Exploiting Reaction-Diffusion Conditions to Trigger Pathway Complexity in the Growth of a MOF

Coordinationpolymers(CPs),includingmetal-organicframeworks(MOFs),are crystallinematerialswithpromisingapplicationsin electronics,magnetism,catalysis,andgas storage/separation.However,the mechanismsandpath-waysunderlyingtheirformationremainlargelyundisclosed.Herein,we demonstratethatdiffusion-control...

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Detalles Bibliográficos
Autores: Calvo Galve, Néstor, Abrishamkar, Afshin, Sorrenti, Alessandro, Di Rienzo, Lorenzo, Satta, Mauro, D'Abramo, Marco, Coronado, Eugenio, De Mello, Andrew J., Mínguez Espallargas, Guillem, Puigmartí-Luis, Josep
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2021
País:España
Institución:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/185127
Acceso en línea:https://hdl.handle.net/2445/185127
Access Level:acceso abierto
Palabra clave:Polímers
Cristal·lització
Microfluídica
Polymers
Crystallization
Microfluidics
Descripción
Sumario:Coordinationpolymers(CPs),includingmetal-organicframeworks(MOFs),are crystallinematerialswithpromisingapplicationsin electronics,magnetism,catalysis,andgas storage/separation.However,the mechanismsandpath-waysunderlyingtheirformationremainlargelyundisclosed.Herein,we demonstratethatdiffusion-controlledmixingofreagentsat the veryearlystagesof the crystallizationprocess(i.e., within 40 ms),achievedby usingcontinuous-flowmicrofluidicdevices,can be usedto enablenovelcrystallizationpathwaysofaprototypicalspin-crossover MOFtowards itsthermodynamicproduct.In particular,twodistinctandunprecedentednucleation-growth pathwayswere experimen-tallyobservedwhencrystallizationwas triggeredundermicro-fluidicmixing.Full-atommoleculardynamicssimulationsalsoconfirmthe occurrenceof thesetwo distinctpathwaysduringcrystalgrowth.In sharpcontrast,acrystallizationby particleattachmentwas observedunderbulk(turbulent)mixing.Theseunprecedentedresultsprovideasoundbasisfor understandingthe growth of CPsand openup newavenuesfor the engineer-ing of porousmaterialsby usingout-of-equilibriumconditions