Granted Patent B2

US 12,458,922 · App. 17/851,318 · Granted Nov 4, 2025

Inventors: Cameron Rogers (Malden, MA); Sahag Voskian (Boston, MA); Alexander Reath (Melrose, MA)

Assignee: Verdox, Inc.

B01D53/326C07C50/04C07C50/12C07C50/18B01D2253/206

Abstract

Claims (169)

1 . An electroactive species comprising a quinone core structure and at least one stabilizing group covalently bound thereto;

wherein the stabilizing group comprises a cationic group, a hydrogen bond donor, or a combination thereof;

wherein the electroactive species comprises

an oxidized state, and

at least one reduced state capable of bonding with a Lewis acid gas to form an anion adduct between the Lewis acid gas and the reduced electroactive species; and

wherein the presence of the stabilizing group

kinetically favors the forming the anion adduct from the reduced electroactive species and the Lewis acid gas, or

thermodynamically favors forming the anion adduct in a thermodynamic equilibrium between the anion adduct and the reduced electroactive species, or

kinetically favors forming the anion adduct from the reduced electroactive species and thermodynamically favors the forming of the anion adduct in the thermodynamic equilibrium between the anion adduct and the reduced electroactive species.

2 . The electroactive species of claim 1 , wherein

the quinone core structure is of formula (I) or (II)

wherein the dashed lines of formula (I) and (II) indicate the optional presence of additional substituted or unsubstituted aryl groups; and

the stabilizing group A is covalently bound to the quinone core structure via a linking group -(L) z -, wherein z is 0 or 1, provided that z is 1 when A is the hydrogen bond donor.

3 . The electroactive species of claim 1 , wherein the electroactive species is of formula (VI) to (X), or a combination thereof:

wherein

each R 1 is independently at each occurrence hydrogen, halogen, a substituted or unsubstituted C 1-30 alkyl group, a substituted or unsubstituted C 1-30 alkoxy group, a poly(C 1-30 alkylene oxide) group; a substituted or unsubstituted C 3-30 cycloalkyl group, a substituted or unsubstituted C 6-30 aryl group, a substituted or unsubstituted C 2-30 heteroaryl group, a nitrile group, a nitro group, a thiol group, or a vinyl group;

each R x is independently at each occurrence the group-(L) z -A;

x is independently at each occurrence 1 to 4;

y is independently at each occurrence 0 to 3, provided that the sum of x and y is 4;

R b is independently at each occurrence R 1 or R x ;

e is independently at each occurrence 0 to 4, provided that at least one occurrence of e is 1,

f is independently at each occurrence 0 to 4, provided that the sum of each e-f pair is 4; and

c and d are each independently 0 to 4, provided that the sum of c and d is 4, and provided that when c is 0, at least one of R b is R x .

4 . The electroactive species of claim 1 , wherein

the cationic group comprises a substituted or unsubstituted C 1-6 alkyl ammonium group, a substituted or unsubstituted C 1-6 alkyl phosphonium group, a substituted or unsubstituted C 7-30 arylalkyl ammonium group, a chelated metal cation, a substituted or unsubstituted anilinium group, a substituted or unsubstituted pyridinium group, or a substituted or unsubstituted imidazolium group; and

the hydrogen bond donor comprises a hydroxyl group, a carboxylic acid group, an amine group, an aniline group, an amide group, or a thiol group.

5 . The electroactive species of claim 3 , wherein the electroactive species is a compound of formula (VI), (VII), or (VIII).

6 . The electroactive species of claim 5 , wherein the electroactive species is a compound of formula (VIII) wherein

c is 0;

d is 4; and

at least one occurrence of R b is -(L) z -A, wherein

z is 1;

L is a substituted or unsubstituted phenylene group; and

A is

a —NR 2 R 3 R 4 ammonium group, wherein R 2 , R 3 and R 4 are independently at each occurrence a substituted or unsubstituted C 1-6 alkyl group or a substituted or unsubstituted benzyl group, or

a hydroxyl group.

7 . The electroactive species of claim 6 , wherein

both occurrences of R b are -(L) z -A, wherein each occurrence of z is 1 and each occurrence of L is a substituted or unsubstituted phenylene group;

A is the —NR 2 R 3 R 4 ammonium group; and

R 1 is hydrogen.

8 . The electroactive species of claim 6 , wherein

A is a hydroxyl group, an amine group, an amide group, or a thiol group; and

R 1 is hydrogen.

9 . The electroactive species of claim 5 , wherein the electroactive species is a compound of formula (VIII) wherein

c is 0;

d is 4;

at least one occurrence of R b is -(L) z -A wherein

z is 0; and

A is a substituted or unsubstituted pyridinium group or imidazolium group.

10 . The electroactive species of claim 5 , wherein the electroactive species is a compound of formula (VIII) wherein

c is 2;

d is 2;

R b is independently at each occurrence hydrogen or a substituted or unsubstituted phenyl group;

R x is independently at each occurrence -(L) z -A wherein

z is 0; and

A is

a —NR 2 R 3 R 4 ammonium group, wherein R 2 , R 3 and R 4 are independently at each occurrence a substituted or unsubstituted C 1-6 alkyl group or a substituted or unsubstituted benzyl group, or

a hydroxyl group.

11 . The electroactive species of claim 3 , wherein the electroactive species is a compound of formula (IX).

12 . The electroactive species of claim 11 , wherein

each occurrence of e is 1,

each occurrence of f is 3,

each occurrence of R x is -(L) z -A, wherein A is

a —NR 2 R 3 R 4 ammonium group, wherein R 2 , R 3 and R 4 are independently at each occurrence a substituted or unsubstituted C 1-6 alkyl group or a substituted or unsubstituted benzyl group, or

a hydroxyl group, an amine group, an amide group, or a thiol group, preferably a hydroxyl group.

13 . The electroactive species of claim 11 , wherein the electroactive species is a compound of the formula (IXb)

wherein

R 1 is independently at each occurrence hydrogen, halogen, a C 1-30 alkyl group, a C 1-30 alkoxy group, a poly (C 1-30 alkylene oxide) group; a C 3-30 cycloalkyl group, a C 3-30 branched alkyl group, a C 6-30 aryl group, a C 2-30 heteroaryl group, a C 1-30 fluoroalkyl group, a nitrile group, a nitro group, a thiol group, or a vinyl group;

D is independently at each occurrence oxygen or nitrogen;

r is 0 or 1;

R 5 and R 6 are independently at each occurrence a C 1-6 alkyl group, a poly(C 2-3 alkylene oxide) group, or a poly(C 2-3 alkylene diamine) group, wherein R 5 is optionally combined with R 6 to form a cyclic group; and

E is a metal cation.

14 . The electroactive species of claim 13 , wherein

R 1 is hydrogen;

R 5 and R 6 are methyl;

D is oxygen or nitrogen; and

r is 0.

15 . The electroactive species of claim 13 , wherein

R 1 is hydrogen;

D is oxygen;

r is 0; and

R 5 and R 6 are poly(ethylene oxide) groups, wherein R 5 and R 6 combine to form a cyclic ether.

16 . The electroactive species of claim 3 , wherein the electroactive species is of formula (X).

17 . The electroactive species of claim 16 , wherein

A is a —NR 2 R 3 R 4 ammonium group;

z is 0;

R 1 is hydrogen;

each occurrence of e is 1; and

each occurrence of f is 3.

18 . The electroactive species of claim 16 , wherein

A is a hydroxyl group, an amine group, an amide group, or a thiol group;

z is 1;

L is a linking group comprising a C 6 arylene group;

R 1 is hydrogen;

each occurrence of e is 1; and

each occurrence of f is 3.

19 . The electroactive species of claim 1 , wherein the stabilizing group A is 10 atoms or less away from at least one ketone group of the electroactive species or wherein the stabilizing group A is 1 to 10 atoms from at least one ketone group of the electroactive species.

20 . A polymer or oligomer wherein at least a portion of the repeating units comprise the electroactive species of claim 1 .

21 . A polymer or oligomer comprising repeating units derived from

a first monomer comprising a polymerizable group and an electroactive species comprising a quinone core structure, and

a second monomer comprising a polymerizable group and a stabilizing group comprising a cationic group, a hydrogen bond donor, or a combination thereof;

wherein the electroactive species comprises

an oxidized state, and

at least one reduced state capable of bonding with a Lewis acid gas to form an anion adduct between the Lewis acid gas and the reduced electroactive species; and

wherein the presence of the stabilizing group:

kinetically favors the forming the anion adduct from the reduced electroactive species and the Lewis acid gas, or

thermodynamically favors forming the anion adduct in a thermodynamic equilibrium between the anion adduct and the reduced electroactive species, or

kinetically favors forming the anion adduct from the reduced electroactive species and thermodynamically favors the forming of the anion adduct in the thermodynamic equilibrium between the anion adduct and the reduced electroactive species.

22 . A method for separating a Lewis acid gas from a fluid mixture comprising the Lewis acid gas, the method comprising:

contacting the fluid mixture with the electroactive species of claim 1 , wherein the electroactive species is in a reduced state, to form an anion adduct between the Lewis acid gas and the electroactive species in the reduced state.

23 . The method of claim 22 , wherein the contacting is in the presence of an electrolyte.

24 . The method of claim 22 , wherein an association constant between the reduced electroactive species comprising the stabilizing group and the Lewis acid gas is greater than an association constant between the reduced electroactive species not including the stabilizing group and the Lewis acid gas.

25 . The method of claim 22 ,

wherein the forming of the anion adduct from the reduced electroactive species comprising the stabilizing group and the Lewis acid gas is kinetically more favorable than forming an anion adduct from the reduced electroactive species not including the stabilizing group and the Lewis acid gas; or

wherein the forming of the anion adduct from the reduced electroactive species comprising the stabilizing group and the Lewis acid gas is thermodynamically more favorable than forming an anion adduct from the reduced electroactive species not including the stabilizing group and the Lewis acid gas; or

wherein the forming of the anion adduct from the reduced electroactive species comprising the stabilizing group and the Lewis acid gas is kinetically and thermodynamically more favorable than forming an anion adduct from the reduced electroactive species not including the stabilizing group and the Lewis acid gas.

26 . The method of claim 22 , wherein the stabilizing group is a cationic group, and

forming of the anion adduct from the reduced electroactive species comprising the stabilizing group and the Lewis acid gas is kinetically more favorable than forming an anion adduct from a reduced state of a nonionic electroactive species having a reduction potential that is the same as the reduced electroactive species comprising the stabilizing group and the Lewis acid gas; or

forming of the anion adduct from the reduced electroactive species comprising the stabilizing group and the Lewis acid gas is thermodynamically more favorable than forming an anion adduct from a reduced state of a nonionic electroactive species having a reduction potential that is the same as the reduced electroactive species comprising the stabilizing group and the Lewis acid gas; or

forming of the anion adduct from the reduced electroactive species comprising the stabilizing group and the Lewis acid gas is kinetically and thermodynamically more favorable than forming an anion adduct from a reduced state of a nonionic electroactive species having a reduction potential that is the same as the reduced electroactive species comprising the stabilizing group and the Lewis acid gas.

27 . The method of claim 22 , wherein the stabilizing group is a hydrogen bond donor, and

forming of the anion adduct from the reduced electroactive species comprising the stabilizing group and the Lewis acid gas is kinetically more favorable than forming an anion adduct from a reduced state of a nonionic electroactive species having a reduction potential that is the same as the reduced electroactive species comprising the stabilizing group and the Lewis acid gas; or

forming of the anion adduct from the reduced electroactive species comprising the stabilizing group and the Lewis acid gas is thermodynamically more favorable than forming an anion adduct from a reduced state of a nonionic electroactive species having a reduction potential that is the same as the reduced electroactive species comprising the stabilizing group and the Lewis acid gas; or

forming of the anion adduct from the reduced electroactive species comprising the stabilizing group and the Lewis acid gas is kinetically and thermodynamically more favorable than forming an anion adduct from a reduced state of a nonionic electroactive species having a reduction potential that is the same as the reduced electroactive species comprising the stabilizing group and the Lewis acid gas.

28 . The method of claim 22 , wherein

the Lewis acid gas is CO 2 , COS, SO 2 , SO 3 , R 2 SO 4 , NO 2 , NO 3 , R 3 PO 4 , R 2 S, RCOOR′, RCHO, R′ 2 CO, R′NCO, R′NCS, BR″ 3 , R″ 3 BO 3 , or a combination thereof, wherein

each R is independently hydrogen, C 1-12 alkyl, C 3-12 cycloalkyl, C 1-12 heterocycloalkyl, C 6-20 aryl, or C 1-12 heteroaryl;

each R′ is independently C 1-12 alkyl, C 3-12 cycloalkyl, C 1-12 heterocycloalkyl, C 6-20 aryl, or C 1-12 heteroaryl; and

each R″ is independently hydrogen, halogen, C 1-12 alkyl, C 3-12 cycloalkyl, C 1-12 heterocycloalkyl, C 6-20 aryl, or C 1-12 heteroaryl.

29 . An electrochemical apparatus comprising:

a chamber comprising a negative electrode in electronic communication with an electroactive species in a reduced state, and an electrolyte, wherein the chamber is configured to receive a fluid mixture comprising a Lewis acid gas,

wherein the electroactive species comprises a quinone core and at least one stabilizing group covalently bound thereto;

wherein the stabilizing group comprises a cationic group, a hydrogen bond donor, or a combination thereof; and

wherein the electroactive species comprises

an oxidized state, and

at least one reduced state capable of bonding with a Lewis acid gas to form an anion adduct between the Lewis acid gas and the reduced electroactive species; and

wherein the presence of the stabilizing group:

kinetically favors the forming the anion adduct from the reduced electroactive species and the Lewis acid gas, or

thermodynamically favors forming the anion adduct in a thermodynamic equilibrium between the anion adduct and the reduced electroactive species, or

kinetically favors forming the anion adduct from the reduced electroactive species and thermodynamically favors the forming of the anion adduct in the thermodynamic equilibrium between the anion adduct and the reduced electroactive species.

30 . An electrochemical apparatus comprising:

a chamber comprising a negative electrode in electronic communication with an electroactive species in a reduced state, and an electrolyte, wherein the chamber is configured to receive a fluid mixture comprising a Lewis acid gas,

wherein the electroactive species comprises a polymer or oligomer according to claim 20 .

31 . An electrochemical apparatus comprising:

a chamber comprising a negative electrode in electronic communication with an electroactive species in a reduced state, and an electrolyte, wherein the chamber is configured to receive a fluid mixture comprising a Lewis acid gas,

wherein the electroactive species comprises a polymer or oligomer according to claim 21 .

32 . A gas separation system, comprising a plurality of electrochemical cells in fluid communication with a gas inlet and a gas outlet, wherein each of the plurality of electrochemical cells comprises:

a first electrode comprising an electroactive species in a reduced state wherein the electroactive species comprises an oxidized state and at least one reduced state which bonds with a Lewis acid gas to form an anion adduct;

a second electrode comprising a complementary electroactive layer;

a first separator between the first electrode and the second electrode; and

an electrolyte;

wherein the electroactive species comprises a quinone core and at least one stabilizing group covalently bound thereto;

wherein the stabilizing group comprises a cationic group, a hydrogen bond donor, or a combination thereof; and

wherein the presence of the stabilizing group:

kinetically favors the forming the anion adduct from the reduced electroactive species and the Lewis acid gas, or

thermodynamically favors forming the anion adduct in a thermodynamic equilibrium between the anion adduct and the reduced electroactive species, or

kinetically favors forming the anion adduct from the reduced electroactive species and thermodynamically favors the forming of the anion adduct in the thermodynamic equilibrium between the anion adduct and the reduced electroactive species.

33 . A gas separation system, comprising a plurality of electrochemical cells in fluid communication with a gas inlet and a gas outlet, wherein each of the plurality of electrochemical cells comprises:

a first electrode comprising an electroactive species in a reduced state wherein the electroactive species comprises an oxidized state and at least one reduced state which bonds with a Lewis acid gas to form an anion adduct;

a second electrode comprising a complementary electroactive layer;

a first separator between the first electrode and the second electrode; and

an electrolyte;

wherein the electroactive species comprises a polymer or oligomer according to claim 20 .

34 . A gas separation system, comprising a plurality of electrochemical cells in fluid communication with a gas inlet and a gas outlet, wherein each of the plurality of electrochemical cells comprises:

a first electrode comprising an electroactive species in a reduced state wherein the electroactive species comprises an oxidized state and at least one reduced state which bonds with a Lewis acid gas to form an anion adduct;

a second electrode comprising a complementary electroactive layer;

a first separator between the first electrode and the second electrode; and

an electrolyte;

wherein the electroactive species comprises a polymer or oligomer according to claim 21 .

Assignments (1)

Continuity (2)

References Cited (36)