METAL-ORGANIC FRAMEWORK CATALYSTS, AND USES THEREOF
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.
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-M 2 -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.
2 . 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.
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:
M 1 is a metal atom,
X is halo or tetrahydrofuran, and
R 1 is —COOH, methyl, or ethyl,
wherein the metal salt is M 2 Y 2 ,
M 2 is zinc or zirconium, and
Y is NO 3 , 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-M 2 -O bonds, and
wherein a cobalt carbonyl moiety occupies at least a portion of the plurality of pores.
4 - 7 . (canceled)
8 . 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.
9 . The method of claim 8 , wherein the base is a hydroxide salt.
10 . (canceled)
11 . The method of claim 8 , wherein the alcohol is methanol or ethanol.
12 . The method of claim 8 , wherein the solvent comprises tetrahydrofuran.
13 . (canceled)
14 . (canceled)
15 . The method of claim 1 , wherein M 1 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).
16 . (canceled)
17 . The method of claim 1 , wherein X is chloro.
18 . The method of claim 1 , wherein the metal salt is Zn(NO 3 ) 2 , ZrCl 4 , or Zn(OAc) 2 .
19 . 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 M 2 site.
20 . The method of claim 1 , wherein the amine-based solvent is a dialkylformamide solvent.
21 . (canceled)
22 . The method of claim 1 , wherein the cobalt solution comprises cobalt hydroxide, or a salt thereof.
23 - 26 . (canceled)
27 . A metal-organic framework comprising repeating cores, wherein the cores comprise a linker coordinated to a secondary building unit through O-M 2 -O bonds, wherein:
the linker is
wherein
M 1 is a metal atom,
X is halo or tetrahydrofuran, and
R 1 is —COOH,
wherein M 2 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.
28 - 31 . (canceled)
32 . The metal-organic framework of claim 27 , wherein M 1 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).
33 . (canceled)
34 . (canceled)
35 . The metal-organic framework of claim 27 , wherein the metal-organic framework is doped with copper or nickel, or a combination thereof, at the M 2 site.
36 . The metal-organic framework of claim 27 , wherein the cobalt carbonyl moiety is Co(CO) 4 − or Co 2 (CO) 6 − .
37 - 42 . (canceled)
43 . The method of claim 1 , wherein the porphyrin linker has the following structure:
wherein M 1 is a metal atom, X is halo or tetrahydrofuran, and R 1 is —COOH.
44 . The method of claim 1 , wherein the metal salt is M 2 Y 2 , M 2 is zinc or zirconium, and Y is nitrate, halo, or acetate.
45 . The method of claim 1 , wherein the metal organic framework further comprises a plurality of pores.