i

“Chemical iProcess iDesign iProject”

Title
Synthesis iof imetal iorganic iframework ifor idye
idegradation
Supervisor: i i iDr. iMuhammad iAslam

Group iMembers

Name Registration i#
Syed iZamin iKazmi FA19-CHE-034-LHR
Abdul iHanan iWali FA19-CHE-042-LHR
Muhammad iZubair FA19-CHE-086-LHR
Ashar iAli ikhan FA19-CHE-096-LHR
Syed iM. iTaqqi iHaider FA19-CHE-100-LHR

Department iof iChemical iEngineering

 ii

COMSATS iUniversity iIslamabad, iLahore iCampus

Table iof iContents

Abstract .......................................................................................................................................... 1
Introduction ..................................................................................................... ............................... 1
MIL-101(Fe) ..................................................................................................................... .......... 2
Literature iReview .......................................................................................................................... 2
Materials iand iMethods ................................................................................................................. 4
FTIR iAnalysis ............................................................................................................................ 5
Effect iof iAdsorbents ion iAdsorption iPerformance .................................................................. 6
Adsorption iKinetics ................................................................................................................... 7
Application ................................................................................................................. .................... 8
Pharmacy .......................................................................................................................... ......... 9
Clean iRoom .......................................................................................................... .................. 10
Automotive .................................................................................................................. ............. 10
Mobile iIndustry iand iPersonal iComputers............................................................................. 10
Security iApplications ............................................................................................................... 10
Sensing itoxic igases................................................................................................................ 10
Separating ihydrocarbons ........................................................................................................ 11
Automotive iand itoxic igas istorage ......................................................................................... 11
Application iof iMil-101(Fe) .......................................................................................................... 11
Metal–organic iframework iMIL-101(Fe) ifor idrug idelivery ...................................................... 11
Metal–organic iframework iMIL-101(Fe) ifor iartificial ikidney iapplication ............................... 12
Metal–organic iframework iMIL-101(Fe) ifor ithe iremoval iof idyes ............................................. 12
Conclusion ............................................................................................................................. ...... 13
References ............................................................................................................. ..................... 13
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CPDP iProject iFinal iReport

Abstract

The ipurpose iof ithis ireport iis ithe iproduction iof iMetal-organic iframework iMIL–
101 i(Fe). i iThe imain ireason ifor ithe iproduction iis idue ito ithe ihigh iporosity inature.
iOther iresearches ihave ibeen idone ion ithe iproduction iof iMOFs iwhich iinclude ilarge
ifamilies iof iMOFs iwith ia ilarge isurface iarea. i iThe iMIL iwas iproduced iby
isolvothermal iapproach. i iBy iobtaining iFTIR iAnalysis iwe ihave iconcluded ithat ithe
ipeaks iwere ifound iat i746.92, i1018.48, i1394.06, i1608.68 iand i1702cm-1, ithis
ishowed ithat iour iMIL-101(Fe) iwas isynthesized. i iIn ithe iUV-Vis ispectroscopy ithe
iamount iof iabsorbed ilight iwas iobserved. iThis ishows ithe isuccessful iproduction iof
iour iMIL-101(Fe).

Introduction

Metal–organic iframeworks igives ia iremarkable itype iof ichemical istructure iwith

iultrahigh iporosity i(about i90% iempty ispaces) iand ilarge iinternal isurface iareas,
imore ithan i6000 im2/g. iThis icomplex ihave iboth ithe iorganic iand iinorganic
icomponents iin itheir istructures, iwhich igive iMOFs ihigh ipotential iuse iin icleaning,
imost iremarkably ias istorage iagent ifor igases ilike ias ihydrogen iand imethane, iand
ias imuch ieffective iadsorbents ito imeet ivarious iseparation iprocesses. iIn iaddition ito
ithis iis iused iin imembranes, ithin-film iequipment, icatalysis, iand ibiomedical iimaging
iare iworth itaking iprocesses.
Industrial iManufacturer ilike iPaint iindustry iand itextile isector ion idaily ibasis
ireleases ia ilarge iamount iof iwater ias iwastage iwhich icarries ihighly itoxic ielement
iand icompounds, iincludes idyes. iThis iwastage iis ihighly iharmful ifor iour
ienvironment iand iecosystem iand icannot ibe iremoved ieasily ibecause iof itheir
ichemical iproperties iand icomplex ichemical istructure i[1]
 2

MIL-101(Fe)

In i2005 iFerey iet. iAL[2]. iFirst itime iinvented iMIL-101(Fe) iwhich iwas isynthesized
ifrom iHF-Cr(NO3)3-1,4-dicarboxylic iacid- i(H2BDC-) iH2O. iSince ithe iformation iof
ithis iMOF, ilarge inumber iof ivariant ihas ibeen iadded ito iMOF ifamily. iThis iis idue
ito iit iexceptional iqualities ilike ilargest isurface iarea i(4500 m2/g), ipore isize i(29–
34 Å), iand icell ivolume i(702.000 Å). iMany iscientist ihave itried ito iform ithis
ithrough igas iabsorption imethod. iHowever, iit iis ihard ito iform idue ito iits ihigh iBET
iplane iwhich iis imore ithan i3200 m2/g. iMethyl iorange ihas ia iwide irange iof
iapplication iin itextile iindustry idue ito iits ireactivity, ibut ihas icomplex istructure.
iMany imethods ihave ibeen iintroduce ito iseparate ithe idye ifrom iwastage ilike
ielectrochemistry, iadsorption, iand ibiosorption. i

Literature iReview

Currently, imasses iof iwaste iwater ihaving idyes ihave ibeen igenerated ifrom imany
iindustries ilike itextile, ileather, ipaper, iprinting, idye istuff, iplastic, iand iso ion. i
iRemoval iof idye imaterials ifrom iwater imay ibe ivery icrucial ibecause iwater
iexcellent iis igreatly iinfluenced iby imeans iof ishade ior ieven ismall iamounts iof idyes
iare inotably iseen iand iunwanted. imoreover, imany idyes iare iconsidered ipoisonous
ior ieven icarcinogenic. i iIt iis idifficult ito idegrade idye imaterials idue ito ithe ifact
ithat ithey're ivery isolid ito imild iand ioxidation. i iFor ithe ielimination iof idye
imaterials ifrom iinfected iwater, iseveral imethods itogether iwith ibodily, ichemical iand
iorganic imethods ihad ibeen iinvestigated. ia inumber iof ithe iproposed itechniques,
ielimination iof idyes iby iusing iadsorption itechnologies iis iregarded ias ione iof ithe
icompetitive istrategies idue ito ithe ifact iadsorption idoes inow inot iwant ia ihigh
ioperation itemperature iand iseveral icoloring isubstances imay ibe ieliminated
isimultaneously. i iMethyl iorange i(MO) iis ione iof ithe ifamous iacidic/anionic idyes,
iand ihas ibeen ibroadly iutilized iin ifabric, iprinting, ipaper, imeals iand ipharmaceutical
iindustries iand istudies ilaboratories. i iThe ielimination iof iMO ifrom iwater icould ibe
 3

ivery icrucial ibecause iof iits itoxicity. i iHarmful iMO ibecome iselected ion ithis
iexamine ias ia iconsultant iacidic idye. i iThe istructure iof iMO iis iproven iin ifigure i1.

iFigure i1; iStructure iof imethyl iorange

Metallic–organic iframeworks i(MOFs), ialso icalled iporous icoordination ipolymers ior

iporous icoordination inetworks i(PCNs), iare imetal iions ior isteel iclusters iand iorganic
iligands iwith imultiple ibinding iweb isites i(N ior iO iatoms), iwhere ia iselfassembled
isingle-factor icrystal icomplicated ieventually ipaperwork ia itwodimensional i(2d) ior
i3-dimensional i(3D) iinfinitely iextending icoordination inetwork iin iarea. iAn iMOF
ihas ino ilonger ionly iultrahigh ifloor iregion, imassive ipore ivolume, iand iadjustable
isurface iproperties i(unsaturated imetallic isites) ihowever ialso iexcellent istructural
iproperties i(pore isize iand igeometry). i iThere iare inumerous iforms iof imetallic–
organic iframework imaterials, ifor iexample, iMIL101(Cr), iMIL-88(Fe), iMIL-53(Al),
icobalt-based itotally imaterial iZIF-8 i(ZIF i= izeolite iimidazole isalt iskeleton), iand
icopper-based itotally imaterial iCu-BTC, iwhich ican ibe icarried iout ito idiverse ifields,
iwhich iincludes igas istorage iand iseparation, iphotocatalysis, idrug ishipping, iand
iother ifields. i iThese idays, iMOFs ihave iattracted itremendous iattention iinside ithe
itreatment iof ipollutants iin iwastewater. i iThe iiron-primarily ibased imetallic–organic
iframework imaterial, ii.e., iMIL101(Fe), iis ione iof ithe imost iconsultant isubstances
iwithin ithe iMIL-n icollection. iMIL-101 i(Fe) iis ia imultistage ipore istructure, iand iits
ihuge ipore idiameter iprovides iremarkable iadsorption icapacity. iMIL-101(Fe) iis
igreater isolid iin iwater isince iit ican ibind iactive icomponents iwhich iincludes iguest
imolecules iand imetallic inanoparticles ito irestrict iit iin iits ipores ior iin ia icage ito
ienhance iits iadsorption ioverall iperformance. i iTherefore, iin ithis itake ia ilook iat,
 4

iMIL-101(Fe) iwas isynthesized iwith igraphene ioxide i(pass) ito ienhance iits
iadsorption ipotential. i iThere iare ifew iresearchers iwho ihave istudied ithe icenter–
shell istructure icomposite i(move-MIL-101(Fe)) ithat iis iimplemented iin
iphotocatalysis; ihowever, inone ihas igenuinely ishown iand idescribed ithe ishape iof
ithe icomposite i(pass-MIL-101(Fe)). i iThis ilook iat ifocused ion iMIL-101(Fe) ias ian
iexquisite-small ilively ipolyhedron ithat imay ibe isynthesized iwith igo iand igrown iat
ithe isurface iof ithe imaterial ilayers iwith irobust isolid ihomes iand ia isheet ishape; ithe
ivariety iof iits ilively isites iare irelatively iconstrained ifor ithe iremoval iof inatural
ipollutants ifrom iwaste iwater. i[3]

Materials iand iMethods

 Synthesis

The iMIL-101(Fe) imaterial iwas isynthesized iby ithe isolvothermal iapproach. i iIn ithis
imethod, i0.428 ig iof iterephthalic iacid iand i1.468 ig iof iFeCl3·6H2O ihad ibeen
idissolved iin i30 imL iof iN, iN-dimethylformamide iand ithen istirred icontinuously ifor
i1 ihour iat iroom itemperature. i iThen, ithe iblended isolution iis itransferred iright iinto
ia iresponse ikettle icovered iwith ipoly(tetrafluoroethylene) iwhich iis itermed ias
iautoclave iand iplaced iin ian ioven iat i120 i°C ifor ia iconstant itemperature iresponse
ifor i24 ih. i iAfter ithat, ithe ireaction ikettle iturned iinto icooled ito iroom itemperature
iand ithe iobtained isample ibecame icentrifuged i(4000RPM ifor i10min) ifor ithe
iseparation. i iSolid iparticles isettled idown iin icentrifuge itube iand isolvent iform ilayer
ion ithe itop iof itube iwhich iis ithen idrained iout. i iNow iwashed ithe isample iusing
icentrifuged i(6000 iRPM ifor i10min) irepeatedly ithree itimes iwith iDMF iand ithree
itimes iwith iethanol. i iThen, ithe ipattern ibecomes idried iin ian ioven iat i120 i°C ifor
i24 ihours. iFinally, i0.53 igrams iof iMil-101 i(Fe) iwere iobtained.
 5

Figure i2; iMil-101 i(Fe)

 Characterization

FTIR iAnalysis

The icharacteristic ipeaks iof iMIL-101-(Fe) iwere ilocated iat i746.92, i1018.48,
i1394.06, i1608.68 iand i1702cm-1, iwhich iproved ithat iMIL-101(Fe) iwas isuccessfully
isynthesized. i iThe ipeak iat i545 icm-1 iwas iassigned ito ithe iFe–O ibond, iwhich
iappeared iin iMIL-101(Fe) ipeaks iat i746.92 iand i1018.48 icm-1 iwas iassigned ito iC–
H ibending ivibrations iand iC– iO i– iC, irespectively. i iThe ipeaks ilocated iat i1394.06
iand i1608.68 icm-1 icorresponded ito ithe isymmetric iand iasymmetric ivibrations iof
iO–C═O, iand ithe ipeak iat i1702 icm-1 icorresponded ito ithe iC═ iO ibond iin icarboxyl
igroups iand iwas iin iline iwith ithe ireported iliterature.
 6

Figure i3; iFTIR iAnalysis iof isample iof iMIL-101(Fe)

UV-Vis Spectroscopy Analysis:

UV-Vis Spectroscopy (or Spectrophotometry) is a quantitative technique used to measure

how much a chemical substance absorbs light. This is done by measuring the intensity
of light that passes through a sample with respect to the intensity of light through a
reference sample.

Effect of Adsorbents on Adsorption Performance

The effect of Methyl orange and the different concentration ratios of MIL-101(Fe) on the
removal of MO. It can be seen that the adsorption capacity of MO on MIL-101(Fe) has
been significantly improved and the adsorption capacity of (C4) (35mg) MIL101(Fe) is
the highest. As the concentration ratio of MIL-101(Fe) decreases continuously, the
adsorption performance of MO decreased gradually. Due to the presence of a small
amount of MIL-101(Fe) that occupied the pores of the material, the pores of the composite
and the surface-active sites of the adsorbent decreased, and thus the adsorption of MO
was also reduced. When the concentration is increased, the pores of the composite and
 7

the surface-active sites of absorbent is increased and thus the absorption of MO is

increased.

Concentration change
10
9
8
7
6
5
4
3
2
1
0
200 250 300 350 400 450 500 550 600 650 700
Wavelength(nm)
MO solution C1(10mg) C2(15mg) C3(25mg) C4(35mg)

Figure i4; iUV-Vis iSpectroscopy iAnalysis, iEffect iof ichanging iConcentration iof
iMIL101(Fe) ion iabsorption iof iMethyl iOrange.

Figure i5; iAbsorption iof iMO ion ithe isurface iof iMil-101(Fe)
 8

Adsorption iKinetics

The ieffects iof itime ion ithe iadsorption iof iMIL-101(Fe). i iIt ican ibe iseen ithat ithe
iadsorption icapacity iof iMO iby iMIL-101(Fe) iincreased irapidly ibefore i30 imin. i
iThis iwas idue ito ithe ilarge ispecific isurface iarea iof iMIL-101(Fe) iand ia ilarge
inumber iof iactive iadsorption isites ion ithe isurface. i iWith ithe iincrease iof itime,
imost iof ithe iadsorptive iactive isites iwere igradually ioccupied iand ithe iadsorption
irate islowed idown iafter i60 imin, ifinally ireaching ithe iequilibrium. i iThe iadsorption
icapacity iof iMO iwas i60% iand ihigher iin iMIL-101(Fe).

Effect of change in time on absorption

4

3.5

2.5

1.5

0.5

0
0 10 20 30 40 50 60 70
Absorbance
MO 10 min 20 min 30 min 40 min

Figure i6; iUV-Vis iSpectroscopy iAnalysis, iEffect iof ichanging itime iduration iof
iAbsorption iof iMO ion ithe isurface iof iMIL-101(Fe).

Application

Metal iorganic iframeworks ihave imany iapplications iin ivarious iindustries:

 9

Pharmacy
MOFs iare iused ito iextract iActive iPharmaceutical iSubstances i(API) ior idrugs iin ia
icentered iway ior ito isafety ithe iAPI iin iunfavorable iconditions igastric iacid. iA
isteady irelease iof iactive isubstances isuch ias ivaccines iare iproduced iby ituning
imetal-organic iframeworks iaccordingly.

Clean iRoom

The iconditions iin iwhich iclean irooms ican ibe itested iand icontrolled iby iusing iMOFs
iin ivarious iapplications. i iThis iincludes ihumidity imanipulate, iadsorptions iof itoxic
igases iand iair ipurification iprocess.

Automotive

MOFs igrowths igasoline istorage iin iCNG-powered iautomobiles ior iimprove ibatteries
iin ielectric ipowered icars. iFurthermore, iclimatization iand icabin iair ichange ican ibe
isupported iby iMOFs.

Mobile iIndustry iand iPersonal iComputers

The iupgrades ion ibatteries idue ito iMOFs idirectly itransfer ito ipersonal iPC iand iyour
imobile iphones.

Security iApplications

Detection iand ineutralization iof itoxic imaterials ivia imetal-organic iframeworks ioffer
imany iimplementations ito isave ilives.
 10

Sensing itoxic igases

The idetection iof itoxic igases ineeds ihighly isensitive iand iquick isensing iprocedures.
iMetal-organic iframeworks iare iable ito iquickly idetect igases iat ismall iconcentrations
iand iare irelevant iafter iquick iregeneration. iThese iproperties imake iit iperfect ifor
isensor iapplications.

Separating ihydrocarbons

The iseparation iof ihydrocarbons, iparticularly iethane iand iethylene, iis ia icomplex
iprocess iin ithe ichemical iindustry. iMetal-organic iframeworks ioffer ihigh iselectivities
itoward ithe ineeded igas, iwhich ioffer inew iroutes ito igas iseparation iprocess.

Automotive iand itoxic igas istorage

Due ito itheir ilow idensities iwhile iproviding ihigh isurface iarea, iMOFs iare ihired ifor
igasoline istorage ilike inatural igas ior itoxic igases i(e.g., iarsines). iThe ifuel imolecules
iget istacked iin ithe ipores iand ihave iinteraction iwith ithe isurface iof ithe iMOF. iThis
imuti iadsorption ieffect iinside ithe ipores isignificantly iincreases ithe iamount iof igas
ithat iis istored iin ia igas icontainer.

Furthermore, igases ican ibe iproperly istored iin isub-atmospheric ipressure i(under i1
iatm), istopping ispillage iin icase iof ia ileak iinside ithe icontainer. i[4]
 11

Application iof iMil-101(Fe)

Metal–organic iframework iMIL-101(Fe) ifor idrug idelivery

 This iis ialso iused iin ipharmaceutical iindustry, itwo imembers iof iTetracycline
ifamily iare imanufactured ithrough iNanostructures iMOF iof iMIL-101(Fe). iIts
istructure icontains iDoxycycline imonohydrate iand iTetracycline
ihydrochloride ion ieach iside.
 Large ipores iand ia ihigh isurface iarea imake iMIL-101 ian iideal icarrier ifor
idrug idelivery ipurposes iused.
 It ihas ibeen ifound ithat iit iused ifor iencapsulating iseveral idrugs isuch ias
idoxorubicin, iibuprofen, icaffeine, iand iaspirin iin ihigh iloading icapacities
icompared ito iconventional imethods.
 MIL-101 i(Fe) ias ia istable iand isafe icapsule ifor iseveral ismall imolecule
idrugs. i[5]

Metal–organic iframework iMIL-101(Fe) ifor iartificial ikidney iapplication

❖ Metal–organic iframework iMIL-101(Fe) iwas idiscovered ias ia inovel isorbent

ifor iartificial ikidney iapplication ito itake iout ia itypical iuremic itoxin
icreatinine iwith ihigh iadsorption icapacity iand iexcellent ireusability. i[6] i i i

Figure i7; iRemoval iof icreatinine ifrom ithe iblood iusing iMil-101 i(Fe)
 12

Metal–organic iframework iMIL-101(Fe) ifor ithe iremoval iof idyes

MO iis iwidely iused iin ithe itextile, ifood, ipaper, ipharmaceutical, iand iprinting
iindustry, iand idue ito iits i−N═N– istructure iand ilow ibiodegradability, iit imay icause
inumerous ihuman ihealth iand ienvironmental iproblems. i iBut iit ican ibe iremoved iby
iusing ithe iMIL-101(Fe). i iOne igram iof iMOF ican ihave ia isurface iarea iequal ito ia
iFIFA isoccer ifield. i iThat iequal ito i7000 isquare imeter isurface iper i1 igram iof iMOF
imaterial. i iThe ilarge isurface iarea igives imore ispace ifor ichemical ireactions iand
iadsorption iof imolecules. iBut ithis iis inot icome ito ithe iend ifor ithe igrowing
iengagement iof iindustries iand iacademia itowards imetalorganic iframeworks.
Following iis ithe idegradation igraph iof imethyl iorange iin isolution; i[7]

Figure i8: iEffect iof ithe idosage iof iMIL-101 i(Fe) ion ithe

idecolorization iof iAO7 iat idifferent itimes: i(1) i0-24 ih, iin iwhich i2 img
i(a), i3 img(b), i4 img(c), i5 img(d), i6 img(e), i7 img(f), i8 img(g), i9 img(h),
iand i0 img(i) iadsorbent iwere iused; i(2) iat i4 ih. i[8]

Conclusion

We iconclude ithat ithe iproduction iof iML-101 i(Fe) iwas isuccessfully icompleted
iwhich ican ibe ishown iby ithe idifferent imethod itests iwhich iwere iconducted. i
iDifferent itests iwere iconcluded iwhich iinclude iFTIR itest, iUV-Vis iSpectroscopy
ianalysis iand iAdsorption ikinetics itest. i iAll iof ithese itests ihave ishown ia ipositive
iresult iconfirming ithat iour iMOF iMIL-101 i(Fe) iwas isynthesized isuccessfully.
 13

References

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iLong, iand iOmar iM. iYaghi, iChem. iRev. i2012, i112, i2, i673–674, iJanuary i26,
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[2] iMetal-Organic iFramework iMIL-101: iSynthesis iand iPhotocatalytic

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[4] iNano-Society: iPushing ithe iBoundaries iof iTechnology, i iMichael iBerger,

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iChengXiong iYang iet. iAL, iRSC iAdv., i2014,4, i40824-40827, iAug i22, i2014.

[7 i& i8] iAdsorptive iremoval iof iacid iorange i7 ifrom iaqueous isolution iwith imetal–
organic iframework imaterial, iiron i(III) itrimesate, iFang-Chang iTsai, iYue iXia, iNing
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