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

COMSATS iUniversity iIslamabad, iLahore iCampus
Contents
Abstract..............................................................................................................................1

Introduction........................................................................................................................1

MIL-101(Fe)..................................................................................................................2

Literature Review..............................................................................................................2

Materials and Methods......................................................................................................4

FTIR Analysis................................................................................................................5

Effect of Adsorbents on Adsorption Performance.....................................................6

Adsorption Kinetics.......................................................................................................8

Application........................................................................................................................8

Pharmacy.......................................................................................................................9

Clean Room...................................................................................................................9

Automotive....................................................................................................................9

Mobile Industry and Personal Computers.....................................................................9

Security Applications.....................................................................................................9

Sensing toxic gases......................................................................................................10

Separating hydrocarbons.............................................................................................10

Automotive and toxic gas storage................................................................................10

Application of Mil-101(Fe).............................................................................................11

Metal–organic framework MIL-101(Fe) for drug delivery.........................................11

Metal–organic framework MIL-101(Fe) for artificial kidney application..................11

Metal–organic framework MIL-101(Fe) for ithe iremoval of dyes.................................12

Conclusion.......................................................................................................................12

References........................................................................................................................13
 1

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
 3

iwater icould ibe 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
 4

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, 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
 7

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

Concentration change
10
9
8
7
Absorbance

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

3
Wavelength i(nm)

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 itheidecolorization
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
 13

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.

References

[1] iIntroduction ito iMetal–Organic iFrameworks, iHong-Cai iZhou, iJeffrey iR.

iLong, iand iOmar iM. iYaghi, iChem. iRev. i2012, i112, i2, i673–674, iJanuary i26,
i2012.

[2] iMetal-Organic iFramework iMIL-101: iSynthesis iand iPhotocatalytic

iDegradation iof iRemazol iBlack iB iDye, iPham iDinh iDu iet. iAL, iVolume i2019 i|
Article iID i6061275 i|, iMay i14, i2019.

[3] iRevisiting ithe iMIL-101 imetal–organic iframework: idesign, isynthesis,

imodifications, iadvances, iand irecent iapplications, iMahmoud iY. iZorainy iet. iAL,
iJ. iMater. iChem. iA, i2021,9, i22159-22217, i Sep i15, i2021.

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

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[5] iMetal–Organic iFramework iNanocarriers ifor iDrug iDelivery iin iBiomedical

iApplications, iYujia iSun iet. iAL, iNano-Micro iLetters ivolume i12, iArticle inumber:
i103 i(2020), iMay i2, i2021.

[6] iMetal–organic iframework iMIL-100(Fe) ifor iartificial ikidney iapplication,

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 iMa, iWen-Chin iTsen, iDesalination iand iWater iTreatment i57(7):1-9
iDOI:10.1080/19443994.2014.982199, iNov i14, i2014.