Trans.NonferrousMet.Soc.

China22(2012) 117123

PreparationofCu nanoparticleswith NaBH4 by aqueousreduction method

1,2 1,2 2 2 2 LIUQingming , ZHOUDebi , Yuya YAMAMOTO ,Ryoichi ICHINO ,MasazumiOKIDO

1.SchoolofChemistryandChemicalEngineering,CentralSouthUniversity,Changsha 410083, China 2.DepartmentofMaterialsScience,GraduateSchoolofEngineering,NagoyaUniversity,Nagoya4648603,Japan Received12January 2011accepted16 May 2011

2+ Abstract: Cu nanoparticles were prepared by reducing Cu ions with NaBH4 in alkaline solution. The effects of NaBH4 concentration and dripping rate on the formation of Cu nanoparticles were studied. The optimum conditions are found to be 0.2 2+ mol/LCu , solution with pH=12, temperature of 313 K and 1% gelatin as dispersant, to which 0.4 mol/LNaBH4 is added at a drippingrateof50mL/min.NH3H2OisfoundtobetheoptimalcomplexanttoformtheCuprecursor.Aseriesexperimentswere conductedtostudythereactionprocess atdifferenttimepoints. Key words:Cunanoparticles aqueousreductionmethod precursorreactionprocess

1Introduction
Inrecentyears,thepreparationofCunanoparticles hasbecomeanintensiveareaofscientificresearchasCu nanoparticles exhibit many excellent physical and chemical properties such as high electrical conductivity and chemical activity. Cu nanoparticles are considered possible replacements for Ag and Au particles in some potential applications, such as in catalysts and conductive pastes [14]. There are many wellknown procedures for preparation of Cu nanoparticles, such as the radiation method [5], microemulsion technique [6], supercritical technique [7], thermal reduction [8], sonochemical reduction [9], laser ablation [10], metal vapor synthesis [11], vacuum vapor deposition [12] and aqueous reduction method [13]. Among these methods, aqueous reduction method is most widely employed becauseofitsadvantagessuchassimpleoperation,high yield and quality, limited equipment requirements and ease of control. Because of its strong reducing ability, NaBH4 is widely used as a reductant for this aqueous reduction process. According tothe previously reported research, much work has been done to explore the optimum conditions for preparation of copper nanoparticles[14].However,thereactionmechanismhas beenseldomreported.Inthis research,themechanismof reaction process was investigated based on the optimizing of thereactionconditions.

2Experimental
All the reagents used in the experiments were of analytical grade and obtained from Nacalai Tesque (Kyoto). The flowchart of the experimental process is shown in Fig. 1. Prior to carrying out the experiments, 50 mL CuSO4 solution and NaBH4 solutions were prepared, and argon was bubbled through both the solutionsfor30min.EachpHvaluewasadjustedtothe same value using H2SO4 and NaOH solutions, respectively.Then1%gelatin(massfraction)wasadded into the CuSO4 solution as a dispersant. The NaBH4 solutionwasthenaddeddropwisetotheCuSO4 solution in a beaker at 313 K with magnetic rod stirring. The color of the mixture was changed from blue to brown, indicating the precipitation of Cu nanoparticles. When the reactionwascompleted,asmallquantityoftheslurry was collected for size distribution measurements using an electrophoretic light scattering spectrophotometer (Model: ELS8000NS, Otsuka Electronics Co. Ltd., Japan).Cuparticleswereformedbyprecipitation,which were separated by centrifugation, washed several times with distilled water and ethanol, and finally dried in a vacuumstoveatroomtemperaturefor severaldays.The SEMimageswereobtainedbyusingascanningelectron microscope(model:S800,HitachiCo.Ltd.,Japan)and theXRDpatternsofthespecimenwererecordedusing

Correspondingauthor:LIUQingming Tel:+81527893353Fax:+81527893355Email:luisman@126.com DOI:10.1016/S10036326(11)611497

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Fig.1 Flowchartofexperimentprocess

an Xray diffractometer (model: XRD6000, Shimadzu Co.Ltd.,Japan)withCu K radiation.

3Resultsanddiscussion
3.1 Effect of NaBH4 concentration on Cu nanoparticlespreparation Inaqueoussolution,thereactiontakesplaceas
4Cu2+ +BH4Cu+ B(OH)O 4 + 8OH = 4 + 4H 2
2+

(1)

In theory, the stoichiometric ratio of Cu ions to 2+ NaBH4 is 4:1. In the experiment, Cu concentration is fixedat0.2mol/L,thus,theNaBH4 concentrationshould ideally be 0.05 mol/L. With a fixed concentration (1%, mass fraction) gelatin as the dispersant and solution pH of 12, the effect of NaBH4 concentration on the Cu particleswasinvestigated.TheresultsareshowninFig. 2. It is observed that the average size of the Cu nanoparticles decreases with increasing NaBH4 concentration. When the NaBH4 concentration is 0.4 mol/L (8 times greater than the stoichiometric dosage),Cunanoparticleswithanaveragesizeof37nm are obtained. The XRD patterns show that at a low NaBH4 concentration, the resultant particles contain Cu(OH)2 and Cu2O. At a higher NaBH4 concentration, the Cu(OH)2 contaminant disappears, but Cu2O disappears only when the NaBH4 concentration reaches several times the stoichiometric value. The analysis by XRD reveals that Cu(OH)2 and Cu2O contaminants are the intermediateproductsof thereductionprocess. 3.2 Effect of NaBH4 dripping rate on Cu nanoparticlespreparation Intheexperiments,itisfoundthatthedrippingrate hasasignificanteffecton theaveragesizeandshapeof

the Cunanoparticles. The effect of the NaBH4 dripping rate was investigated under constant condition of 0.2 2+ mol/LCu , 0.4 mol/LNaBH4, 1% gelatin and pH=12. TheCuparticleswerepreparedwiththeNaBH4dripping rateof5and50mL/min,respectively.Theresultsofthis experimentareshown in Fig.3.Theaverage size ofCu particlespreparedat adripping rateof5mL/minislarger thanthatobtainedat50mL/min.TracesofCu(OH)2 are also found, indicating that the reduction reaction is incomplete. The Cu nanoparticles obtained at dripping rate of 50 mL/min are smaller due tothe occurrence of explosive nucleation when the two solutions are combined. According to the classical theory of nucleation, formation of Cu nanoparticles usually undergoes three stages: prenucleation, nucleation and crystal nucleus growth [15]. Explosive nucleation involves the generation of a large number of nuclei duringtheinitialstagesofnucleation.Sincemostofthe 2+ Cu ionsareconsumedfornucleation,the aggregationis limited.Thus,Cunanoparticleswithverysmallsizecan beobtained. 3.3 Effect of complexant on Cu nanoparticles preparation Appropriate complexants in the CuSO4 solution could not only eliminate the agglomeration of the Cu particles,butalsochangethemorphologyoftheresultant particles. In this work, three types of complexants were adoptedintheexperiments,NH3H2O,potassiumsodium tartrate (KNaC4H4O6)andtrisodiumcitrate(C6H5O7Na3). The reduction reactions can be represented by the followingequations. WhenNH3H2Oisadoptedascomplexant,

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Fig.2 SEM imagesandXRDpatternsofcopperparticlesobtainedusing NaBH4 withdifferentconcentration:(a), (a)0.05mol/L (b), (b) 0.1mol/L (c), (c) 0.2mol/L (d), (d) 0.4 mol/L
2 + Cu2+ + 4NH Cu(NH O 3 H 2O= 3 ) 4 + 4H 2 2 + 4Cu(NH 3) 4 +BH 4 + 8OH = 4Cu+ B(OH)4 + 16NH 3 + 4H 2O

(2)

2 - Cu2+ +2C4H4O2 2 = Cu(C 4H 4O 6) 2 4Cu(C O6)2 4H 4 2 +BH 4 + 8OH =

(4)

(3)

2 4Cu+ B(OH)4 + 8(C 4H 4O 6) 2 + 4H 2O

(5)

WhenKNaC4H4O6 isadoptedascomplexant,

And when C6H5O7Na3 is adopted as complexant,

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3 4 - Cu2+ +2C O O 6H 5 7 = Cu(C 6H 5 7) 2 4Cu(C O7)4 6H 5 2 +BH 4 + 8OH = 3 4Cu+ B(OH)O 4 + 8C 6H 5 7 + 4H 2O

(6)

(7)

2+ With fixed values of 0.2 mol/L Cu , 0.4 mol/L NaBH4, 1% gelatin and pHof12, the effect of different complexants on Cu nanoparticles preparation was investigated. The results are shown in Fig. 4. With 1.2 mol/LNH3 H2 O,0.6mol/LKNaC4 H4 O6 and0.6mol/L

Fig.3 SEM images andXRD patternsofcopperparticlesobtainedusing NaBH4 at differentdrippingrates:(a), (a) 5mL/min (b), (b) 50mL/min

Fig.4SEMimagesofcopperparticles obtained using different complexants: (a)1.2 mol/LNH3H2O (b) 0.6 mol/L KNaC4H4O6 (c)0.6 mol/L C6H5O7Na3

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C6H5O7Na3 asthe complexants, theaverage sizes of Cu particles obtainedare42, 115and 108nm,respectively. Thus,NH3H2O is the optimalcomplexantfor precursor formation. 3.4 Reductionprocessatdifferentreactiontime A series experiments were conducted to study the reactions occurring during Cu nanoparticles formation. 2+ Atfixedvaluesof0.2mol/L Cu ,0.4mol/L NaBH4,1% gelatin and pH=12, the size distribution, SEM images and XRD patterns of the Cu nanoparticles at different reactiontimepoints(0,0.5,1,3,5,10and60min)were examined.TheresultsareshowninFig.5.TheSEM

images and XRD patterns show that during the initial stages of the reaction, the majority of the particles is rodshaped Cu(OH)2. Within 5 min, Cu(OH)2 disappeared. The XRD patterns at 10 and 60 min are similar to that obtained at 5 min, indicating the completion of the reduction reaction within 5 min. The 2+ XRD patterns also show that all the Cu ions are transformed to Cu(OH)2 before the two solutions are mixed. Cu(OH)2 isthenreduced to Cu nanoparticles by NaBH4. Thefinalreactionprocesscanberepresentedas Cu2+ + 2OH- = Cu(OH)2
4Cu(OH)2 +BH4Cu+ B(OH)O 4 = 4 + 4H 2

(8) (9)

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LIUQingming,etal/Trans.NonferrousMet.Soc.China22(2012) 117123

Fig.5SEMimagesandXRDpatternsofcopperparticlesobtainedatdifferenttimepoints:(a), (a)Beforemixing(b),(b)After0.5 min(c), (c)After1min(d), (d)After3min(e), (e)After5min(f), (f)After10min(g), (g)After60min

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4Conclusions
1)TheaveragesizeoftheCunanoparticlesreduces 2+ 2+ withincreasingexcessofNaBH4 toCu .WhentheCu and NaBH4 concentration are 0.2 and 0.4 mol/L, the drippingrateis50mL/min,gelatinconcentrationis1%, pH=12 andsolutiontemperature is 313 K,thefinest Cu nanoparticles(37nm)areobtained. 2) Among NH3H2O, KNaC4H4O6 and C6H5O7Na3, the optimal complexant is found to be NH3H2O for precursor formation. The smallest Cu nanoparticles are obtainedwith1.2 mol/L NH3H2O. 2+ 3)Duringthereactionprocess,Cu istransformed toCu(OH)2 beforecombinationofthesolutionsandthen this Cu(OH)2 is reduced by the addition of NaBH4 solution.

[6]

[7]

[8]

[9]

[10]

[11]

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NaBH4
1,21,2222
1. 410083 2. 4648603
2+ NaBH4 Cu NaBH4 Cu 2+ 0.2mol/L Cu pH 12 313K1% 0.4 mol/L NaBH4

50mL/min CuSO4
(Editedby FANGJinghua)