Unveiling ZIF‑8 Nucleation Mechanisms through Molecular Simulation: Role of Temperature, Solvent, and Reactant Concentration
Synthesizing new metal–organic frameworks (MOFs) is a challenging task, as the size, morphology, polymorph, and type and number of defects present on the synthesis product may depend on many variables, including temperature, solvent, concentration and nature of reactants, among others. A deeper unde...
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| _version_ | 1849927644261384192 |
|---|---|
| author | Sahar Andarzi Gargari (22675844) |
| author2 | Rocio Semino (1437952) |
| author2_role | author |
| author_facet | Sahar Andarzi Gargari (22675844) Rocio Semino (1437952) |
| author_role | author |
| dc.creator.none.fl_str_mv | Sahar Andarzi Gargari (22675844) Rocio Semino (1437952) |
| dc.date.none.fl_str_mv | 2025-11-24T16:43:33Z |
| dc.identifier.none.fl_str_mv | 10.1021/acs.chemmater.5c02028.s002 |
| dc.relation.none.fl_str_mv | https://figshare.com/articles/media/Unveiling_ZIF_8_Nucleation_Mechanisms_through_Molecular_Simulation_Role_of_Temperature_Solvent_and_Reactant_Concentration/30686294 |
| dc.rights.none.fl_str_mv | CC BY-NC 4.0 info:eu-repo/semantics/openAccess |
| dc.subject.none.fl_str_mv | Biophysics Biochemistry Medicine Chemical Sciences not elsewhere classified Physical Sciences not elsewhere classified zn – 2 prenucleation building units phase mainly consists intermediate species observed molecular level mechanisms similar nucleation speed synthesizing new mofs synthesis conditions determine free energy associated solvothermal nucleation process reactant concentration lead free energy nucleation process simulations lead molecular simulation smaller nuclei ring populations partially amorphous obtained material multiple polymorphs many variables lifetimes within larger variety highly connected force field final state experimental observations early steps direct experiments dimethyl sulfoxide defects present deeper understanding changing concentration challenging task based zifs among others 8 relying |
| dc.title.none.fl_str_mv | Unveiling ZIF‑8 Nucleation Mechanisms through Molecular Simulation: Role of Temperature, Solvent, and Reactant Concentration |
| dc.type.none.fl_str_mv | Dataset Media info:eu-repo/semantics/publishedVersion dataset |
| description | Synthesizing new metal–organic frameworks (MOFs) is a challenging task, as the size, morphology, polymorph, and type and number of defects present on the synthesis product may depend on many variables, including temperature, solvent, concentration and nature of reactants, among others. A deeper understanding of how synthesis conditions determine the obtained material is crucial to optimize the use of resources when synthesizing new MOFs. In this contribution, we study the impact of changing concentration, solvent and temperature on the molecular level mechanisms of the solvothermal nucleation process of ZIF-8 relying on molecular dynamics simulations using a force field that incorporates metal–ligand reactivity. We find that the nucleation is faster when the synthesis is performed in dimethyl sulfoxide than when it is performed in methanol, in alignment with experimental observations. In the early steps of the nucleation process, we observe the formation of linear oligomers containing metal ions and ligands, which start forming cycles later on. All simulations lead to the formation of a final state that is highly connected and partially amorphous, which could be correlated to an intermediate species observed in direct experiments. The mechanism of formation of this phase mainly consists of the merging of smaller nuclei. Even though increasing temperature or reactant concentration lead to a similar nucleation speed-up, there are differences in ring populations and lifetimes within the highly connected amorphous intermediate phases formed in each case. Finally, important differences in the free energy of Zn–2-methylimidazolate versus Zn–imidazolate subsequent binding events are revealed and discussed. Interestingly, the free energy associated with subsequent binding events seems to be correlated with the formation of a larger variety of prenucleation building units in the case of imidazolate-based ZIFs, which could be at the onset of the existence of multiple polymorphs for this MOF. |
| eu_rights_str_mv | openAccess |
| id | Manara_4899fbe1920438a3e1703f9e182e31c6 |
| identifier_str_mv | 10.1021/acs.chemmater.5c02028.s002 |
| network_acronym_str | Manara |
| network_name_str | ManaraRepo |
| oai_identifier_str | oai:figshare.com:article/30686294 |
| publishDate | 2025 |
| repository.mail.fl_str_mv | |
| repository.name.fl_str_mv | |
| repository_id_str | |
| rights_invalid_str_mv | CC BY-NC 4.0 |
| spelling | Unveiling ZIF‑8 Nucleation Mechanisms through Molecular Simulation: Role of Temperature, Solvent, and Reactant ConcentrationSahar Andarzi Gargari (22675844)Rocio Semino (1437952)BiophysicsBiochemistryMedicineChemical Sciences not elsewhere classifiedPhysical Sciences not elsewhere classifiedzn – 2prenucleation building unitsphase mainly consistsintermediate species observedmolecular level mechanismssimilar nucleation speedsynthesizing new mofssynthesis conditions determinefree energy associatedsolvothermal nucleation processreactant concentration leadfree energynucleation processsimulations leadmolecular simulationsmaller nucleiring populationspartially amorphousobtained materialmultiple polymorphsmany variableslifetimes withinlarger varietyhighly connectedforce fieldfinal stateexperimental observationsearly stepsdirect experimentsdimethyl sulfoxidedefects presentdeeper understandingchanging concentrationchallenging taskbased zifsamong others8 relyingSynthesizing new metal–organic frameworks (MOFs) is a challenging task, as the size, morphology, polymorph, and type and number of defects present on the synthesis product may depend on many variables, including temperature, solvent, concentration and nature of reactants, among others. A deeper understanding of how synthesis conditions determine the obtained material is crucial to optimize the use of resources when synthesizing new MOFs. In this contribution, we study the impact of changing concentration, solvent and temperature on the molecular level mechanisms of the solvothermal nucleation process of ZIF-8 relying on molecular dynamics simulations using a force field that incorporates metal–ligand reactivity. We find that the nucleation is faster when the synthesis is performed in dimethyl sulfoxide than when it is performed in methanol, in alignment with experimental observations. In the early steps of the nucleation process, we observe the formation of linear oligomers containing metal ions and ligands, which start forming cycles later on. All simulations lead to the formation of a final state that is highly connected and partially amorphous, which could be correlated to an intermediate species observed in direct experiments. The mechanism of formation of this phase mainly consists of the merging of smaller nuclei. Even though increasing temperature or reactant concentration lead to a similar nucleation speed-up, there are differences in ring populations and lifetimes within the highly connected amorphous intermediate phases formed in each case. Finally, important differences in the free energy of Zn–2-methylimidazolate versus Zn–imidazolate subsequent binding events are revealed and discussed. Interestingly, the free energy associated with subsequent binding events seems to be correlated with the formation of a larger variety of prenucleation building units in the case of imidazolate-based ZIFs, which could be at the onset of the existence of multiple polymorphs for this MOF.2025-11-24T16:43:33ZDatasetMediainfo:eu-repo/semantics/publishedVersiondataset10.1021/acs.chemmater.5c02028.s002https://figshare.com/articles/media/Unveiling_ZIF_8_Nucleation_Mechanisms_through_Molecular_Simulation_Role_of_Temperature_Solvent_and_Reactant_Concentration/30686294CC BY-NC 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/306862942025-11-24T16:43:33Z |
| spellingShingle | Unveiling ZIF‑8 Nucleation Mechanisms through Molecular Simulation: Role of Temperature, Solvent, and Reactant Concentration Sahar Andarzi Gargari (22675844) Biophysics Biochemistry Medicine Chemical Sciences not elsewhere classified Physical Sciences not elsewhere classified zn – 2 prenucleation building units phase mainly consists intermediate species observed molecular level mechanisms similar nucleation speed synthesizing new mofs synthesis conditions determine free energy associated solvothermal nucleation process reactant concentration lead free energy nucleation process simulations lead molecular simulation smaller nuclei ring populations partially amorphous obtained material multiple polymorphs many variables lifetimes within larger variety highly connected force field final state experimental observations early steps direct experiments dimethyl sulfoxide defects present deeper understanding changing concentration challenging task based zifs among others 8 relying |
| status_str | publishedVersion |
| title | Unveiling ZIF‑8 Nucleation Mechanisms through Molecular Simulation: Role of Temperature, Solvent, and Reactant Concentration |
| title_full | Unveiling ZIF‑8 Nucleation Mechanisms through Molecular Simulation: Role of Temperature, Solvent, and Reactant Concentration |
| title_fullStr | Unveiling ZIF‑8 Nucleation Mechanisms through Molecular Simulation: Role of Temperature, Solvent, and Reactant Concentration |
| title_full_unstemmed | Unveiling ZIF‑8 Nucleation Mechanisms through Molecular Simulation: Role of Temperature, Solvent, and Reactant Concentration |
| title_short | Unveiling ZIF‑8 Nucleation Mechanisms through Molecular Simulation: Role of Temperature, Solvent, and Reactant Concentration |
| title_sort | Unveiling ZIF‑8 Nucleation Mechanisms through Molecular Simulation: Role of Temperature, Solvent, and Reactant Concentration |
| topic | Biophysics Biochemistry Medicine Chemical Sciences not elsewhere classified Physical Sciences not elsewhere classified zn – 2 prenucleation building units phase mainly consists intermediate species observed molecular level mechanisms similar nucleation speed synthesizing new mofs synthesis conditions determine free energy associated solvothermal nucleation process reactant concentration lead free energy nucleation process simulations lead molecular simulation smaller nuclei ring populations partially amorphous obtained material multiple polymorphs many variables lifetimes within larger variety highly connected force field final state experimental observations early steps direct experiments dimethyl sulfoxide defects present deeper understanding changing concentration challenging task based zifs among others 8 relying |