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Research ArticlePreparation of Na2Ti3O7Titanium Peroxide Composites andTheir Adsorption Property on Cationic Dyes

Meixia Zhao1 Jiguo Huang1 Xueting Guo1 Haitao Chen1

Hai Zhao1 Lili Dong23 and Xing-juan Liu1

1Key Laboratory of Groundwater Resources and Environment Ministry of Education Jilin University Changchun 130026 China2Key Laboratory of Songliao Aquatic Environment Ministry of Education Jilin Jianzhu University Changchun 130118 China3School of Environment Northeast Normal University Changchun 130117 China

Correspondence should be addressed to Lili Dong zmxlwl126com

Received 4 February 2015 Accepted 16 March 2015

Academic Editor Jose Morillo Aguado

Copyright copy 2015 Meixia Zhao et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Na2Ti3O7titanium peroxide composites (TN-TP) were successfully prepared with the reaction of Ti foils NaOH and H

2O2at

60∘C for 24 h in water bath The Na2Ti3O7appeared as nanorods in composites Water bath temperature water bath time and

the concentration of H2O2and NaOH were crucial The reaction mechanism was proposed TN-TP was characterized by X-ray

diffraction (XRD) Fourier transform infrared spectroscopy (FT-IR) scanning electron microscopy (SEM) X-ray photoelectronspectroscopy (XPS) and thermogravimetric and differential scanning calorimetry (TG-DSC) TN-TP was a mesoporous materialand exhibited stronger adsorption capability for neutral red (NR) malachite green (MG) methylene blue (MB) and crystalviolet (CV) than pure Na

2Ti3O7and pure titanium peroxide and the saturated adsorption capacities were 49021 38613 32281

and 29274mgg at 25∘C respectively It was found that the pseudo-second-order kinetic model and the Langmuir model couldwell describe the adsorption kinetic and isotherm of cationic dyes studied The results of this work are of great significance forenvironmental applications of TN-TP as a promising adsorbent material for dyeing water purification

1 Introduction

Cationic dyes are extensively used in industry leading tothe increasing discharge of dye to the water [1] The dyeingwastewater reduces the solar light penetration and retardsthe photosynthetic activity of aquatic plant [2] In additionthe colored effluence also triggers an increasing toxicity andcarcinogenicity which threatens thewater security for humanand animals [3] This resulted in a demand to remove thedyes from effluents Therefore the treatment of cationic dyesraised much attention and adsorption has been found to besuperior to other techniques for dyeing water purificationin terms of initial cost and flexibility [4 5] For exampleactivated carbon has been regarded as an excellent adsorbentand was used widely However it was sometimes treatedas one-off adsorbent due to the high regeneration cost [67] It is necessary to search for more efficient and cheaperalternate adsorbents It had been found that titanate playsimportant roles of adsorbent in the removal of dyes [8 9]

In addition titanium peroxide also causes some concernsin recent researches Titanium peroxide was first reportedas a stable orange solution obtained by the coordination ofTi4+ and O

2

2minus in 1891 [10] Later the reaction was applied tomeasure the concentration of Ti4+ and O

2

2minus [11] In 1970 theinfluence of pH on the structure of titanium peroxide wasoriginally studied [12] In recent years some studies choosetitanium peroxide as a precursor for preparing nanotitaniumdioxide [13ndash15] It is reported [16ndash18] that titanium superox-ide could catalyze the selective oxidation of aromatic primaryamines and phenols Friese et al [19] found peroxotitaniumcomplexes can oxidize 2-propanol Zhao [20] firstly preparedthe titanium peroxide power with the reaction of titaniumsulfate and H

2O2 which showed good selective adsorption

property on cationic dyes There is little research aboutNa2Ti3O7titanium peroxide composites at present

In this work we successfully prepared Na2Ti3O7tita-

nium peroxide composites (TN-TP) with the reaction of Tifoils and the mixed solution of NaOH and H

2O2(volume

Hindawi Publishing CorporationJournal of ChemistryVolume 2015 Article ID 363405 12 pageshttpdxdoiorg1011552015363405

2 Journal of Chemistry

ration 1 1) at 60∘C in water bath The adsorption capabilitiesfor cationic dyes of TN-TP were studied The adsorptionkinetic and isotherm were also studied It certificated thatTN-TP was a promising adsorbent material for dyeing watertreatment So this work is of great significance

2 Materials and Methods

21 Materials Cold-rolled titanium foil 995 in puritywas purchased from Baoji Fuxin Nonferrous Metal ProductsCo Ltd China Hydrochloric acid (37) sodium hydroxide(NaOH) and nitric acid (67) were purchased from BeijingChemical Works Hydrofluoric acid (40) was purchasedfromTianjin Chemical Reagent Research Institute Hydrogenperoxide (30) was obtained fromXilong Chemical Co Ltd(China) Methylene blue (MB) neutral red (NR) and crystalviolet (CV) were obtained fromTianjin Guangfu Fine Chem-ical Research Institute (China) Malachite green (MG) wasobtained from Tianjin Bodi Chemical Co Ltd All reagentswere of analytical grade The water used was distilled

22 Preparation Ti foils (5 cmtimes 5 cmtimes 02mm)were pickledin with a volume ratio of HF HNO

3 H2O = 1 3 6 about

30 s at ambient temperature After ultrasonical cleaning indistilled water each two pieces of cleaned Ti foils were soakedin themixed solution (sodiumhydroxide solution (10molL)hydrogen peroxide solution (30) or both of them) Thenthe reactants were kept at designated temperature in waterbath for a certain time After cooling to room temperatureprecipitates were washed by distilled water for several timesuntil the pH = 7 and dried by water bath at 40∘CThe sampleswere obtained after grinding the dried precipitates Sampleswere labeled in Table 1

23 Characterization XRD patterns were acquired on an X-ray diffraction spectrometer (BRUKER AXS D8 ADVANCECu K120572 120582 = 154056 A) FT-IR curves were recorded onSHIMADZU 8400s Fourier transform infrared spectrometerThe SEM images were recorded with a model XL 30 ESEMFEG from Micro FEI Philips at room temperature XPSmeasurements were carried out with a Thermo ESCALAB250 spectrometer using an Al K120572 (14866 eV) X-ray sourceTGDSC analyses were performed on a NETZSCH DSC 204PC Instrument from 30 to 650∘C at a heating rate of 10∘Cminunder N

2(50 cm3min at normal temperature and pressure)

All of the measurements were carried out at room tempera-ture (25 plusmn 2∘C)The specific surface area was calculated fromthe N

2adsorption isotherm using the Brunauer-Emmett-

Teller (BET)method and the pore size distributionwas deter-mined using the Barrett-Joyner-Halenda (BJH)mathematicalmodel The sample was degassed at 50∘C for 12 h before test

24 Adsorption Test All the adsorption experiments wereconducted under stirring at room temperature (25∘C) in thedark The general experimental process was described asfollows 02 g of the sample was added to 200mL of dye solu-tion with certain initial concentration At appropriate timeintervals the aliquots were withdrawn from the suspension

Table 1 Samples prepared on different conditions

SampleWater bathtemperature

(∘C)

Water bathtime (h) 119881NaOH 119881H2O2 State

a 60 24 1 1 Solidb 70 24 1 1 Solidc 60 12 1 1 Solidd 60 24 1 2 Solide 60 24 2 1 Solidf 60 24 Only H2O2 Liquidg 60 24 Only NaOH Liquid

and the adsorbents were separated from the suspension viacentrifugation SDPTOPUV2600PC spectrophotometer wasadopted to measure the concentration of residual dyes

3 Results and Discussion

31 Preparation of TN-TP As shown in Figure 1(a) thereaction product of Ti and H

2O2(30) was buff gel with no

precipitates after water bath in the study The yellow gel wasproved to be Ti(OH)

2O2according to the literature [21] The

reaction product of Ti and NaOH (10molL) was colorlesstransparent liquid without precipitates as well (Figure 1(b))This indicated that the insoluble TiO

2and titanate did not

generate in alkaline condition However large amounts oflight yellow precipitates appeared in the reaction products ofTiH2O2 andNaOH(Figure 1(c)) As a result the precipitates

were the product of the reaction of Ti H2O2 and NaOH

When the pH of the precipitates-containing solution is lowerthan 7 (hydrochloric acid added) the solution turned tobe orange and precipitates in solution began to dissolve(Figure 1(e)) this phenomenon was in accordance with thecharacteristic of titanium peroxide in low pH solution [12]After water washing and being dried the precipitates turnedto be yellow (Figure 1(d)) which might be ascribed to theabsorbed O

2

2minus on the surface of precipitates or the O2

2minus

provided by the titanium peroxide which was one part ofthe precipitates [20] As solid titanate was white and solidtitanium peroxide was yellow it could be hypothesized thatthe precipitate maybe titanate with large amounts of O

2

2minus

absorbed on its surface a kind of titanatetitanium peroxidecomposites or pure titanium peroxide

As titanate was crystallizable XRD was adopted to iden-tify the reaction product of Ti H

2O2 and NaOH after wash-

ing being dried and grinding As shown in Figure 2 all ofthe samples (solid) exhibited a strong peak around 10∘ andthe other three weak broad peaks were around 245∘ 2834∘and 483∘ respectively Peaks of XRD could be approximatelycontributed to sodium titanate (Na

2Ti3O7JCPDSnumber 72-

0148) with low crystallinity [22 23] In addition peaks at 10∘were concentrated with increasing water bath temperature(sample (a)rarr (b)) and the concentration of H

2O2(sample

(e)rarr (a)rarr (d)) which showed that the interlayered ionscrystallinity of Na

2Ti3O7in samples was enhanced [8]

Na2Ti3O7was generated in each preparation condition but

Journal of Chemistry 3

(a) (b) (c) (d) (e)

Figure 1 (a) Reaction product of Ti and H2O2(30) (b) Reaction product of Ti and NaOH (10molL) (c) Reaction product of Ti H

2O2

and NaOH before washing (d) Reaction product of Ti H2O2 and NaOH after washing being dried and grinding (e) Add hydrochloric acid

in reaction product of Ti H2O2 and NaOH (pH lt 7)

0 10 20 30 40 50 60 70 80 90

Inte

nsity

(au

)

2120579 (deg)

(a) (60∘C-24h-1 1)

(b) (70∘C-24h-1 1)

(c) (60∘C-12h-1 1)

(d) (60∘C-24h-1 2)

(e) (60∘C-24h-2 1)

Figure 2 XRD patterns of samples

crystallinities of them were different so the reaction productof Ti H

2O2 and NaOH after washing being dried and

grinding (solid samples) was not the pure titanium peroxideAs shown in Figure 3 sample (b) prepared at relatively

high temperature condition (70∘C) and sample (d) preparedat relatively high concentration of H

2O2condition consisted

of netlike structures with an average diameter of 50 nmand 40 nm respectively Titanium peroxide is amorphousin nature [20] therefore there was no titanium peroxidein sample (b) and sample (d) The netlike structure wasidentified to be Na

2Ti3O7[24] with low crystallinity accord-

ing to XRD results Compared to sample (b) sample (a)which was prepared at relatively low temperature (60∘C)consisted of short nanorods and amorphous particles thatwere adhered on the surface of the short nanorods Sample (c)was built up by layered sheets (terraces-likemorphology) andlittle amorphous particles in the interlayers of large sheetsSample (e) was just a large chunk and its surface was smoothThe titanate sheets could split into nanowires by prolonging

the time of Ti foils treated in mixed solution of NaOH andH2O2and then the nanowire layers formed with longer time

finally the netlike structure could be constructed [25] Themorphology change of sample (c) to that of sample (a) wasin keeping with the formation of titanate nanowires fromthe sheets structure Additionally high temperature and highconcentration of H

2O2were conductive to the generation of

netlike Na2Ti3O7[26] So both XRD and SEM observations

presented the coincident results and showed that the shortnanorods of sample (a) and the layered sheets of sample (c)were Na

2Ti3O7

In order to identify the relationship of amorphous par-ticles and O

2

2minus FT-IR was adopted Figure 4 shows FT-IRspectra of samples Differences of bands in the region of 400ndash4000 cmminus1 observedwere subtle except sample (e) which justhad two obvious bands at 1630 cmminus1 and 453 cmminus1 The pres-ence of Ti-OH and hydroxyl groups adsorbed on the surfaceof sampleswere confirmedby the appearance of broad intensebands at 3400 cmminus1 and 3180 cmminus1 respectively [9 27]Therewere almost no adsorbed hydroxyl groups on the surface ofsample (e) The characteristic peaks around 1630 cmminus1 and1385 cmminus1 could be assigned to H-O-H binding vibrationmode and the Ti-O vibrations [9]The wide band at 453 cmminus1in the sample spectra can be assigned to the crystal latticevibration of TiO

6octahedra inNa

2Ti3O7[9 28] It confirmed

the existence of Na2Ti3O7in samples which was consistent

with XRD results The peak at 895 cmminus1 resulted in the per-oxogroups provided by titanium peroxide [20] or excess O

2

2minus

absorbed on the surface of Na2Ti3O7 Peaks of sample (a) and

sample (c) at 895 cmminus1 were obviously stronger than otherswhich means that they possessed relatively larger amounts ofO2

2minus In addition the peak height at 895 cmminus1 in descendingorder was sample (a) sample (c) sample (d) sample (b) andsample (e) Combined with SEM results the amount of O

2

2minus

was proportional to the amount of amorphous particles insample (a) and sample (c) As a result the O

2

2minus in sample(a) and sample (c) maybe mainly provided by the amorphous


Figure 3 SEM images of samples

3000 2000 1000

3180453

89513851630

Inte

nsity

(au

)

3400

(a) (60∘C-24h-1 1)

(b) (70∘C-24h-1 1)

(c) (60∘C-12h-1 1)

(d) (60∘C-24h-1 2)

(e) (60∘C-24h-2 1)

Wavenumber (cmminus1)

Figure 4 FT-IR spectra of samples

particles As sample (d) is prepared at a relatively high con-centration of H

2O2 the number of residual O

2

2minus absorbed onits surface was not the largest Obviously the amount of O

2

2minus

absorbed on the surface of samples was limitedThe titaniumperoxide was the real O

2

2minus provider Sample (a) possessedthe largest amount of O

2

2minus It could be hypothesized thattitanium peroxide was present in sample (a)

According to the SEM image of sample (e) the surface ofsample (e) was smooth and few hydroxyl groups and waterwere adsorbed on it which could explain why the FR-IRcurve of sample (e) had no obvious band at about 3180 cmminus1and 1630 cmminus1 Combined with the XRD result sample (e)was considered to be the Na

2Ti3O7chunk dropped from the

Ti foilsTheXPSwas adopted to identify the existing formofO

2

2minus

(absorbed on the surface of Na2Ti3O7or covalently bound

to Ti4+ to form the titanium peroxide) in sample (a) BeforeXPS test sample (a) was dried at 100∘C to remove the surfacewater and surface O

2

2minus Figure 5 shows the XPS spectra ofsample (a) The peaks at 4588 eV and 4644 eV indicatedthe presence of oxidation state of Ti4+ [29] The O1s spectrashowed amain peak at 5303 eVwith two shoulders at 5317 eVand 5330 eV The main peak at 5303 eV was assigned to theTi-O in Na

2Ti3O7 The shoulder peak at 5317 eV may be

attributed to theTi-OH in titaniumperoxide [20]Thepeak at5330 eV indicated the existence of structural O

2

2minus in sample(a) [29] The existence of Ti-OH and structural O

2

2minus insample (a) confirmed that sample (a) contains Na

2Ti3O7and

titanium peroxide The presence of Na1s spectra at 10719 eVindicated the existence of Na-O owing to Na

2Ti3O7[30]The

XPS results provided evidence on the existence of titaniumperoxide in sample (a)


1200 1000 800 600 400 200 0 470 465 460 455

C1s

Cou

nts (

s)

Bonding energy (eV)

Na1sO1s

Ti2p

Ti2p

Ti2p12

Bonding energy (eV)

Ti2p32

540 538 536 534 532 530 528 526 524

Ti-O Ti-OH

Inte

nsity

(au

)

Bonding energy (eV)

O1s

1080 1075 1070 1065

Inte

nsity

(au

)In

tens

ity (a

u)

Bonding energy (eV)

Na-O

Na1s

O22minus

4643 eV

4587 eV

5303 eV5317 eV

5330 eV

10719 eV

Figure 5 XPS spectra of sample (a)

0 100 200 300 400 500 60075

80

85

90

95

100

Endo

TG

DSC

Mas

s (

) Exo

2

1

0

Hea

t flow

(mW

mg)

4460∘C

665∘C

Temperature (∘C)

minus1

Figure 6 TG-DSC curves of TN-TP

From the above analysis sample (a) was proved to bethe Na

2Ti3O7titanium peroxide composites (TN-TP) The

thermal analysis has been adopted to evaluate the thermalstability of TN-TP to be used as an adsorbent Figure 6 showsthe TG-DSC curves of TN-TP It could be found that thecurve of theDSC exhibited strong endothermic changes fromroom temperature to 200∘C with about 20 weight losseswhich should be attributed to residual water evaporationand dehydroxylation on the surface of TN-TP [31] From

200∘C to 400∘C there was no obvious peak in the curveof DSC with just about 4 weight losses due to the releaseof oxygen which was from the decomposition of peroxideroot provided by titanium peroxide [20] There was noobvious weight loss after 400∘C so water in TN-TP hadalmost released completely The Na

2Ti3O7was thermally

stable from 200∘C to 600∘C In the following stage there wasan exothermic peak that appeared at 4460∘C The titaniumperoxide had decomposed to TiO

2and crystallized with the

phase transformation at 4460∘C in this stage It had beenrecognized that the temperature was about 450∘C at whichthe transition of anatase to rutile starts [32] TN-TP possessedgood thermal stability from room temperature to 440∘C

The N2adsorptionminusdesorption isotherm of TN-TP indi-

cated a specific surface area of 3226m2g by BET analysisThe corresponding BJH analysis (curve inserted) suggesteda predominant pore diameter distribution of 174 nm and atotal pore volume of 0233 cm3g The BJH results indicatedthat TN-TP belonged to mesoporous material

32 Reaction Mechanism The reaction mechanism of TiH2O2 and NaOH was proposed to explain the generating

process of Na2Ti3O7titaniumperoxide composites (TN-TP)

In alkaline solution dissociation of H2O2formed the OOHminus

ion in reaction (1) Then the OOHminus ions reacted with Tito form a metastable and highly soluble peroxide complex(TiO2(OH)119899minus2

4minus119899) Reaction (4) took place immediately in


0 30 60 90 120 150 180

02

04

06

08

10

Time (min)

CC

0

(a) 60∘C-24h-1 1

(b) 70∘C-24h-1 1

(c) 60∘C-12h-1 1

(d) 60∘C-24h-2 1

(e) 60∘C-24h-1 2

Figure 7 Removal efficiency of samples for MB (initial concentration 400mgL pH = 7 and temperature 25∘C)

0 60 120 180 240 300 3600

100

200

300

400

500

Adso

rptio

n (m

gg)

Time (min)

NR

0 60 120 180 240 300 3600

100

200

300MB

Adso

rptio

n (m

gg)

Time (min)

0 60 120 180 240 300 3600

100

200

300

400 MG

Adso

rptio

n (m

gg)

Time (min)0 60 120 180 240 300 360

0

100

200

300 CV

Adso

rptio

n (m

gg)

Time (min)

600mgL400mgL200 mgL

100 mgL50mgL

600mgL400mgL200 mgL

100 mgL50mgL

Figure 8 The adsorption curves of NR MB MG and CV at different initial concentration (TN-TP dosage 10 gL)


0 60 120 180 240 300

0

2

4

6

NR

Time (min)0 60 120 180 240

0

2

4

6

MB

Time (min)

0 60 120 180

0

2

4

6MG

Time (min)0 60 120 180 240

0

2

4

6 CV

Time (min)

ln(q

eminus

qt)

ln(q

eminus

qt)

minus2

ln(q

eminus

qt)

ln(q

eminus

qt)

minus2

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL

Figure 9 Pseudo-first-order kinetic plots for NR MB MG and CV

the case of excess OOHminus ions and reaction (5) followed togenerate theNa

2Ti3O7[24] Additionally with the concentra-

tion of Na+ and OOHminus decreasing TiO2(OH)119899minus2

4minus119899 wasgoing to condense to be stable Ti

2O5

2+ and then the Ti2O5

2+

further formed the titanium peroxide (reaction (6)) [12]High temperature and high concentration of H

2O2were

conducive to the generation of Na2Ti3O7but not conducive

to the generation of titanium peroxide so sample (b) andsample (e) were pure Na

2Ti3O7without titanium peroxide

By prolonging water bath time Na2Ti3O7generated with the

reaction of excess Ti and NaOH in solution Ti + NaOH +H2OrarrNa

2Ti3O7+ H2[33] which ensured the high con-

centration of Na2Ti3O7to form the Na

2Ti3O7nanorods

Combined with the previous analyses the best condition toprepare the Na

2Ti3O7titanium peroxide composites (TN-

TP) was 60∘C-24 h-1 1

H2O2997888rarr OOHminus +H+ (1)

H+ +OHminus 997888rarr H2O (2)

Ti +OOHminus + (119899 minus 1)OHminus

997888rarr TiO2(OH)119899minus2

4minus119899+H2O + 2eminus (119899 le 6)

(3)

TiO2(OH)119899minus2

4minus119899+ (119899 minus 3)OOHminus

997888rarr HTiO3

minus+ (119899 minus 3)H

2O + (119899 minus 3)O

2

(4)

3HTiO3

minus+ 2Na+ 997888rarr Na

2Ti3O7+H2O +OHminus (5)


4minus119899997888rarr Ti

2O5

2+larrrarr Ti

2O5(OH)+

larrrarr Ti2O5(OH)2larrrarr Ti

2O5(OH)3

minus

larrrarr Ti2O5(OH)4

2minuslarrrarr and so forth

(6)

33 Adsorption Experiment The adsorption activities ofsamples were demonstrated with MB (400mgL) As shownin Figure 7 all curves exhibited the same regularity (1)Theconcentration ofMBdecreased dramatically in the first 5minThis was due to the strong electrostatic interaction betweenpositively charged MB and negatively charged titanium per-oxide and Na

2Ti3O7with hydroxyl groups absorbed on its


0 60 120 180 240 300 360

0

1

2

NR

Time (min)0 60 120 180 240 300 360

0

1

2 MB

Time (min)

0 60 120 180 240 300 360

0

1

2

3

4MG

Time (min)0 60 120 180 240 300 360

0

1

2

3

4CV

Time (min)

tqt

(min

(m

gg)

)

tqt

(min

(m

gg)

)t

qt

(min

(m

gg)

)

tqt

(min

(m

gg)

)

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL

Figure 10 Pseudo-second-order kinetic plots for NR MB MG and CV

surface [20 34 35] (2) Subsequently the concentration ofMB slowed down and the adsorption rate was slower thanthat at the beginning stage It could be explained that thedecreasing adsorption points and vacant surface becamemore difficult to be occupied with reaction advanced due tothe repulsion between adsorbed MB molecules [8]

It was obvious that the curve of sample (a) (TN-TP) dec-reased fastest in all curves From SEM analysis as the tita-niumperoxide adhered on the surface ofNa

2Ti3O7nanorods

its molecular structure was not easily damaged and hydroxylgroups firmly bound to the Ti

2O5

2+ to keep its negativityIn addition as the titanium peroxide was condensed bythe TiO

2(OH)119899minus2

4minus119899 which can help maintain the hydroxylgroups absorbed on the surface of Na

2Ti3O7nanorods

the negative charges of TN-TP can be stable which wasconstructive to the electrostatic adsorption As a result itpossessed stronger adsorption ability than pure Na

2Ti3O7

network structure (sample (c) and sample (e)) As sample(c) was terraces-like morphology its specific surface area wassmaller than that of TN-TP and so was the adsorption ability

Four different cationic dyes including MB MG CV andNR were used to study the adsorption property of TN-TP Ascan be seen from Figure 8 TN-TP showed great adsorption

effect on them In addition the adsorption rates on NR MGMB and CV were different (NR gt MB gt MG gt CV) Asthe molecular structures were same to each other [20] thesmaller the size of the molecular is the easier the adsorptionis The result also showed that the experimental saturatedadsorption capacities for NR MG MB and CV were 4902138613 32281 and 29274mgg at 25∘C respectively Com-pared with the pure Na

2Ti3O7or pure titanium peroxide the

adsorption capacity of TN-TP increased [9 20]In order to investigate the mechanism and characteristics

of TN-TP adsorption in dyes removal the linear plots ofpseudo-first-order and pseudo-second-order kinetic modelswere shown in Figures 9 and 10 and the adsorption kineticparameters related to models were figured out in Table 2 Itcan be seen that the trend line of the pseudo-first-ordermodeldeviated obviously from the experimental data but the trendline of the pseudo-second-order model passed through thewhole experimental data Correspondingly the correlationcoefficient values of pseudo-first-order model were lowerthan those of pseudo-second-order which were higher than09994 The values of 119902

119890cal estimated from pseudo-second-order model were comparable with the experimentally deter-mined values of 119902

119890exp which indicated a better applicability


Table 2 Equations and parameters of kinetic models and kinetic parameters of dyes onto TN-TP

Kinetic model Pseudo-first-order kinetic model Pseudo-second-order kinetic modelEquation ln(119902

119890minus 119902119905) = ln 119902

119890minus 1198961119905 119905119902

119905= (1119902

119890)119905 + 1(119902

119890

21198962)

Capacity term119902119905 119902119890 the amounts of dyes adsorbed (mgg) at time 119905 and at equilibrium respectively

1198961 the first-order equilibrium rate constant (minminus1)1198962 the second-order equilibrium rate constant (g(mgsdotmin))

Parameters 119902119890exp (mgg) 119902

119890cal (mgg) 1198961(minminus1) 119877

1

2119902119890cal (mgg) 119896

2

(g(mgsdotmin)) 1198772

2

Concentration ofNR (mgL)

50 4894 23698 00043 084331 4975 0000074 099976100 9765 20296 00403 076211 9901 0000019 099985200 19390 2515 00428 073929 19455 0000008 099997400 37702 1633 00476 096544 39063 0000002 099989600 49021 1342 00163 095304 50505 0000002 099986

Concentration ofMB (mgL)

50 4918 3046 00480 096565 5236 0000107 099940100 9707 4192 00359 089483 10040 0000027 099985200 18813 11249 00377 097510 19841 0000005 099994400 30702 17795 00329 096500 32258 0000002 099995600 32281 14465 00173 092772 33113 0000002 099997

Concentration ofMG (mgL)

50 4941 1829 00493 087652 5025 0000136 099997100 9823 3460 00325 089785 10040 0000028 099997200 19489 8763 00361 094685 20080 0000006 099995400 35998 15206 00285 092692 37037 0000001 099996600 38613 15042 00244 093031 39370 0000001 099997

Concentration ofCV (mgL)

50 4798 1165 00368 083537 4861 0000172 099997100 9484 1248 00316 066735 9533 0000044 099998200 17756 8206 00306 092221 18382 0000007 099989400 27981 14273 00257 093305 29070 0000002 099992600 29274 16454 00186 096956 30395 0000002 099994

40 45 50 55 60 65

0

2

4

6Freundlich model

CV

MB

MG

NR

0 50 100 150 200 250 300

00

02

04

06

08

10 Langmuir model

lnC

e

lnqe Ce (mgL)

Ceq

e(g

L)

NRMBMG

CVLinear regression

NRMBMG

CVLinear regression

Figure 11 Langmuir and Freundlich sorption isotherms of NR MB MG and CV on TN-TP


Table 3 Isotherm coefficients according to Freundlich and Langmuir

Elements 119902maxexp (mgg)Freundlich Langmuir119902119890= 119896119891119862119890

1119899119902119890= 119902max119862119890(119860 + 119862119890)

119896119891(mgg) 119899 119877

2119902max (mgg) 119860 (mgL) 119877

2

NR 49021 05349 617 times 10minus4 090387 49751 1045 099991

MB 32281 03467 720 times 10minus6 091099 33113 695 099978

MG 38613 03901 170 times 10minus5 085848 39526 468 099993

CV 29274 03807 545 times 10minus5 090667 30488 1237 099961

3000 2000 1000

1392

1327

11701363

1334

TN-TPInte

nsity

(au

)

1193

1363 1170


(TN-TP)-CV

(TN-TP)-MG

(TN-TP)-MB

(TN-TP)-NR

Figure 12 FT-IR spectra of the TN-TP and dyes adsorbed on TN-TP

of pseudo-second-order model to the adsorption of cationicdyes in this study It also suggested that the rate of the adsorp-tion process was controlled by the chemical adsorptionwhich involved valence forces through sharing or exchangeof electrons between adsorbent and adsorbate [36]

The adsorption process was further studied by two clas-sical isotherm models Langmuir and Freundlich as shownin Figure 11 Their corresponding equations and parametersfor adsorption of dyes onto the sample are listed in Table 3It can be seen that the Langmuir model was quite suitable tothe adsorption and the correlation coefficients were higherthan 09996 In addition the 119902max of NR MB MG and CVcalculated through the Langmuir model were 49751 3311339526 and 30488mgg which was in accordance with the119902max acquired from the experiment

The FT-IR spectra of the TN-TP and dyes adsorbedon TN-TP were shown in Figure 12 Compared to TN-TPthe additional peaks at 1327 1193 cmminus1 (TN-TP-NR) 13921334 cmminus1 (TN-TP-MB) and 1170 1367 cmminus1 (TN-TP-MGTN-TP-CV) were attributed to the characteristic peaks ofNR MB MG and CV respectively [37ndash40] This confirmedthe strong electrostatic interaction between the negativelycharged TN-TP and positively chargedNRMBMG andCV

4 Conclusion

In summary the Na2Ti3O7titanium peroxide composites

(TN-TP) were successfully prepared through the reaction

between Ti foils and the mixed solution of NaOH and H2O2

(volume ration 1 1) at 60∘C for 24 h in water bath Highwater bath temperature (70∘C) and high concentration ofH2O2(volume ration 1 2) were conducive to the generation

of Na2Ti3O7without titanium peroxide In the reactions

the TiO2(OH)119899minus2

4minus119899 was crucial TN-TP exhibited strongeradsorption capability for NR MB MG and CV than pureNa2Ti3O7and pure titanium peroxide and the adsorption

capacities were 49021 32281 38613 and 29274mgg at25∘C respectively It was found that the pseudo-second-order kinetic model and the Langmuir model could welldescribe the adsorption kinetic and isotherm of the cationicdyes studied Results of this work are of great significancefor environmental applications of TN-TP as a promisingadsorbent material used for dyeing water purification

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgments

This work was supported by the analysis and testing foun-dation of Jilin University and the National Natural ScienceFoundation of China (no 51308252)

References

[1] A Ozturk andEMalkoc ldquoAdsorptive potential of cationic BasicYellow 2 (BY2) dye onto natural untreated clay (NUC) fromaqueous phase mass transfer analysis kinetic and equilibriumprofilerdquo Applied Surface Science vol 299 pp 105ndash115 2014

[2] M T Yagub T K Sen S Afroze and H M Ang ldquoDye and itsremoval fromaqueous solution by adsorption a reviewrdquoAdvan-ces in Colloid and Interface Science vol 209 pp 172ndash184 2014

[3] P Wang M Cao C Wang Y Ao J Hou and J Qian ldquoKineticsand thermodynamics of adsorption ofmethylene blue by amag-netic graphene-carbon nanotube compositerdquo Applied SurfaceScience vol 290 pp 116ndash124 2014

[4] M Rafatullah O Sulaiman R Hashim and A AhmadldquoAdsorption of methylene blue on low-cost adsorbents areviewrdquo Journal of HazardousMaterials vol 177 no 1ndash3 pp 70ndash80 2010

[5] V K Gupta R Kumar A Nayak T A Saleh andM A BarakatldquoAdsorptive removal of dyes from aqueous solution onto carbon


nanotubes a reviewrdquo Advances in Colloid and Interface Sciencevol 193-194 pp 24ndash34 2013

[6] M Visa C Bogatu and A Duta ldquoSimultaneous adsorption ofdyes and heavy metals from multicomponent solutions usingfly ashrdquo Applied Surface Science vol 256 no 17 pp 5486ndash54912010

[7] Y Wang G Wang H Wang C Liang W Cai and L ZhangldquoChemical-template synthesis of micronanoscale magnesiumsilicate hollow spheres for waste-water treatmentrdquo ChemistrymdashA European Journal vol 16 no 11 pp 3497ndash3503 2010

[8] J Huang Y Cao Z Liu Z Deng and W Wang ldquoApplicationof titanate nanoflowers for dye removal a comparative studywith titanate nanotubes and nanowiresrdquo Chemical EngineeringJournal vol 191 pp 38ndash44 2012

[9] M Feng W You Z Wu Q Chen and H Zhan ldquoMildlyalkaline preparation and methylene blue adsorption capacity ofhierarchical flower-like sodium titanaterdquoACSAppliedMaterialsamp Interfaces vol 5 no 23 pp 12654ndash12662 2013

[10] F P Dunnington ldquoOn metatitanic acid and the estimationof titanium by hydrogen peroxiderdquo Journal of The AmericanChemical Society vol 13 no 7 pp 210ndash211 1991

[11] C D Nordschow andA R Tammes ldquoAutomaticmeasurementsof hydrogen peroxide utilizing a xylenol orange-titanium sys-temrdquo Analytical Chemistry vol 40 no 2 pp 465ndash466 1968

[12] J Muhlebach K Muller and G Schwarzenbach ldquoThe peroxocomplexes of titaniumrdquo Inorganic Chemistry vol 9 no 11 pp2381ndash2390 1970

[13] J Liao L Shi S Yuan Y Zhao and J Fang ldquoSolvothermalsynthesis of TiO

2nanocrystal colloids from peroxotitanate

complex solution and their photocatalytic activitiesrdquo Journal ofPhysical Chemistry C vol 113 no 43 pp 18778ndash18783 2009

[14] MNag S Ghosh R K Rana and SVManorama ldquoControllingphase crystallinity and morphology of titania nanoparticleswith peroxotitanium complex experimental and theoreticalinsightsrdquo Journal of Physical Chemistry Letters vol 1 no 19 pp2881ndash2885 2010

[15] A Bandgar S Sabale and S H Pawar ldquoStudies on influenceof reflux time on synthesis of nanocrystalline TiO

2prepared by

peroxotitanate complex solutionsrdquo Ceramics International vol38 no 3 pp 1905ndash1913 2012

[16] G K Dewkar T M Shaikh S Pardhy S S Kulkarni andA Sudalai ldquoTitanium superoxide catalyzed selective oxidationof phenols to p-quinones with aq H

2O2rdquo Indian Journal of

Chemistry B vol 44 no 7 pp 1530ndash1532 2005[17] T M Shaikh P U Karabal G Suryavanshi and A Sudalai

ldquoTitanium superoxide a heterogeneous catalyst for anti-Markovnikov aminobromination of olefinsrdquo Tetrahedron Let-ters vol 50 no 23 pp 2815ndash2817 2009

[18] R S Reddy T M Shaikh V Rawat et al ldquoA novel synthesisand characterization of titanium superoxide and its applicationin organic oxidative processesrdquo Catalysis Surveys from Asia vol14 no 1 pp 21ndash32 2010

[19] D H Friese C Hattig M Rohe K Merz A Rittermeierand M Muhler ldquoOxidation of 2-propanol by peroxo titaniumcomplexes a combined experimental and theoretical studyrdquoJournal of Physical Chemistry C vol 114 no 45 pp 19415ndash194182010

[20] X-G Zhao J-G Huang B Wang Q Bi L-L Dong andX-J Liu ldquoPreparation of titanium peroxide and its selectiveadsorption property on cationic dyesrdquo Applied Surface Sciencevol 292 pp 576ndash582 2014

[21] P Tengvall H Elwing and I Lundstrom ldquoTitanium gel madefrom metallic titanium and hydrogen peroxiderdquo Journal ofColloid and Interface Science vol 130 no 2 pp 405ndash413 1989

[22] N Chau Thanh J L Falconer D le Minh and W-D YangldquoMorphology structure and adsorption of titanate nanotubesprepared using a solvothermal methodrdquo Materials ResearchBulletin vol 51 pp 49ndash55 2014

[23] Y Chen N Li Y Zhang and L Zhang ldquoNovel low-cost Fenton-like layered Fe-titanate catalyst preparation characterizationand application for degradation of organic colorantsrdquo Journalof Colloid and Interface Science vol 422 pp 9ndash15 2014

[24] Y Wu M Long W Cai et al ldquoPreparation of photocatalyticanatase nanowire films by in situ oxidation of titanium platerdquoNanotechnology vol 20 no 18 Article ID 185703 2009

[25] X Huang and Z Liu ldquoSynthesis and growth mechanism of net-like titanate nanowire films via low-temperature and low-alkali-concentration routerdquo Nano-Micro Letters vol 5 no 2 pp 93ndash100 2013

[26] J Been and D Tromans ldquoTitanium corrosion in alkalinehydrogen peroxiderdquoCorrosion vol 56 no 8 pp 809ndash818 2000

[27] V C Ferreira and O C Monteiro ldquoNew hybrid titanateelongated nanostructures through organic dye molecules sen-sitizationrdquo Journal of Nanoparticle Research vol 15 article 19232013

[28] M Vithal S R Krishna G Ravi S Palla R Velchuri and SPola ldquoSynthesis of Cu2+ and Ag+ doped Na

2Ti3O7by a facile

ion-exchange method as visible-light-driven photocatalystsrdquoCeramics International vol 39 no 7 pp 8429ndash8439 2013

[29] J Ouyang X Sun X Chen J Chen and X Zhuang ldquoPrepa-ration of layered bioceramic hydroxyapatitesodium titanatecoatings on titanium substrates using a hybrid technique ofalkali-heat treatment and electrochemical depositionrdquo Journalof Materials Science vol 49 no 4 pp 1882ndash1892 2014

[30] L L Marciniuk P Hammer H O Pastore U Schuchardt andD Cardoso ldquoSodium titanate as basic catalyst in transesterifi-cation reactionsrdquo Fuel vol 118 pp 48ndash54 2014

[31] X Bu G Zhang and C Zhang ldquoEffect of nitrogen doping onanatase-rutile phase transformation of TiO

2rdquo Applied Surface

Science vol 258 no 20 pp 7997ndash8001 2012[32] J-G Huang X-G Zhao M-Y Zheng S Li Y Wang and

X-J Liu ldquoPreparation of N-doped TiO2by oxidizing TiN

and its application on phenol degradationrdquo Water Science andTechnology vol 68 no 4 pp 934ndash939 2013

[33] B Chi E S Victorio and T Jin ldquoSynthesis of TiO2-based

nanotube on Ti substrate by hydrothermal treatmentrdquo Journalof Nanoscience and Nanotechnology vol 7 no 2 pp 668ndash6722007

[34] J Ma F Yu L Zhou et al ldquoEnhanced adsorptive removal ofmethyl orange and methylene blue from aqueous solution byalkali-activated multiwalled carbon nanotubesrdquo ACS AppliedMaterials amp Interfaces vol 4 no 11 pp 5749ndash5760 2012

[35] Y Tang Z Jiang Q Tay et al ldquoVisible-light plasmonic pho-tocatalyst anchored on titanate nanotubes a novel nanohybridwith synergistic effects of adsorption and degradationrdquo RSCAdvances vol 2 no 25 pp 9406ndash9414 2012

[36] J Huang Y Cao Z Liu Z Deng F Tang and W WangldquoEfficient removal of heavy metal ions from water system bytitanate nanoflowersrdquo Chemical Engineering Journal vol 180pp 75ndash80 2012

[37] S Jain and R V Jayaram ldquoRemoval of basic dyes from aqueoussolution by low-cost adsorbent wood apple shell (Feroniaacidissima)rdquo Desalination vol 250 no 3 pp 921ndash927 2010


[38] HMAbdel-Azi A A El-Zahhar andT Siyam ldquoSorption stud-ies of neutral red dye onto poly(acrylamide-co-maleic acid)-kaolinitemontmorillonite compositesrdquo Journal of Applied Poly-mer Science vol 124 no 1 pp 386ndash396 2012

[39] M Angels Olivella N Fiol F de la Torre J Poch and I Villaes-cusa ldquoA mechanistic approach to methylene blue sorption ontwo vegetable wastes cork bark and grape stalksrdquo BioResourcesvol 7 no 3 pp 3340ndash3354 2012

[40] E Akar A Altinisik and Y Seki ldquoUsing of activated carbonproduced from spent tea leaves for the removal of malachitegreen from aqueous solutionrdquo Ecological Engineering vol 52pp 19ndash27 2013

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


ration 1 1) at 60∘C in water bath The adsorption capabilitiesfor cationic dyes of TN-TP were studied The adsorptionkinetic and isotherm were also studied It certificated thatTN-TP was a promising adsorbent material for dyeing watertreatment So this work is of great significance

2 Materials and Methods

21 Materials Cold-rolled titanium foil 995 in puritywas purchased from Baoji Fuxin Nonferrous Metal ProductsCo Ltd China Hydrochloric acid (37) sodium hydroxide(NaOH) and nitric acid (67) were purchased from BeijingChemical Works Hydrofluoric acid (40) was purchasedfromTianjin Chemical Reagent Research Institute Hydrogenperoxide (30) was obtained fromXilong Chemical Co Ltd(China) Methylene blue (MB) neutral red (NR) and crystalviolet (CV) were obtained fromTianjin Guangfu Fine Chem-ical Research Institute (China) Malachite green (MG) wasobtained from Tianjin Bodi Chemical Co Ltd All reagentswere of analytical grade The water used was distilled

22 Preparation Ti foils (5 cmtimes 5 cmtimes 02mm)were pickledin with a volume ratio of HF HNO

3 H2O = 1 3 6 about

30 s at ambient temperature After ultrasonical cleaning indistilled water each two pieces of cleaned Ti foils were soakedin themixed solution (sodiumhydroxide solution (10molL)hydrogen peroxide solution (30) or both of them) Thenthe reactants were kept at designated temperature in waterbath for a certain time After cooling to room temperatureprecipitates were washed by distilled water for several timesuntil the pH = 7 and dried by water bath at 40∘CThe sampleswere obtained after grinding the dried precipitates Sampleswere labeled in Table 1

23 Characterization XRD patterns were acquired on an X-ray diffraction spectrometer (BRUKER AXS D8 ADVANCECu K120572 120582 = 154056 A) FT-IR curves were recorded onSHIMADZU 8400s Fourier transform infrared spectrometerThe SEM images were recorded with a model XL 30 ESEMFEG from Micro FEI Philips at room temperature XPSmeasurements were carried out with a Thermo ESCALAB250 spectrometer using an Al K120572 (14866 eV) X-ray sourceTGDSC analyses were performed on a NETZSCH DSC 204PC Instrument from 30 to 650∘C at a heating rate of 10∘Cminunder N

2(50 cm3min at normal temperature and pressure)

All of the measurements were carried out at room tempera-ture (25 plusmn 2∘C)The specific surface area was calculated fromthe N

2adsorption isotherm using the Brunauer-Emmett-

Teller (BET)method and the pore size distributionwas deter-mined using the Barrett-Joyner-Halenda (BJH)mathematicalmodel The sample was degassed at 50∘C for 12 h before test

24 Adsorption Test All the adsorption experiments wereconducted under stirring at room temperature (25∘C) in thedark The general experimental process was described asfollows 02 g of the sample was added to 200mL of dye solu-tion with certain initial concentration At appropriate timeintervals the aliquots were withdrawn from the suspension

Table 1 Samples prepared on different conditions

SampleWater bathtemperature

(∘C)

Water bathtime (h) 119881NaOH 119881H2O2 State

a 60 24 1 1 Solidb 70 24 1 1 Solidc 60 12 1 1 Solidd 60 24 1 2 Solide 60 24 2 1 Solidf 60 24 Only H2O2 Liquidg 60 24 Only NaOH Liquid

and the adsorbents were separated from the suspension viacentrifugation SDPTOPUV2600PC spectrophotometer wasadopted to measure the concentration of residual dyes

3 Results and Discussion

31 Preparation of TN-TP As shown in Figure 1(a) thereaction product of Ti and H

2O2(30) was buff gel with no

precipitates after water bath in the study The yellow gel wasproved to be Ti(OH)

2O2according to the literature [21] The

reaction product of Ti and NaOH (10molL) was colorlesstransparent liquid without precipitates as well (Figure 1(b))This indicated that the insoluble TiO

2and titanate did not

generate in alkaline condition However large amounts oflight yellow precipitates appeared in the reaction products ofTiH2O2 andNaOH(Figure 1(c)) As a result the precipitates

were the product of the reaction of Ti H2O2 and NaOH

When the pH of the precipitates-containing solution is lowerthan 7 (hydrochloric acid added) the solution turned tobe orange and precipitates in solution began to dissolve(Figure 1(e)) this phenomenon was in accordance with thecharacteristic of titanium peroxide in low pH solution [12]After water washing and being dried the precipitates turnedto be yellow (Figure 1(d)) which might be ascribed to theabsorbed O

2

2minus on the surface of precipitates or the O2

2minus

provided by the titanium peroxide which was one part ofthe precipitates [20] As solid titanate was white and solidtitanium peroxide was yellow it could be hypothesized thatthe precipitate maybe titanate with large amounts of O

2

2minus

absorbed on its surface a kind of titanatetitanium peroxidecomposites or pure titanium peroxide

As titanate was crystallizable XRD was adopted to iden-tify the reaction product of Ti H

2O2 and NaOH after wash-

ing being dried and grinding As shown in Figure 2 all ofthe samples (solid) exhibited a strong peak around 10∘ andthe other three weak broad peaks were around 245∘ 2834∘and 483∘ respectively Peaks of XRD could be approximatelycontributed to sodium titanate (Na

2Ti3O7JCPDSnumber 72-

0148) with low crystallinity [22 23] In addition peaks at 10∘were concentrated with increasing water bath temperature(sample (a)rarr (b)) and the concentration of H

2O2(sample

(e)rarr (a)rarr (d)) which showed that the interlayered ionscrystallinity of Na

2Ti3O7in samples was enhanced [8]

Na2Ti3O7was generated in each preparation condition but


(a) (b) (c) (d) (e)


2O2



0 10 20 30 40 50 60 70 80 90

Inte

nsity

(au

)

2120579 (deg)

(a) (60∘C-24h-1 1)

(b) (70∘C-24h-1 1)

(c) (60∘C-12h-1 1)

(d) (60∘C-24h-1 2)

(e) (60∘C-24h-2 1)















2Ti3O7


2


6octahedra inNa




2

2minus




2

2minus


2




3000 2000 1000

3180453

89513851630

Inte

nsity

(au

)

3400

(a) (60∘C-24h-1 1)

(b) (70∘C-24h-1 1)

(c) (60∘C-12h-1 1)

(d) (60∘C-24h-1 2)

(e) (60∘C-24h-2 1)





2


2

2minus


2


2





2

2minus



2




2


2


2Ti3O7and


2Ti3O7[30]The



1200 1000 800 600 400 200 0 470 465 460 455

C1s

Cou

nts (

s)

Bonding energy (eV)

Na1sO1s

Ti2p

Ti2p

Ti2p12

Bonding energy (eV)

Ti2p32

540 538 536 534 532 530 528 526 524

Ti-O Ti-OH

Inte

nsity

(au

)

Bonding energy (eV)

O1s

1080 1075 1070 1065

Inte

nsity

(au

)In

tens

ity (a

u)

Bonding energy (eV)

Na-O

Na1s

O22minus

4643 eV

4587 eV

5303 eV5317 eV

5330 eV

10719 eV


0 100 200 300 400 500 60075

80

85

90

95

100

Endo

TG

DSC

Mas

s (

) Exo

2

1

0

Hea

t flow

(mW

mg)

4460∘C

665∘C

Temperature (∘C)

minus1






2Ti3O7was thermally












0 30 60 90 120 150 180

02

04

06

08

10

Time (min)

CC

0

(a) 60∘C-24h-1 1

(b) 70∘C-24h-1 1

(c) 60∘C-12h-1 1

(d) 60∘C-24h-2 1

(e) 60∘C-24h-1 2


0 60 120 180 240 300 3600

100

200

300

400

500

Adso

rptio

n (m

gg)

Time (min)

NR

0 60 120 180 240 300 3600

100

200

300MB

Adso

rptio

n (m

gg)

Time (min)

0 60 120 180 240 300 3600

100

200

300

400 MG

Adso

rptio

n (m

gg)

Time (min)0 60 120 180 240 300 360

0

100

200

300 CV

Adso

rptio

n (m

gg)

Time (min)

600mgL400mgL200 mgL

100 mgL50mgL

600mgL400mgL200 mgL

100 mgL50mgL



0 60 120 180 240 300

0

2

4

6

NR

Time (min)0 60 120 180 240

0

2

4

6

MB

Time (min)

0 60 120 180

0

2

4

6MG

Time (min)0 60 120 180 240

0

2

4

6 CV

Time (min)

ln(q

eminus

qt)

ln(q

eminus

qt)

minus2

ln(q

eminus

qt)

ln(q

eminus

qt)

minus2

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL






2O5


2+


2O2were








2Ti3O7nanorods



TP) was 60∘C-24 h-1 1






(3)



997888rarr HTiO3


2O + (119899 minus 3)O

2

(4)

3HTiO3





2O5

2+larrrarr Ti

2O5(OH)+


2O5(OH)3

minus

larrrarr Ti2O5(OH)4


(6)




0 60 120 180 240 300 360

0

1

2

NR

Time (min)0 60 120 180 240 300 360

0

1

2 MB

Time (min)

0 60 120 180 240 300 360

0

1

2

3

4MG

Time (min)0 60 120 180 240 300 360

0

1

2

3

4CV

Time (min)

tqt

(min

(m

gg)

)

tqt

(min

(m

gg)

)t

qt

(min

(m

gg)

)

tqt

(min

(m

gg)

)

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL




2Ti3O7nanorods


2O5


2(OH)119899minus2


2Ti3O7nanorods


2Ti3O7












119890minus 119902119905) = ln 119902

119890minus 1198961119905 119905119902

119905= (1119902

119890)119905 + 1(119902

119890

21198962)




119890cal (mgg) 1198961(minminus1) 119877

1

2119902119890cal (mgg) 119896

2


2


50 4894 23698 00043 084331 4975 0000074 099976100 9765 20296 00403 076211 9901 0000019 099985200 19390 2515 00428 073929 19455 0000008 099997400 37702 1633 00476 096544 39063 0000002 099989600 49021 1342 00163 095304 50505 0000002 099986


50 4918 3046 00480 096565 5236 0000107 099940100 9707 4192 00359 089483 10040 0000027 099985200 18813 11249 00377 097510 19841 0000005 099994400 30702 17795 00329 096500 32258 0000002 099995600 32281 14465 00173 092772 33113 0000002 099997


50 4941 1829 00493 087652 5025 0000136 099997100 9823 3460 00325 089785 10040 0000028 099997200 19489 8763 00361 094685 20080 0000006 099995400 35998 15206 00285 092692 37037 0000001 099996600 38613 15042 00244 093031 39370 0000001 099997


50 4798 1165 00368 083537 4861 0000172 099997100 9484 1248 00316 066735 9533 0000044 099998200 17756 8206 00306 092221 18382 0000007 099989400 27981 14273 00257 093305 29070 0000002 099992600 29274 16454 00186 096956 30395 0000002 099994

40 45 50 55 60 65

0

2

4

6Freundlich model

CV

MB

MG

NR

0 50 100 150 200 250 300

00

02

04

06

08

10 Langmuir model

lnC

e

lnqe Ce (mgL)

Ceq

e(g

L)

NRMBMG

CVLinear regression

NRMBMG

CVLinear regression





1119899119902119890= 119902max119862119890(119860 + 119862119890)

119896119891(mgg) 119899 119877

2119902max (mgg) 119860 (mgL) 119877

2

NR 49021 05349 617 times 10minus4 090387 49751 1045 099991

MB 32281 03467 720 times 10minus6 091099 33113 695 099978

MG 38613 03901 170 times 10minus5 085848 39526 468 099993

CV 29274 03807 545 times 10minus5 090667 30488 1237 099961

3000 2000 1000

1392

1327

11701363

1334

TN-TPInte

nsity

(au

)

1193

1363 1170


(TN-TP)-CV

(TN-TP)-MG

(TN-TP)-MB

(TN-TP)-NR





4 Conclusion











Acknowledgments


References




















2prepared by

















2Ti3O7by a facile




























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


(a) (b) (c) (d) (e)


2O2



0 10 20 30 40 50 60 70 80 90

Inte

nsity

(au

)

2120579 (deg)

(a) (60∘C-24h-1 1)

(b) (70∘C-24h-1 1)

(c) (60∘C-12h-1 1)

(d) (60∘C-24h-1 2)

(e) (60∘C-24h-2 1)















2Ti3O7


2


6octahedra inNa




2

2minus




2

2minus


2




3000 2000 1000

3180453

89513851630

Inte

nsity

(au

)

3400

(a) (60∘C-24h-1 1)

(b) (70∘C-24h-1 1)

(c) (60∘C-12h-1 1)

(d) (60∘C-24h-1 2)

(e) (60∘C-24h-2 1)





2


2

2minus


2


2





2

2minus



2




2


2


2Ti3O7and


2Ti3O7[30]The



1200 1000 800 600 400 200 0 470 465 460 455

C1s

Cou

nts (

s)

Bonding energy (eV)

Na1sO1s

Ti2p

Ti2p

Ti2p12

Bonding energy (eV)

Ti2p32

540 538 536 534 532 530 528 526 524

Ti-O Ti-OH

Inte

nsity

(au

)

Bonding energy (eV)

O1s

1080 1075 1070 1065

Inte

nsity

(au

)In

tens

ity (a

u)

Bonding energy (eV)

Na-O

Na1s

O22minus

4643 eV

4587 eV

5303 eV5317 eV

5330 eV

10719 eV


0 100 200 300 400 500 60075

80

85

90

95

100

Endo

TG

DSC

Mas

s (

) Exo

2

1

0

Hea

t flow

(mW

mg)

4460∘C

665∘C

Temperature (∘C)

minus1






2Ti3O7was thermally












0 30 60 90 120 150 180

02

04

06

08

10

Time (min)

CC

0

(a) 60∘C-24h-1 1

(b) 70∘C-24h-1 1

(c) 60∘C-12h-1 1

(d) 60∘C-24h-2 1

(e) 60∘C-24h-1 2


0 60 120 180 240 300 3600

100

200

300

400

500

Adso

rptio

n (m

gg)

Time (min)

NR

0 60 120 180 240 300 3600

100

200

300MB

Adso

rptio

n (m

gg)

Time (min)

0 60 120 180 240 300 3600

100

200

300

400 MG

Adso

rptio

n (m

gg)

Time (min)0 60 120 180 240 300 360

0

100

200

300 CV

Adso

rptio

n (m

gg)

Time (min)

600mgL400mgL200 mgL

100 mgL50mgL

600mgL400mgL200 mgL

100 mgL50mgL



0 60 120 180 240 300

0

2

4

6

NR

Time (min)0 60 120 180 240

0

2

4

6

MB

Time (min)

0 60 120 180

0

2

4

6MG

Time (min)0 60 120 180 240

0

2

4

6 CV

Time (min)

ln(q

eminus

qt)

ln(q

eminus

qt)

minus2

ln(q

eminus

qt)

ln(q

eminus

qt)

minus2

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL






2O5


2+


2O2were








2Ti3O7nanorods



TP) was 60∘C-24 h-1 1






(3)



997888rarr HTiO3


2O + (119899 minus 3)O

2

(4)

3HTiO3





2O5

2+larrrarr Ti

2O5(OH)+


2O5(OH)3

minus

larrrarr Ti2O5(OH)4


(6)




0 60 120 180 240 300 360

0

1

2

NR

Time (min)0 60 120 180 240 300 360

0

1

2 MB

Time (min)

0 60 120 180 240 300 360

0

1

2

3

4MG

Time (min)0 60 120 180 240 300 360

0

1

2

3

4CV

Time (min)

tqt

(min

(m

gg)

)

tqt

(min

(m

gg)

)t

qt

(min

(m

gg)

)

tqt

(min

(m

gg)

)

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL




2Ti3O7nanorods


2O5


2(OH)119899minus2


2Ti3O7nanorods


2Ti3O7












119890minus 119902119905) = ln 119902

119890minus 1198961119905 119905119902

119905= (1119902

119890)119905 + 1(119902

119890

21198962)




119890cal (mgg) 1198961(minminus1) 119877

1

2119902119890cal (mgg) 119896

2


2


50 4894 23698 00043 084331 4975 0000074 099976100 9765 20296 00403 076211 9901 0000019 099985200 19390 2515 00428 073929 19455 0000008 099997400 37702 1633 00476 096544 39063 0000002 099989600 49021 1342 00163 095304 50505 0000002 099986


50 4918 3046 00480 096565 5236 0000107 099940100 9707 4192 00359 089483 10040 0000027 099985200 18813 11249 00377 097510 19841 0000005 099994400 30702 17795 00329 096500 32258 0000002 099995600 32281 14465 00173 092772 33113 0000002 099997


50 4941 1829 00493 087652 5025 0000136 099997100 9823 3460 00325 089785 10040 0000028 099997200 19489 8763 00361 094685 20080 0000006 099995400 35998 15206 00285 092692 37037 0000001 099996600 38613 15042 00244 093031 39370 0000001 099997


50 4798 1165 00368 083537 4861 0000172 099997100 9484 1248 00316 066735 9533 0000044 099998200 17756 8206 00306 092221 18382 0000007 099989400 27981 14273 00257 093305 29070 0000002 099992600 29274 16454 00186 096956 30395 0000002 099994

40 45 50 55 60 65

0

2

4

6Freundlich model

CV

MB

MG

NR

0 50 100 150 200 250 300

00

02

04

06

08

10 Langmuir model

lnC

e

lnqe Ce (mgL)

Ceq

e(g

L)

NRMBMG

CVLinear regression

NRMBMG

CVLinear regression





1119899119902119890= 119902max119862119890(119860 + 119862119890)

119896119891(mgg) 119899 119877

2119902max (mgg) 119860 (mgL) 119877

2

NR 49021 05349 617 times 10minus4 090387 49751 1045 099991

MB 32281 03467 720 times 10minus6 091099 33113 695 099978

MG 38613 03901 170 times 10minus5 085848 39526 468 099993

CV 29274 03807 545 times 10minus5 090667 30488 1237 099961

3000 2000 1000

1392

1327

11701363

1334

TN-TPInte

nsity

(au

)

1193

1363 1170


(TN-TP)-CV

(TN-TP)-MG

(TN-TP)-MB

(TN-TP)-NR





4 Conclusion











Acknowledgments


References




















2prepared by

















2Ti3O7by a facile




























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



3000 2000 1000

3180453

89513851630

Inte

nsity

(au

)

3400

(a) (60∘C-24h-1 1)

(b) (70∘C-24h-1 1)

(c) (60∘C-12h-1 1)

(d) (60∘C-24h-1 2)

(e) (60∘C-24h-2 1)





2


2

2minus


2


2





2

2minus



2




2


2


2Ti3O7and


2Ti3O7[30]The



1200 1000 800 600 400 200 0 470 465 460 455

C1s

Cou

nts (

s)

Bonding energy (eV)

Na1sO1s

Ti2p

Ti2p

Ti2p12

Bonding energy (eV)

Ti2p32

540 538 536 534 532 530 528 526 524

Ti-O Ti-OH

Inte

nsity

(au

)

Bonding energy (eV)

O1s

1080 1075 1070 1065

Inte

nsity

(au

)In

tens

ity (a

u)

Bonding energy (eV)

Na-O

Na1s

O22minus

4643 eV

4587 eV

5303 eV5317 eV

5330 eV

10719 eV


0 100 200 300 400 500 60075

80

85

90

95

100

Endo

TG

DSC

Mas

s (

) Exo

2

1

0

Hea

t flow

(mW

mg)

4460∘C

665∘C

Temperature (∘C)

minus1






2Ti3O7was thermally












0 30 60 90 120 150 180

02

04

06

08

10

Time (min)

CC

0

(a) 60∘C-24h-1 1

(b) 70∘C-24h-1 1

(c) 60∘C-12h-1 1

(d) 60∘C-24h-2 1

(e) 60∘C-24h-1 2


0 60 120 180 240 300 3600

100

200

300

400

500

Adso

rptio

n (m

gg)

Time (min)

NR

0 60 120 180 240 300 3600

100

200

300MB

Adso

rptio

n (m

gg)

Time (min)

0 60 120 180 240 300 3600

100

200

300

400 MG

Adso

rptio

n (m

gg)

Time (min)0 60 120 180 240 300 360

0

100

200

300 CV

Adso

rptio

n (m

gg)

Time (min)

600mgL400mgL200 mgL

100 mgL50mgL

600mgL400mgL200 mgL

100 mgL50mgL



0 60 120 180 240 300

0

2

4

6

NR

Time (min)0 60 120 180 240

0

2

4

6

MB

Time (min)

0 60 120 180

0

2

4

6MG

Time (min)0 60 120 180 240

0

2

4

6 CV

Time (min)

ln(q

eminus

qt)

ln(q

eminus

qt)

minus2

ln(q

eminus

qt)

ln(q

eminus

qt)

minus2

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL






2O5


2+


2O2were








2Ti3O7nanorods



TP) was 60∘C-24 h-1 1






(3)



997888rarr HTiO3


2O + (119899 minus 3)O

2

(4)

3HTiO3





2O5

2+larrrarr Ti

2O5(OH)+


2O5(OH)3

minus

larrrarr Ti2O5(OH)4


(6)




0 60 120 180 240 300 360

0

1

2

NR

Time (min)0 60 120 180 240 300 360

0

1

2 MB

Time (min)

0 60 120 180 240 300 360

0

1

2

3

4MG

Time (min)0 60 120 180 240 300 360

0

1

2

3

4CV

Time (min)

tqt

(min

(m

gg)

)

tqt

(min

(m

gg)

)t

qt

(min

(m

gg)

)

tqt

(min

(m

gg)

)

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL




2Ti3O7nanorods


2O5


2(OH)119899minus2


2Ti3O7nanorods


2Ti3O7












119890minus 119902119905) = ln 119902

119890minus 1198961119905 119905119902

119905= (1119902

119890)119905 + 1(119902

119890

21198962)




119890cal (mgg) 1198961(minminus1) 119877

1

2119902119890cal (mgg) 119896

2


2


50 4894 23698 00043 084331 4975 0000074 099976100 9765 20296 00403 076211 9901 0000019 099985200 19390 2515 00428 073929 19455 0000008 099997400 37702 1633 00476 096544 39063 0000002 099989600 49021 1342 00163 095304 50505 0000002 099986


50 4918 3046 00480 096565 5236 0000107 099940100 9707 4192 00359 089483 10040 0000027 099985200 18813 11249 00377 097510 19841 0000005 099994400 30702 17795 00329 096500 32258 0000002 099995600 32281 14465 00173 092772 33113 0000002 099997


50 4941 1829 00493 087652 5025 0000136 099997100 9823 3460 00325 089785 10040 0000028 099997200 19489 8763 00361 094685 20080 0000006 099995400 35998 15206 00285 092692 37037 0000001 099996600 38613 15042 00244 093031 39370 0000001 099997


50 4798 1165 00368 083537 4861 0000172 099997100 9484 1248 00316 066735 9533 0000044 099998200 17756 8206 00306 092221 18382 0000007 099989400 27981 14273 00257 093305 29070 0000002 099992600 29274 16454 00186 096956 30395 0000002 099994

40 45 50 55 60 65

0

2

4

6Freundlich model

CV

MB

MG

NR

0 50 100 150 200 250 300

00

02

04

06

08

10 Langmuir model

lnC

e

lnqe Ce (mgL)

Ceq

e(g

L)

NRMBMG

CVLinear regression

NRMBMG

CVLinear regression





1119899119902119890= 119902max119862119890(119860 + 119862119890)

119896119891(mgg) 119899 119877

2119902max (mgg) 119860 (mgL) 119877

2

NR 49021 05349 617 times 10minus4 090387 49751 1045 099991

MB 32281 03467 720 times 10minus6 091099 33113 695 099978

MG 38613 03901 170 times 10minus5 085848 39526 468 099993

CV 29274 03807 545 times 10minus5 090667 30488 1237 099961

3000 2000 1000

1392

1327

11701363

1334

TN-TPInte

nsity

(au

)

1193

1363 1170


(TN-TP)-CV

(TN-TP)-MG

(TN-TP)-MB

(TN-TP)-NR





4 Conclusion











Acknowledgments


References




















2prepared by

















2Ti3O7by a facile




























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


1200 1000 800 600 400 200 0 470 465 460 455

C1s

Cou

nts (

s)

Bonding energy (eV)

Na1sO1s

Ti2p

Ti2p

Ti2p12

Bonding energy (eV)

Ti2p32

540 538 536 534 532 530 528 526 524

Ti-O Ti-OH

Inte

nsity

(au

)

Bonding energy (eV)

O1s

1080 1075 1070 1065

Inte

nsity

(au

)In

tens

ity (a

u)

Bonding energy (eV)

Na-O

Na1s

O22minus

4643 eV

4587 eV

5303 eV5317 eV

5330 eV

10719 eV


0 100 200 300 400 500 60075

80

85

90

95

100

Endo

TG

DSC

Mas

s (

) Exo

2

1

0

Hea

t flow

(mW

mg)

4460∘C

665∘C

Temperature (∘C)

minus1






2Ti3O7was thermally












0 30 60 90 120 150 180

02

04

06

08

10

Time (min)

CC

0

(a) 60∘C-24h-1 1

(b) 70∘C-24h-1 1

(c) 60∘C-12h-1 1

(d) 60∘C-24h-2 1

(e) 60∘C-24h-1 2


0 60 120 180 240 300 3600

100

200

300

400

500

Adso

rptio

n (m

gg)

Time (min)

NR

0 60 120 180 240 300 3600

100

200

300MB

Adso

rptio

n (m

gg)

Time (min)

0 60 120 180 240 300 3600

100

200

300

400 MG

Adso

rptio

n (m

gg)

Time (min)0 60 120 180 240 300 360

0

100

200

300 CV

Adso

rptio

n (m

gg)

Time (min)

600mgL400mgL200 mgL

100 mgL50mgL

600mgL400mgL200 mgL

100 mgL50mgL



0 60 120 180 240 300

0

2

4

6

NR

Time (min)0 60 120 180 240

0

2

4

6

MB

Time (min)

0 60 120 180

0

2

4

6MG

Time (min)0 60 120 180 240

0

2

4

6 CV

Time (min)

ln(q

eminus

qt)

ln(q

eminus

qt)

minus2

ln(q

eminus

qt)

ln(q

eminus

qt)

minus2

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL






2O5


2+


2O2were








2Ti3O7nanorods



TP) was 60∘C-24 h-1 1






(3)



997888rarr HTiO3


2O + (119899 minus 3)O

2

(4)

3HTiO3





2O5

2+larrrarr Ti

2O5(OH)+


2O5(OH)3

minus

larrrarr Ti2O5(OH)4


(6)




0 60 120 180 240 300 360

0

1

2

NR

Time (min)0 60 120 180 240 300 360

0

1

2 MB

Time (min)

0 60 120 180 240 300 360

0

1

2

3

4MG

Time (min)0 60 120 180 240 300 360

0

1

2

3

4CV

Time (min)

tqt

(min

(m

gg)

)

tqt

(min

(m

gg)

)t

qt

(min

(m

gg)

)

tqt

(min

(m

gg)

)

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL




2Ti3O7nanorods


2O5


2(OH)119899minus2


2Ti3O7nanorods


2Ti3O7












119890minus 119902119905) = ln 119902

119890minus 1198961119905 119905119902

119905= (1119902

119890)119905 + 1(119902

119890

21198962)




119890cal (mgg) 1198961(minminus1) 119877

1

2119902119890cal (mgg) 119896

2


2


50 4894 23698 00043 084331 4975 0000074 099976100 9765 20296 00403 076211 9901 0000019 099985200 19390 2515 00428 073929 19455 0000008 099997400 37702 1633 00476 096544 39063 0000002 099989600 49021 1342 00163 095304 50505 0000002 099986


50 4918 3046 00480 096565 5236 0000107 099940100 9707 4192 00359 089483 10040 0000027 099985200 18813 11249 00377 097510 19841 0000005 099994400 30702 17795 00329 096500 32258 0000002 099995600 32281 14465 00173 092772 33113 0000002 099997


50 4941 1829 00493 087652 5025 0000136 099997100 9823 3460 00325 089785 10040 0000028 099997200 19489 8763 00361 094685 20080 0000006 099995400 35998 15206 00285 092692 37037 0000001 099996600 38613 15042 00244 093031 39370 0000001 099997


50 4798 1165 00368 083537 4861 0000172 099997100 9484 1248 00316 066735 9533 0000044 099998200 17756 8206 00306 092221 18382 0000007 099989400 27981 14273 00257 093305 29070 0000002 099992600 29274 16454 00186 096956 30395 0000002 099994

40 45 50 55 60 65

0

2

4

6Freundlich model

CV

MB

MG

NR

0 50 100 150 200 250 300

00

02

04

06

08

10 Langmuir model

lnC

e

lnqe Ce (mgL)

Ceq

e(g

L)

NRMBMG

CVLinear regression

NRMBMG

CVLinear regression





1119899119902119890= 119902max119862119890(119860 + 119862119890)

119896119891(mgg) 119899 119877

2119902max (mgg) 119860 (mgL) 119877

2

NR 49021 05349 617 times 10minus4 090387 49751 1045 099991

MB 32281 03467 720 times 10minus6 091099 33113 695 099978

MG 38613 03901 170 times 10minus5 085848 39526 468 099993

CV 29274 03807 545 times 10minus5 090667 30488 1237 099961

3000 2000 1000

1392

1327

11701363

1334

TN-TPInte

nsity

(au

)

1193

1363 1170


(TN-TP)-CV

(TN-TP)-MG

(TN-TP)-MB

(TN-TP)-NR





4 Conclusion











Acknowledgments


References




















2prepared by

















2Ti3O7by a facile




























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


0 30 60 90 120 150 180

02

04

06

08

10

Time (min)

CC

0

(a) 60∘C-24h-1 1

(b) 70∘C-24h-1 1

(c) 60∘C-12h-1 1

(d) 60∘C-24h-2 1

(e) 60∘C-24h-1 2


0 60 120 180 240 300 3600

100

200

300

400

500

Adso

rptio

n (m

gg)

Time (min)

NR

0 60 120 180 240 300 3600

100

200

300MB

Adso

rptio

n (m

gg)

Time (min)

0 60 120 180 240 300 3600

100

200

300

400 MG

Adso

rptio

n (m

gg)

Time (min)0 60 120 180 240 300 360

0

100

200

300 CV

Adso

rptio

n (m

gg)

Time (min)

600mgL400mgL200 mgL

100 mgL50mgL

600mgL400mgL200 mgL

100 mgL50mgL



0 60 120 180 240 300

0

2

4

6

NR

Time (min)0 60 120 180 240

0

2

4

6

MB

Time (min)

0 60 120 180

0

2

4

6MG

Time (min)0 60 120 180 240

0

2

4

6 CV

Time (min)

ln(q

eminus

qt)

ln(q

eminus

qt)

minus2

ln(q

eminus

qt)

ln(q

eminus

qt)

minus2

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL






2O5


2+


2O2were








2Ti3O7nanorods



TP) was 60∘C-24 h-1 1






(3)



997888rarr HTiO3


2O + (119899 minus 3)O

2

(4)

3HTiO3





2O5

2+larrrarr Ti

2O5(OH)+


2O5(OH)3

minus

larrrarr Ti2O5(OH)4


(6)




0 60 120 180 240 300 360

0

1

2

NR

Time (min)0 60 120 180 240 300 360

0

1

2 MB

Time (min)

0 60 120 180 240 300 360

0

1

2

3

4MG

Time (min)0 60 120 180 240 300 360

0

1

2

3

4CV

Time (min)

tqt

(min

(m

gg)

)

tqt

(min

(m

gg)

)t

qt

(min

(m

gg)

)

tqt

(min

(m

gg)

)

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL




2Ti3O7nanorods


2O5


2(OH)119899minus2


2Ti3O7nanorods


2Ti3O7












119890minus 119902119905) = ln 119902

119890minus 1198961119905 119905119902

119905= (1119902

119890)119905 + 1(119902

119890

21198962)




119890cal (mgg) 1198961(minminus1) 119877

1

2119902119890cal (mgg) 119896

2


2


50 4894 23698 00043 084331 4975 0000074 099976100 9765 20296 00403 076211 9901 0000019 099985200 19390 2515 00428 073929 19455 0000008 099997400 37702 1633 00476 096544 39063 0000002 099989600 49021 1342 00163 095304 50505 0000002 099986


50 4918 3046 00480 096565 5236 0000107 099940100 9707 4192 00359 089483 10040 0000027 099985200 18813 11249 00377 097510 19841 0000005 099994400 30702 17795 00329 096500 32258 0000002 099995600 32281 14465 00173 092772 33113 0000002 099997


50 4941 1829 00493 087652 5025 0000136 099997100 9823 3460 00325 089785 10040 0000028 099997200 19489 8763 00361 094685 20080 0000006 099995400 35998 15206 00285 092692 37037 0000001 099996600 38613 15042 00244 093031 39370 0000001 099997


50 4798 1165 00368 083537 4861 0000172 099997100 9484 1248 00316 066735 9533 0000044 099998200 17756 8206 00306 092221 18382 0000007 099989400 27981 14273 00257 093305 29070 0000002 099992600 29274 16454 00186 096956 30395 0000002 099994

40 45 50 55 60 65

0

2

4

6Freundlich model

CV

MB

MG

NR

0 50 100 150 200 250 300

00

02

04

06

08

10 Langmuir model

lnC

e

lnqe Ce (mgL)

Ceq

e(g

L)

NRMBMG

CVLinear regression

NRMBMG

CVLinear regression





1119899119902119890= 119902max119862119890(119860 + 119862119890)

119896119891(mgg) 119899 119877

2119902max (mgg) 119860 (mgL) 119877

2

NR 49021 05349 617 times 10minus4 090387 49751 1045 099991

MB 32281 03467 720 times 10minus6 091099 33113 695 099978

MG 38613 03901 170 times 10minus5 085848 39526 468 099993

CV 29274 03807 545 times 10minus5 090667 30488 1237 099961

3000 2000 1000

1392

1327

11701363

1334

TN-TPInte

nsity

(au

)

1193

1363 1170


(TN-TP)-CV

(TN-TP)-MG

(TN-TP)-MB

(TN-TP)-NR





4 Conclusion











Acknowledgments


References




















2prepared by

















2Ti3O7by a facile




























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


0 60 120 180 240 300

0

2

4

6

NR

Time (min)0 60 120 180 240

0

2

4

6

MB

Time (min)

0 60 120 180

0

2

4

6MG

Time (min)0 60 120 180 240

0

2

4

6 CV

Time (min)

ln(q

eminus

qt)

ln(q

eminus

qt)

minus2

ln(q

eminus

qt)

ln(q

eminus

qt)

minus2

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL






2O5


2+


2O2were








2Ti3O7nanorods



TP) was 60∘C-24 h-1 1






(3)



997888rarr HTiO3


2O + (119899 minus 3)O

2

(4)

3HTiO3





2O5

2+larrrarr Ti

2O5(OH)+


2O5(OH)3

minus

larrrarr Ti2O5(OH)4


(6)




0 60 120 180 240 300 360

0

1

2

NR

Time (min)0 60 120 180 240 300 360

0

1

2 MB

Time (min)

0 60 120 180 240 300 360

0

1

2

3

4MG

Time (min)0 60 120 180 240 300 360

0

1

2

3

4CV

Time (min)

tqt

(min

(m

gg)

)

tqt

(min

(m

gg)

)t

qt

(min

(m

gg)

)

tqt

(min

(m

gg)

)

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL




2Ti3O7nanorods


2O5


2(OH)119899minus2


2Ti3O7nanorods


2Ti3O7












119890minus 119902119905) = ln 119902

119890minus 1198961119905 119905119902

119905= (1119902

119890)119905 + 1(119902

119890

21198962)




119890cal (mgg) 1198961(minminus1) 119877

1

2119902119890cal (mgg) 119896

2


2


50 4894 23698 00043 084331 4975 0000074 099976100 9765 20296 00403 076211 9901 0000019 099985200 19390 2515 00428 073929 19455 0000008 099997400 37702 1633 00476 096544 39063 0000002 099989600 49021 1342 00163 095304 50505 0000002 099986


50 4918 3046 00480 096565 5236 0000107 099940100 9707 4192 00359 089483 10040 0000027 099985200 18813 11249 00377 097510 19841 0000005 099994400 30702 17795 00329 096500 32258 0000002 099995600 32281 14465 00173 092772 33113 0000002 099997


50 4941 1829 00493 087652 5025 0000136 099997100 9823 3460 00325 089785 10040 0000028 099997200 19489 8763 00361 094685 20080 0000006 099995400 35998 15206 00285 092692 37037 0000001 099996600 38613 15042 00244 093031 39370 0000001 099997


50 4798 1165 00368 083537 4861 0000172 099997100 9484 1248 00316 066735 9533 0000044 099998200 17756 8206 00306 092221 18382 0000007 099989400 27981 14273 00257 093305 29070 0000002 099992600 29274 16454 00186 096956 30395 0000002 099994

40 45 50 55 60 65

0

2

4

6Freundlich model

CV

MB

MG

NR

0 50 100 150 200 250 300

00

02

04

06

08

10 Langmuir model

lnC

e

lnqe Ce (mgL)

Ceq

e(g

L)

NRMBMG

CVLinear regression

NRMBMG

CVLinear regression





1119899119902119890= 119902max119862119890(119860 + 119862119890)

119896119891(mgg) 119899 119877

2119902max (mgg) 119860 (mgL) 119877

2

NR 49021 05349 617 times 10minus4 090387 49751 1045 099991

MB 32281 03467 720 times 10minus6 091099 33113 695 099978

MG 38613 03901 170 times 10minus5 085848 39526 468 099993

CV 29274 03807 545 times 10minus5 090667 30488 1237 099961

3000 2000 1000

1392

1327

11701363

1334

TN-TPInte

nsity

(au

)

1193

1363 1170


(TN-TP)-CV

(TN-TP)-MG

(TN-TP)-MB

(TN-TP)-NR





4 Conclusion











Acknowledgments


References




















2prepared by

















2Ti3O7by a facile




























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


0 60 120 180 240 300 360

0

1

2

NR

Time (min)0 60 120 180 240 300 360

0

1

2 MB

Time (min)

0 60 120 180 240 300 360

0

1

2

3

4MG

Time (min)0 60 120 180 240 300 360

0

1

2

3

4CV

Time (min)

tqt

(min

(m

gg)

)

tqt

(min

(m

gg)

)t

qt

(min

(m

gg)

)

tqt

(min

(m

gg)

)

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL

Linear regression

600mgL400mgL200 mgL

100 mgL50mgL




2Ti3O7nanorods


2O5


2(OH)119899minus2


2Ti3O7nanorods


2Ti3O7












119890minus 119902119905) = ln 119902

119890minus 1198961119905 119905119902

119905= (1119902

119890)119905 + 1(119902

119890

21198962)




119890cal (mgg) 1198961(minminus1) 119877

1

2119902119890cal (mgg) 119896

2


2


50 4894 23698 00043 084331 4975 0000074 099976100 9765 20296 00403 076211 9901 0000019 099985200 19390 2515 00428 073929 19455 0000008 099997400 37702 1633 00476 096544 39063 0000002 099989600 49021 1342 00163 095304 50505 0000002 099986


50 4918 3046 00480 096565 5236 0000107 099940100 9707 4192 00359 089483 10040 0000027 099985200 18813 11249 00377 097510 19841 0000005 099994400 30702 17795 00329 096500 32258 0000002 099995600 32281 14465 00173 092772 33113 0000002 099997


50 4941 1829 00493 087652 5025 0000136 099997100 9823 3460 00325 089785 10040 0000028 099997200 19489 8763 00361 094685 20080 0000006 099995400 35998 15206 00285 092692 37037 0000001 099996600 38613 15042 00244 093031 39370 0000001 099997


50 4798 1165 00368 083537 4861 0000172 099997100 9484 1248 00316 066735 9533 0000044 099998200 17756 8206 00306 092221 18382 0000007 099989400 27981 14273 00257 093305 29070 0000002 099992600 29274 16454 00186 096956 30395 0000002 099994

40 45 50 55 60 65

0

2

4

6Freundlich model

CV

MB

MG

NR

0 50 100 150 200 250 300

00

02

04

06

08

10 Langmuir model

lnC

e

lnqe Ce (mgL)

Ceq

e(g

L)

NRMBMG

CVLinear regression

NRMBMG

CVLinear regression





1119899119902119890= 119902max119862119890(119860 + 119862119890)

119896119891(mgg) 119899 119877

2119902max (mgg) 119860 (mgL) 119877

2

NR 49021 05349 617 times 10minus4 090387 49751 1045 099991

MB 32281 03467 720 times 10minus6 091099 33113 695 099978

MG 38613 03901 170 times 10minus5 085848 39526 468 099993

CV 29274 03807 545 times 10minus5 090667 30488 1237 099961

3000 2000 1000

1392

1327

11701363

1334

TN-TPInte

nsity

(au

)

1193

1363 1170


(TN-TP)-CV

(TN-TP)-MG

(TN-TP)-MB

(TN-TP)-NR





4 Conclusion











Acknowledgments


References




















2prepared by

















2Ti3O7by a facile




























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




119890minus 119902119905) = ln 119902

119890minus 1198961119905 119905119902

119905= (1119902

119890)119905 + 1(119902

119890

21198962)




119890cal (mgg) 1198961(minminus1) 119877

1

2119902119890cal (mgg) 119896

2


2


50 4894 23698 00043 084331 4975 0000074 099976100 9765 20296 00403 076211 9901 0000019 099985200 19390 2515 00428 073929 19455 0000008 099997400 37702 1633 00476 096544 39063 0000002 099989600 49021 1342 00163 095304 50505 0000002 099986


50 4918 3046 00480 096565 5236 0000107 099940100 9707 4192 00359 089483 10040 0000027 099985200 18813 11249 00377 097510 19841 0000005 099994400 30702 17795 00329 096500 32258 0000002 099995600 32281 14465 00173 092772 33113 0000002 099997


50 4941 1829 00493 087652 5025 0000136 099997100 9823 3460 00325 089785 10040 0000028 099997200 19489 8763 00361 094685 20080 0000006 099995400 35998 15206 00285 092692 37037 0000001 099996600 38613 15042 00244 093031 39370 0000001 099997


50 4798 1165 00368 083537 4861 0000172 099997100 9484 1248 00316 066735 9533 0000044 099998200 17756 8206 00306 092221 18382 0000007 099989400 27981 14273 00257 093305 29070 0000002 099992600 29274 16454 00186 096956 30395 0000002 099994

40 45 50 55 60 65

0

2

4

6Freundlich model

CV

MB

MG

NR

0 50 100 150 200 250 300

00

02

04

06

08

10 Langmuir model

lnC

e

lnqe Ce (mgL)

Ceq

e(g

L)

NRMBMG

CVLinear regression

NRMBMG

CVLinear regression





1119899119902119890= 119902max119862119890(119860 + 119862119890)

119896119891(mgg) 119899 119877

2119902max (mgg) 119860 (mgL) 119877

2

NR 49021 05349 617 times 10minus4 090387 49751 1045 099991

MB 32281 03467 720 times 10minus6 091099 33113 695 099978

MG 38613 03901 170 times 10minus5 085848 39526 468 099993

CV 29274 03807 545 times 10minus5 090667 30488 1237 099961

3000 2000 1000

1392

1327

11701363

1334

TN-TPInte

nsity

(au

)

1193

1363 1170


(TN-TP)-CV

(TN-TP)-MG

(TN-TP)-MB

(TN-TP)-NR





4 Conclusion











Acknowledgments


References




















2prepared by

















2Ti3O7by a facile




























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




1119899119902119890= 119902max119862119890(119860 + 119862119890)

119896119891(mgg) 119899 119877

2119902max (mgg) 119860 (mgL) 119877

2

NR 49021 05349 617 times 10minus4 090387 49751 1045 099991

MB 32281 03467 720 times 10minus6 091099 33113 695 099978

MG 38613 03901 170 times 10minus5 085848 39526 468 099993

CV 29274 03807 545 times 10minus5 090667 30488 1237 099961

3000 2000 1000

1392

1327

11701363

1334

TN-TPInte

nsity

(au

)

1193

1363 1170


(TN-TP)-CV

(TN-TP)-MG

(TN-TP)-MB

(TN-TP)-NR





4 Conclusion











Acknowledgments


References




















2prepared by

















2Ti3O7by a facile




























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of















2prepared by

















2Ti3O7by a facile




























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of














Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

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