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：2013-02-28。：2013-05-15。(No.21271172)(No.2012J01058)。＊。E-mail：ydq@fjirsm.ac.cn,Tel:0591-83792525-俱战锋袁大强＊(结构化学国家重点实验室，中国科学院福建物质结构研究所，福州350002)：-/，。6MOFsMOFs。：-；；；：O641.4；O647.32；O647.11：A：1001-4861(2013)08-1633-06DOI：10.3969/j.issn.1001-4861.2013.00.303InitialTheoreticalEvaluationofPoreStructureforMetal-OrganicFrameworksJUZhan-FengYUANDa-Qiang＊(StateKeyLaboratoryofStructureChemistry,FujianInstituteofResearchontheStructureofMatter,ChineseAcademyofSciences,Fuzhou350002,China)Abstract:Asnewlyemergingporousmaterials,metal-organicframeworks(MOFs)havebeenstudiedforapplicationsingasstorageandseparation.Inthisarticle,weintroducesomecomputationaltoolsforsystematiccharacterizationoftheporestructureforMOFsandgivesomeexamplestodiscusstheusageofthesetools.Keywords:metal-organicframework;specificsurfacearea;porevolume;poresizedistribution10，-(Metal-OrganicFrameworks，MOFs)[1]。MOFs，，X-[2]。MOFs，MOFs、。(、)，MOFs、，MOFs[3-4]。MOFs、、、[5-10]，MOFs，MOFs[11-14]。MOFs、、。MOFs，。、、。。MOFs，MOFs，，，N2(77K)Ar(87K)，。，、。，MOFs，29820138Vol．29No．81633-1638CHINESEJOURNALOFINORGANICCHEMISTRY29，。，MOFs，；，，。MOFs，Platon[15]、MaterialsStudio[16]、Poreblazer[17]。6MOFs：IRMOF-1(MOF-5)、HKUST-1、FJI-1、UiO-66、MOF-74(Mg)、PCN-61，MOFs1。(a)IRMOF-1;(b)HKUST-1;(c)FJI-1;(d)UiO-66;(e)MOF-74(Mg);(f)PCN-6116MOFsFig.1CrystalstructureforsixMOFs1Vp，。，77KN21。Vp=PaVadsVmRT(1)Vp:totalporevolume(cm3·g-1);Vads:volumeofgasadsorbed(cm3·g-1);Vm:molarvol.ofliquidadsorbate(N234.7cm3·mol-1);Pa:101.325kPa;T:273.15K;R:8314kPa·cm3·K-1·mol-1MOFs，。，(2)：Vp=Vcell×PorosityWcell=Vcell×PorosityVcell×Density=PorosityDensity(2)Vcell:volumeofunitcell(nm3);Wcell:massofunitcell(g).Density:(g·cm-3)(Porosity)，。MOFs，。Platon、Mercury，Materialsstudio，Poreblazer16348：-MOFomics[18]。2，“solventaccessiblesurface”“contactsurface”，，。PlatonMOFomics“contactsurface”，Poreblazer“solventaccessiblesurface”，MercuryMaterialsstudio2。Platon，Platon。PlatonSpek，、、CIF。Platon“SearchforandAnalysisofSolventAccessibleVoidsintheStructure”，“TotalPotentialSolventAreaVol”。Platon：(1)platon，*.cif、*.ins*.res；(2)Platon，“calcvoid”。IRMOF-1，：TotalPotentialSolventAreaVol12992.4Ang^3perUnitCellVol16913.2Ang^3[76.8%]IRMOF-176.8%，Platon，0.12nm，*.lis，N2(~0.18nm)。，，“calcvoidprobe[?]”，。0.18nm，N2，IRMOF-175.7%，。，，IRMOF-11.25cm3·g-1。16MOFs。1，HKUST-1、MOF-74PCN-61，MOFs，，；FJI-1IRMOF-1，IRMOF-1，；UiO-66，，，，，UiO-66(0.43cm3·g-1)[18]。，MOFs，，，。，MOFs。2，S(specificsurfacearea，m2·g-1)。MOFs，MOFs。MOF，、1MOFsTable1TheoreticandexperimentaltotalporevolumedataofsomeMOFsmaterialsMaterialsDensitya/(g·cm-3)PorositybVpb/(cm3·g-1)PorositycVpc/(cm3·g-1)Vpd/(cm3·g-1)IRMOF-10.60576.8%1.2775.7%1.250.41~1.54[19]HKUST-10.87969.5%0.7965.9%0.750.75[20]FJI-10.40580.3%1.9879.1%1.951.43[21]UiO-661.23553.3%0.4347.7%0.390.52[22]MOF-74(Mg)0.91559.8%0.6557.3%0.630.59[23]PCN-610.56177.1%1.3775.7%1.351.36[24]Note:aCalculateddensitywithallguestsremoved;btheproberadiusis0.12nm;ctheproberadiusis0.18nm;dtheexperimentaldata163529。。MOFs，MOFs，。、BET，。BETBET(SBET)，BET，BET。，MOFs。MOFs[25]，2MOFs，，(5000)，。2：“Accessiblesurfacearea”“Connollysurfacearea”。AccessiblesurfaceareaBET，。MOFsMaterialsStudio、PoreblazerMOFomics。MaterialsStudio，，。MaterialsStudio，Tools“AtomVolumes&Surfaces”，1.8，“Accessiblesurfacearea”“Connollysurfacearea”。MaterialsStudio，MOFs。MaterialsStudio，3。SMS=ScellDensity×Vcell×10000(3)PoreblazerSarkisov[13]。Poreblazer“Accessiblesurfacearea”、“Geometricporesizedistribution”、“Structureconnectivity”“Porespaceaccessibility”。Poreblazer，MaterialsStudio，Poreblazer，。Poreblazer(hardspheresurface)(potentialminimumsurface)，，。MaterialsStudioPoreblazer，2MOFs。2MaterialsStudioPoreblazer，Poreblazer3，。，2Fig.2Illustrationofthetheoreticsurfacearea2MOFs。Table2TheoreticandexperimentalspecificsurfaceareaofsomeMOFsmaterialsMaterialsSMS/(m2·g-1)Shs/(m2·g-1)Spot/(m2·g-1)SBET/(m2·g-1)IRMOF-1358636583359570~3800HKUST-12198236619261507FJI-14647473645644043UiO-6610611230689969MOF-74(Mg)1607173015221530PCN-613742385135193000163683MOFs。Table3TheoreticporesizeinformationsofsomeMOFsmaterialsMaterialsPorelimitingdiameter/nmMaximumporediameter/nmPorespaceaccessibilityIRMOF-10.7651.4853dimensionsporesHKUST-10.6371.2743dimensionsporesFJI-10.7522.0063dimensionsporesUiO-660.3500.8273dimensionsporesMOF-74(Mg)1.0691.1561dimensionchannelsPCN-610.6241.8693dimensionspores36MOFsFig.3GeometricPSDofthesixMOFs，BET。，。3(poresizedistribution,PSD)。MOFs，MOFs。MOFs，PoreblazerMOFomics。MOFomicsMOFs，(1d)，。PoreblazerMOFs、、，。3PoreblazerMOFs。3PorelimitingdiameterMOFs，MaximumPorediameter。2，，。Poreblazer，，，。Porelimitingdiameter，MOFs，MOFs。MOFs，3MOFs。3，，。PCN-61，：-1637294，。PoreblazerMOFs，。4，、。MOFs，，MOFs，MOFs。、MOFs，/，，，[26]。：[1]FarrussengD.Metal-OrganicFrameworks:ApplicationsfromCatalysistoGasStorage.Weinheim:Wiley-VCHVerlagGmbH&Co.KGaA,2011:1-18[2]ZhouH-C,LongJR,YaghiOM.Chem.Rev.,2012,112(2):673-674[3]O’KeeffeM,YaghiOM.Chem.Rev.,2011,112(2):675-702[4]CookTR,ZhengYR,StangPJ.Chem.Rev.,2012,113(1):734-777[5]CuiY,YueY,QianG,etal.Chem.Rev.,2011,112(2):1126-1162[6]KrenoLE,LeongK,FarhaOK,etal.Chem.Rev.,2011,112(2):1105-1125[7]ZhangW,XiongRG.Chem.Rev.,2011,112(2):1163-1195[8]ZH