si draft 2s2 1. experimental methods 1.1. ztc synthesis: the zeolite nay template 2 g, hsz 320naa,...
TRANSCRIPT
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SupportingInformation
AtomisticStructuresofZeolite‐TemplatedCarbon
ErinE.Taylor,KaitlinGarman,andNicholasP.Stadie*
DepartmentofChemistry&Biochemistry,MontanaStateUniversity,Bozeman,Montana,
59717,UnitedStates
*Correspondingauthor:[email protected]
Contents:
1. ExperimentalMethods s2
2. ExperimentalStructuralPackingDensity s4
3. TheoreticalX‐RayDiffractionPatternSimulation s5
4. TheoreticalSurfaceAreaandPoreSizeDistribution s6
5. TheoreticalStructuralPackingDensity s7
6. ManipulationoftheAtomisticModels s8
7. ExaminationofClaimsofBraunandCoworkers s17
8. SupportingReferences s20
s2
1.ExperimentalMethods
1.1.ZTCSynthesis:ThezeoliteNaYtemplate 2g,HSZ320NAA,TosohCorp. wasde‐
gassedina2‐neckround‐bottomflaskat300°Cfor24hunderoil‐freevacuum 2
10‐3mbar .Thedriedzeolitewasthencombinedwith20mLoffurfurylalcohol FA,
99%,Aldrich viasyringeandthemixturewasstirredatroomtemperaturefor24h.The
impregnatedsolidwasthencollectedbyvacuumfiltrationinair,washedthreetimes
with10mLaliquotsofmesitylene 97%,Aldrich ,anddriedundersuctiononthefilter
fritfor15min.Theimpregnatedandrinsedzeolitewasthenplacedinanaluminaboat
10 30 107mm whichwasinsertedintoaquartztube ø45mm installedinahor‐
izontaltubefurnace HST12/600,CarboliteGero .Thetubewaspurgedunderdryar‐
gonflow 200sccm atambientpressure.TheFAwithinthezeoliteporeswasfirstpol‐
ymerizedbyheatingupto80°Cviaa10minrampandheldfor24h.Thepoly‐FAwas
thencarbonizedbyheatingupto700°Cviaa2hrampandheldfor30min.Furthercar‐
bonimpregnationwasaccomplishedviapropyleneCVDat700°C;thegasflowwas
switchedto7mol%propyleneinargon 99.99%propylenein99.999%argon at200
sccm.Afterambient‐pressureCVDfor5h,thegasflowwasreturnedtodryargonat200
sccm.Anannealingstepwasperformedbyheatingthezeolite‐carboncompositeupto
900°Cviaa1hramp,andheldforanadditional1h.Thesystemwasthencooledover‐
night,thegasflowwasstopped,andtheannealedzeolite‐carboncompositewascol‐
lected.Removalofthezeolitetemplatewasaccomplishedbythreesequentialdissolu‐
tionsin35mLofaqueoushydrofluoricacid HF,40%,Sigma‐Aldrich .ThefinalZTC
productwascollectedbycentrifugation,washedthreetimeswith35mLaliquotsofdis‐
tilledwater,andthendriedinairat40°Ctoobtain“archetypicalFAU‐ZTC.”
1.2.PowderX‐RayDiffraction:PowderX‐raydiffraction XRD measurementswere
performedonaRigakuUltimaIVdiffractometerusingCuKαradiation λ 1.54Å ,gen‐
eratedat40kVand40mA,inBragg‐Brentanogeometry.Thepowderwasthinlydis‐
persedona“zero‐background”sampleholdercomprisedoforientedcrystallinesilicon.
Thedatawereanalyzedbydirectsubtractionofthecontributionfromthesampleholder
determinedbyperforminganidenticalexperimentwithoutanysample.TheXRDpat‐
ternofarchetypicalFAU‐ZTCisshowninFigureS1.
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FigureS1.XRDpatternofarchetypicalFAU‐ZTC.
1.3.NitrogenAdsorption:Nitrogenadsorption/desorptionisothermsweremeasured
at77Kbetween10‐4and100kPausinganautomatedvolumetricinstrument 3Flex,Mi‐
cromeriticsInstrumentCorp. .SpecificsurfaceareaswerecalculatedbytheBrunauer‐
Emmett‐Teller BET methodbetweenP/P0 0.000004‐0.11.Pore‐sizedistributions
weredeterminedbynonlocaldensityfunctionaltheory NLDFT calculationsusinga
dedicatedsoftwarepackage MicroActiveShare,MicromeriticsInstrumentCorp. using
acarbonslit‐poremodel.Thenitrogenadsorption/desorptionisothermonarchetypical
FAU‐ZTCisshowninFigureS2.
FigureS2.EquilibriumN2adsorption/desorptionisothermofarchetypicalFAU‐ZTCat77K filled/unfilled,respectively .
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1.4.ThermalGravimetricAnalysis:Thermalgravimetrywasperformedusingamicro‐
balance DiscoveryTGA,TAInstruments underflowingdryair GradeDbreathingair
withmoisturetrap .Zeolite‐carboncompositecollectedpriortoHFtreatmentwassus‐
pendedinthesampleenclosure,andthetypicalstartingsampleweightwas~5mg.The
balanceflowratewas1.0mLmin‐1andthetemperatureprogramwasspecifiedasfol‐
lows:thesamplewasfirstheldat50°Cfor15minunderdryairtopurge,waterremoval
wasperformedbyheatingupto300°Cviaa20°Cmin‐1ramp.Theweightattheendof
thisdehydrationstepwastakentobetheinitialmass,mi.Thecarbonwasthenoxidized
byheatingupto800°Cviaa5°Cmin‐1rampandheldfor120min,andfinallythere‐
mainingsamplewascooledto300°Ctodeterminethefinalweightdifference.The
weightchangecorrespondingtotheoxidation/removalofarchetypicalFAU‐ZTC within
itsnativezeoliteNaYtemplate isshowninFigureS3.
FigureS3.ThermalgravimetricanalysisofarchetypicalFAU‐ZTC.Threeregionsof
weightlossareobserved:waterlossat50°Cduringpurge 0‐12min ,waterlossbe‐
tween50‐300°C 12‐42min ,andoxidationofZTCabove300°C 87‐158min .
2.ExperimentalStructuralPackingDensity SPD
Equations1‐3inthemaintextdefinethreemetricsofevaluationforthecomparison
ofZTCstructuredensity includingcarbonalongwithhydrogenandoxygen packing
withinthezeolitetemplate,akeyindicatorofboththetemplatefidelityandstructureof
thefinalZTCproductafterremovalofthetemplate.Analysisoftherawthermalgravim‐
etrymeasuredforarchetypicalFAU‐ZTCisshowninFigureS3.Theweightlosscorre‐
spondingtotheweightofthecarbonaceousZTCoccursabove300°C,afteraclearplat‐
eauisachievedfollowingthelow‐temperatureweightlossassociatedwithadsorbed
water.
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ThecalculationsofSPD ,SPD ,andSPD , forarchetypicalFAU‐ZTC corre‐
spondingtothemeasurementinFigureS3 areasfollows:
SPD . .
. 0.355g g EquationS1
SPD 0.355g g .
. 0.39g g EquationS2
SPD , 0.389g g 1.327gSiO cm 0.52g cm EquationS3
3.TheoreticalX‐RayDiffractionPatternSimulation
PowderXRDpatternsweresimulatedforeachoftheperiodicatomisticmodelsof
FAU‐ZTCusingopenlyaccessiblesoftware Mercury,v4.1.3,CambridgeCrystallographic
DataCentre usingasimulatedwavelengthof1.54056Å,astepsizeof2θ 0.02°,anda
full‐widthhalf‐maximum FWHM of2θ 0.1°.S1TheresultsareshowninFigure12in
themaintext.Theanglescorrespondingtothe 111 and 220 reflectionsaretabulated
inTableS1.
TableS1.ExperimentalandTheoreticalXRDReflectionsofFAU‐ZTC.
Model/Material 111 220
RousselModel2006 6.16 10.06
NishiharaModel0a2009 6.31 10.32
NishiharaModel0b2009 5.80 9.48
NishiharaModelI2009 6.36 8.99
KimModel2016 6.11 9.98
NishiharaModelII2018 6.36 10.39
BraunModelNR2018 6.11 9.98
BraunModelR2018 5.98‐6.09 11.42‐11.68
TanakaModelIV2018 6.36 10.39
ArchetypicalFAU‐ZTC 6.32 10.40
TosohZeoliteNaY 6.28 10.26
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4.TheoreticalSurfaceAreaandPoreSizeDistribution
Nitrogenaccessiblesurfaceareacalculationswereperformedusingopenlyaccessible
software Zeo ,v.0.3,http://www.zeoplusplus.org/ assumingachannelradiusand
proberadiusof2.27Å correspondingtoN2 with2000MonteCarlosamplesper
atom.S2TheresultsareshowninTable2inthemaintext.Likewise,pore‐sizedistribu‐
tionsweresimulatedusingthesameassumptionsexceptwith50000MonteCarlosam‐
plesperatom.Thepore‐sizedistributionsforeachmodelcomparedtoarchetypical
FAU‐ZTC determinedusingNLDFTanalysisofN2adsorptionmeasurementsat77K
areshowninFigureS4.
FigureS4.ExperimentalandtheoreticalN2‐accessiblepore‐sizedistributionsforallperi‐odicFAU‐ZTCmodelsandarchetypicalFAU‐ZTC.
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5.TheoreticalStructuralPackingDensity
Structuralpackingdensitieswerecalculatedforalloftheperiodicatomisticmodelsof
FAU‐ZTCbydeterminingthenumber andmass ofallatomswithintheunitcellper
unitcellvolumeusingthereportedcrystallographicinformationfile CIF ormolecular
coordinatefileforeachstructure.Then,basedonthedensityofidealSiO2faujasite
frameworktypeFAU,InternationalZeoliteAssociation of1.327gmL‐1,thevolumetric
SPDcell,volwasconvertedtoagravimetricquantity,SPDcell,inunitsofg g .Asnotedin
themaintext,theseunitsnominallyimplythatthemassofFAU‐ZTCiscomprisedsolely
of“carbon”despitethatsomeofthemodelsaswellastherealZTCmaterialsareactually
comprisedofC,H,andO.Weemphasizethatinthecaseofthemodels,valuesforSPDcell
andSPDcell,volincludecontributionsfromallatomsintheunitcellofthatmodel.
TableS2.TheoreticalStructuralPackingDensities.
perUnitCell
ModelCarbon
Atoms
Mass
Da
Volume
nm3
SPDcell,vol
SPDcell
RousselModel2006 630 7569 15.34 0.82 0.62
NishiharaModel0a2009 728 8746 14.23 1.02 0.77
NishiharaModel0b2009 272 3268 9.16 0.59 0.45
NishiharaModelI2009*** 288 3460 13.95 0.41 0.32
NueangnorajModel2013 970 11654 27.00 0.54 0.72
KimModel2016* 217 2535 15.71 0.28 0.21
KimModel2016** 1202 14008 15.71 1.53 1.15
NishiharaModelII2018*** 2351 28245 111.56 0.94 0.33
BraunModelNR2018 186 2235 3.93 0.91 0.71
BraunModelR2018 186 2235 4.09 0.83 0.68
TanakaModelIV2018 8937 107369 376.40 0.47 0.36
BoonyoungModel2019 200 2403 25.60 1.60 1.21
*partialoccupationoflatticesites**fulloccupationoflatticesites***hydrogenincluded
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ArepresentativecalculationofSPD andSPD , foracarbon‐onlymodel inthis
case,theRousselModel isshownbelow:
SPD ,.
. 0.82g cm EquationS4
SPD 0.82g cm 0.753cm g 0.62g g EquationS5
Likewise,arepresentativecalculationofSPD andSPD , foracarbon‐andhy‐
drogen‐bearingmodel inthiscase,NishiharaModelII isshownbelow:
SPD ,. .
. 0.42g cm EquationS6
SPD 0.42g cm 0.753cm g 0.32g g EquationS7
6.ManipulationoftheAtomisticModels
Forcomparisonoftheatomisticmodelsreportedbyseveraldifferentresearchgroups
overthetimeperiodbetween2007‐2019,itwasnecessarytoobtainorcreateacrystal‐
lographicinformationfile CIF foreachmodelthatcouldbeusedforXRDpatternsimu‐
lationandsurfaceareaandpore‐sizedistributioncalculations.Ofthetenmodelsre‐
viewedherein,onemolecularcoordinatefile XYZfile andthreeCIFswereobtained
directlyfromthepublishedliterature theBoonyoung,Kim,andBraunModels,respec‐
tively ,andthreemolecularcoordinatefiles XYZandPBDfiles andfiveCIFswereob‐
taineddirectlyfromtheirauthorsandusedwiththeauthors’permission the
Nueangnoraj,Roussel,Nishihara,andTanakaModels .SincetheRoussel,Nueangnoraj,
andBoonyoungmodelsonlyexistedasmolecularcoordinatefiles,aneffortwasmade
hereintogenerateCIFsfromtheoriginalfiles.ACIFwasgeneratedfromthemolecular
coordinatefileprovidedfortheRousselmodel.However,itwasdeterminedthatthe
NueangnorajModelandBoonyoungModelweretoodistortedandtoosmall,respec‐
tively,togenerateaCIFthatwouldaccuratelyreplicatethereportedmodel’sstructure.
AllofthemodelsreviewedinthisworkareshownindetailinFiguresS5‐S20.Several
ofthemodelshavemultiplevariants,asexplainedinthemaintext.Thefiguresdepict
a a sectionofconnectivitybetweentwo“nodes”oftheFAU‐ZTCstruc‐
ture,formedwithinandbetweentwosupercagesoftheoriginalFAUzeoliteframework,
and b anextendedmulti‐celldepictionoftheFAU‐ZTCstructureshowingpore‐to‐pore
regularitywitharepeatdistanceof~1.4nm correspondingtothedominant 111 re‐
flectiongiveninTableS1 .Structuralfilesofallmodelsareavailableasadditionalsup‐
portinginformationinthiswork.
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FigureS5.RousselModel 2006 : a atwo‐cellclosed‐strutsubunitand b anextendedmulti‐cellstructure.
FigureS6.NishiharaModel0a 2009 : a atwo‐cellclosed‐strutsubunitand b anex‐tendedmulti‐cellstructure.
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FigureS7.NishiharaModel0b 2009 : a atwo‐cellclosed‐strutsubunitand b anex‐tendedmulti‐cellstructure.
FigureS8.NishiharaModelI 2009 : a atwo‐cellopen‐blade"buckybowl"subunitandb anextendedmulti‐cellstructure.Hydrogenisexcludedforclarity.
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FigureS9.NishiharaModelI 2009 : a atwo‐cellopen‐blade"buckybowl"subunitandb anextendedmulti‐cellstructure.Hydrogenisshowninwhite.
FigureS10.NueangnorajModel 2013 : a atwo‐cellclosed‐strutfullerene‐likesubunitand b anextendedmulti‐cellstructure.
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FigureS11.NueangnorajModel 2013 :atwo‐cellclosed‐strutfullerene‐likesubunitwithoxygenshowninredandhydrogenshowninwhite.
FigureS12.KimModel 2016 : a tetrahedrally‐coordinated“closed‐strut”subunitwithpartialoccupancyoneachlatticesite probabilityofoccupationindicatedbyshadingfromdarkgrey,22%,towhite,10% and b anextendedmulti‐cellstructure.
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FigureS13.KimModel 2016 : a arepresentativesubunitwithpartialoccupancyoneachlatticesiteand b anextendedmulti‐cellstructure.
FigureS14.NishiharaModelII 2018 : a arepresentativetwo‐cellopen‐bladesubunitoutof36differentsubunitswithinthe2 2 2supercell and b anextendedmulti‐cellstructure.Hydrogenisexcludedforclarity.
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FigureS15.NishiharaModelII 2018 : a arepresentativetwo‐cellopen‐bladesubunitoutof36differentsubunitswithinthe2 2 2supercell and b anextendedmulti‐cellstructure.Hydrogenisshowninwhite.
FigureS16.NishiharaModelII 2018 : a arepresentativetwo‐cellopen‐bladesubunitoutof36differentsubunitswithinthe2 2 2supercell and b anextendedmulti‐cellstructure.Oxygenandhydrogenareshowninredandwhite,respectively.
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FigureS17.BraunModelNR 2018 : a tetrahedrally‐coordinated,negativelycurved“closed‐strut”subunitand b anextendedmulti‐cellstructure.
FigureS18.BraunModelR 2018 : a tetrahedrally‐coordinated,negativelycurved“closed‐strut”subunitand b anextendedmulti‐cellstructure,afterstructuralrelaxa‐tion.
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FigureS19.TanakaModelIV 2018 : a arepresentativetwo‐cellopen‐bladesubunitoutof100differentsubunitswithinthe3 3 3supercell and b anextendedmulti‐cellstructure.
FigureS20.BoonyoungModel 2019 :tetrahedrally‐coordinated“closed‐strut”subunit.
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7.ExaminationofClaimsofBraunandCoworkers
Inrecentwork,Braunandcoworkersclaimedto“establish”thatcurrentlysynthe‐
sizedZTCscanbemodeledandunderstoodasaformofschwarzite.S3Severaloftheir
keyclaimsarereproducedbelow:
“Aswewillshow,thesimilaritybetweenZTCsandschwarzitesis
striking,andweexplorethissimilaritytoestablishthatthetheoryof
schwarzites/TPMSsisausefulconcepttounderstandZTCs.” page
1 S3
“Inthiswork,wedevelopanimprovedmoleculardescriptionofZTCs,
showthattheyareequivalenttoschwartzites sic ,andthusmakethe
experimentaldiscoveryofschwarzitesexpostfacto.” page1 S3
“Althoughschwarziteshavebeenapurelyhypotheticalconcept,our
worksuggeststhatZTCsareschwarzitesincarnate.” page6 S3
Intheanalysisperformedinthisreview,ithasbeenclearlyshownthatnoneofthe
modelsproposedbyBraunandcoworkersrepresentarchetypicalFAU‐ZTC.Thesimu‐
latedXRDpatternoftheBraunModelexhibitsmultiplepeaksabove12°whichhavenot
beenobservedforarchetypicalFAU‐ZTCoranyothercarbonsynthesizedinsideazeo‐
litetemplate.Furthermore,thesimulatedsurfaceareaoftheBraunModelis1440‐1480
m2g‐1,closertothatofaone‐sidedgraphenesheetthanthatofarchetypicalFAU‐ZTC.
Theveryhighsurfaceareaofwell‐replicateZTCssynthesizedinthelaboratoryareindic‐
ativeofopen‐bladestructuresasopposedtoclosed‐tubestructuresliketheBraun
Model.Lastly,thecalculatedSPDoftheBraunModelisroughlytwicethatofarchetypi‐
calFAU‐ZTCwhencarefulconsiderationofthenatureofthezeolitetemplateistaken.It
shouldalsobenotedthattheBraunModelandallothercarbon‐onlymodelsarehighly
misrepresentativeoftheactualchemicalcompositionoflaboratory‐synthesizedZTCs
whichcontainaveryhighcontentofhydrogen afactorthatdistinguishesZTCsfromac‐
tivatedcarbons aswellasoxygen.
Braunandcoworkersincorrectlyclaim:
“WehavedevelopedatheoreticalframeworktogenerateaZTCmodel
fromanygivenzeolitestructure,whichweshowcansuccessfullypre‐
dictthestructureofknownZTCs.” abstract S3
“OurmethodcorrectlydescribesthestructuresoftheknownZTCs…”
page6
s18
“ T hislibraryshouldserveto…providecomputationalscientists
withrealisticatomisticmodels.” page6 S3
“Indeed,theexperimentalpropertiesofZTCsareexactlythosewhich
havebeenpredictedforschwarzites…” page1 S3
Weemphasizethatwhiletheaboveclaimsarefactuallyincorrect,allofthemodelsre‐
portedintheirworkareinterestingpurelyforfundamentalreasons;theyrepresenthy‐
potheticalschwarzitematerialsthat besynthesizedwithinazeolitetemplateun‐
derthecorrectsyntheticconditions.
ItisimportanttonotethatBraunandcoworkerswerenotthefirsttoestablishahy‐
potheticallinkbetweenZTCsandschwarzites.ThislinkisattributedbothtoKyotaniand
coworkersovermanyyearsintheirresearch,aswellasRousselandcoworkerswho
firstpublishedthisideain2007.S4Furthermore,themodelsreportedbyBraunand
coworkersshouldbemoreaccuratelydefinedas“non‐balanced”schwarzitessincethey
donotseparatespaceintotwoidenticalvolumes.Twoexamplesoffalseclaimsastothe
noveltyofthelinkbetweenZTCsandschwarzitesaspresentedin2019arereproduced
below:
“ O urresultsestablishtherelationshipbetweenZTCsand
schwarzites—carbonmaterialswithnegativeGaussiancurvaturethat
resembleTPMSs—linkingtheresearchtopicsanddemonstratingthat
schwarzitesshouldnolongerbethoughtofaspurelyhypotheticalma‐
terials.” page1 S3
“ W ehaveshownhowZTCscanbeassociatedwithTPMSs,linking
theresearchtopicsofZTCsandschwarzites.” page6 S3
WhiletheBraunmodelsretainimportanceasidealizedhypotheticalschwarzitesthat
mayeventuallybesynthesizedinthelaboratoryunderconditionsstillunknowntothe
experimentalcommunity,theabovefalseclaimsarealreadyleadingtoveryimportant,
erroneousmisrepresentationsofZTCsinrecentreportsbyotherresearchers.Thefol‐
lowingareseveralexamplesofmistakendepictionsoftheBraunmodelsasaccuraterep‐
resentationsofexperimentalZTCs,orofthegeneralconclusionthatZTCsarenowtobe
classifiedasschwarzites.
“UCBerkeleychemistshaveprovedthatthreecarbonstructuresre‐
centlycreatedbyscientistsinSouthKoreaandJapanareinfactthe
long‐soughtschwarzites…” paragraph2 S5
s19
“... zeolite‐templatedcarbons werebeinginvestigatedforpossible
interestingproperties,thoughthecreatorswereunawareoftheir
identityasschwarzites,whichtheoreticalchemistshaveworkedon
fordecades.” paragraph3 S5
“Theteamdeterminedthat,oftheapproximately200zeolitescreated
todate,only15canbeusedasatemplatetomakeschwarzites,and
onlythreeofthemhavebeenusedtodatetoproduceschwarzite
ZTCs.” paragraph17 S5
“Ithasbeenrecentlyreportedthatthegrowthofcarboninsidethe
hardporousmaterials,so‐calledtemplatecarbonization,hassuccess‐
fullysynthesizedcarbonswithstructuresthatfitsthedescriptionof
schwarzites.” page1 S6
“Recently,Braunetal.developedatheoreticalframeworktogenerate
aZTCmodelfromanygivenzeolitestructure,predictingthestructure
ofknownZTCs...” page93 S7
“...a3Dgraphenethatmaintainstheuniqueelectronicpropertiesof
planargraphene...canbeachievedviatemplatingstrategies...assug‐
gestedcomputationallyviazeolitetemplating.” page5 S8
“ R ecently,Braunetal.developedanefficientcomputationalap‐
proachtogenerateanaccurateZTCstructureatatomiclevelsin
agreementwithexperimentdata.” page2 S9
“InZTCwhichisrecognizedasschwarzite,sp2carbonsurfacedivides
astructureintotwodisjointspaceswhichdon'texchangemolecules.”
page4 S9
s20
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