exploring the thermodynamic criteria for responsive adsorption processes jack d. evans资料.pdf

该【exploring the thermodynamic criteria for responsive adsorption processes jack d. evans资料 】是由【赖大文档】上传分享，文档一共【7】页，该文档可以免费在线阅读，需要了解更多关于【exploring the thermodynamic criteria for responsive adsorption processes jack d. evans资料 】的内容，可以使用淘豆网的站内搜索功能，选择自己适合的文档，以下文字是截取该文章内的部分文字，如需要获得完整电子版，请下载此文档到您的设备，方便您编辑和打印。ChemicalScienceViewArticleOnlineEDGEARTICLEViewJournal|ViewIssueriteriaforresponsiveadsorptionprocesses?Citethis:.,2019,10,,*SimonKrause,StefanKaskel,??eldformalismoftheosmoticpotential,,wefocusonrecreating?exibleadsorptionanicframeworks,especiallytherecentlydiscoveredReceived15thMarch2019e?ectofnegativegasadsorption(NGA).WeidentifythekeycharacteristicsrequiredforthemodeltoAccepted29thMarch2019generateunusualadsorptionprocessesandsubsequentlyemployanextensiveparametricstudytoDOI:--(np)statetomoreporousopenpore(op)state,,itwasNewfamiliesofporouscrystalshavecaptivatedthee?ortsanddemonstratedthatthise?ectcanbeexploitedtomaximizethe9imaginationofresearchersand,,3ABreathingprocesses,however,beginwithanopenandhighparticularclassofthesematerialsaresoporouscrystalsporosityconformation(op)atzeroorlowpressureofadsorbate.(SPCs),whichincorporateadynamicandadaptiveporeUponadsorption,thestructurespontaneouslycollapsesintoThisarticleislicensedunderanetwork,exibilityalessporousstate(np).ThedeformationtoanpstatearisesexhibitedbySPCsprovidesadvancedfunctionssuchasfromthestrongadsorptionenthalpyattributedtosmallerpore14responsivematerials,,:58:,elec-adsorbedleadstoasecondtransitionbacktotheopcongu-tricelds,,,includingsensing,drugdeliveryandimprovedgascongurationisonlyastableemptyhostcon–9acertainthresholdtemperature,whichcanresultinthe16SPCmaterialsthatareresponsivetothespeci-theirgasadsorptionisotherms,attributedtostructuraltrans-dynamicsofthesetransitions,whichhasenabledtheproduc-,17,18adsorptionprocessesincludegate-,previousworkhasnotanicframework(MOF)consideredadiverseassortmentofhostfreeenergyproles,,12Gate-openingreferstoaparticular(andsome-whicharerepresentativeofdi?)workatOfparticularinterestinthisworkisthepossibilityforaspeci“opens”essibleporevolumetotheadsorbingresultintheadsorptionprocesspopulatingmetastablestatesmoleculesproducingatransitionfromlowporositynarrowporeand,upontransitiontothenpform,someoftheadsorbateisactuallyreleasedbacktothegasphase,leadingtonegativegasadsorption(NGA).19NGAphenomenawererecentlydiscovered20hemistry,TechnischeUniversitat¨Dresden,Bergstra?e66,formethaneandn-butaneadsorptioninDUT-,-mail:jack.******@tu-,UniversityofEdinburgh,EdinburghEH93FB,UKthee?ectofcrystallitesizeandthecollectivenatureofthe?Electronicsupplementaryinformation(ESI):,22Evans,?.,2019,10,5011–5017|-,muchoftheinvestiga-porousmaterialsaretreatedasasimpleslitporewithaspringtionofNGAhascenteredononematerial(DUT-49).However,inattachedtoitswalls,(DFT)callydevelopageneral,minimaltheoreticalfordirectcalculationofthegrandpotentialoftheadsorbedmodelcapableofreproducingresponsiveadsorptionprocessesuidinaporeofxedwidth(?cienttechniquethanMonteCarlo,forthispurpose).Theseveralrecentstudiesonadsorptionphenomenainexiblemean--namicsofadsorptionin,theyproposedthesolid,eldsimpliongurationalforthedevelopmentoftheminimumnumberofparameterspartitionfunction,whichleadstoanelegantseparationofrequiredtoformulateanewmodelcapableofcapturingthevariableswithinthecongurationalintegral—asimpleNGAe?,weinvestigatethegeneralHelmholtzformulationoftheosmoticpotentialintermsofthefreeenergyfreeenergyproleofthehostmaterialandtheexternalther-ofthesolidphaseandtheadsorptionisothermof-(NLDFT)-(os)and,asdiscussedpreviously,weadoptthemean(1),whereFhostistheinsteadofNLDFT,acommonapproachbeguntoemergewhereHelmholtzfreeenergyoftheporoushost,PisgaspressureandtheexibleporousstructureistreatedasaslitporewithU(T,P,w)isthegrandpotentialoftheadsorbed(T,P,w)?F(w)+PV+U(T,P,w)anddeformationmodesthatcanbeadequatelyrepresentedasoshost(1),?NumaguchiandcoworkersdevelopedatheoreticaldescriptionTogeneratealibraryofstates(ofdierentporewidth)oftheUThisarticleislicensedunderaofstructuraltransitionsinELM-,Sideriusandsystemandcorrespondinggrandpotential((T,P,w))weusebinationofat-histogramsamplingclassicaldensityfunctionaltheory(DFT)forsimpleuids-:58:-layermaterials,suchasELM-?-.(a)Aseriesofisothermsadi?erentporewidths,identi?edbydi?erentshadesofblue.(b)Thefreeenergypro?ledescribingtheporewidth.(c)Aresponsiveisothermcalculatedfromtheseriesofisotherms,astheminimumofUos,andidenti?|.,2019,10,5011–5017Thisjournalis?TheRoyalSocietyofChemistry2019ViewArticleOnlineEdgeArticleChemicalScienceallowfortheexplorationofadsorptionphenomenainAnexampleofthecodeusedtogeneratetheresponsiveasimpli,,ifhttps:///jackevansadl/supp--hegrandpotentialfunctionaloftheaverageone-(r),eqn(2),whereF[r(r)]istheintrinsicHelm-Theresults,illustratedhere,aredisplayedinreducedunitsholtzfree-energyfunctional,Vextistheexternalpotentialand(denotedby*)relativetothelengthoftheLennard-Jonesm(rB)isthereservoiruidchemicalpotential,whichisdeter-diameteroftheadsorbateuidparticle(s?)anduid–uidminedbythereservoirbulkdensity(rB).interactionstrength(3?).Forexample,temperatureinreducedekTunitsisgivenasT*?:AfulldescriptionofthereducedU?rerT??F?rerT?àdrrerTemerTàVexterTTB(2)3ffunitsissummarizedintheESI(TableS1?),,inthisstudyadsorptionisothermsarepresented30developedand,inthiswork,weemploystandardmeaneldasadsorbeddensity(N*)asafunctionofcongurationalactivityDFTwithafundamentalmeasurefunctionalforthehard(l*),whichiscalculatedfromthechemicalpotentialasrm*spheretermwithintheHelmholtzfreeenergyfunctionalF[].l*?e:Thisprovidesalargekernelofadsorptionisothermsfor?dierentslitporewidth(w),includingdataofadsorbedamountResultsanddiscussionandthegrandpotential,ctech-?les,,??dierentporewidths,,binedwiththeenergeticsassociatedwithgaspleteadsorptionproleforaexibleporeisgeneratedadsorption,allowfor,wedemonstratetheInthisstudy,weconsideredtwoathermalfunctionsofresultofthreedi?erentpotentialprolesdictatingthebehaviorHelmholtzfreeenergytodescribetheexibility,orphases,ofoftheslitporesystemexempli-typeFirstly,atightharmonicpotentialwithasti?nessk*?10,potentialforasystemwithasingleminimum(eqn(3))andcase1,producesatypicaltype-1gasadsorptionrepresentativeabistable-typepotential(eqn(4)),,,thusnour(?).F?kewàcT2hosteharmonicT2(3):58:<,orcongurationalactivityl*,Fhost(bistable)?c1(wàc2)àc3(wàc4)+c5(wàc6)(4)(kandc)ofeqn(3)arechosentogenerateWhenthesystemreachesacharacteristicgate-openingpressureapotentialsurfacecenteredonporewidth(wmin)withagiventhesystemexpandstowwide,allowingforincreasedamountofsti?ness,orlooseness,denedby(k).Similarly,thecoe?cientsgasuptakeproducingagate-openingadsorptionpro?(ci)ofeqn(4)areselectedtoproduceapotentialsurfacewithosmoticpotentialduringthisadsorptionprocess()minimaatchosenwidthvalues(wthin,wwide),learlyshowsthatthesmallerwidthminimumisfurtherstability(Ethin,Ewide)andbarrierheight,measuredfromthestabilizedatlowpressure,butathighpressurethel