Synthesis of nanostructured metal–, semiconductor–, and

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Availableonlineatwww.sciencedirect.com

Journal of Applied Research and Technology

www.jart.ccadet.unam.mx JournalofAppliedResearchandTechnology14(2016)232–238

Original

Synthesis of nanostructured metal–, semiconductor–, and

metal/semiconductor–mordenite composites from geothermal waste

Oscar E. Jaime-Acu˜na

^a,∗

, Humberto Villavicencio-García

^b

, Rogelio Vázquez-González

^c

, Vitalii Petranovskii

^b

, Oscar Raymond-Herrera

^d

aCentrodeInvestigaciónCientíﬁcaydeEducaciónSuperiordeEnsenada–CentrodeNanocienciasyNanotecnología-UniversidadNacionalAutónomade México,Ensenada,BajaCalifornia,Mexico

bCentrodeNanocienciasyNanotecnología,UniversidadNacionalAutónomadeMéxico,Km107CarreteraTijuana-Ensenada,CP22860,A.P.14, Ensenada,BajaCalifornia,Mexico

cDepartamentodeGeofísicadeExploración,CentrodeInvestigaciónCientíﬁcaydeEducaciónSuperiordeEnsenada,CarreteraEnsenada-TijuanaNo.3918, ZonaPlayitas,CP22860,A.P.360,Ensenada,BajaCalifornia,Mexico

dCentrodeNanocienciasyNanotecnología,UniversidadNacionalAutónomadeMéxico,Km107CarreteraTijuana-Ensenada,CP22860,A.P.14,Ensenada, BajaCalifornia,Mexico

Received4September2015;accepted31May2016 Availableonline3July2016

Abstract

Successfulsynthesisofmetal–,semiconductor–,andmetal/semiconductor–mordenitenanocomposites,usinggeothermalsolidwasteasprecursor isreported.Powdersofnanostructuredcomposites,consistingofmetaland/orsemiconductornanoparticlesgrownonamordenite-typezeolitic matrixsurface,weresynthesizedbyaone-stepsolvent-freeandorganictemplate-freeprocess.Thedevelopedmethodologyiscapableofcontrolling andtuningthefinalpropertiesofcompositesfromtheirsynthesisandisalsoreproducibleandrepeatable.Forcomparisonanddemonstrationofthe applicationofthefinalproducts,dyephotocatalysisdegradationtestsweredoneusingcommercialTiO2asreference(degradationreached∼75%

in215min,k=0.004min⁻¹),[M]–S–MORsamplesrevealedbetterperformance(≥95%in100min,k=0.009min⁻¹).

Keywords: Organicpollutionremediation;Multifunctionalnanocomposites;Aqueoussynthesis;Photocatalysis;Geothermalwasteremediation

1. Introduction

Contemporary chemical industries are searching for new techniquesthatreducemanufacturingcostsandmitigateenvi- ronmentalimpact.Processeswithoutemissionsandfreeofrisky chemicalshavethereforebecome achallengefor researchers, technologistsandengineers(Ambec,Cohen,Elgie,&Lanoie, 2013). The lagoonof mineralizedwaters at the Cerro Prieto geothermal plant,inMexicali,Mexico (Fig. 1a), is anexcel- lent sourceof silicon;inan areaof approximately 12.5km², itislocatedbetween115^◦12 and115^◦18 westlongitudeand between 32^◦22 and 32^◦26 northlatitude, 36km away from

∗Correspondingauthor.

E-mailaddress:[email protected](O.E.Jaime-Acu˜na).

PeerReviewundertheresponsibilityofUniversidadNacionalAutónomade México.

Mexicalicity.Besidetheprocessofgeothermalenergyconver- sion,thesaturatedsilicawaterisconductedtotheprecipitation lagoontoseparatethesilicaresiduesfromthereinjectionwater.

Thesilicasaltsprecipitateasamorphoussilica,whichisusedin thiswork.

On the other hand, porousmaterials have potential applications in the chemical industry; likewise, the inclusion of transition metalsand/orsemiconductorsintomatricestomod- ifytheirpropertieshasgainedimportanceforthedevelopment of conveniencematerials(Bibby&Dale,1985;Cooperetal., 2004).Inthefieldofporousnanostructuredmaterials,zeolites havebeenappliedinareassuchascatalysis,watertreatment,H2

production,amongothers(Zaarour,Dong,Naydenova,Retoux,

&Mintova,2014).

In this work, nanostructured composites based on metal, semiconductor or metal/semiconductor nanoparticles were grown on a mordenite-type zeolite matrix from geothermal

http://dx.doi.org/10.1016/j.jart.2016.05.006

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0

2 km

10

Intensity (a.u.)

0 20 30 40

2 theta (degree)

50 60

a

b

c

60 µm

Fig.1.(a)AerialviewoflagoonofmineralizedwatersatCerroPrieto,Mexicali (INEGI-GOOGLE,2015),(b)SEMimage,and(c)DRXpatternofsolidwaste powders.

energy conversion solid waste materials by a solvent- and organictemplate-freeprocess,withtheinclusionofdesiredion or ioncombinationsinaonestep processleadingtoaseries ofmaterialswithseveralpotentialapplications.Todemonstrate

someof thepotentialapplications,theuseof[M]–S–MORas photocatalystisreported.

2. Materialsandmethods

Precursor SiO2 powders (Fig. 1(b)) were obtained from geothermal energy conversionsolid waste materials at Cerro Prietoplant.

Solid materials obtained from Cerro Prieto were cleaned by two mechanical wash processes, briefly, consist of mix- ingbystirringthesolidresidueobtained fromthegeothermal plant with deionized water, these washings are necessary to remove the clay that mayhavebeen mixed withthe residue.

X-ray diffraction(XRD) pattern analysis (Fig.1(c)) revealed only an amorphous phase with the morphology shown in Fig.1(b).

Elementalanalysisbyenergydispersivespectroscopy(EDS) confirmedthe absence of any other element that couldcome fromclays(Table1).

Using this amorphous SiO2 source, metal/mordenite ([M]–MOR) composites were synthesized with M=lithium, sodium, magnesium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, strontium, molybdenum, silver, cadmium, barium, lanthanum, gold, bismuth, and/or their mixtures, following the one-step routedescribed in the MX/a/2012/013218 patent(Raymond, 2012). Thisprocess is solvent-,seed-,andorganic template-free(avoidingthe calci- nation processes toremove templates commonly used in the synthesisofzeolites), whichinvolves110mLofamixtureof 0.1Maqueoussolutionsofsodiumsilicateandaluminumsul- fate(withSiO2/Al2O3molarrelationof15)thatwasstirredfor 30min;then,30mLof0.1–0.3Maqueoussolutionof desired ionsaltwasmixedwiththefirstsolution(thisstepisresponsi- bletoformnanoparticlesindifferentconcentrations).Thefinal solution,withpHvalueof9±1,wasautoclavedat155^◦Cfor 48h.Iteliminatesthetypicalionexchangeprocess(toclarify, ionexchangeisthemostfollowedroutetoembednanoparticles insiliconmatrices,briefly,matriceswereexposedtoanconcen- tratedsolutionsofthedesiredionsaltforatleast48hthenbe washed)asitenablestheinclusionofthedesiredion(typeand concentration)beforethereaction.Thepossibilitytoselectthe ionsbeforesynthesisallowstuningtheelectro-opticalproper- tiesanddrasticallyreducestheobtainingtimeforthiskindof materialsbecauseitdoesnotrequireacalcinationorevapora- tion process(Ren etal.,2012).Thesemiconductor/mordenite composites([M]–S–MOR)aresynthesizedbyexposureofthe activated composites toan H2S atmosphere for 24h atroom temperature.

Materialcomposition,morphologyandstructurewerestud- ied by XRD with a Philips X’Pert diffractometer (CuK␣

radiation),bySEMusingaJEOLJSM-5300microscopewith EDSattachment;byTEMwithaJEOLJEM-2010(withacceler- atingvoltageof200kV),andbyN2adsorptionisothermsusing aTristarII3020SurfaceAreaAnalyzer.Opticalpropertieswere studiedbyUV–VisspectroscopyusinganAvaSpec-ULS2048- UA-50spectrophotometer.

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Table1

WeightpercentobtainedbySEM–EDSchemicalanalysisandsuperficialareavaluesfromrepresentativesynthesizedmaterials.

Weightpercent Waste SiO2

[Na]–

MOR

[Mn]–

MOR

[Fe]–

MOR

[Ag]–

MOR

[Ti,Ba,Sr]–

MOR

[Cr,Ti,Fe]–

MOR

[Ni,Co,Mo]–

MOR

[Co,Mn]–

S–MOR

[Cd,Zn,Ag]–

S–MOR

[Cd,Zn]–

S–MOR

O 33.2 51.8 51.3 51.3 44.9 49.3 48.4 50.4 50.3 50.8 49.9

Na 0 2.7 1.7 1.7 1.8 2.1 4.6 2.4 2.6 1.4 2.3

Al 0 5.5 4.4 5 3.8 4.4 3.9 4.9 4.0 4.7 5.0

Si 66.3 40.4 40.5 40 26.3 35.9 33.0 38.7 39.2 39.6 38.6

M 0 0 1 1 15 7.4 10.3 3.3 3.5 5.2 1.5

S 0 0 0 0 0 0 0 0 1 1 1.3

Si/Al N/A 7 9 8 9 8 8 8 10 8 8

S.A. 1 328 240 275 210 247 185 301 83 74 101

S.A:superficialarea(m²/g).

3. Resultsanddiscussion

XRDpatternsofallsynthesizedcompositesexhibitadefined single phase which matches well with the ICSD 68445 file reported for Na-mordenite; Figure 2 shows patterns of some [M]–MORsamples.

SEMandTEManalysesshowthetypicalMORmorphology (Fig.3),whichconsistsofdisc-shapedgrainsasarrangements ofmordeniteneedle-likecrystals.TheSEMmicrographofsul- fided [M]–S–MORsample (Fig.3(d), as representative case) showsthe samemorphologyas [M]–MOR.The TEMmicro- graph(Fig.3(e))shows thegeneralgrowthfeatures of metal, semiconductor or metal/semiconductor nanoparticles (darker zones),stronglybondedtothemordenitematrixsurfaceinall samples,whicharehomogeneouslydispersedwithanaverage size of 20nm. Suchfeatures significantlyincrease the active surface required for multiple applications in catalysis, water

40 30

20 10

[Bi]-MOR

[La]-MOR

[Ni]-MOR

[Co]-MOR

[Li]-MOR

[Na]-MOR

ICSD 68445

Relative intensity

2 theta (degree)

Fig.2.XRDpatternsofsomesynthesizedmordenitescomparedwiththeICSD 68445file.

treatments,andothers(Liuetal.,2016;Mota,Eliáˇsová,Jung,

&Ryoo,2016).

Table 1 summarizes the weight percent of each element for all materialsandgeothermalsilica, obtained byEDS. An average value of 8.3 for the Si/Al ratio, obtained from EDS analysis, means that the mordenites have several acid sites used as cleavage centers for the nanoparticles; the particular ion at these acid sites determines the size of the nanoparticles.Fig.4showsademonstrativeschemeofthemetaland/or semiconductor–mordenitecomposite.SituationsAandBillus- tratepossible clustersgrowninsidethe mordeniteframework channels.Thenanoparticlesthatgrowoutsidetheframeworkare stronglyorientedbytheSi–O–Alsurfaceofthezeolitematrix.

Figure 5 shows arepresentative N2 adsorption–desorption isotherm of the synthesized nanocomposite powders, which givesinformationaboutthemicro-andmesoporositystructure andiscloselyrelatedwiththepotentialapplications.Adsorp- tionatverylowpartialpressuresisassociatedwiththezeolitic matrixmicroporesystem(poresize<2nm),i.e.,withthecavity andchannelvolumesinsidethezeoliteframework.Moreover, theN2adsorptionextendsathigherpressures,andaslightcon- tinuousslopeatmediumrelativepressuresarisesfromtheN2

adsorption ontheexternalsurfaceof thezeoliteparticles. An increaseintheslopeisalsoobservedathighrelativepressures (P/P0>0.8),describingahysteresiscycle,whichindicatesthe presenceofmesoporosity(poresizebetween2nmand50nm), i.e., the porosity generated on the composite surface and on theinter-crystallitesvolumeinsidethegrainsascanbeseenin Figure3.

From the N2 adsorption–desorption isotherm analysis (Table1)wefoundthatthe[M]–MORsampleshaveanaverage surfaceareaof240m²/g,whilesulfided[M]–S–MORcompos- itesshowedaloweraveragesurfaceareaof60m²/g.

Ontheotherhand,UV–Visspectroscopyresults(Fig.6(a)) revealed the optical-electronic properties for different metal composite samples.The [Na]–MORspectrumwas subtracted fromallspectra.Thespectrashowedthattheopticalbehaviorof the[M]–MORnanocompositescanbetuneddependingonthe kindofmetal.

Belowarelistedpotentialapplicationsforrepresentativesam- ples,derivedfromtheresultsinthespectraofFig.6(a).

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[Na]-MOR

[Ti,Ba,Sr]-MOR

[Cd,Zn]-S-MOR

[Fe]-MOR

10 µm 20 µm

a b

c

d

e

10 µm 10 µm

20 nm

Fig.3.(a–d)SEMand(e)TEMmicrographsofrepresentativesamples.

A. For [Mn]–MOR two bands are evident, the band at

∼500nmisattributedtomanganesecoordinationinMn3O4or MnO;thebandat250–270nmisassociatedtoligand-to-metal charge-transfertransitionontetrahedralcoordination(Azizi&

EhsaniTilami,2013;Selvarajetal.,2005).SuchMnsignalsare relatedtothecoexistenceofthe2+and4+oxidationstatesand

Nanoparticle

MOR

B

A

Fig.4.Demonstrativeschemeofthemetal-and/orsemiconductornanoparticles growninsideandoutsidethemordeniteframework.

theirintensityisattributedtotheexistenceofcoordinationwith Si.Itisknownthat[Mn]–MORcompositesareusedinthepro- duction of methylamines(Hidaka, Higuchi,&Kawai, 2003), inthe wateroxidation process,andinhydrocarbon oxidation (Mengetal.,2013).

B.The[Fe]–MORsampledisplaysabandat∼240nmwhich maybeattributedtometal–electrontransfertransitions(Hailu etal.,2015).Moreover,aweakbandat∼500nmisrelatedto high-spintetrahedralcomplexesofFe³⁺(Fe2O3)(Hailuetal., 2015). [Fe]–MOR is suitable for Fentontreatments (Salazar, Brillas,&Sirés,2012),inthe oxidizing processonreformed gas(Watanabe,2004),selectivecatalyticreductiononautomo- tiveemissions(Colombo,Koltsakis,Nova,&Tronconi,2012), conversionof methaneonmethanol(Hammond etal.,2012), gasolineproductionbytheFischer–Tropschreaction(Sunetal., 2012),amongothers.

C.Forthe[Co]–MORsample,threebandsappearat∼230,

∼530 and ∼635nm; the two former transition bands corre- spondtoCo²⁺ inoctahedralcoordination;whilethetransition at∼635nmisduetotetrahedralofCoO4coordinationpresent

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78 80 82 84 86

Quantity adsorbed (cm3/g)

0.2

Relative presure (P/Po)

0.6 0.4

[ Mn]-MOR

0.8 1.0

Fig. 5.Representative N2 adsorption–desorption isotherm of synthesized [M]–MORforM=Mn.

whenCosubstitutesSiatomsonthemordeniteframework(Azizi

& Ehsani Tilami, 2013; Kato, Ikeda, Kodaira, & Takahashi, 2011).[Co]–MORispresentlybeingusedasaFischer–Tropsch catalyst, to make liquid fuels from biosyngas (Sartipi et al., 2013).

D.Forthe[Ni]–MORsampletheabsorbancearound700nm isassociatedwiththe2+stateoftheNiatoms.Theabsorbance between 270 and300nm may be related tooctahedral coor- dinated Ni ions, surrounded by oxygen atoms of zeolite in electron–donor–acceptorcomplexes.[Ni]–MORhasbeenused foroligomerizationsfrompropeneforlubricantsanddetergents (Mlinar,Shylesh,Ho,&Bell,2014),andconversionof cellu- losetopolyolssuchassorbitolandmannitol(Shrotri,Tanksale, Beltramini,Gurav,&Chilukuri,2012).

E.The[Cu]–MORsampleshowsatransitionbandat240nm associated with Cu⁺; the shoulder at ∼500nm is attributed to coppernanoparticles on the mordenitesurface which corresponds to the capacity of copper to occupy acid sites on the mesoporosity. The signal at ∼700nm corresponds to the spin-allowed d–d transition of Cu²⁺ on zeolite matrices (López-Bastidas,Petranovskii,&Machorro,2012).[Cu]–MOR is used in the carbonylation process for organic molecule

100

UV radiation

[Cd]-S-MOR [Zn]-S-MOR [Cd,Zn]-S-MOR

TiO₂

Residual concentration, %

80

60

40

20

0

0 60 120

Time (min)

180 240

Fig.7.AR114dyephotodegradationunderUVradiation.

production, oxidations of organic moleculestoobtain phenol (Tabler,Häusser,&Roduner,2013),andinactivationofviruses (Imaietal.,2012).

F. The [Ag]–MOR shows a typical absorbance spectrum associated toaplasmonresonanceinthe340–530nmregion.

[Ag]–MORis usedinpesticidedegradation (Kanan&Nusri, 2013); in green chemistry, and in the production of impor- tantpharmacologicalmoleculessuchasspiroketals(Borghèse, Drouhin,Bénéteau,Louis,&Pale,2013).

Furthermore,thesulfided[M]–S–MORUV–Visabsorbance spectra (Fig. 6(b)) show the modifications of the absorption spectrum foreach example. Thesechangescanbe associated to thegrowth of sulfidednanoparticles asreported elsewhere (Jaime-Acu˜na etal., 2014). Anoticeable increase of the sul- fidesamplesabsorptionspectraisobservedinthe225–550nm range. This effect is due to the formation of semiconductor nanoparticles whichare stronglyphotoactive andare respon- sibleforthehighyieldofUV–Vislightharvesting.Thistypeof nanocompositesweretestedinthephotocatalyticdegradationof theorganicmoleculesreaction(Eqs.(1)–(5));briefly,a20ppm ofsome[M]–S–MORnanocompositesand50ppmofacidred 114(AR114)dyewerestirredunderUVlight(254nm).Acom- mercialTiO2sample wasusedas reference.Fig.7 showsthe

225

Absorbance (a.u.)

300 375 450 Wavelength (nm)

525 600 675 750 [Mn]-MOR

a b

[Ni]-MOR [Cu]-MOR [Co]-MOR [Fe]-MOR [Ag]-MOR

225

Absorbance (a.u.)

300 375

Wavelength (nm) 450 525

Unsulfided samples [Co,Mn]-MOR [Cd,Zn]-MOR [Cd,Zn,Mn]-MOR

[Co,Mn]-S-MOR [CCd,Zn]-S-MOR [Cd,Zn,Mn]-S-MOR Sulfided samples

600 675 750

Fig.6.UV–Visspectraof(a)singlemetalnanocomposites,and(b)comparisonbetweenunsulfidedandsulfidedmixedmetalcomposites.

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residualconcentrationbehavioroftheAR114dyeasafunction oftime.

[M]–S–MOR+hv→ [M]–S–MOR(e_BC– +h_BV⁺) (1)

[M]–S–MOR(hvBV+) + H2O

→ [M]–S–MOR+ H⁺+OH– (2)

[M]–S–MOR(hv_BV⁺) + OH–→ [M]–S–MOR +OH^• (3) O2

•– +H⁺→ HO2

• (4)

AR114 +O2

•−+HO2

•+OH^•+OH–→ photodegradation (5)

As shown in Figure 7, while for the commercial TiO2

the degradation reached ∼75% in215min (k=0.004min⁻¹), the [M]–S–MOR samples revealed a significantly better performance. The [Cd,Zn]–S–MOR sample shows the best performance with a degradation of ≥95% in only 100min (k=0.009min⁻¹), the explanation of the calculation of the reactionratecouldbefoundelsewhere(Trejo-Tzab,Alvarado- Gil,Quintana,&Bartolo-Pérez,2012).Thus,the[M]–S–MOR nanocompositesheredevelopedexhibithigherphotoactivityand betterharvestingofthe lightmakingourproductsindustrially competitive.

4. Conclusions

Wastesolidmaterials,derivedfromthe geothermalenergy conversion process, were successfully used in solvent- and organic-freesynthesisofnanostructured compositesbasedon mordenite.

This route for synthesizing metal–MOR, semiconductor–

MORandmetal/semiconductor–MORnanostructuredcompos- iteshas the followingadvantages: (i) reduction of pollutants (nosolventsareused);(ii)savingenergyandsimplifyingsyn- theticprocedures(noorganictemplatesareusedwhichmeans nocalcinationprocessisrequired);(iii)designationofthetype andconcentrationofionsupportedonMORfromthebeginning ofthesynthesis.Withtheseconsiderations,theproposedsyn- thesisroutebecomes relevant forthe industrial productionof nanostructuredcompositesbasedonsyntheticzeolite.

The developed methodology allows control and tuning of the final properties of nanocomposites from their synthesis in addition to being reproducible and repeatable.

Metal–semiconductor–andmetal/semiconductor–MORnano- structuredcompositescouldbewidelyusedinindustryandare strongcandidatesas materialsfor newdevelopments inopto- electronics,catalysis,andespeciallyinphotocatalysis.

Conﬂictofinterest

Theauthorshavenoconflictsofinteresttodeclare.

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