Low temperature process for the synthesis of MOF carboxylate nanoparticles

Patent metadata

Field	Value
Publication number	US-11034711-B2
Application number	US-201816480531-A
Country	US
Kind code	B2
Filing date	Jan 29, 2018
Priority date	Feb 2, 2017
Publication date	Jun 15, 2021
Grant date	Jun 15, 2021

Abstract

The present invention relates to low temperature process for preparing nanoparticles of porous crystalline Fe-, Al- or Ti-based MOF carboxylate materials with low polydispersity index, and uses thereof, particularly as catalyst support for carrying out heterogeneously catalyzed chemical reactions, or as gas storage/separation/purification material, or as matrix for encapsulating active principles (medicine, cosmetics).

First claim

The invention claimed is:

1. A microwave-free process for preparing nanoparticles of porous crystalline Fe-, Al- or Ti-based MOF carboxylate material, comprising steps of:
A) mixing in an aqueous solvent system:
(i) at least a first inorganic metallic precursor in the form of a metal M, a salt of a metal M or a coordination complex comprising the metal ion M z+ selected from Fe 2+ , Fe 3+ , Ti 3+ , Ti 4+ or Al 3+ ;
(ii) at least one precursor ligand L′ having the structure R1-(C(═O)—R3) q wherein:
q represents an integer from 2 to 6;
each occurrence of R 3 is independently selected from a halogen atom, —OH, —OR 4 , —O—C(═O)R 3A or —NR 3A R 3B , wherein R 3A and R 3B , identical or different, represent C 1-12 alkyl radicals; and wherein R 3 is not —OY wherein Y represents an alkali metal cation and R 4 is not —OM i where M i represents an alkali metal cation;
R 1 independently represents:
(a) a C 1-12 alkyl, C 2-12 alkenyl or C 2-12 alkynyl radical;
(b) a fused or non-fused monocyclic or polycyclic aryl radical, comprising 6 to 50 carbon atoms;
(c) a fused or non-fused monocyclic or polycyclic heteroaryl, comprising 4 to 50 carbon atoms;

R 1 optionally bearing one or more substituents independently selected from a halogen atom, —OH, —NH 2 , —NO 2 or C 1-6 alkyl;
each occurrence of R 4 independently represents —OH, a halogen atom, or a —OR 5 , —O—C(═O)R 5 or —NR 5 R 5 ′ moiety, wherein R 5 and R 5 ′ independently represent C 1-12 alkyl; and

B) allowing the mixture obtained in step A) to react at a temperature ≤75° C.; so as to obtain the said nanoparticles;
wherein the process is carried out in the absence of a base additive or an acid additive other than L′=R 1 —(C(═O)—OH) q ; the process is carried out under dilute conditions whereby the inorganic metallic precursor concentration is ≤50 mM; and the resulting nanoparticles have a polydispersity index 0.05≤PDI≤0.3 as calculated under ISO standard 13321:1996 E and ISO 22412:2008.

2. The process of claim 1 , wherein L′ is a di-, tri-, tetra- or hexadentate precursor ligand selected from:

wherein R 3 is as defined in claim 1 ,
s represents an integer from 1 to 4,
each occurrence oft independently represents an integer from 1 to 4,
u represents an integer from 1 to 7,
each occurrence of R L1 and R L2 independently represent H, a halogen or a C 1 to C 6 alkyl, and
each occurrence of R L3 independently represents H, a halogen atom, —OH, —NH 2 , —NO 2 or C 1-6 alkyl
X represents a covalent bond, C═O, CH 2 , N═N, NH, O, S, SO 2 , C═C, —O—(CH 2 ) p —O—, —NH—(CH 2 ) p —NH— or —S—(CH 2 ) p —S— where p represents an integer ranging from 1 to 4;
each occurrence of m independently represents an integer from 1 to 3; and each occurrence of R 1 independently represents H, a halogen atom, OH, NH 2 , NO 2 or a C 1-6 alkyl; and

each occurrence of R 4 independently represents —OH, a halogen atom, or a —OR 5 , —O—C(═O)R 5 or —NR 5 R 5 ′ moiety, wherein R 5 and R 5 ′ independently represent C 1-12 alkyl.

3. The process of claim 1 , wherein the precursor ligand L′ is a di-, tri- or tetracarboxylic acid selected from: C 2 H 2 (CO 2 H) 2 (fumaric acid), C 2 H 4 (CO 2 H) 2 (succinic acid), C 3 H 6 (CO 2 H) 2 (glutaric acid), C 4 H 4 (CO 2 H) 2 (muconic acid), C 4 H 8 (CO 2 H) 2 (adipic acid), C 7 H 14 (CO 2 H) 2 (azelaic acid), C 5 H 3 S(CO 2 H) 2 (2,5-thiophenedicarboxylic acid), C 6 H 4 (CO 2 H) 2 (terephthalic acid), C 6 H 2 N 2 (CO 2 H) 2 (2,5-pyrazine dicarboxylic acid), C 10 H 6 (CO 2 H) 2 (naphthalene-2,6-dicarboxylic acid), C 12 H 8 (CO 2 H) 2 (biphenyl-4,4′-dicarboxylic acid), C 12 H 8 N 2 (CO 2 H) 2 (azobenzenedicarboxylic acid), C 6 H 3 (CO 2 H) 3 (benzene-1,2,4-tricarboxylic acid), C 6 H 3 (CO 2 H) 3 (benzene-1,3,5-tricarboxylic acid), C 24 H 15 (CO 2 H) 3 (benzene-1,3,5-tribenzoic acid), C 6 H 2 (CO 2 H) 4 (benzene-1,2,4,5-tetracarboxylic acid, C 10 H 4 (CO 2 H) 4 (naphthalene-2,3,6,7-tetracarboxylic acid), C 10 H 4 (CO 2 H) 4 (naphthalene-1,4,5,8-tetracarboxylic acid), C 12 H 6 (CO 2 H) 4 (biphenyl-3,5,3′,5′-tetracarboxylic acid); modified analogs selected from 2-aminoterephthalic acid, 2-nitroterephthalic acid, 2-methylterephthalic acid, 2-chloroterephthalic acid, 2-bromoterephthalic acid, 2,5-dihydroxoterephthalic acid, tetrafluoroterephthalic acid, tetramethylterephthalic acid, dimethyl-4,4′-biphenydicarboxylic acid, tetramethyl-4,4′-biphenydicarboxylic acid, dicarboxy-4,4′-biphenydicarboxylic acid, or 2,5-pyrazyne dicarboxylic acid; or ligand derivatives selected from 2,5-diperfluoroterephthalic acid, azobenzene-4,4′-dicarboxylic acid, 3,3′-dichloro-azobenzene-4,4′-dicarboxylic acid, 3,3′-dihydroxo-azobenzene-4,4′-dicarboxylic acid, 3,3′-diperfluoro-azobenzene-4,4′-dicarboxylic acid, 3,5,3′,5′-azobenzene tetracarboxylic acid, 2,5-dimethylterephthalic acid, or perfluoroglutaric acid.

4. The process of claim 1 , wherein the inorganic metallic precursor is a Fe 3+ salt, and the precursor ligand L′ is benzene-1,3,5-tricarboxylic acid or benzene-1,2,4-tricarboxylic acid.

5. The process of claim 1 , wherein the inorganic metallic precursor is Fe 3+ salt, and the precursor ligand L′ is benzene-1,2,4,5-tetracarboxylic acid.

6. The process of claim 1 , wherein the aqueous solvent system is H 2 O, or H 2 O mixed with one or more of ethanol, isopropanol, dimethyl carbonate, ethylene glycol, ethyl lactate, ethyl acetate, sulfolane, and benzyl alcohol.

7. The process of claim 1 , wherein the process is carried out in H 2 O as sole solvent system, at 60° C.±5° C.

8. The process of claim 1 , wherein the process is carried out under 1·10 5 Pa (ambient pressure conditions).

9. The process of claim 1 , wherein, in addition to the first inorganic metallic precursor, a second inorganic metallic precursor, in the form of a metal M 1 , a salt of a metal M 1 of formula (I) or a hydroxide or oxide of a metal M 1 , is added to the reaction mixture;
M 1 Y p .n H 2 O  (I)

wherein M 1 is a metal selected from Cu, Fe, Co, Ni, Al, Ti, Mn, V, Cr, Ru, Sn or Nb;
Y represents Cl − , NO 3 − , SO 4 2− , AcO − , or

wherein the concentration of the second inorganic precursor is ≤50 mM.

10. The process of claim 1 , wherein the process is carried in the presence of particles of iron oxide, to produce core-shell particles, where the iron oxide core is encapsulated within a MOF shell.

11. The process of claim 1 , wherein the process leads to nanoparticles of average size <90 nm.

12. A process according to claim 1 , further comprising a step of introducing at least one pharmaceutically active ingredient into said porous MOF material.

Assignees

• Centre Nat Rech Scient
• Univ De Versailles—Saint Quentin En Yvelines

Inventors

• Panchal Monik
• Nouar Farid
• Serre Christian
• Benzaqui Marvin
• Sene Saad
• Steunou Nathalie
• Giménez Marqués Monica

Classifications

• C07F15/025 Primary

  without a metal-carbon linkage · CPC title

• C07F7/003

  without C-Metal linkages · CPC title

• B82Y40/00

  Manufacture or treatment of nanostructures · CPC title

• C07F5/069

  without C-aluminium linkages · CPC title