Project 9 from 2012

Design of organic spacers for constructing metal- organic frameworks (MOFs) – Towards a better control on the porous architecture and active catalytic sites

Duration: 36 months (2012-2015)

Project Summary

The overall project goal is to develop a rational way for synthesis of new metal-organic frameworks and to demonstrate the effectiveness in practical applications such as catalysis, energy storage, luminescence etc.. Research will focus on getting new stable structure by controlling the strength of metal-ligand bonds in the bridge, surface of new materials and reproducible synthesis of new materials, the stability of metal-organic frameworks synthesized in applied conditions and flexibility of active sites.

General objectives and expected results

  1. Design, synthesis and characterization of new family of organic spacers, precursors for metal-organic frameworks with default topologies.
  2. Design, synthesis and characterization of new organio-metallic spacers and new potential organometallic nodes.
  3. Getting MOSs based on new organic and organometallic spacers.
  4. Optimizing MOF architectures by improving the design of spacers and organometallic nodes.
  5. Optimizing MOF properties by post-synthesis processes.
  6. Generating acidic and basic sites in MOF which will show optimized properties by capture of metal nanoparticles and post-synthesis functionalization.
  7. Evaluation of the capacity of selective sorption of MOFs for various molecules;
  8. Investigation of the possibilities of gas storage of synthesized MOFs.


Coordinating institution

University of Bucharest

Faculty of Chemistry

Department of Organic Chemistry, Biochemistry and Catalysis

Bucuresti, bd. Mihail Kogalniceanu, nr.36-46, tel. 0213077300, fax. 0213131760, cod fiscal (CUI) 4505502


Consortiului:

  • Team 1University of Bucharest, Faculty of Chemistry, Department of Inorganic, «Theoretical Inorganic and Applied Chemistry» Research Center, Acad. Marius Andruh
  • Team2University of Bucharest, Faculty of Chemistry, Department of Organic Chemistry, Biochemistry and Catalysis, «Catalysts and Catalytic Processes» Research Center, Prof. Dr. Vasile Parvulescu
  • Team 3 : Babes-Bolyai University, Faculty of Chemistry and Chemical Engineering, Department of Inorganic Chemistry, Prof. Dr. Cristian Silvestru, m. c. of Romanian Academy
  • Team 4: Babes-Bolyai University, Faculty of Chemistry and Chemical Engineering, Department of Organic Chemistry,Prof. Dr. Ion Grosu.


Contracting authority

Executive Agency for Higher Education, Research, Development and Innovation Funding(UEFISCDI),

Bucureşti, Str. D. I. Mendeleev nr. 21-25, sector 1, tel 021 3023850, fax. 021 3115992, cod fiscal 12354176, cont IBAN RO83 TREZ 7015 003X XX01 1609, Trez. Sect.1, e-mail office@uefiscsdi.ro


Implementation plan

TASK 1. Testing the ability of commercially available cage-like spacers (e.g. hexamethylenetetramine and derivatives) to generate non-interpenetrating 3D networks.

Task 1.1.  Synthesis of new non-interpenetrating 3D networks.

Task 1.2.  Structural and spectral characterization of obtained compounds. 

TASK 2. Synthesis and structural investigation of cyclophane-like and C3 spacers.

Task 2.1. Design of layered compounds with cyclophanes and C3 spacers, synthesis and structural investigations of intermediates.

Task 2.2. Synthesis, structural investigations, and properties of layered compounds with cyclophanes.

Task 2.3. Synthesis and structural investigations of intermediates for the synthesis of layered compounds with cyclophanes and C3 spacers.

TASK 3. Synthesis and structural investigation of robust, air-stable organometallic tectons.

Task 3.1. Synthesis and structural investigations of air stable Hg(II) tectons.

Task 3.2. Synthesis and structural investigations of air stable organoSn/Pb(IV) tectons.

Task 3.3. Synthesis and structural investigations of air stable organoSb/Bi(III) tectons.

TASK 4. Synthesis and characterization of MOFs based upon spacers synthesized in Tasks 2 - 3. Assembling cations: Cu(II), Ln(III). For the neutral spacers, metal triflates will be also used in the assembling process.

Task 4.1. Synthesis and characterization of MOFs with cyclophanes and C3 spacers.

Task 4.2. Synthesis and structural investigations of MOFs with organometallic tectons.

TASK 5. Synthesis and characterization of new organometallic halides useful as potential nodes and functionalizing groups and the corresponding MOFs.

TASK 6. Post-synthetic processings for the optimization of MOFs properties (Task 3). The removal of solvent molecules and weakly coordinated ligands.

Task 6.1. Optimization of MOFs properties (Task 3) by removing the solvent molecules filling the channels.

Task 6.2. Optimization of MOFs properties (Task 3) by removing the weakly coordinated ligands. 

Task 7. Optimizations of the design of spacers; synthesis and characterization of new MOFs.

Task 7.1. Design of optimized layered compounds with cyclophanes and C3 spacers, synthesis and structural investigations of new intermediates.

Task 7.2. Synthesis, structural investigation, and properties of optimized layered compounds with cyclophanes and of C3 spacers.

Task 7.3. Synthesis and structural investigations of optimized cyclophane-like and C3 organometallic tectons.

Task 7.4. Synthesis and characterization of new MOFs. 

TASK 8. Investigation of the sorption or/and catalytical properties of the MOFs synthesized during previous Tasks (3, 4, 5).

Task 8.1. Measurements of sorption capability of MOFs in waters already treated for the degradation of various organic compounds resulted from the depletion of pharmaceutical products.

Task 8.2. Evaluation of sorption capability from TOC (total organic carbon) measurements of waters before and after the exposure to MOF.

TASK 9. Synthesis and characterization of tetrahedral synthons (purely organic and organometallic).

Task 9.1. Synthesis and structural investigation of intermediary products in the synthesis of organic tetrahedral synthons.

Task 9.2. Synthesis, structural investigation, and properties of organic tetrahedral synthons.

Task 9.3. Synthesis and structural investigations of organometallic tetrahedral synthons.

TASK 10. Synthesis and characterization of diamondoid networks using tetrahedral synthons. Assembling cations: Cu(II), Co(II), Ni(II), etc.

Task 10.1. Synthesis of new diamantoid networks.

Task 10.2. Structural and spectral characterization of diamantoid networks.

TASK 11. Post-synthetic processings of the MOFs obtained in Task 8. The removal of solvent and weakly coordinated ligands.

Task 11.1. Post-synthetic processings of the MOFs obtained in Task 8.

Task 11.2. Removal of solvent and weakly coordinated ligands for MOFs obtained in Task 8. 

TASK 12. Functionalization of selected MOFs by nanoconfinement with metal nanoparticles and post-synthetic functionalization for generation of acidic and basic sites.

Task 12.1. Functionalization of selected MOFs by nanoconfinement with metal nanoparticles.

Task 12.2. Post-synthetic functionalization of selected MOFs for generation of acidic and basic sites 

TASK 13. Investigation of the sorption and catalytic properties of the MOFs constructed in Tasks 8, 9, and 10. Sorption properties will be investigated in relation to the energy storage of these materials. Thus, the main issue would be to increase the methane intake. Functionalization of these systems with triflate groups will make them very attractive for alkylation reactions of aromatic derivatives.  Postfunctionalization with formate structures will be investigated in relation to the hydrogen storage efficiency. These structures will be investigated in aerobic oxidation of alcohols and in the capture of CO2 in the reaction with methanol and ethanol or/and in the selective oxidation of aliphatic and aromatic amines to the corresponding nitriles.

TASK 14. Synthesis and characterization of chiral spacers and the corresponding MOFs.

Task 14.1. Design, synthesis, structural investigations, and properties of chiral spacers.

Task 14.2. Synthesis and structural investigations of chiral organometallic spacers.

Task 14.3 Synthesis of MOFs with chiral spacers.

TASK 15. Investigation of enantioselective organic reactions catalyzed by chiral MOFs. For that, functionalized MOFs with acid and base groups will be investigated in the asymetric aldol reaction between representative ketones with various aromatic aldehydes under solvent-free conditions.

TASK 16. Investigation of luminescent properties. Study of the influence of guest molecules on the luminescence behavior. Encapsulation of sensitizers will allow the investigation of energy storage capability.

TASK 17. Test the ability of the synthesized MOFs in decontamination processes. More specifically, MOFs will be used as adsorbents for the molecules resulted from the degradation of pharmaceutical compounds via either liquid phase catalytic oxidation or plasma.



Bugetul proiectului 

7000000lei


Project leader contact data

Acad. Marius Andruh

Tel 0212103497/0744870656

Email marius.andruh@dnt.ro


Final results

  1. E. Ilyes, M. Florea, A.M. Madalan, I. Haiduc, V.I. Parvulescu, M. Andruh,  A Robust Metal-Organic Framework Constructed from Alkoxo-bridged Binuclear Nodes and Hexamethylenetetramine Spacers: Crystal Structure and Sorption Studies, Inorg. Chem. 51 (2012) 7954−7956.
  2. N.Candu, M.Tudorache, M. Florea, E. Ilyes, S.M. Coman, I. Haiduc, M. Andruh, V.I. Parvulescu, Postsynthetic modification of a MOF structure for enantioselective catalytic epoxidation, ChemPlusChem78 (2013) 443–450.

 

 

 

Pagină actualizată la 26 Iunie 2013.