94PCE din 01/07/2025
PCE PN-IV-P1-
PCE-2023- 1254
MOFs-COFs composites for the
selective and stereoselective catalytic reactions
Compozite MOFs-COFs pentrru reactii selective si stereoselective
Abstract
Nowadays, the fine chemistry
synthesis, the large chemical production and also the environmental limitations
impose more selective reactions, higher turnovers, reduced energy consume, less
pollutant synthesis routes and enhanced productivities. In answers to all these
concerns, catalysis may offer efficient solutions through: i)
reducing the metal contents by the use of nanoparticles, ii) replacing the
inorganic supports by organic parts also affording a recognition of the
substrates and the products (selectivity), and iii) replacing the volatile
solvents with greener ones. Based on this state of the art and the
requirements of the moment the MOF-COF-COMP project proposes, as new
challenges, new composite catalytic materials such as 2D-Metal-organic-framework-
2D covalent organic framework (2D-MOF-2D-COF) and 3D-MOF-2D-COF providing
multifunctional synergetic properties such as a strong enhancement in the
reduction of consume of the metals, recyclable catalysts and a better
selectivity. With these aims the project proposed the development of new
composites in which the metal will provide a catalytic hydrogenation/oxidation
activity while the organic functionalities of the COF, and also MOF, will
generate acid/base functionalities for the consecutive reactions and chirality.
Not at the end, the texture of the organic framework will afford a
shape-selectivity control. Envisaged reactions are of current interest.
În prezent,
sinteza chimica fina, producția chimică industriala și, de
asemenea, limitările de mediu, impun reacții mai selective,
randamente mari, consum redus de energie, cai de sinteză mai puțin
poluante și productivități sporite. Ca răspuns la toate
aceste preocupări, cataliza poate oferi soluții eficiente prin: i)
reducerea conținutului de metal prin utilizarea de nanoparticule, ii)
înlocuirea suporturilor anorganice cu suporturi organice stabile termic, permițând
recunoașterea substraturilor și a produsilor de reactie
(selectivitate) și iii) înlocuirea solvenţilor volatili cu alţii
mai verzi. Pornind de la aceasta stare de fapt și de la cerințele
momentului, proiectul MOF-COF-COMP propune, ca noi provocări, materiale
catalitice compozite noi precum retele 2D-Metal-organice-2D covalent organice
(2D-MOF-2D-COF) și 3D-MOF-2D-COF oferind proprietăți sinergetice
multifuncționale, cum ar fi o reducere a consumului de metale,
catalizatori reciclabili și o selectivitate mai ridicata. Cu aceste
obiective proiectul isi propune proiectarea de compozite noi în care metalul va
genera activitatea catalitică in reactii de hidrogenare/oxidare în timp ce
funcționalitățile organice ale COF, dar și MOF, vor genera
funcționalități acid/bază pentru reacții consecutive, și
chiralitate. Nu in cele din urma, textura scheletului organic va permite un
control al selectivității. Reacțiile preconizate sunt de interes
curent.
Budget: 1147368.00 RON (229473.60
EUR)
Research team
DIRECTOR – Prof.
Vasile Parvulescu
Member –
researcher – Dr. Octavian D. Pavel
Member – researcher
– Dr. Bogdan Cojocaru
Member –
Postdoctoral researcher – Dr. Sabina G. Ion
Member –
Doctoral researcher – Oana Petcuta
Member –
Doctoral researcher – Mihai Bordeiasu
Working plan
Stage one –
2025 - Consecutive enantioselective ring opening of epoxides through an
asymmetric organocatalytic reaction on functionalized 2DCOF-3DMOF (139150 RON)
Deliverables:
3 2D-MOF-2D-COF composites, synthesized and characterized.
Report on the
performance of the composites in consecutive enantioselective ring opening of
epoxides.
Act. 1.1 - Synthesis
of new 2D-MOF-COF composites.
Act. 1.2 -
Exhaustive characterization of new materials and understanding of the
mechanistic behavior using in situ and opera
Act. 1.3 -
Demonstration of the efficiency of the new synthesized 2D composites in
reactions of interest carried out in both liquid and gas phases: Consecutive
enantioselective ring opening of epoxides through a reaction.
Asymmetric
organocatalytic reaction catalyzed by a functionalized CO, followed by an
allylic alkynylation catalyzed by an encapsulated MOF asymmetric metal
catalyst.
Stage report
i)
the preparation and characterization methodologies of some MOF materials and
derived composites, COF@MOF, based on Co, Ni and Cu;
ii) catalytic
studies in condensation reactions following the catalytic activity of the
synthesized materials
Starting from
these objectives, the following were studied:
1.
Consecutive enantioselective opening of the epoxide ring through an asymmetric
organocatalytic reaction on functionalized 2DCOF-3DMOF catalysts
2. Synthesis
of metal-organic frameworks (MOF) and COF@MOF composite materials
i)
To obtain MOF frameworks, as precursors, nickel, cobalt and copper nitrates
were used which were complexed with terephthalic acid and 2-aminoterephthalic
acid ligands using DMF as dispersion medium followed by a heat treatment at 110℃
for 24h in an autoclave lined with Teflon interior. Using this protocol, six
compounds defined as: Co-BDC, Co-ABDC, Ni-BDC, Ni-ABDC, Cu-BDC and Cu-ABDC were
synthesized.
ii) To obtain
COF@MOF composite materials, a protocol was applied: by which metal salt
solutions (Ni(NO3)2 or Co(NO3)2
and H2BDC (2-Hydroxy-terephthalic acid) were added to the obtained dispersion.
The mixture obtained was then subjected to magnetic stirring and a solvothermal
treatment at 110℃ for 24h. Using this protocol, four
composite materials were synthesized, respectively, COFAF8@Co-BDC,
COFAF8@Ni-BDC, COFAF9@Co-BDC and COFAF9@Ni-BDC.
iii)
Exhaustive characterization of the new materials and understanding of the
mechanistic behavior through in situ and operando investigations. The obtained
materials were characterized by a series of techniques including: i) textural analysis by nitrogen adsorption; ii) X-ray
diffraction; iii) FT=IR, Raman, NIR spectroscopy; iV)
UV-Vis spectroscopy; V) X-ray spectroscopy. Most of
these investigations were performed on powder, but investigations were also
performed on tableted catalysts, especially for COF and MOF, and COF-MOF
composites.
iV)
Demonstration of the efficiency of the new 2D composites was proven in
reactions in both liquid and gas phases. These included: i)
consecutive enantioselective ring opening of epoxides through an asymmetric
organocatalytic reaction; ii) multicomponent condensation between benzaldehyde,
ethyl acetylacetate and urea; iii) condensation of
benzaldehyde with ethyl acetylacetate; V)
depolymerizations combining COF-MOF structures (MOF with zinc, cobalt or nickel
and BDC (benzene-1,4-dicarboxylic acid or terephthalic acid); V) cyanosilylation reactions in chiral catalysis; Vi)
oxidation and epoxidation and condensation reactions with the formation of
heteroaromatic compounds.
Deliverables
achieved:
- 10
2D-MOF-2D-COF composites, synthesized and characterized with proof of
reproducibility.
- 8 syntheses
of unsaturated ketones and aldehydes by the Knoevanagel
reaction
- 4 syntheses
of cyano-silylate compounds
- 5
encapsulated nano-particle catalysts and their evaluation in 10 oxidation and
epoxidation reactions
Publications
in 2025
1. Zăvoianu, R.; Taha, S.E.; Culiţă,
D.C.; Raciulete, M.; Popescu, D.G.; Parvulescu, V.I.; Cojocaru, B.,
Pavel, O.D., The impact of organic alkalis in the tailoring of MgCuAl-LDH-based composites as a catalyst for
Claisen-Schmidt condensation, Molecular Catalysis, 589, 115592, 2026.
2. Bordeiasu, M., Goscianska, J., Panek, R., ... Parvulescu, V.I., Coman, S.M., Magnetic Fe,Co-Nanocarbon
Frameworks Derived from Fe-Doped Zeolitic Imidazolate Framework-67 as Highly
Active Catalysts for 5-Hydroxymethylfurfural Oxidation, Chemsuschem,
18(17), e202500678, 2025.
3. Pavel, O.,
Tirsoaga, A., Cojocaru, B.,
... Parvulescu, V., Garcia, H., Nb2C Mxene as a bifunctional acid-base and
oxidation/hydrogenation catalystEs Catalysis, 3(4),
856–869, 2025.
4. Arora, Z.,
Pârvulescu, V.I., Philippot,
K., Durand, J., Gouygou, M., Immobilization of a
chiral rhodium catalyst on carbon nanotubes via non-covalent interaction for
heterogeneous asymmetric hydrogenation, Catalysis Science and Technology,
15(10), pp. 3075–3081, 2025.
5. Arora, Z.,
Pârvulescu, V.I., Philippot,
K., Durand, J., Gouygou, M., Non-Covalent
Immobilization of Chiral Rhodium Catalysts on Carbon Nanotubes for Asymmetric
Hydrogenation, Chemnanomat, 11(2), e202400125, 2025.
6. Ramírez
Grau, R., Garcia-Aznar, P., Sastre, G., ... Primo,
A., García, H., MXenes as Heterogeneous Thermal
Catalysts: Regioselective Anti-Markovnikov Hydroamination of Terminal Alkynes
with 102 h-1 Turnover Frequencies, Journal of the American Chemical Society,
147(4), pp. 3315–3332, 2025
7. Espita, O.H.L., Coman, S.M.,
Gallego, M.A.C., Pârvulescu, V.I., Biomass
Transformation into Chemicals Using Zeolites and MOFs, Zeolites and Metal
Organic Frameworks from Lab to Industry, pp. 117–147, 2025
8. Petcuta, O.A., Guzo, N.C., Bordeiasu, M., ... Parvulescu,
V.I., Coman, S.M., Ru/Beta Zeolite Catalysts for Levulinic Acid Hydrogenation: The Importance of Catalyst
Synthesis Methodology, Catalysts, 15(1), 80, 2025