Metal-organic frameworks with a high density of highly charged exposed metal cation sites

Patent metadata

Field	Value
Publication number	US-2016250618-A1
Application number	US-201415033748-A
Country	US
Kind code	A1
Filing date	Nov 4, 2014
Priority date	Nov 4, 2013
Publication date	Sep 1, 2016
Grant date	—

Abstract

The disclosure provides for Metal-Organic Frameworks comprising M 2 (m-dobdc)-based cores, and methods of use thereof, including gas separation, gas storage, sensing, and other applications utilizing a high density of exposed metal cation sites.

First claim

1 . A porous metal-organic framework (MOF) comprising a plurality of cores, wherein the plurality of cores comprise two or more metals, metal ions, and/or metal containing complexes that are linked together by forming covalent bonds with oxide and/or carboxylate linking clusters of 4,6-dioxido-1,3-benzenedicarboxylate (“m-dobdc”) based linking moieties.

2 . The MOF of claim 1 , wherein one or more cores comprise linking moieties having a structure of Formula I:

wherein,
R 1 -R 2 are independently selected from H, D, optionally substituted FG, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkenyl, optionally substituted heteroalkenyl, optionally substituted alkynyl, optionally substituted heteroalkynyl, optionally substituted aryl, optionally substituted heteroaryl, CN, CO, NH 2 , OR, NR 2 , PR 2 , SR, F, Cl, Br, and I.

3 . The MOF of claim 1 , wherein one or more cores comprise linking moieties having a structure of Formula I:

wherein,
R 1 -R 2 are independently selected from H, D, optionally substituted FG, optionally substituted (C 1 -C 6 )alkyl, optionally substituted (C 1 -C 5 )heteroalkyl, optionally substituted (C 1 -C 6 )alkenyl, optionally substituted (C 1 -C 5 )heteroalkenyl, optionally substituted (C 1 -C 6 )alkynyl, optionally substituted (C 1 -C 5 )heteroalkynyl, optionally substituted aryl, optionally substituted heteroaryl, NH 2 , NR 2 , OR, PR 2 , SR, F, Cl, Br, and I.

4 . The MOF of claim 1 , wherein one or more cores comprise linking moieties having a structure of Formula I(a):

5 . The MOF of claim 1 , wherein the one or more cores comprise metals, metal ions, and/or metal containing complexes that are selected from Li + , Na + , K + , Rb + , Cs + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Sc 2+ , Sc + , Y 3+ , Y 2+ , Y + , Ti 4+ , Ti 3+ , Ti 2+ , Zr 4+ , Zr 3+ , Zr 2+ , Hf 4+ , Hf 3+ , V 5+ , V 4+ , V 3+ , V 2+ , Nb 5+ , Nb 4+ , Nb 3+ , Nb 2+ , Ta 5+ , Ta 4+ , Ta 3+ , Ta 2+ , Cr 6+ , Cr 5+ , Cr 4+ , Cr 3+ , Cr 2+ , Cr + , Cr, Mo 6+ , Mo 5+ , Mo 4+ , Mo 3+ , Mo 2+ , Mo + , Mo, W 6+ , W 5+ , W 4+ , W 3+ , W 2+ , W + , W, Mn 7+ , Mn 6+ , Mn 5+ , Mn 4+ , Mn 3+ , Mn 2+ , Mn + , Re 7+ , Re 6+ , Re 5+ , Re 4+ , Re 3+ , Re 2+ , Re + , Re, Fe 6+ , Fe 4+ , Fe 3+ , Fe 2+ , Fe + , Fe, Ru 8+ , Ru 7+ , Ru 6+ , Ru 4+ , Ru 3+ , Ru 2+ , Os 8+ , Os 7+ , Os 6+ , Os 5+ , Os 4+ , Os 3+ , Os 2+ , Os + , Os, Co 5+ , Co 4+ , Co 3+ , Co 2+ , Co + , Rh 6+ , Rh 5+ , Rh 4+ , Rh 3+ , Rh 2+ , Rh + , Ir 6+ , Ir 5+ , Ir 4+ , Ir 3+ , Ir 2+ , Ir + , Ir, Ni 3+ , Ni 2+ , Ni + , Ni, Pd 6+ , Pd 4+ , Pd 2+ , Pd + , Pd, Pt 6+ , Pt 5+ , Pt 4+ , Pt 3+ , Pt 2+ , Pt + , Cu 4+ , Cu 3+ , Cu 2+ , Cu + , Ag 3+ , Ag 2+ , Ag + , Au 5+ , Au 4+ , Au 3+ , Au 2+ , Au + , Zn 2+ , Zn + , Zn, Cd 2+ , Cd + , Hg 4+ , Hg 2+ , Hg + , B 3+ , B 2+ , B + , Al 3+ , Al 2+ , Al + , Ga 3+ , Ga 2+ , Ga + , In 3+ , In 2+ , In 1+ , Tl 3+ , Tl + , Si 4+ , Si 3+ , Si 2+ , Si + , Ge 4+ , Ge 3+ , Ge 2+ , Ge + , Ge, Sn 4+ , Sn 2+ , Pb 4+ , Pb 2+ , As 5+ , As 3+ , As 2+ , As + , Sb 5+ , Sb 3+ , Bi 5+ , Bi 3+ , Te 6+ , Te 5+ , Te 4+ , Te 2+ , La 3+ , La 2+ , Ce 4+ , Ce 3+ , Ce 2+ , Pr 4+ , Pr 3+ , Pr 2+ , Nd 3+ , Nd 2+ , Sm 3+ , Sm 2+ , Eu 3+ , Eu 2+ , Gd 3+ , Gd 2+ , Gd + , Tb 4+ , Tb 3+ , Tb 2+ , Tb + , Db 3+ , Db 2+ , Ho 3+ , Er 3+ , Tm 4+ , Tm 3+ , Tm 2+ , Yb 3+ , Yb 2+ , Lu 3+ , and any combination thereof, including any complexes which contain the metals or metal ions listed above, and any corresponding metal salt counter-anions.

6 . The MOF of claim 5 , wherein the one or more cores comprise metal ions selected from Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 2+ , Y 2+ , Ti 2+ , Zr 2+ , V 2+ , Nb 2+ , Ta 2+ , Cr 2+ , Mo 2+ , W 2+ , Mn 2+ , Re 2+ , Fe 2+ , Ru 2+ , Os 2+ , Co 2+ , Rh 2+ , Ir 2+ , Ni 2+ , Pd 2+ , Pt 2+ , Cu 2+ , Ag 2+ , Au 2+ , Zn 2+ , Cd 2+ , B 2+ , Al 2+ , Ga 2+ , Si 2+ , Sn 2+ , Pb 2+ , Hg 2+ , As 2+ , Te 2+ , La 2+ , Ce 2+ , Pr 2+ , Sm 2+ , Gd 2+ , Nd 2+ , Db 2+ , Tb 2+ , Tm 2+ and Yb 2+ .

7 . The MOF of claim 5 , wherein the one or more cores comprise metal ions selected from Mg 2+ , Mn 2+ , Fe 2+ , Co 2+ , and Ni 2+ .

8 . The MOF of claim 1 , wherein pores of the MOF are activated by removal of any guest molecules and/or solvent.

9 . The MOF of claim 1 , wherein the MOF is reacted with one or more post framework reactants.

10 . The MOF of claim 9 , wherein one or more post framework reactants adds at least one effect to the MOF selected from:
modulates the gas storage ability of the MOF; modulates the sorption properties of the MOF; modulates the gas separation properties of the MOF; modulates the adsorbate storage ability of the MOF; modulates the adsorbate separation ability of the MOF; modulates the density of exposed metal cation sites; modulates the charge distribution in the framework; modulates the charge density at the exposed metal cation site; modulates the pore size of the MOF; modulates the catalytic activity of the MOF; modulates the conductivity of the MOF; and modulates the sensitivity of the MOF to the presence of an analyte of interest.

11 . The MOF of claim 1 , further comprising one or more absorbed or adsorbed chemical species.

12 . The MOF of claim 11 , wherein the adsorbed or absorbed chemical species is selected from gases, optionally substituted (C 1 -C 25 ) organic molecules, inorganic molecules, liquids, and combinations thereof.

13 . The MOF of claim 12 , wherein the adsorbed or absorbed chemical species is hydrogen.

14 . A method to separate or store one or more gases from a mixed gas mixture comprising contacting the gas mixture with the MOF of claim 1 .

15 . The method of claim 14 , wherein a gas that is separated from the gas mixture and stored is hydrogen.

16 . The method of claim 14 , wherein the gas mixture comprises hydrogen gas formed from steam reforming, electrolysis, and thermolysis processes.

17 . A method to separate or store one or more adsorbates from a mixture of adsorbates comprising contacting the mixture with the MOF of claim 1 .

18 . A device comprising the MOF or a mixture of the MOF and binder of claim 1 .

19 . The device of claim 18 , wherein the device is a gas storage or gas separation device.

20 . The device of claim 19 , wherein the gas storage or gas separation device is selected from purifiers, filters, scrubbers, pressure or temperature swing adsorption devices, hollow fiber membranes, ceramic membranes, cryogenic air separation devices, and hybrid gas separation devices.

21 . The MOF of claim 1 , wherein an adsorbed or absorbed chemical species is selected from methane, natural gas, carbon dioxide, carbon monoxide, oxygen, nitrogen, helium, neon, argon, krypton, xenon, ethane, ethylene, acetylene, propane, propylene, butane, 2-methylpropane, 1-butene, cis-2-butene, trans-2-butene, 2-methylpropene, ammonia, SO 2 , SO 3 , NO, NO 2 , N 20 , or other adsorbates in a gas or liquid phase.

22 . The MOF of claim 1 , wherein an exposed metal cation sites (open metal coordination sites) adsorb, absorb, or interact with a substrate or guest in the MOF.

23 - 25 . (canceled)

26 . The MOF of claim 1 , wherein the MO

Assignees

• Univ California

Inventors

• Long Jeffrey R
• Kapelewski Matthew T
• Geier Stephen J

Classifications

• C01B3/0015

  Organic compounds, e.g. liquid organic hydrogen carriers [LOHC] or metalorganic compounds; Solutions thereof · CPC title

• B01D53/04

  with stationary adsorbents {(B01D53/025 takes precedence)} · CPC title

• B01J31/1691

  Coordination polymers, e.g. metal-organic frameworks [MOF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F) · CPC title

• C07C65/05

  o-Hydroxy carboxylic acids · CPC title

• B01D2253/204

  Metal organic frameworks (MOF's) · CPC title