research article room-temperature synthesis of ni

Research ArticleRoom-Temperature Synthesis of Ni Nanoparticles asthe Absorbent Used for Sewage Treatment

Genhua Zhang Jianchen Li Guangshu Zhang and Lijun Zhao

Key Laboratory of Automobile Materials (Jilin University) Ministry of Education and School of Materials Science and EngineeringJilin University Changchun 130022 China

Correspondence should be addressed to Lijun Zhao lijunzhaojlueducn

Received 18 November 2014 Revised 14 July 2015 Accepted 15 July 2015

Academic Editor Belal F Yousif

Copyright copy 2015 Genhua Zhang et alThis 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

The magnetic Ni nanoparticles of 10ndash30 nm in size were synthesized by the reduction of Ni2+ by NaBH4at room temperature The

amount of added water in the formation of Ni nanoparticles is a significant factor which ensures that Ni nanoparticles are notoxidized by oxygen XRD patterns and FESEM micrographs showed the constituent and structure and micromorphology Congored was used as adsorbate to quantitatively examine the adsorption capability of Ni nanoparticles for the organic dyes in industrywastewater The magnetic hysteresis measurement indicated that the Ni nanoparticles presented ferromagnetic properties Theexperimental results showed the as-obtained Ni nanoparticles might be a potential adsorbent in sewage treatment process

1 Introduction

With the development of modern industry the treatment ofvarious harmful organic chemicals especially the dye fromtextiles and mining industries which can affect aquatic lifeand food chains due to their carcinogenic and mutageniceffects [1] is more and more concerned all over the worldOn the other hand since the end of the 1980s there hadbeen growing interest in fabrication of nanostructures withspecific morphologies and functions This was due to theirsignificantly different physical chemical thermodynamicand mechanical properties from the bulk counterparts as aresult of surface or quantum size effects Among them thenanoscaledmagneticmaterials were paid particular attentionfor their unique properties and uses in high-densitymagneticrecording magnetic sensors and researching magnetic phe-nomena in low-dimensional systems [2ndash6]

In the past decades magnetic materials are regarded asthe potential adsorbents for dyes in sewage owing to theirhigh specific surface area and convenient magnetic sepa-ration Nickel is one of the typical ferromagnetic materialswhich have been studied for many years [7ndash12] Variousmethods were developed to fabricate Ni nanostructures such

as template synthesis [8] solid-phase pyrolysis of organome-tallic precursor [13] laser ablation [14] reduction of metalsalts [6 15] and solvothermal methods [16] In solution-phase methods surfactants were used to prevent the fabri-catedmaterials from aggregationHowever because the adsorp-tion process occurs on the metal surfaces the presence ofsurfactants goes against the adsorptive applications Hereinwe fabricatedNi nanoparticles free of any surfactants at roomtemperature in the air which reduced fabrication cost and con-tamination to environments compared to methods above andconformed to the development tendency of green chemistry

Most often the aqueous solution of Congo red (CR) akind of azo dye was chosen as the sewage to investigate theadsorption capacity of fabricated materials For instance asfar back as 2002 Namasivayam and Kavitha reported theadsorption capacity of activated carbon prepared from coirpith an agricultural solid waste Dyes Pigments although theequilibrium adsorbed concentration was 67mgsdotgminus1 [17] In2010 Afkhami and Moosavi prepared maghemite nanopar-ticles to remove the Congo red in the aqueous solutionswith the equilibrium adsorbed concentration which reached2083mgsdotgminus1 [18] In our previous works the removal capac-ity for Congo red using various micronanomaterials ranged

Hindawi Publishing CorporationAdvances in Materials Science and EngineeringVolume 2015 Article ID 973648 4 pageshttpdxdoiorg1011552015973648

2 Advances in Materials Science and Engineering

from 170 to 800mgsdotgminus1 [19ndash21] which have refreshed to9667mgsdotgminus1 in the present work

2 Experimental

All chemicals used in this work were of analytical grade with-out further purification and were purchased from SinopharmChemical Reagent Beijing Co Ltd In the typical process02 g NiCl

2sdot6H2O and 01 g NaBH

4were put into mortar and

pestled adequately when mixed powders became blackThen10mL of H

2O was added into mortar and the hydrogen gas

was released immediately After the reaction was completedblack precipitate was collected with a magnet and washedwith deionized water and ethanol several times The as-obtained powders were naturally dried at ambient tempera-ture in the air until they became dry

During the reaction process NaBH4acted as a reducing

agent which reduced the Ni2+ and water to Ni0 andH2via the

following reactions respectively

4Ni2+ +BHminus4 + 2H2O 997888rarr 4Ni+BOminus2 + 8H+ (1)

BHminus4 + 2H2O 997888rarr BOminus2 + 4H2 (2)

Usually the stability of the nanoparticles is apt to beaffected by their extreme activity toward water and oxygenSo the amount of H

2O added into the mortar should be

as small as possible to ensure that the Ni nanoparticleswere not oxidized by oxygen dissolving in water Fortunatelygenerating hydrogen gas could assist in excluding a largeproportion of oxygen in the water which further avoided theoxidization of Ni nanoparticles

A standard CR solution with an initial concentration of130mgsdotLminus1 was firstly prepared Then 6mg of dry nickelpowders was added to 50mL of the above solution understirring After a specified time the solid and liquid wereseparated by a magnet and UV-Vis adsorption spectra weremeasured by an Agilent Cary 50UV-Vis spectrophotometerto determine the CR concentration in remaining solutions

The equilibrium adsorbed concentration 119902119890 was calcu-

lated according to the following equation [18]

119902

119890=

(1198620 minus 119862119890) times 119881

119882

(3)

where 1198620 is the initial concentration of CR mgsdotLminus3 119862119890is the

equilibrium concentration in solution mgsdotLminus3 119881 is the totalvolume of the solution dm3 and 119882 is the dry mass of theNi nanoparticles g The equilibrium adsorbed concentrationindicates the adsorptive capacity of the measured samplesand all the investigations were carried out in triplicate toavoid any discrepancy in experimental results

The phases were identified by means of X-ray diffraction(XRD) with a Rigaku Dmax 2500pc X-ray diffractome-ter with Cu K120572 radiation (120582 = 154156 A) The mor-phologies were characterized by a JEOLJSM-6700F field-emission scanning electron microscopy (FESEM) operatedat an acceleration voltage of 110 kV Transmission electronmicroscopy (TEM) patterns were obtained and were carriedout on a JEOL 2100F with an emission voltage of 200 kV

20 30 40 50 60 70 80 90

(111

)

(220

)

(200

)

Inte

nsity

(au

)

2120579 (deg)

Figure 1 XRD pattern of room-temperature prepared Ni nanopar-ticles

IR spectra of the samples were characterized using a FTIRspectrophotometer (NEXUS 670) in KBr pellets Hysteresisloops of the sample were obtained on a VSM-7300 vibratingsample magnetometer (VSM) at room temperature

3 Results and Discussion

Figure 1 shows the XRD patterns of Ni nanoparticles Asshown in the patterns this is typical XRD profile of face-centered-cubic (FCC) nickel phase (JCPDS 04-0850) inwhich there are three diffraction peaks at 2120579 = 445∘ 518∘and 764∘ corresponding to the crystal planes of (111) (200)and (220)

Figures 2(a) and 2(b) are the FESEM and TEM micro-graph respectively which show that Ni nanoparticles haveirregular shapes with a size range of 10 to 30 nm This maybe because there are no surfactants applied in the reactionprocess which made the rapid growth of Ni nanoparticlestake place along a prior crystal orientation in the processof violent reaction and finally formed particles of variousshapes On the other hand small quantity of heat released bythe redox reaction only supported the particles to grow up tothe size range of 10ndash30 nm

Subsequently the adsorption capacity of Ni powders forCR was investigatedThemolecular structure of CR is shownin Figure 3(a) As shown in Figure 3(a) the variation of theadsorption amount with adsorption time which illustratesthat 83 of CR can be removed after 5min and the finalequilibrium adsorbed concentration reaches 9667mgsdotgminus1after 60min The adsorption capacity of the as-preparedNi powders is superior to that of the materials reportedbefore [22ndash24] Furthermore we carried out FT-IR testingfor the Ni particles before and after adsorption using infraredspectrometer to prove that CR have been absorbed into thesample Figure 3(b) shows the curves of puremetal nickel andnickel after adsorption from which a weak peak at 1058 of C-N indicates the presence of CR So they can be potentially

Advances in Materials Science and Engineering 3

(a) (b)

Figure 2 (a) SEM image and (b) TEMmicrograph of Ni nanoparticles

0 10 20 30 40 50 600

200

400

600

800

1000

Contact time (min)

S SOO OO

OminusNa+ OminusNa+

N N N N

NH2 NH2

Qe

(mgmiddot

gminus1)

(a)

2000 1800 1600 1400 1200 1000 800 600

1058 C-N

Nickel after adsorption

Pure nickel

Tran

smitt

ance

()

Wavenumber (cmminus1)

(b)

Figure 3 (a) Curve of adsorption capacities of Ni nanoparticles for CR and (b) FT-IR spectra of Ni nanoparticles before and after adsorptionInset is the molecular structure of CR

used as absorbent in the treatment of industrial wastewatercontaining CR within a short time

The magnetic properties of the sample have been mea-sured at room temperature (Figure 4) As shown in themagnetic hysteresis loop curve the value of saturation mag-netization (Ms) is 26 emusdotgminus1 and the value of coercivity(Hc) is 131Oe Compared to the bulk nickel material (Ms =50 emusdotgminus1 and Hc = 100Oe) the decreasingMs and increas-ingHcmay be attributed to the incomplete crystallization andhigh surfacevolume ratio due to the nanosized diameter ofparticles through quick chemical action at room temperatureInset in Figure 4 represented the photograph of adsorptionand magnetic separation behavior A colorless solution wasgained More importantly simple and rapid separation ofCR-loaded magnetite adsorbent from treated water can beachieved via an externalmagnetic fieldThis indicates that theas-prepared sample belongs to ferromagnetic material and socan be easily separated from the dispersion system with themagnetic bar

0 5000 10000

0

10

20

30

0 250 500

01020

Mag

netiz

atio

n (e

mu

g)

Applied field (Oe)minus10000

minus30minus20

minus10

minus5000

minus500minus250

minus20

minus10

Figure 4 Magnetic hysteresis curve of Ni nanoparticles Inset inturn is CR solution mixing with the magnetic absorbents and sep-aration of the adsorbent from solution with a magnet after adsorp-tion respectively


4 Conclusions

In summary magnetic metallic nickel nanoparticles withthe particle sizes in the range of 10 to 30 nm have beenprepared by an easy NaBH

4reduction process at atmosphere

temperature The sample shows high adsorption capacity of9667mgsdotgminus1 and fast adsorption rate of 83 within 5minfor the CR solution Furthermore the Ms value of the Ninanoparticles is 26 emusdotgminus1 which contribute to the removalof Ni with CR In conclusion the as-prepared product canbe used as a potential adsorbent in the process of industrywastewater especially containing CR

Conflict of Interests

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

Acknowledgment

This work was financially supported by the Social Develop-ment Projects of Jilin Province (20120406)

References

[1] G Crini ldquoNon-conventional low-cost adsorbents for dyeremoval a reviewrdquo Bioresource Technology vol 97 no 9 pp1061ndash1085 2006

[2] Y-W Jun Y-Y Jung and J Cheon ldquoArchitectural control ofmagnetic semiconductor nanocrystalsrdquo Journal of the AmericanChemical Society vol 124 no 4 pp 615ndash619 2002

[3] B Kim S L Tripp and A Wei ldquoSelf-organization of large goldnanoparticle arraysrdquo Journal of the American Chemical Societyvol 123 no 32 pp 7955ndash7956 2001

[4] Y H Ni X W Ge Z C Zhang and Q Ye ldquoFabricationand characterization of the plate-shaped 120574-Fe

2O3nanocrystalsrdquo

Chemistry of Materials vol 14 no 3 pp 1048ndash1052 2002[5] M P Pileni ldquoNanocrystal self-assemblies fabrication and col-

lective propertiesrdquoThe Journal of Physical Chemistry B vol 105no 17 pp 3358ndash3371 2001

[6] P-Z Li A Aijaz and Q Xu ldquoHighly dispersed surfactant-freenickel nanoparticles and their remarkable catalytic activity inthe hydrolysis of ammonia borane for hydrogen generationrdquoAngewandte Chemie vol 51 no 27 pp 6753ndash6756 2012

[7] N Cordente M Respaud F Senocq M-J Casanove C Amiensand B Chaudret ldquoSynthesis and magnetic properties of nickelnanorodsrdquo Nano Letters vol 1 no 10 pp 565ndash568 2001

[8] J C Bao C Y Tie Z Xu Q F Zhou D Shen and Q MaldquoTemplate synthesis of an array of nickel nanotubules and itsmagnetic behaviorrdquoAdvancedMaterials vol 13 no 21 pp 1631ndash1633 2001

[9] J Bao Y Liang Z Xu and L Si ldquoFacile synthesis of hollownickel submicrometer spheresrdquo Advanced Materials vol 15 no21 pp 1832ndash1835 2003

[10] H L Niu Q W Chen M Ning Y S Jia and X J Wang ldquoSyn-thesis and one-dimensional self-assembly of acicular nickelnanocrystallites under magnetic fieldsrdquo Journal of PhysicalChemistry B vol 108 no 13 pp 3996ndash3999 2004

[11] X M Ni Q B Zhao D Zhang X J Zhang and H G ZhengldquoNovel hierarchical nanostructures of nickel self-assembly ofhexagonal nanoplateletsrdquo Journal of Physical Chemistry C vol111 no 2 pp 601ndash605 2007

[12] O Metin V Mazumder S Ozkar and S Sun ldquoMonodispersenickel nanoparticles and their catalysis in hydrolytic dehydro-genation of ammonia boranerdquo Journal of the AmericanChemicalSociety vol 132 no 5 pp 1468ndash1469 2010

[13] A S Manukyan A A Mirzakhanyan G R Badalyan et alldquoNickel nanoparticles in carbon structures prepared by solid-phase pyrolysis of nickel-phthalocyaninerdquo Journal of Nanopar-ticle Research vol 14 no 7 article 982 2012

[14] J Zhang and C Q Lan ldquoNickel and cobalt nanoparticles pro-duced by laser ablation of solids in organic solutionrdquoMaterialsLetters vol 62 no 10-11 pp 1521ndash1524 2008

[15] L Y Bai F L Yuan and Q Tang ldquoSynthesis of nickel nanopar-ticles with uniform size via a modified hydrazine reductionrouterdquoMaterials Letters vol 62 no 16 pp 2267ndash2270 2008

[16] G Zhang X Zhao and L Zhao ldquoPreparation of single-crystal-line nickel nanoflowers and their potential application in sew-age treatmentrdquo Materials Letters vol 66 no 1 pp 267ndash2692012

[17] C Namasivayam and D Kavitha ldquoRemoval of Congo Red fromwater by adsorption onto activated carbon prepared from coirpith an agricultural solid wasterdquoDyes and Pigments vol 54 no1 pp 47ndash58 2002

[18] A Afkhami and R Moosavi ldquoAdsorptive removal of Congored a carcinogenic textile dye from aqueous solutions bymaghemite nanoparticlesrdquo Journal of Hazardous Materials vol174 no 1ndash3 pp 398ndash403 2010

[19] L X Wang J C Li Y Q Wang L J Zhao and Q JiangldquoAdsorption capability for Congo red on nanocrystallineMFe

2O4

(M = Mn Fe Co Ni) spinel ferritesrdquo Chemical EngineeringJournal vol 181-182 pp 72ndash79 2012

[20] G S Zhang and L J Zhao ldquoSynthesis of nickel hierarchicalstructures and evaluation on their magnetic properties andCongo red removal abilityrdquo Dalton Transactions vol 42 no 10pp 3660ndash3666 2013

[21] XM Liang and L J Zhao ldquoRoom-temperature synthesis of air-stable cobalt nanoparticles and their highly efficient adsorptionability for Congo redrdquo RSC Advances vol 2 no 13 pp 5485ndash5487 2012

[22] S Chatterjee M W Lee and S H Wooa ldquoAdsorption of congored by chitosan hydrogel beads impregnated with carbon nano-tubesrdquo Bioresource Technology vol 101 no 6 pp 1800ndash18062010

[23] LWang andA-QWang ldquoRemoval of Congo red from aqueoussolution using a chitosanorgano-montmorillonite nanocom-positerdquo Journal of Chemical Technology and Biotechnology vol82 no 8 pp 711ndash720 2007

[24] S ChatterjeeMW Lee and SHWoo ldquoInfluence of impregna-tion of chitosan beads with cetyl trimethyl ammonium bromideon their structure and adsorption of Congo red from aqueoussolutionsrdquo Chemical Engineering Journal vol 155 no 1-2 pp254ndash259 2009

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of



CeramicsJournal of


CompositesJournal of

NanoparticlesJournal of



International Journal of

Biomaterials


NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014


CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research



MetallurgyJournal of


BioMed Research International

MaterialsJournal of


Nano

materials


Journal ofNanomaterials


from 170 to 800mgsdotgminus1 [19ndash21] which have refreshed to9667mgsdotgminus1 in the present work

2 Experimental

All chemicals used in this work were of analytical grade with-out further purification and were purchased from SinopharmChemical Reagent Beijing Co Ltd In the typical process02 g NiCl

2sdot6H2O and 01 g NaBH

4were put into mortar and

pestled adequately when mixed powders became blackThen10mL of H

2O was added into mortar and the hydrogen gas

was released immediately After the reaction was completedblack precipitate was collected with a magnet and washedwith deionized water and ethanol several times The as-obtained powders were naturally dried at ambient tempera-ture in the air until they became dry

During the reaction process NaBH4acted as a reducing

agent which reduced the Ni2+ and water to Ni0 andH2via the

following reactions respectively

4Ni2+ +BHminus4 + 2H2O 997888rarr 4Ni+BOminus2 + 8H+ (1)

BHminus4 + 2H2O 997888rarr BOminus2 + 4H2 (2)

Usually the stability of the nanoparticles is apt to beaffected by their extreme activity toward water and oxygenSo the amount of H

2O added into the mortar should be

as small as possible to ensure that the Ni nanoparticleswere not oxidized by oxygen dissolving in water Fortunatelygenerating hydrogen gas could assist in excluding a largeproportion of oxygen in the water which further avoided theoxidization of Ni nanoparticles

A standard CR solution with an initial concentration of130mgsdotLminus1 was firstly prepared Then 6mg of dry nickelpowders was added to 50mL of the above solution understirring After a specified time the solid and liquid wereseparated by a magnet and UV-Vis adsorption spectra weremeasured by an Agilent Cary 50UV-Vis spectrophotometerto determine the CR concentration in remaining solutions

The equilibrium adsorbed concentration 119902119890 was calcu-

lated according to the following equation [18]

119902

119890=

(1198620 minus 119862119890) times 119881

119882

(3)

where 1198620 is the initial concentration of CR mgsdotLminus3 119862119890is the

equilibrium concentration in solution mgsdotLminus3 119881 is the totalvolume of the solution dm3 and 119882 is the dry mass of theNi nanoparticles g The equilibrium adsorbed concentrationindicates the adsorptive capacity of the measured samplesand all the investigations were carried out in triplicate toavoid any discrepancy in experimental results

The phases were identified by means of X-ray diffraction(XRD) with a Rigaku Dmax 2500pc X-ray diffractome-ter with Cu K120572 radiation (120582 = 154156 A) The mor-phologies were characterized by a JEOLJSM-6700F field-emission scanning electron microscopy (FESEM) operatedat an acceleration voltage of 110 kV Transmission electronmicroscopy (TEM) patterns were obtained and were carriedout on a JEOL 2100F with an emission voltage of 200 kV

20 30 40 50 60 70 80 90

(111

)

(220

)

(200

)

Inte

nsity

(au

)

2120579 (deg)

Figure 1 XRD pattern of room-temperature prepared Ni nanopar-ticles

IR spectra of the samples were characterized using a FTIRspectrophotometer (NEXUS 670) in KBr pellets Hysteresisloops of the sample were obtained on a VSM-7300 vibratingsample magnetometer (VSM) at room temperature

3 Results and Discussion

Figure 1 shows the XRD patterns of Ni nanoparticles Asshown in the patterns this is typical XRD profile of face-centered-cubic (FCC) nickel phase (JCPDS 04-0850) inwhich there are three diffraction peaks at 2120579 = 445∘ 518∘and 764∘ corresponding to the crystal planes of (111) (200)and (220)

Figures 2(a) and 2(b) are the FESEM and TEM micro-graph respectively which show that Ni nanoparticles haveirregular shapes with a size range of 10 to 30 nm This maybe because there are no surfactants applied in the reactionprocess which made the rapid growth of Ni nanoparticlestake place along a prior crystal orientation in the processof violent reaction and finally formed particles of variousshapes On the other hand small quantity of heat released bythe redox reaction only supported the particles to grow up tothe size range of 10ndash30 nm

Subsequently the adsorption capacity of Ni powders forCR was investigatedThemolecular structure of CR is shownin Figure 3(a) As shown in Figure 3(a) the variation of theadsorption amount with adsorption time which illustratesthat 83 of CR can be removed after 5min and the finalequilibrium adsorbed concentration reaches 9667mgsdotgminus1after 60min The adsorption capacity of the as-preparedNi powders is superior to that of the materials reportedbefore [22ndash24] Furthermore we carried out FT-IR testingfor the Ni particles before and after adsorption using infraredspectrometer to prove that CR have been absorbed into thesample Figure 3(b) shows the curves of puremetal nickel andnickel after adsorption from which a weak peak at 1058 of C-N indicates the presence of CR So they can be potentially


(a) (b)


0 10 20 30 40 50 600

200

400

600

800

1000

Contact time (min)

S SOO OO

OminusNa+ OminusNa+

N N N N

NH2 NH2

Qe

(mgmiddot

gminus1)

(a)

2000 1800 1600 1400 1200 1000 800 600

1058 C-N


Pure nickel

Tran

smitt

ance

()


(b)




0 5000 10000

0

10

20

30

0 250 500

01020

Mag

netiz

atio

n (e

mu

g)


minus30minus20

minus10

minus5000

minus500minus250

minus20

minus10



4 Conclusions






Acknowledgment


References






















2O4














CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




(a) (b)


0 10 20 30 40 50 600

200

400

600

800

1000

Contact time (min)

S SOO OO

OminusNa+ OminusNa+

N N N N

NH2 NH2

Qe

(mgmiddot

gminus1)

(a)

2000 1800 1600 1400 1200 1000 800 600

1058 C-N


Pure nickel

Tran

smitt

ance

()


(b)




0 5000 10000

0

10

20

30

0 250 500

01020

Mag

netiz

atio

n (e

mu

g)


minus30minus20

minus10

minus5000

minus500minus250

minus20

minus10



4 Conclusions






Acknowledgment


References






















2O4














CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




4 Conclusions






Acknowledgment


References






















2O4














CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials



research article room-temperature synthesis of ni

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