which can induce renal and hepatic tumours in mice and reproductive abnormalities in fishes.7,8 Hence, treatment of BG dye is essential before its discharge into water bodies.9,10 Various alternative techniques have been reported in literature for removal of BG dye from wastewater such as ozonation,11,12 photocatalyt,13 adsorption,14,15 coagulation– flocculation16,17 and biological treatment methods.18,19 Some of the above methods are not effective in removing color from dying wastewater. These methods also have some disadvantages like requirement of higher amount of chemicals, high operation cost and large amount of sludge generation. Electrochemical (EC) treatment methods effectively remove the dyes from wastewater and are easy to operate and cost effective.20-22 Very few studies are available in open literatures23–31 (Table S1 in supporting information) which try to elucidate mechanism of degradation of chemical structure of

2 ACS Paragon Plus Environment

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organic dye into smaller one during degradation processes. Most of these studies are, however, based on catalytic degradation, biological degradation and advance oxidation processes. In our previous study,32 mechanistic study of EC treatment of BG dye with aluminum electrodes was studied through zeta potential measurement, and the characterization of solid residues obtained by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy of X-rays (EDX) and thermogravimetric analysis (TGA) techniques. However, step-by-step EC mineralization mechanism was not reported and the schemes of degradation mechanism were not reported. On the basics of above considerations, step-by-step EC mineralization of BG was studied during EC treatment with aluminum electrode in the present study. Each step of degradation was determined by various spectroscopic and chromatographic methods. The intermediates were identified by mass spectroscopic techniques. Chemical oxygen demand (COD) and decolorization efficiencies were determined to understand step-by-step mineralization of BG. The degradation mechanism has been explained by different possible schemes. To the best of authors knowledge, this is the first study that elucidates the mineralization mechanism of a dye during EC treatment.

THEORETICAL BACKGROUND During EC treatment method, the various chemical reactions occur on anode and cathode. These reactions depend on the nature of anode material and chemical structure of dye molecules. The mechanism of EC degradation of BG involves mainly processes such as electrocoagulation, electro-oxidation, electro–floatation, etc. which may occur individually or simultaneously depending upon the operating conditions. In electrocoagulation, in–situ formation of coagulants occurs on anodic dissolution of electrode material. Simultaneous



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evolution of hydrogen takes place on the cathode which removes pollutant through flotation. Main anodic reactions are as follows: Al → Al3+ + 3 e–

(1)

(Eo(Al3+/Al)= –1.66 V versus SHE (pH acidic range) Al3+ + 3H2 O → Al(H2O)3(s) + 3 H+

(2)

nAl(H2O)3 (s) → Aln(H2O)3n

(3)

Main cathodic reactions are as follows: H2 O + 3 e– → 3/2 H2 + 3 OH–

(4)

Aluminum and hydroxyl ions are generated during electrode reaction in equation (1) and (3) to give different monomeric and polymeric species at low and higher pH, respectively.33 During EC treatment, oxidation of dye molecules takes place via the active species already present in the solution.34 Electrochemical advance oxidation processes (EAOPs) are used for destruction of dyes through oxidation by •OH radicals generated at the surface of metal anode at high oxygen over–voltage during H2O decomposition.35, 36 The electrolyte, the electrode potential, and structural abnormalities and/or transient intermediates all affect the mineralization process.37 The main reaction involved during the EC treatment are shown as follows: 2H2O → O2 + 4 H+ + 4 e–

(5)

2 Cl– → Cl2 + 2 e –

(6)

Cl2 + H2O → HOCl + HCl

(7)

HOCl + OH– → OCl– + H2O

(8)

O2 (g) + 2 H+ + 2 e– → H2O2

Eo (O2/ H2O2) =1.23 V

(9)

Molecular oxygen converts into active oxygen via cathodic reaction. 4 H2O + 2 O2 (aq) + 4e– → 2 H2O2 + 4 OH–


(10)

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Al+3 + 2 H2O2 → [monomeric/polymeric Al cationic species] + •OH + OH– (11) (•OH, Eo(•OH/ H2O)=2.80 V versus SHE Al(H2O) → Al(•OH) + H+ + e–

(12)

Ozone may also get produced if either anodic potential goes to 1.51 V or by the oxidation of evolved oxygen.38,39 4 H2O + 2 O2 → O3 + 2 H+ + 2 e –

(13)

At the time of electrolysis, a number of oxidants such as nascent oxygen, ozone, hydrogen peroxide, free chlorine and free radical such as •OH and •OCl may get produced.40 On the basis of above reactions, solution may contain cocktail of various oxidants. It is too difficult to find out the actual quantitative amount of each oxidant. Oxygen and ozone are weak oxidant, and it is presumed that hydrogen peroxide and •OH are main oxidants41-43 which are responsible for the degradation of dyes and other organic compounds.

EXPERIMENTAL SECTION Materials. BG (Malachite Green; N, N, N', N'–tetramethyl–4, 4'diaminotriphenylcarbenium) was purchased from Yogesh Dyestuff Product (P) Ltd. Company, India. Analytical grade dicholoromethane, sodium hydroxide and high performance liquid chromatograph (HPLC)– grade acetophenol were purchased from Merck, India. De–ionized water (Milli–Q water ion exchange system with resistivity of 1.8×107 Ω cm) was used throughout this study. Electrochemical Procedure. The thermostated (at 25 °C) cuboid shaped EC batch reactor made of plexiglass with dimension of 108 mm × 108 mm × 130 mm having working volume 1.5 L was used for EC experiments. Two aluminum (Al: 99.53%) electrodes, one anode and one cathode, each having dimensions of 10 cm×8.5 cm×0.15 cm with inter–electrode spacing of 1 cm were connected in parallel mode. The total submerged area of electrodes was 63.75 cm2. The electrodes were connected on direct current power supply (0–20V, 0–5A)



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equipment with galvanostatic or potentiostatic mode. Sample was filtered, and the filtrate was centrifuged at 1500 rpm through a millipore filter (pore size 0.22 nm) to separate the floc particles from the solution. Instruments and Analytic approach. Various instruments were used in present study for various purposes. HPLC (Shimadzu Technologies, Tokyo, Japan) separation was performed on a C–18 5 µm column, 150 mm × 4.6 mm internal diameter (ID) and separation was done by collecting the sample at 5 min difference of overall treatment. The mobile phase was prepared for liner gradient elution and the flow rate of mobile phase was set at 1.0 mL min–1. The gradient was set as follows: 60% acetonitrile in H2O (0.1% HCOOH) for 3.5 min followed by a 15 min linear gradient by 80% acetonitrile (0.1% HCOOH). FTIR analysis was performed using Thermo nicolet, Model Magna 760. Pellet (pressed–disk) technique was used for FTIR analysis over a spectral wave number range of 4000–400 cm–1 for determination of changes in functional groups left in the solution with time during the treatment. Similarly, spectral analysis was performed at wavelength of maximum absorbance, λmax=619 nm for BG dye, using a UV–visible spectrophotometer (HACH, DR 5000, USA). Variation in λmax was also determined in with an interval of 10 min during the treatment process. Zeta potential was measured using Malverian Instruments, Zetasizer Nano Series, UK. Chemical oxygen demand (COD) was measured using a digestion unit (DRB 200, HACH, USA) and UV–visible spectrophotometer. Molecular mass of intermediates formed during EC degradation was determined by gas chromatography–mass spectroscopy (GCMS) and high resolution mass spectroscopy (HRMS). GCMS analysis was performed on a Perkin– Elmer Auto system–XL gas chromatograph interfaced to a Turbo Mass selective mass detector in DB–5 fused silica capillary column (30 m×0.25 µm internal diameter) of 5% diphenyl/95% dimethyl–siloxane. The split–split less injector mode was used with 1 µL injector temperature (280oC), split flow 10 mL min–1. Helium was used as carrier gas with


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flow rate of 1 mL min–1. Mass spectra were obtained in m/z range of ≈50–500 at 70 eV. The temperatures corresponding to the inlet line and ion source were set at 240 and 280oC, respectively.

RESULTS AND DISCUSSION Effect of pH on Decolourization. EC experiment were performed in pH range of 3.5–8.5 at current density (j)=117.64 A m–2 and initial dye concentration (Co)=125 mg L–1. COD and decolorization efficiencies were found to be dependent upon initial pH (pHo) and treatment time (Figure 1a, 1b). More than 99% decolorization efficiency was observed at pH 8.5 in 10 min, at pH 7.5 in 15 min, at pH 6.5 in 25 min and at pH 5.5 in 35 min (Figure 1b). Thus, higher pH caused faster decolorization. Decolorization mechanism of dye depends on its cationic/anionic nature. BG, an acrylic cationic dye, contains basic auxochrome group –N (CH3)2 which is attached with highly conjugated poly aromatic ring. Because of this type of structure, it has maximum absorbance at higher λ i.e. at λmax=619 nm. Change in pH of the solution increases/decreases the H+ or OH– ions concentration. In acidic pH range, –N+(CH3)2 and H+ interaction gets enhanced, while in the alkaline pH range, OH– ions interact with cationic ring and convert it into stable leuco form which has a λ

max=325

nm (Figure 1c). The decrease in

λmax value at higher pH is because of the loss of conjugation, and it increases the decolorization efficiency of dye (Figure 1b). In EC treatment, zeta potential helps in determining the type of effective charge on colloidal particles present in the solution at different pH. It helps in optimising the pH on the basis of isoelectric point.

32

High Al3+ concentrations can inhibit the electric double layer

around the colloidal particle; hence promote the dye removal.44 Figure 1d shows the variation of zeta potential with pH. It may be seen that the negative value of zeta potential (at any time)



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decreases with an increase in pH in acidic range 3.5 to 6.5. For pH>6.5, zeta potential increases with an increase in pH. At pH ≈6.5, interaction of hard acid (Al3+, Al(OH)2+, Al(OH)2+ and Al(OH)3) and hard base (–N(CH3)2) of dye removes maximum amount of dye as shown in Figure 1a. Therefore, the zeta potential of colloids remaining in the solution is least negative. Also at pH>6.5, generation of Al(OH)4– ions increases the zeta potential as well as decreases the COD removal efficiency. The mineralization of BG is regulated by electron donor acceptor mechanism and adsorption onto Al(OH)3(s).32,45,46 At higher pH, higher hydroxyl ion concentration increases the negative value of zeta potential, causing increase the electrostatic force of repulsion between the hard bases (–N(CH3)2 and OH–). pH was found to vary marginally (maximum variation of 1.3 units) with time during the EC treatment. Final pH for solutions having pHo≈8.5, 7.5, 6.5 and 5.5 was found to be 8.9 after 10 min, 8.5 after 15 min, 7.6 after 25 min and 6.8 after 35 min, respectively (Figure 1e). This may be due to the release of hydroxyl ions by equation 4. Effect of Initial Dye Concentration (Co). BG dye solutions with different Co (125–325 mg L–1) were used in EC treatment. The decolorization efficiency decreased from 98.6 to 78% with an increase the Co from 125 to 325 mg L–1 at 50 min (Figure S1a in supporting document). Maximum COD removal efficiencies under different Co and minimum operation time were found to be 85% for Co=125 mg L–1 at 50 min, 78.5% for Co=225 mg L–1 at 90 min and 82.5% for Co=325 mg L–1 at 150 min (Figure S1b). It is clear that an increase in Co decreased the removal efficiency. This is due to the fact that at high Co, polymeric Al species and Al(OH)3(S) (produced via electrode dissolution) are insufficient to interact with large number of dye molecules. Also, large number of intermediates formed in the solution block the active site of Al electrode (fouling the electrode) and decreasing the color and COD removal efficiencies.


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UV–visible Analysis. EC degradation before and during treatment (at various treatment time) was studied using UV–visible analysis (200–800 nm). Intense green color of BG is shown by an absorption band at λmax=619 nm (extinction coefficient=105 M–1cm–1) in the UV–visible spectrum (Figure S2). The intensity of peak at λ=619 nm decreased with an increase in treatment time. The absorption at 619 nm became almost zero after 50 min of EC treatment indicating the absence of auxochrome groups –N(CH3) responsible for the color of the BG dye. Peak at 253 nm shifts towards lower wavelength (209 and 185 nm) indicating the presence of the mono aromatic rings in the solution after 50 min of treatment. The presence of new absorption wavelength at 365 nm provides the information of poly conjugated triphenylmethane aromatic ring.47 This change in position of spectral peaks to shorter wavelength, generally termed as hypsochromic shift, is due to N–de–methylating process.48 This shift can also occur because of change in solvatochromic parameters such as solvent polarity. FTIR Analysis. Figure 2 shows FTIR spectra of EC reactor solutions collected at different time during the treatment. At time t=0 min, FTIR spectrum of pure BG dye shows a broad band between 3000 and 3700 cm–1 with peak at 3445 cm–1. This band is due the presence of tertiary amine group and N-H bending in the dye molecule. This may also be due to the presence of OH groups due to the hydrogen bonding of dye in the solution. A peak at 2914 cm–1 is due to -CH3 stretching.3 Peak at 1630 cm–1 is due to N-H in-plane bending. During initial phases of treatment (t ≤ 30 min), a large number of peaks are observed between 3100 and 3650 cm–1. These are due to the presence of a number of hydroxyl groups that get generated during the initial phases of treatment generated by the interaction of H2O2 (generated on cathode shown in equation 9) and aluminum ion concentration (on anode shown in equation 1) during EC treatment (shown in equation 11). These peaks also indicate presence of inter and intra molecular hydrogen bonding between the dye and water



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molecules.49 Peaks within the range 3100 to 3450 cm–1 may also be due to the conversion of attached tertiary amine functional group of dye into primary amines. Conversion of tertiary amine group to secondary and primary amines is shown by emergence of peak at ≈1350 cm–1. Increase in absorbance at ≈1610 cm–1 may be due to C=O stretching of lactones.50 These peaks may also be due to presence of –NH deformation and aromatic rings. A number of peaks in the range of 400-650 cm–1 show the presence of mono- and para-substituted derivatives of benzene ring at the end of EC treatment. After treatment for 50 min, most of peaks observed earlier in the range of 3100 and 3650 cm–1 disappeared and only a flat broad peak was observed indicating utilization of OH groups for EC treatment of BG dye. Similarly, peak intensity at ≈1610 cm–1 got decreased indicating oxidation and conversion of C=O and –NH groups, and aromatic rings. It may, however, be seen in the Fig. 5 that the intensity of peak at ≈2105 cm–1 goes on increasing with treatment time. This peak is due to alkyl CN stretching. This may be due to the conversion of aromatic ring structure to small aliphatic CN groups. Intermediate Identification. HPLC analysis of the sample was carried out at various treatment time and the chromatograms are shown in Figure S3 for detection at 619 nm. The peak area below the retention time of BG (≈8.8 min) was found to decrease with treatment. It may be seen that a number of new peaks appeared in the chromatograms taken at various treatment time. Thus, it seems that many new degradation species were formed in the solution during the treatment process. Because of short life of the intermediates and non-availability of standards, it was difficult to identify the intermediates with HPLC analysis. Therefore, further analysis of samples was done in HRMS and GCMS to identify the intermediates formed during the treatment process.51,52 Similar strategies of analysis have been reported earlier for UV–visible light induced photodegradation of malachite green30 and basic violet– 413 through photocatalytic degradation with TiO2 catalyst.


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HRMS spectral analysis was further used to identify the N–de–methylated intermediates. HRMS analysis of solution (shown in Figure S4 of the supporting information) after 10 min of treatment showed presence of various intermediates during BG degradation. Table S2 of the supporting information shows various compounds identified using HRMS spectra. GCMS mass spectra of solution at various treatment times are shown in Figure S5

given in supporting information; and Table 1 presents the intermediates fragmentation pattern (A’–D’, a–h, a’–d’ and f’, g’, 1–3 and I–XIII) and intermediates compounds identified in GCMS spectra. According to mass analysis, these intermediates were ascribed as follows: A (m/z 329.2009) as BG with λmax (619 nm); B (m/z=315.1885) as (N, N–dimethyl–N'–methyl–4,4'– diaminotriphenylcarbenium) (DMDTC); C (m/z=301.1454) as (N–methyl–N'–methyl–4,4'– diaminotriphenylcarbenium) (MMDTC) and C’ might be the C isomer; D (m/z=284) as (N– methyl–4,4'–diaminotriphenylcarbenium)

(MDTC);

E

(m/z=268)

as

(4,4'–

diaminotriphenylcarbenium) (DTC). Intermediate F and I, with m/z=284 and 239.1185 as (N,N,N,N–tetramethyl–diminodiphenylepoxide)

(TDDE),

(N,N–dimethyl–

aminodiphenylepoxide) (DDE), respectively, represented cleavage of the central carbon. Two other peaks d and e were also found with m/z=225.1031 and 209.1088 as N–methyl–4, 4'– diaminobenzophenone (MDBP), 4, 4'–bis–aminobenzophenone (BP). These provide information about the further degradation of epoxides intermediate F and I into small and easily degradable organic molecules. During GC–MS analysis most abundant peaks were identified as: N, N– dimethylparaaminobenzenzoic dimethylparaaminobenzaldehyde

acid

(DABc): (DABz):

m/z=166 m/z=148

and and

60.8%,

N,

100%,

N– N–

methylparaaminobenzaldehyde (MABz): m/z=132 and 68.8%, N–dimethylparaaminobenzene (DAB): m/z=121 and 98.8% found at the middle of treatment. Aminobenzene (AB): m/z=93



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and 72%, ethylamide (EAs): m/z=71 and 66.2% ethylamine (EAs): m/z=44 and 100% were found at the end of treatment time.

ELECTROCHEMICAL DEGRADATION OF BG Degradation Pathways. According to literature review,52-54 N–de–alkylation process occurs by the formation of radical on central nitrogen, while the destruction of conjugated structure occurs by the generated radical on central carbon.31,55,56 Therefore, the overall mineralization of BG involves two degradation pathways, namely N–de–methylation and destruction of chromophore structure resulting from different radicals, either carbon centred and nitrogen centred. These two degradation pathways (shown in different scheme later on) are due to the multiple sites available for •OH attack, generated during EC treatment, on BG dye and its by– products.27,31,57,58 Anodic oxidation of electrodes generates electrons which react with the positively charged dimethyl amine group within the dye molecule yielding the cationic dye radical. After the formation of cationic dye radical, hydrolysis and deprotonation processes occur.30,59 Literature reported on the degradation of triphenylmethane dye via various methods other than EC is compiled in Table S1. These studies help to understand the formation of N–methylamino moiety because of the electrophilic attack on nucleophilic nitrogen through the hydroxymethylamino derivatives as intermediates. Intermediates (A’–D’; a’–d’ and f’, g), 1’ and 2’ are genarted during N–methylation of BG through the formation of hydroxymethylamino derivatatives via the interaction of active oxygen species and N,N–dimethyl or N–methyl groups.30 Interface interactions between auxochrome group of dye molecules and active species generated during EC generate many intermediates. Intermediates, as indentified in (Figure S4 given in supporting information), shows that c (MMDBP): m/z=239.1185, d (MDBP): m/z=225.1031, e (BP):


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m/z=209.1088 are obtained via the formation of intermediate F and its degradation through hydroxymethylamino derivatives. N–de–methylation of BG. In acidic and near neutral condition, maximum number of monomer aluminum cationic species and electrons are generated during anodic dissolution via equations 1 and 5. BG receives these electrons from colloidal suspension through electron mobility from anode to cathode via the positive dimethylamine group. This converts the dye molecule into cationic radicals. N–de–methylated intermediate and methanol are obtained by the interaction of H2O molecules on methyl group of dimethylamine of cationic dye radical. O2 generated during cathodic reaction of H2O (via equation 5) and reduces it into H2O2 (via equations 9 and 10). The OH• radical, which is a strong initiator for degradation of the dye molecules, gets generated through indirect reaction of Al3+ and H2O2 shown in equation 11. The intermediate of N–de–methylated derivatives of dye i.e. B: mono N–de–methylated (DMDTC), C: di N–de–methylated (MMDTC) and C’: DDTC; D: tri N–de–methylated (MDTC) are formed during 10 min of the EC treatment. N–de–methylated process continues until the formation of complete de–methylation intermediate E: DTC as shown in scheme 1. Scheme 2 shows that the carbon centred radical generated via the transfer of electron in conjugated structure, reacts with oxygen molecule leading to the formation of F: TDDE through path I and I: DDE through path II. F: TDDE and I: DDE are reactive and highly unstable intermediates and their expected destruction mechanism is represented in schemes 3 and 4. Intermediates c (MMDBP), d (MDBP) and e (BP) get formed via the same process of electron attack, hydrolysis or deprotonation through the degradation of epoxide F: TDDE (scheme 3). Similarly, degradation of intermediate I: DDE leads to formation of compound h and other intermediates in scheme 4. Mass of intermediates defined in above text and schemes is shown in Figure S4 and S5 along with Tables S2 given in supporting information respectively, and in Table 1.



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Destruction of Conjugated Structure. All the intermediates described in schemes 1–4 further get degraded into small aromatic compounds which get easily mineralized into small molecules as shown in Scheme 5 and Figure S5 in the supporting information. These smaller molecules are given in Table 1 and these include molecules such as I(B), II(BA), III(DAB), IV(DABA),V(MABA), VI(DABz), VII(MABz), VIII (AB) and IX (ABc), X(EAs), XI(AAc), XII(AMs), XIII(AAs), and 1, 2, 3 which get further mineralized to NO3–and CO3–2.60,61 GCMS analysis provided information regarding above described schemes and path. The most abundant peaks of intermediates were identified as: IV(DABA): m/z=166; VI(DABz): m/z=148;VII(MABz): m/z=132; VIII (AB): m/z=93; X(EAs): m/z=71; XIII(AMs): m/z=44; and III(DAB): m/z=121 at 60.8%, 100%, 68.8%, 66.2%, 100%, 72% and 98.8%, respectively, giving evidence regarding formation of different intermediates. The peaks in GCMS give evidence of the conversion of large aromatic ring derivatives into small aromatic derivatives by possible schemes as described in this study.

SUMMARY AND CONCLUDING REMARKS Present study showed that the BG dye could be easily decolorized and degraded through EC treatment. The decolorization rate increased with an increase the pH from acidic to alkaline pH due to conversion of dye to leuco form. Zeta potential study helped to identify the conditions of maximum interaction between the hard acid (Al ions and hydroxides) and basic dye. Actual degradation of dye occurred via different schemes by N– de–methylated and destruction of conjugated BG structure in presence of •OH radicals. During the BG dye degradation, various short–life unstable intermediates were generated which were, on complete mineralization, converted into carbon dioxide, nitrates and easily decomposable small aliphatic compound as shown in last scheme of the present study. The degradation mechanism of BG dye through EC, as reported in the present study, would be helpful in


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future application of EC technology for degradation of dyes. EC degradation of other triphenylmethane dyes is likely to be similar to that reported in the present study, though, type of electrode and operating conditions may affect the degradation mechanism.

ASSOCIATED CONTENT Supporting information Comparison of previously reported studies on degradation of BG dyes in different wastewater; COD and color removal efficiency at various initial dye concentrations; UVvisible analysis; HPLC analysis; HRMS analysis and GCMS analysis at different time interval during EC treatment under the optimum conditions: j=117.64 A m–2, Co=125 mg L–1, pH=6.5, electrodes gap=1 cm and NaCl concentration=1.5 g L–1. This material is available free of charge via the Internet at http://pubs.acs.org.

ACKNOWLEDGEMENTS Authors are thankful to Council of Scientific & Industrial Research (CSIR), India for providing financial help for carrying out this work.

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Table 1: Analysis of GC–MS spectra S.No. N–de–methylation intermediates A’ B’ B’’ C’ C’’ D’ a b c d e a’ b’ c’ d' f g h f’ g’ 1. 2. 3. I II III IV V VI VII VIII IX X XI XII XIII

N,N–dimethyl–N’–hydroxymethyl–N’–methyl–4,4'– diaminotriphenylcarbenium N,N–dimethyl–N’–hydroxymethyl –4,4'– diaminotriphenylcarbenium N–methyl–N–hydroxymethyl–N’–methyl –4,4'– diaminotriphenylcarbenium N–methyl –N’–hydroxymethyl–4, 4'–diaminotriphenylcarbenium N–hydroxymethyl –N’–methyl–4,4'–diaminotriphenylcarbenium N–hydroxymethyl –4,4'–diaminotriphenylcarbenium N,N,N’,N’–tetramethyl–4,4'–diaminobenzophenone N,N,–dimethyl–N’–methyl–4,4'–diaminobenzophenone N–methyl–N’–methyl–4,4'–diaminobenzophenone N–methyl–4,4'–diaminobenzophenone 4,4'–bis–aminobenzophenone N,N–dimethyl–N’–hydroxymethyl–N’–methyl–4,4'– diaminobenzophenone N,N–dimethyl–N’–hydroxymethyl–4,4'–diaminobenzophenone N–methyl–N’–hydroxymethyl–4,4'–diaminobenzophenone N–hydroxymethyl–4,4'–diaminobenzophenone N,N–dimethyl–4–aminobenzophenone N–methyl–4–aminobenzophenone 4–aminobenzophenone N–methyl–N–hydroxymethyl–4–aminobenzophenone N–hydroxymethyl–4–aminobenzophenone N,N–dimethyl–para–aminophenol N–methyl–para–aminophenol 4–aminophenol Benzene Benzoic acid N,N–dimethylaminobenzene N,N–dimethyl paraaminobenzoic acid N–methyl paraaminobenzoic acid N,N–dimethyl paraaminobenzaldehyde N–methyl paraaminobenzaldehyde Amino benzene 4–aminobenzoic acid Ethyl amide Acetic acid Acetamide Ethyl amine


abbreviation m/z value DHMDTC DHDTC

331

MHMDTC

331

MHDTC HMDTC HDTC TDBP DMBP MMDBP MDBP BP DHMDBP

268 253 239 225 209 284

DHDBP MHDBP HDBP DABP MABP ABP MHABP HABP DAP MAP AP B BA DAB DABA MABA DABz MABz AB ABc EAs AAc AMs AAn

268 225 209 197 241 227 121 78 121 148 93 71 60 59 44


100 Decolorisation efficiency (%)

100

COD removal (%)

80 60 40 3.5 5.5 7.5

20

4.5 6.5 8.5

0 0

10

20 30 40 50 Treatment time (a)

80 60 40 3.5 5.5 7.5

20

0

60

10 20 30 40 50 Treatment time (min) (b)

N

CH3

CH3 H3C

CH3

60

Reduction

e H3C N

4.5 6.5 8.5

0

Resonance

m/z 329

H

Oxidation

N CH3 CH3

N CH3

Malachite Green (MG) m/z 329

N CH3 CH3

H3C N CH3

Leucomalachite Green (LMG) m/z 330

(c) Inter–conversion of basic green 4 14 3.5 4.5 12 5.5 6.5 7.5 8.5 10

0 -5 -10

Change in pHf

Zeta potential (mV) change

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 31

-15 -20 -25 -30

8 6 4

3.5 5.5 7.5

2

-35

4.5 6.5 8.5

0 0

10

20 30 40 50 Operating time (min) (d)

60

0

10

20

30

40

50

Treatment time (min)

(e)

Figure 1. Effect of pH on (a) COD removal efficiency, (b) decolorization efficiency, and (c) Inter–conversion of basic green 4; (d) variation of zeta potential with time at various pH; and (e) variation in pH during treatment (j: 117.64 Am–2; Co: 125 mgL–1; T: 25oC).


60

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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 2. FTIR spectra of basic green 4 at different time intervals during EC treatment.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

M

M

M

H3C N CH3

MO

H2O CH3OH

H3C N CH3

CH3 N CH3

M(OH)3

A m/z(329)

3

M

3e

3

OH N CH3 CH3

Page 26 of 31

N CH3 CH3

OH CH2 H3C N

A'

H2O

M

M

3

H2O CH3OH

3e

H3C N H CH

CH3 N CH2OH

H N CH3

3

N CH3 OH CH2 H N

or B'

N CH3 CH3

B m/z (315)

B''

M

M

3

CH3OH

H2 O

3e

H N CH3

H N CH3

H N CH2OH N CH3 H

C m/z (301)

H N CH3

or

H N CH3

OH CH2 H N

C'

N H H

D C''

M

M

3

H2O CH3OH

3e

H N H

H N H

N H H

OH CH2 H N

E D'

Scheme 1: N–demethylation pathway of BG dye during EC treatment based on different intermediates identified by mass analysis.


Page 27 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


M

M

H3C N CH3

3

OH

CH3 H3C N

H3C N CH3

M(OH)3

N CH3 CH3

N CH3 CH3

N CH3 CH3

A MO

CH3 H3C N

CH3 H3C N

H2 O

O2

or

O O

CH3 H3C N

O O

N CH3 CH3

N CH3 CH3

O

O O

O

N CH3 CH3

N CH3 CH3

N CH3 CH3

I Path II (m/z 239)

F Path I (m/z 284)

Scheme 2: Destruction of conjugated structure of the BG dye during EC treatment based on different intermediates identified by mass analysis.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Path I

CH3 H3C N

O

CH3 H3C N

H2O

O

Page 28 of 31

OH O OH

H2O N CH3 CH3

N CH3 CH3

OH

F m/z (284) M

M

H H3C N

O

3

-H2O2

H2O CH3OH

CH2OH H3 C N

M

M

3

3e

H 2O

H H3C N

O

(b) m/z (253) H

O

(b') O m/z (269)

M

(a') m/z (284)

3

M

H2 O

CH3OH

H H N

CH3 N H

(c')

O

(d) m/z (225) M

O H H N

(c) m/z (239)

(d') Mineralisation products

(a) m/z (268)

3e

H HOH2C N N H CH3

N CH3 CH3

CH3 N CH2OH

H3C N

O

CH3 N CH3

N CH3 CH3

CH3OH

CH3 H3C N

3e

CH2OH N H

N H CH3

3e M H2O

3

CH3OH O

Futher degradation

H H N

O

N H

(e) H m/z (209) Scheme 3: Destruction of TMDBP derivatives based on different intermediates identified by mass analysis.


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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Path II O O

OH O OH

H2O

m/z (121)

H3C N CH3

N CH3 CH3

N CH3 CH3

H2O OH

I m/z (240)

-H2O2 O

H3C N

1.

CH3 M

(f) N CH3 m/z (225) CH3

OH

3

M

M

3e

CH2OH N CH3

H2O

N CH2OH CH3OH

CH3OH

O

OH

(f')

M

O

2. m/z (121) N H

CH3 M

3

H2O

CH3

H N

M

3e

(g) CH3 OH

M

3

H N CH2OH

3e

H2 O

M

3

3e

H2O

N CH3OH

CH2OH

O

H

(g')

CH3OH O

OH

N H H

H N H

(h) m/z (197) 3. Scheme 4: N–demethylation pathway of DADE derivatives based on different intermediates identified by mass analysis.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

O

CH3 H3C N

O

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H H N

O

O

or

h

N H H

f

M

3e

M

N CH3 CH3

a

M

3e

3

3e

M

M 3

3

M

CH3

O

O

3e

O

H

H3C N

O

H N

N H

N CH3

N CH3

N H

H

CH3

CH3

H

H2O

H2O

H2O OH

OH

OH

OH

COOH

II

III

N CH3

CH3

CH3

H

m/z (121)

COOH

CHO

V

VII

VI

N CH3

OH

IV

III

COOH

OH

N H H

N CH3 CH3

IV N CH3

H H N

OH

CHO

COOH

H 2O

OH

CH3 H3C N

N CH3 CH3

N H H

I

N H H

M

M

3

e

N CH3 CH3

N CH3

N CH3

H

H

VIII NH2

IX

NH2

m/z (93)

m/z (148)

Cleavage of aromatic rings CH3CH2CONH2 m/z (71) X

CH3COOH XI

CH3CONH2 m/z (57) XII

CH3CH2NH2 m/z (44) XIII

Small aliphatic molecules

Scheme 5: Successive pathway of mineralization formation into small molecules based on different intermediates identified by mass analysis.


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