Michael TsapatsisChemical Engineering and Materials Science

University of Minnesota

Christodoulos Floudas Memorial Symposium

Contributions to Porous Materials

Christodoulos FloudasGEORGE T. PIERCY PROFESSOR 2008

DEPARTMENT OF CHEMICAL ENGINEERING AND MATERIALS SCIENCE

UNIVERSITY OF MINNESOTA

CEMSleadership(formerdepartmentheadFrankBatesandcurrentheadDanFrisbie)andfacultyexpresstheirprofoundappreciationforthecontributionsofProfessorFloudas tochemicalengineeringandfondlyremembertheirinteractionswithhimduringhisstayinMinnesotaasPiercyvisitingprofessor.

EFRI-HyBi: Conversion of Biomass to Fuels using Molecular Sieve Catalysts and Millisecond Contact Time Reactors

Award 0937706 09/01/09 to 08/31/2014.

Michael Tsapatsis, Aditya Bhan, Dionisios Vlachos, Christodoulos Floudas, Lanny Schmidt

Bai,P.;Olson,D.H..;Tsapatsis,M.;Siepmann J.I. (2014). UnderstandingtheUnusualAdsorptionBehaviorinHierarchicalZeoliteNanosheets. CHEMPHYSCHEM. 15 2225.Baliban,R.C.,Elia,J.A.,Floudas,C.A. (2013). BiomassandNaturalGastoLiquidTransportationFuels:ProcessSynthesis,GlobalOptimization,andTopologyAnalysis. INDUSTRIAL&ENGINEERINGCHEMISTRYRESEARCH. 52 3381.Baliban,R.C.,Elia,J.A.,Floudas,C.A. (2013). Biomasstoliquidtransportationfuels(BTL)systems:processsynthesisandglobaloptimizationframework. EnergyEnviron.Sci.. 6 257.Baliban,R.C.,Elia,J.A.,Floudas,C.A.,Gurau,B.,Weingarten,M.,Klotz,S. (2013). Hardwoodbiomasstogasoline,diesel,andjetfuel:I.Processsynthesisandglobaloptimizationofathermochemicalrefinery. ENERGYFUELS. 27 4302.Baliban,R.C.,Elia,J.A.,Floudas,C.A.,Xiao,X.,Zhang,Z.,Li,J.,Cao,H.,Ma,J.,Qiao,Y.,Hu,X. (2013). Thermochemicalconversionofduckweedbiomasstogasoline,diesel,andjetfuel:Processsynthesisandglobaloptimization. INDUSTRIAL&ENGINEERINGCHEMISTRYRESEARC. 52 11436.Baliban,R.C.,Elia,J.A.,Floudas,C.A. (2013). NovelNaturalGastoLiquidsProcesses:ProcessSynthesisandGlobalOptimizationStrategies. AIChE JOURNAL. 59 505.Baliban,R.C.,Elia,J.A.,Misener,R.,Floudas,C.A. (2012). GlobaloptimizationofaMINLPprocesssynthesismodelforthermochemicalbasedconversionofhybridcoal,biomass,andnaturalgastoliquidfuels. COMPUTERSANDCHEMICALENGINEERING. 42 64.Baliban,R.C.,Elia,J.A.,Weekman,V.,Floudas,C.A. (2012). Processsynthesisofhybridcoal,biomass,andnaturalgastoliquidsviaFischer–Tropsch synthesis,ZSM-5catalyticconversion,methanolsynthesis,methanol-to-gasoline,andmethanolto-olefins/distillatetechnologies. COMPUTERS&CHEMICALENGINEERING. 47 29.Baliban,R.C.;Elia,J.A.;Floudas CA (2011). OptimizationFrameworkfortheSimultaneousProcessSynthesis,HeatandPowerIntegrationofaThermochemicalHybrid Biomass,Coal,andNaturalGasFacility. COMPUTERSANDCHEMICALENGINEERING. 35 1647.Baliban,RC;Elia,JA;Floudas,CA (2010). TowardNovelHybridBiomass,Coal,andNaturalGasProcessesforSatisfyingCurrentTransportationFuelDemands,1: ProcessAlternatives,GasificationModeling,ProcessSimulation,andEconomicAnalysis. INDUSTRIAL&ENGINEERINGCHEMISTRYRESEARCH. 49 7343.Baliban,RC;Elia,JA;Floudas,CA (2012). Simultaneousprocesssynthesis,heat,power,andwaterintegrationofthermochemicalhybridbiomass,coal,andnaturalgasfacilities. COMPUTERS&CHEMICALENGINEERING. 37 297.Bedard J.,HongD.Y.,Bhan A. (2013). CH4dehydroaromatization onMo/H-ZSM-5:1.Effectsofco-processingH2andCH3COO. JOURNALOFCATALYSIS. 306 58.Bedard J.,HongD.Y.,Bhan A. (2013). Co-processingCH4andoxygenatesonMo/H-ZSM-5:2.CH4-CO2andCH4-HCOOHmixtures. PHYSICALCHEMISTRYCHEMICALPHYSICS. 15 12173.Bedard J.;ChiangH.;Bhan A. (2012). Kineticsandmechanismofaceticacidesterificationonzeolites. JournalofCatalysis. 290 210.BlassS.D.,Bhan A.,SchmidtL.D. (2013). Hydroconversion ofliquidhydrocarbonsinastagedautothermal reactor. APPLIEDCATALYSISA-GENERAL. 451 153.Blass,S.D.;Hermann,R.J.;Persson,N.E.;Bhan,A.;Schmidt,L.D. (2014). Conversionofglyceroltolightolefinsandgasolineprecursors. AppliedCatalysisA:General. 475 10.Blass,S.D.;Rosenthal,C.;Bhan,A.;Schmidt,L.D. (2013). ReductivedehydrationofbutanonetobutaneoverPt/γ-Al2O3andHZSM-5. CatalysisCommunications. 42 54.ChristiansenM.A.,Mpourmpakis G.,VlachosD.G. (2013). DensityFunctionalTheory-computedmechanismsofethyleneanddiethyletherformationfromethanolongamma-alumina. ACSCATALYSIS. 3 1965.ChristiansenMA;VlachosDG (2012). Microkinetic modelingofPt-catalyzedethyleneglycolsteamreforming. AppliedCatalysisA:General. 18-24 431.Christiansen,M.A.;Mpourmpakis,G.;Vlachos,D.G. (2014). DFT-drivenMulti-SiteMicrokinetic ModelingofEthanolConversiontoEthyleneandDiethylEtheronγ-Al2O3(111). JOURNALOFCATALYSIS.Elia,J.A.,Baliban,R.C.,Floudas,C.A. (2012). NationwideSupplyChainAnalysisforHybridEnergyFeedstockProcesseswithSignificantCO2EmissionsReduction. AIChE Journal. 58 2142.Elia,J.A.,Baliban,R.C.,Floudas,C.A.,Gurau,B.,Weingarten,M.,Klotz,S. (2013). Hardwoodbiomasstogasoline,diesel,andjetfuel:II.Supplychainoptimizationframeworkforanetworkofthermochemicalrefineries. ENERGYFUELS. 27 4325.Elia,J.A.;Baliban,R.C.,Xiao,X;Floudas,CA (2011). OptimalEnergySupplyNetworkDeterminationandLifeCycleAnalysisforHybridCoal,Biomass,andNaturalGastoLiquid(CBGTL)PlantsUsingCarbon-basedHydrogenProduction. COMPUTERSANDCHEMICALENGINEERING. 35 1399.Elia,J.A.;Baliban,R.C.;Floudas,C.A. (2014). Nationwide,regional,andstatewideenergysupplychainoptimizationfornaturalgastoliquidtransportationfuel(GTL)systems. Ind.Eng.Chem.Res.. 53 5366.Elia,J.A.;Floudas,C.A. (2014). Energysupplychainoptimizationofhybridfeedstockprocesses:areview. Annu.Rev.Chem.Biomol.Eng.. 5 147.Elia,J.A.;Li,J.;Floudas,C.A. (2014). Strategicplanningoptimizationfornaturalgastoliquidtransportationfuel(GTL)systems. Comput.Chem.Eng. .Elia,JA;Baliban,RC;Floudas,CA (2010). TowardNovelHybridBiomass,Coal,andNaturalGasProcessesforSatisfyingCurrentTransportationFuelDemands,2: SimultaneousHeatandPowerIntegration. INDUSTRIAL&ENGINEERINGCHEMISTRYRESEARCH. 49 7371.First,E.L.,Floudas,C.A. (2013). MOFomics:Computationalporecharacterizationofmetal–organicframeworks. MICROPOROUSANDMESOPOROUSMATERIALS. 165 32.First,E.L.,Gounaris,C.E.,Floudas,C.A. (2013). PredictiveFrameworkforShape-SelectiveSeparationsinThree-DimensionalZeolitesandMetal–OrganicFrameworks. LANGMUIR. 29 5599.First,E.L.,Gounaris,C.E.,Wei,J.,Floudas,C.A. (2011). Computationalcharacterizationofzeoliteporousnetworks:anautomatedapproach. Phys.Chem.Chem.Phys.. 13 17339.First,E.L.;Gounaris,C.E.;Floudas,C.A. (2012). Stereochemically ConsistentReactionMappingandIdentificationofMultipleReactionMechanismsthroughIntegerLinearOptimization. J.Chem.Inf.Model.. 52 84.First,E.L.;Hasan,M.M.F.;Floudas,C.A. (2014). Discoveryofnovelzeolitesfornaturalgaspurificationthroughcombinedmaterialscreeningandprocessoptimization. AIChE JOURNAL. 60 1767.Floudas,C.A.,Elia,J.A.,Baliban,R.C. (2012). HybridandSingleFeedstockEnergyProcessesforLiquidTransportationFuels:ACriticalReview. COMPUTERSANDCHEMICALENGINEERING. 41 24.Gounaris,C.E;First,E.L;Floudas,C.A (2013). Estimationofdiffusionanisotropyinmicroporous crystallinematerialsandoptimizationofcrystalorientationinmembranes. J.Chem.Phys.. 139 124703.H.Sun,S.Blass,E.Michor,andL.D.Schmidt (2012). Autothermal ReformingofButanol toButenes inaStagedMillisecondReactor:EffectofCatalystsandIsomers. APPLIEDCATALYSISA-GENERAL. 445 35.Hasan,M.M.F.,Baliban,R.C.,Elia,J.A.,Floudas,C.A. (2012). Modeling,Simulation,andOptimizationofPostcombustion CO2CaptureforVariableFeedConcentrationandFlowRate.1.ChemicalAbsorptionandMembraneProcesses. INDUSTRIAL&ENGINEERINGCHEMISTRYRESEARCH. 51 15642.Hasan,M.M.F.,Baliban,R.C.,Elia,J.A.,Floudas,C.A. (2012). OptimizationofPostcombustion CO2CaptureforVariableFeedConcentrationandFlowRate.2.PressureSwingAdsorptionandVacuumSwingAdsorptionProcesses. INDUSTRIAL&ENGINEERINGCHEMISTRYRESEARCH. 51 15665.Hasan,M.M.F.;Boukouvala,F.;First,E.L.;Floudas,C.A. (2014). Nationwide,regional,andstatewideCO2capture,utilization,andsequestrationsupplychainnetworkoptimization. Ind.Eng.Chem.Res.. 53 7489.Hasan,M.M.F.;First,E.L.;Floudas,C.A. (2013). Cost-effectiveCO2capturebasedoninsilico screeningofzeolitesandprocessoptimization. Phys.Chem.Chem.Phys.. 15 17601.Khaleel,M.;Wagner,A.J.;Mkhoyan,K.A.;TsapatsisM. (2014). OntheRotationalIntergrowthofHierarchicalFAU/EMTZeolites. ANGEWANDTECHEMIE-INTERNATIONALEDITION. 53 9456Liu,D.;Zhang,X.;Bhan,A.;TsapatsisM. (2014). ActivityandselectivitydifferencesofexternalBronsted acidsitesofsingle-unit-cellthickandconventionalMFIandMWWzeolites. MICROPOROUSANDMESOPOROUSMATERIALS. 200 287.Niziolek,A.M.;Onel,O.;Elia,J.A.;Baliban,R.C.;Xiao,X.;Floudas,C.A. (2014). CoalandBiomasstoLiquidTransportationFuels:ProcessSynthesisandGlobalOptimizationStrategies. Ind.Eng.Chem.Res..Onel,O.;Niziolek,A.M.;Hasan,M.;Floudas,C.A. (2014). Municipalsolidwastetoliquidtransportationfuels–PartI:Mathematicalmodelingofamunicipalsolidwastegasifier. Comput.Chem.EngR.,Xiong;S.I.,Sandler;D.G.,Vlachos (2011). AlcoholAdsorptionontoSilicalite fromAqueousSolution. JournalofPhysicalChemistryC. 115 18659.Rangarajan S.,Bhan A.,Daoutidis P. (2012). Language-orientedrule-basedreactionnetworkgenerationandanalysis:ApplicationsofRING. COMPUTERS&CHEMICALENGINEERING. 46 141.Rangarajan S.,Bhan A.,Daoutidis P. (2012). Language-orientedrule-basedreactionnetworkgenerationandanalysis:DescriptionofRIN. COMPUTERS&CHEMICALENGINEERING. 45 114.Rangarajan S.;Bhan A.;Daoutidis P. (2010). Rule-BasedGenerationofThermochemicalRoutestoBiomassConversion. INDUSTRIAL&ENGINEERINGCHEMISTRYRESEARCH. 49 10459.Rangarajan S.;Bhan A.;Daoutidis P. (2014). Identificationandanalysisofsynthesisroutesincomplexcatalyticreactionnetworksforbiomassupgrading. .AppliedCatalysisB:Environmental. 145 149.Skinner,M.J.;Michor,E.;Fan,W.;Tsapatsis,M.;Bhan,A.;Schmidt,L.D. (2011). EthanolDehydrationtoEthyleneinaStratifiedAutothermal MillisecondReactor. CHEMSUSCHEM. 4 1151.SunH.;SchmidtL.D. (2011). Methanoldehydrationtodimethyletherinastagedautothermal millisecondresidencetimereactor. AppliedCatalysisA:General. 404 81.Sun,H.;Rosenthal,C.;Schmidt,LD (2012). Oxidativepyrolysisofpolystyreneintostyrenemonomersinanautothermal fixed-bedcatalyticreactor. ChemSusChem. 5 1883.TsapatsisM. (2014). 2-dimensionalzeolites. AICHEJOURNAL. 60 2374.Xiong,RC;Sandler,SI;Vlachos,DG (2012). MolecularScreeningofAlcoholandPolyol AdsorptionontoMFI-TypeZeolites. LANGMUIR. 28 4491.ZhangH.,Suszynski W.J.,Agrawal K.V.,TsapatsisM.,AlHashimi S.,FrancisL.F. (2012). CoatingofOpenCellFoams. INDUSTRIAL&ENGINEERINGCHEMISTRYRESEARCH. 51 9250.ZhangX.;LiuD.;Asahina S.;Cychosz K;Agrawal Varoon K.;AlWahedi Y.;Bhan A.;AlHashimi S.;Terasaki O.;Thommes M.;TsapatsisM. (2012). Directsynthesisofaself-pillaredsingleunitcellzeolite. SCIENCE. 336 1684.Zhang,XY;Tsapatsis,M (2010). Mesoporous silicananoparticlesfromaclearsolandtheirtransformationtolamellarsilicalite-1particlesandfilms. MICROPOROUSANDMESOPOROUSMATERIALS. 138 239.

PatentsFloudas,C.A.,Baliban,R.C.,Elia,J.A.Processesforproducingsyntheticliquidhydrocarbonsfromcoal,biomass,andnaturalgas.Provisionalapplication#61/605,547,2012.

Floudas,C.A.,First,E.L.,Gounaris,C.E.Methodofdeterminingchemicalreactionmechanisms.Provisionalapplication#61/714,270,2012.

Floudas,C.A.,First,E.L.,Hasan,M.M.F.,Gounaris,C.E.Methodforidentifyingamicroporous material.Provisionalapplication#61/761,436,2013.

Floudas,C.A.,First,E.L.,Hasan,M.M.F.,Gounaris,C.E.Methodforidentifyingamicroporous material.Provisionalapplication#61/765,284,2013.

Web/InternetSitesZEOMICS:ZeolitesandMicroporous StructuresCharacterization(http://helios.princeton.edu/zeomics/).

MOFomics:Metal-OrganicFrameworksCharacterization(http://helios.princeton.edu/mofomics/).

DREAM:DeterminationofReactionMechanisms(http://selene.princeton.edu/dream/).

EFRI Publications/Patents/WebSites. Final Report.

Rational design of shape selective separation and catalysisC.E. Gounaris, C.A. Floudas, J. Wei, Chem. Eng. Sci. 61 (2006) 7933–7948

3D Characterization Framework

Portals Channels Cages Connectivity

• Automatedmethodtosystematicallystudytheporestructureofzeolites

• Characterizationofthevoidspaceintochannelsandcages

• Determinationofconnectivitybetweentheseconstructs

1 2 3 4

Floudas 2010

Portal Identification• Represent structure as

a periodic molecular graph (vertices = atoms, edges = bonds)

• Identify portals by finding isometric cycles (closed paths without a shortcut) using k-cycle enumeration1 and Dijkstra’s2 algorithms

8-ring portal in ACO

1

1 Liu, H., & Wang, J. (2006). A new way to enumerate cycles in graph. In AICT-ICIW '06: Proceedings of the Advanced Int'l Conference on Telecommunications and Int'l Conference on Internet and Web Applications and Services (p. 57). Washington, DC, USA: IEEE Computer Society.2 Dijkstra, E. W. (1959). A note on two problems in connexion with graphs. Numerische Mathematik , 1, 269-271.

Floudas 2010

Channel Building• Find largest void

cylinder linking each pair of portals using non-linear optimization3

• Align cylinders at each portal using non-linear optimization

• Describe channel shape more precisely as the union of several parallel cylindersChannel optimization in ABW

2

3 Floudas,C.A.(1995).NonlinearandMixed-IntegerOptimization:FundamentalsandApplications.OxfordUniversityPress.

Floudas 2010

Cage Finding• Locate large spherical

void regions in the zeolite structure using 3D Delaunay triangulation4

• Identify cages as the union of several overlapping spheres

Large cage in LTA

3

4 Delaunay, B. (1934). Sur la sphére vide. Izvestia Akademii Nauk SSSR, Otdelenie Matematicheskikh i Estestvennykh Nauk , 7, 793-800.

Floudas 2010

Connectivity• Define each channel-

channel and channel-cage intersection as a “junction point”

• Determine channel linkages between junction points

• Construct a periodic connectivity graph (vertices = junction points, edges = linkages)

Several unit cells of LTA

4

Floudas 2010

“We follow a hierarchical approach. First, a screening procedure developed by Gounariset al. and described in detail elsewhere [C.E. Gounaris, C.A. Floudas, J. Wei, Chem.Eng. Sci. 61 (2006) 7933–7948], is used to make a preliminary list of candidateframeworks that exclude (by molecular sieving) certain inhibitors. Out of these lists, weselect commonly available alumino-silicate zeolites. It turns out that MFI is candidate toexclude only vanillin and FER is a candidate to exclude both vanillin and HMF.”

Adsorption of fermentation inhibitors from lignocellulosic biomass hydrolyzates forimproved ethanol yield and value-added product recoveryMicroporous and Mesoporous Materials 122 (2009) 143-148Ranjan R., Thust S., Gounaris C.E., Woo M., Floudas C.A., von Keitz M., Valentas K.J.,Wei J., Tsapatsis M.

Rational Design of Shape Selective Separations and Catalysis: Lattice Relaxation, Locally Optimal Conformations and Effective Aperture SiAIChE Journal 56 (2010) 611-632 (2010) Gounaris C.E., Wei J., Floudas C.A.,Ranjan R., Tsapatsis M. Augmented formulation to account for the flexibility of the zeolitic portal and we conducted sensitivity analysis on the effective size of the aperture, and show how the methodology can be fine–tuned through experimental observations

EquilibriumconcentrationofthexyleneisomersinMFI(T =600K)asafunctionofeffectiveatomicradii(inÅ).

2nm

Nature 543, 690-694(2017)

Ultra-selective High-flux Membranes from Directly Synthesized Zeolite Nanosheets

Siepmann Group

TheNMGCmemberswouldliketoexpresstheirdeepgratitudeforChristodoulos Floudas’pioneeringcontributionstothedevelopmentofgenomicanddata-drivenscienceapproachesandtheirapplicationtonanoporous materialsthatpavedthewayfortheMaterialsGenomeInitiative.IljaSiepmann

3D#Framew

ork#De

tec.on

#

Cleaning#Protocols#

>60k#structures#

5108#structures#

CoRE#MOF#Database#

ABAVIJ#

ABAVOP#

ABEMIF#

ABEXEM#

ABEXUC#

ABEXUC#

ACAKUM#

ZESFUY#

ZIHTEP#

ZNGLUD01#

ZUQVAI#

ZUQVIQ#

ZURQOS#

ZURROT#

."

."

."

>20k#structures#

."

."

."

."

."

."

Pore#Characteriza

.on#

Chem

ical#Bon

d#An

alysis#

Cambridge#Structural#Database#

>600k#structures#

5109%structures%

CoRE-MOF Database

Nanoporous MaterialsExplorer