# US 2021/0277028 A1 · Metal-organic framework catalysts, and uses thereof

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- Number: US 2021/0277028 A1
- Document ID: US20210277028A1
- Status: Published application
- Kind: A1
- Application number: 17/266,230
- Filed: 2019-08-02
- Published: 2021-09-09
- Earliest claimed: 2018-08-09
- Assignees: Novomer, Inc.
- Applicants: Novomer, Inc.
- Inventors: Sadesh H. Sookraj; Derek Williams
- Web page: https://patentgrep.com/patent/US20210277028A1

## CPC

- C07F 5/069: {without C-aluminium linkages}
- B01J 31/1691: {Coordination polymers, e.g. metal-organic frameworks [MOF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F)}
- B01J 31/183: {with more than one complexing nitrogen atom, e.g. phenanthroline}
- B01J 31/223: {At least two oxygen atoms present in one at least bidentate or bridging ligand}
- C01B 37/00: Compounds having molecular sieve properties but not having base-exchange properties
- B01J 2231/321: Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
- B01J 2531/0216: Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
- B01J 2531/0222: Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
- B01J 2531/025: Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
- B01J 2531/26: Zinc
- B01J 2531/31: Aluminium
- B01J 2531/48: Zirconium
- B01J 2531/845: Cobalt
- Y02P 20/582: Recycling of unreacted starting or intermediate materials
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Provided herein are metal-organic frameworks having a repeating core structure that generally includes a linker coordinated to a secondary building unit through O-metal-O bonds. The linkers create a framework with a plurality of pores, where a cobalt carbonyl moiety occupies at least a portion of the plurality of pores. Provided are also methods of making such metal-organic frameworks via a solvothermal reaction. The metal-organic frameworks are suitable for use in carbonylation reactions, such as carbonylation of epoxides. The metal-organic frameworks may be used for producing acrylic acid from ethylene oxide and carbon monoxide on an industrial scale. The production may involve various unit operations, including for example a beta-propiolactone production system configured to produce beta-propiolactone from ethylene oxide and carbon monoxide; a polypropiolactone production system configured to produce polypropiolactone from beta-propiolactone; and an acrylic acid production system configured to produce acrylic acid with a high purity by thermolysis of polypropiolactone.

## Claims

### Claim 1

A method to produce a metal-organic framework, comprising:
solvothermally reacting a porphyrin linker with a metal salt in an amine-based solvent to produce a metal-organic framework, wherein
the metal-organic framework comprises repeating cores, wherein the cores comprise the porphyrin linker coordinated to a secondary building unit through O-M2-O bonds; and
soaking the metal-organic framework in a cobalt solution to incorporate a cobalt carbonyl moiety in at least a portion of the pores in the metal-organic framework.

### Claim 2 (depends on 1)

The method of claim 1, wherein solvothermally reacting the porphyrin linker with the metal salt in the amine-based solvent to produce the metal-organic framework, comprises:
mixing the porphyrin linker with the metal salt in the amine-based solvent to produce a reaction mixture; and
heating the reaction mixture to a temperature between 80° C. and 140° C. to produce the metal-organic framework.

### Claim 3

A method to produce a metal-organic framework, comprising:
combining a porphyrin linker, a metal salt, a cobalt solution, and an amine-based solvent to produce a metal-organic framework, wherein:
the porphyrin linker is
wherein:
M1 is a metal atom,
X is halo or tetrahydrofuran, and
R1 is —COOH, methyl, or ethyl,
wherein the metal salt is M2Y2,
M2 is zinc or zirconium, and
Y is NO3, halo, or acetate,
wherein the metal-organic framework comprises repeating cores and a plurality of pores,
wherein the cores comprise the porphyrin linker coordinated to a secondary building unit through O-M2-O bonds, and
wherein a cobalt carbonyl moiety occupies at least a portion of the plurality of pores.

### Claim at position 4

4-7. (canceled)

### Claim 8 (depends on 1)

The method of claim 1, further comprising hydrolyzing a porphyrin linker precursor to produce the porphyrin precursor including combining the porphyrin linker precursor with a base, an alcohol, water and a solvent.

### Claim 9 (depends on 8)

The method of claim 8, wherein the base is a hydroxide salt.

### Claim 10

(canceled)

### Claim 11 (depends on 8)

The method of claim 8, wherein the alcohol is methanol or ethanol.

### Claim 12 (depends on 8)

The method of claim 8, wherein the solvent comprises tetrahydrofuran.

### Claim 13

(canceled)

### Claim 14

(canceled)

### Claim 15 (depends on 1)

The method of claim 1, wherein M1 is Zn(II), Cu(II), Mn(II), Co(II), Ru(II), Fe(II), Co(II), Rh(II), Ni(II), Pd(II), Mg(II), Al(III), Cr(III), Cr(IV), Ti(IV), Fe(III), Co(III), Ti(III), In(III), Ga(III), or Mn(III).

### Claim 16

(canceled)

### Claim 17 (depends on 1)

The method of claim 1, wherein X is chloro.

### Claim 18 (depends on 1)

The method of claim 1, wherein the metal salt is Zn(NO3)2, ZrCl4, or Zn(OAc)2.

### Claim 19 (depends on 1)

The method of claim 1, further comprising additional copper salt or nickel salt, or a combination thereof, to dope the metal-organic framework at the M2 site.

### Claim 20 (depends on 1)

The method of claim 1, wherein the amine-based solvent is a dialkylformamide solvent.

### Claim 21

(canceled)

### Claim 22 (depends on 1)

The method of claim 1, wherein the cobalt solution comprises cobalt hydroxide, or a salt thereof.

### Claim at position 20

23-26. (canceled)

### Claim 27

A metal-organic framework comprising repeating cores, wherein the cores comprise a linker coordinated to a secondary building unit through O-M2-O bonds, wherein:
the linker is
wherein
M1 is a metal atom,
X is halo or tetrahydrofuran, and
R1 is —COOH,
wherein M2 is zinc or zirconium,
wherein the metal-organic framework comprises a plurality of pores, and
wherein a cobalt carbonyl moiety occupies at least a portion of the plurality of pores.

### Claim at position 22

28-31. (canceled)

### Claim 32 (depends on 27)

The metal-organic framework of claim 27, wherein M1 is Zn(II), Cu(II), Mn(II), Co(II), Ru(II), Fe(II), Co(II), Rh(II), Ni(II), Pd(II), Mg(II), Al(III), Cr(III), Cr(IV), Ti(IV), Fe(III), Co(III), Ti(III), In(III), Ga(III), or Mn(III).

### Claim 33

(canceled)

### Claim 34

(canceled)

### Claim 35 (depends on 27)

The metal-organic framework of claim 27, wherein the metal-organic framework is doped with copper or nickel, or a combination thereof, at the M2 site.

### Claim 36 (depends on 27)

The metal-organic framework of claim 27, wherein the cobalt carbonyl moiety is Co(CO)4− or Co2(CO)6−.

### Claim at position 28

37-42. (canceled)

### Claim 43 (depends on 1)

The method of claim 1, wherein the porphyrin linker has the following structure:
wherein M1 is a metal atom, X is halo or tetrahydrofuran, and R1 is —COOH.

### Claim 44 (depends on 1)

The method of claim 1, wherein the metal salt is M2Y2, M2 is zinc or zirconium, and Y is nitrate, halo, or acetate.

### Claim 45 (depends on 1)

The method of claim 1, wherein the metal organic framework further comprises a plurality of pores.