Selective, adsorbate-induced spin state changes in transition metal-based metal-organic frameworks

Patent metadata

Field	Value
Publication number	US-11517878-B2
Application number	US-201716089199-A
Country	US
Kind code	B2
Filing date	Mar 31, 2017
Priority date	Mar 31, 2016
Publication date	Dec 6, 2022
Grant date	Dec 6, 2022

Abstract

An adsorbate-selective metal organic framework includes a transition metal; and a plurality of organic molecules coordinated to the transition metal so as to preserve open coordination sites for selectively adsorbing molecules that have low-lying π* orbitals. The transition metal has a lowest energy spin state in the presence of the selectively adsorbed molecules that are strongly bonding to the transition metal through π-donating interactions which is different than the lowest energy spin state in the absence of these adsorbed molecules. The transition metal has also a lowest energy spin state in the presence of non-selected molecules that are weakly bonding to the transition metal through σ- and/or π-accepting and/or donating interactions.

First claim

We claim:

1. An adsorbate-selective metal organic framework, comprising:
a transition metal of comprising iron (Fe); and
a plurality of organic molecules coordinated to said transition metal to form a Fe-organic molecule framework so as to preserve open coordination sites for molecules to be selectively adsorbed to provide selectively adsorbed molecules,
wherein said selectively adsorbed molecules have π* orbitals adapted to accept electron density from said transition metal,
wherein said transition metal is in a high-spin electron configuration in the absence of the selectively adsorbed molecules, said high-spin electron configuration defining a high-spin configuration of the transition metal,
wherein said transition metal converts to a low-spin electron configuration defining a low-spin configuration of the transition metal in the presence of said selectively adsorbed molecules that are bonding to said transition metal by donating electron density to the π* orbitals of the selectively adsorbed molecule, such that upon exposure to the selectively adsorbed molecules said transition metal undergoes a spin state transition, and
wherein said transition metal remains high-spin electron configuration in the presence of non-selected molecules that are non-bonding to said transition metal.

2. The adsorbate-selective metal organic framework according to claim 1 , wherein said transition metal is switchable to the high-spin electron configuration by controlling a temperature or a pressure, or both in said adsorbate-selective metal organic framework to enable desorption of said selectively adsorbed molecules.

3. The adsorbate-selective metal organic framework according to claim 2 , wherein said transition metal is switchable to the high-spin electron configuration by increasing the temperature or lowering the pressure, or both in said adsorbate-selective metal organic framework to enable desorption of said selectively adsorbed molecules.

4. The adsorbate-selective metal organic framework according to any one of claims 1 - 3 , wherein said plurality of organic molecules are selected from the group of organic molecules given by the following formulas:

wherein R is selected from hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, substituted aryl, heterocycle, substituted heterocycle, halide, amine, amide, imino, cyano, isocyano, hydroxide, ether, ketone, ester, carboxylate, phosphine, phosphate, thioester, thioether, sulfate, and sulfide groups.

5. The adsorbate-selective metal organic framework according to claim 1 , wherein said plurality of organic molecules are one of H 3 BTTri, H 2 BBTA, or H 2 BTDD, or any combination thereof.

6. The adsorbate-selective metal organic framework according to claim 1 , wherein said selectively adsorbed molecules are at least one of CO, an olefin, O 2 , or N 2 molecules.

7. The adsorbate-selective metal organic framework according to claim 6 , wherein said non-selected molecules are at least one of H 2 , N 2 , CO 2 , CH 4 , C 2 H 4 , C 2 H 6 , or a paraffin.

8. The adsorbate-selective metal organic framework according to claim 1 , wherein said adsorbate-selective metal organic framework is porous so as to allow a fluid containing the selectively adsorbed molecules and the non-selected molecules to pass therethrough and interact with the transition metal,
wherein concentration of selectively adsorbed molecules in said fluid is reduced as these molecules are adsorbed onto the metal organic framework to induce the spin state transition at the transition metal, and
wherein the selectively adsorbed molecules are released by stopping a flow of the fluid and then controlling temperature or pressure parameters.

9. A method of separating a selected component of gas molecules from a mixture of components of gas molecules using a metal organic framework, the method comprising:
exposing a porous material to said mixture of components of gas molecules, the porous material having the metal organic framework comprising:
a transition metal of iron (Fe); and
a plurality of organic molecules coordinated to said transition metal to form a Fe-organic molecule framework so as to preserve open coordination sites for molecules to be selectively adsorbed to provide selectively adsorbed molecules,
wherein said selectively adsorbed molecules have π* orbitals adapted to accept electron density from said transition metal,
wherein said transition metal is in a high-spin electron configuration in the absence of the selectively adsorbed molecules, said high-spin electron configuration defining a high-spin configuration of the transition metal,
wherein said transition metal converts to a low-spin electron configuration defining a low-spin configuration of the transition metal in the presence of said selectively adsorbed molecules that are bonding to said transition metal by donating electron density to the π* orbitals of the selectively adsorbed molecule, such that upon exposure to the selectively adsorbed molecules said transition metal undergoes a spin state transition, and
wherein said transition metal remains high-spin electron configuration in the presence of non-selected molecules that are non-bonding to said transition metal; and

separating said selected component of gas molecules including the selectively adsorbed molecules from said mixture of components of gas molecules after being exposed to said porous material,
wherein said selected component of gas molecules being separated from said mixture of components of gas molecules are adsorbed preferentially by said porous material during said exposing compared to adsorption of other components of gas molecules including the non-selected molecules in said mixture of components of gas molecules.

10. The method of claim 9 , further comprising changing an environment of said porous material having the metal organic framework after said exposing and separating so as to cause the selected component of adsorbed gas molecules to outgas from said porous material.

11. The method of claim 10 , wherein said changing said environment of said porous material having the metal organic framework comprises at least one of changing a temperature or a surrounding gas pressure.

Assignees

• Univ California

Inventors

• Long Jeffrey R
• Keitz Benjamin K
• Reed Douglas

Classifications

• B01D53/04

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

• B01D2256/16

  Hydrogen · CPC title

• C07F15/025

  without a metal-carbon linkage · CPC title

• B01J20/3483

  by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling · CPC title

• B01J20/226 Primary

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