Iron porphyrazines as efficient, catalytic and scalable method to produce chlorine dioxide

1. A cartridge comprising a housing and at least one of an iron porphyrin catalyst or an iron porphyrazine catalyst in the housing, wherein the cartridge is adapted to allow reactants to contact the at least one of an iron porphyrin catalyst or an iron porphyrazine catalyst, and the cartridge further comprises at least one of the reactants or a source of ClO 2 − in the housing, and the reactants comprise ClO 2 − .

2. The cartridge of claim 1 , wherein the iron porphyrin catalyst has a structure of formula I:

wherein the a is the oxidation state II, III or IV of the Fe and R 1 , R 2 , R 3 , and R 4 are independently selected from the group consisting of TM2PyP, TM4PyP, TDMImP, and TDMBImp, which have a structure of formulas II, III, IV, and V, respectively:

and at least one of R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are independently selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, CH 2 —(CH 2 ) n1 —CH 3 where n1=5-20, CH 2 —(CH 2 ) n2 —CH 2 —X where n2=0-20, —CH 2 (CO)—(CH 2 ) n3 —CH 2 —X where n3=0-20, —CH 2 —Ar—X, (CH 2 ) n —X, (CH 2 ) m Ar—X, (CH 2 ) m Ar—Y, (CH 2 ) n —Y, CH 2 CONH—Y; CH 2 COO—Y, CH 2 CO(CH 2 ) P —Y, (OCH 2 CH 2 ) m —Y, (OCH 2 CH 2 ) m —X; Y 2 —X, CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 3 , —CH 2 CO 2 CH 2 CH 3 , alkyl, CH 2 CH 2 OCH 3 , CH 2 CH 2 OCH 2 CH 2 OCH 3 , (CH 2 ) n —X, (CH 2 ) n —Y, (CH 2 ) n Ar—X, (CH 2 ) n Ar—Y, CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 3 , CH 2 CO 2 CH 2 CH 3 , (OCH 2 CH 2 ) m —X, (OCH 2 CH 2 ) m —Y, Y 2 —X, or Y 2 C(Z 1 ) 3 ; where Z 1 is CH 2 OCH 2 (CH 2 ) n X, CH 2 OCH 2 (CH 2 ) n Y, or (CH 2 ) n C(O)Y 2 C(Z 2 ) 3 ; Z 2 is CH 2 OCH 2 CH 2 C(O)Y 2 C(Z 4 ) 3 ; Z 4 is CH 2 OCH 2 CH 2 X or (CH 2 ) n C(O)—Y 2 —C(Z 5 ) 3 ; Z 5 is CH 2 OCH 2 CH 2 C(O)Y 2 C(Z 6 ) 3 ; Z 6 is CH 2 OCH 2 CH 2 C(O)O(CH 2 CH 2 O) m CH 2 CH 2 O, (CH 2 ) n OCH 2 C(CH 2 OH) 3 , (CH 2 ) n OCH 2 CH(CH 2 OH) 2 , (CH) n OCH 2 C(CH 2 OH) 2 (CH 3 ), (CH 2 ) n OCH 2 C[CH 2 OCH 2 C(CH 2 OH) 3 ] 3 , (CH 2 ) n OCH 2 C[CH 2 OCH 2 C(CH 2 O[CH 2 CH 2 O] m CH 2 CH 2 OX) 3 , CH 2 CONH—Y, CH 2 CO—Y, or CH 2 CO(CH 2 ) P —Y; where

Ar is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, or substituted or unsubstituted naphthyl and when Ar is the phenyl in —CH 2 —Ar—X, (CH 2 ) m Ar—X, or (CH 2 ) m Ar—Y, the X or Y is attached ortho- meta- or para to the —CH 2 — attached to pyridoporphyrazine;

n is 1 to 10; m is 1 to 200; p is 1 or 2; X is COOH, COO(alkyl 1 ), CONH 2 , CONH(alkyl 1 ), CON(alkyl 1 ) 2 , CO(CH 2 ) P alkyl 1 , OPO 3 H 2 , PO 3 H 2 , SO 3 H, NH 2 , N(alkyl 1 ) 2 , or N(alkyl 1 ) 3 + , where alkyl 1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl; Y is OH, (O—CH 2 CH 2 ) m —W 1 , or (CH 2 CH 2 ) m —W 2 , where W 1 is OH or (O—(CH 2 CH 2 ) m OH), and W 2 is O-alkyl; and Y 2 is —(CH 2 ) n O—, —(CH 2 ) n NH—, —(CH) n S—; CH 2 CONH—, CH 2 COO—, or CH 2 CO(CH 2 ) p —; and

L 1 and L 2 are, independently absent, halide, oxo, aquo, hydroxo, CN, OPO 3 H, or alcohol.

3. The cartridge of claim 2 , wherein the alkyl is selected from straight-chain or branched-chain alkyl radicals containing from 1 to 22 carbon atoms, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl.

4. The cartridge of claim 2 , wherein R 1 , R 2 , R 3 , and R 4 are TDMBImp.

5. The cartridge of claim 2 , wherein R 1 , R 2 , R 3 , and R 4 are TM2PyP or R 1 , R 2 , R 3 and R 4 are TM4PyP.

6. The cartridge of claim 1 , wherein the iron porphyrazine catalyst has a structure of formula VI:

wherein a is the oxidation state II, III or IV of the Fe and each of A 1 , A 2 , A 3 , A 4 , B 1 , B 2 , B 3 , B 4 , C 1 , C 2 , C 3 , C 4 , D 1 , D 2 , D 3 , and D 4 are independently selected from N + —R n , N, C—H, C—X, and C—R n ;

when N + —R n is selected, only one in each set of A 1 , B 1 , C 1 , and D 1 ; A 2 , B 2 , C 2 , and D 2 ; A 3 , B 3 , C 3 , and D 3 ; or A 4 , B 4 , C 4 , and D 4 is N + —R n ;

when N is selected, only one in each set of A 1 , B 1 , C 1 , and D 1 ; A 2 , B 2 , C 2 , and D 2 ; A 3 , B 3 , C 3 , and D 3 ; or A 4 , B 4 , C 4 , and D 4 is N;

each R, is independently selected from the group consisting of H, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, CH 2 —(CH 2 ) n1 —CH 3 where n1=5-20, CH 2 —(CH 2 ) n2 —CH 2 —X where n2=0-20, CH 2 (CO)—(CH 2 ) n3 —CH 2 —X where n3=0-20, CH 2 —Ar—X, (CH 2 ) n —X; (CH 2 ) m Ar—X, (CH 2 ) m Ar—Y, (CH 2 ) n —Y, CH 2 CONH—Y; CH 2 COO—Y, CH 2 CO—Y, CH 2 CO(CH 2 ) P —Y, (OCH 2 CH 2 ) m —Y, (OCH 2 CH 2 ) m —X, Y 2 —X, CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 OCH 3 , CH 2 CO 2 CH 2 CH 3 , CH 2 CH 2 OCH 3 , CH 2 CH 2 OCH 2 CH 2 OCH 3 , (CH 2 ) n —Y, (CH 2 ) n Ar—X, (CH 2 ) n Ar—Y, and Y 2 C(Z 1 ) 3 ; Z 1 is CH 2 OCH 2 (CH 2 ) n X, CH 2 OCH 2 (CH 2 ) n Y, or (CH 2 ),C(O)Y 2 C(Z 2 ) 3 ; Z 2 is CH 2 OCH 2 CH 2 C(O)Y 2 C(Z 3 ) 3 ; Z 3 is CH 2 OCH 2 CH 2 X or (CH 2 ) n C(O)—Y 2 —C(Z 4 ) 3 ; Z 4 is CH 2 OCH 2 CH 2 C(O)Y 2 C(Z 5 ) 3 ; and Z 5 is CH 2 OCH 2 CH 2 C(O)O(CH 2 CH 2 O) m CH 2 CH 2 O, (CH 2 ) n OCH 2 C(CH 2 OH) 3 , (CH 2 ) n OCH 2 CH(CH 2 OH) 2 , (CH 2 ) n OCH 2 C(CH 2 OH) 2 (CH 3 ), (CH 2 ) n OCH 2 C[CH 2 OCH 2 C(CH 2 OH) 3 ] 3 , (CH 2 ) n OCH 2 C[CH 2 OCH 2 C(CH 2 O[CH 2 CH 2 O] m CH 2 CH 2 OX) 3 , CH 2 CONH—Y, CH 2 CO—Y, or CH 2 CO(CH 2 ) P —Y; where

Ar is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, or substituted or unsubstituted naphthyl and when Ar is the phenyl in —CH 2 —Ar—X, (CH 2 ) m Ar—X, or (CH 2 ) m Ar—Y, the X or Y is attached ortho- meta- or para to the —CH 2 — attached to pyridoporphyrazine;

n is 1 to 10; m is 1 to 200; p is 1 or 2; X is COOH, COO(alkyl 1 ), CONH 2 , CONH(alkyl 1 ), CON(alkyl 1 ) 2 , CO(CH 2 ) P alkyl 1 , OPO 3 H 2 , PO 3 H 2 , SO 3 H, NH 2 , N(alkyl 1 ) 2 , or N(alkyl 1 ) 3 + , where alkyl 1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl; Y is OH, (O—CH 2 CH 2 ) m —W 1 , or (CH 2 CH 2 ) m —W 2 ; W 1 is OH or (O—(CH 2 CH 2 ) m OH); W 2 is O-alkyl; and Y 2 is —(CH 2 ) n O—, —(CH 2 ) n NH—, —(CH 2 ) n S—; CH 2 CONH—, CH 2 COO—, or CH 2 CO(CH 2 ) p —; and

L 1 and L 2 are independently absent, halide, oxo, aquo, hydroxo, CN, OPO 3 H, or alcohol.

7. The cartridge of claim 6 , wherein in the O-alkyl the alkyl is selected from straight-chain or branched-chain alkyl radicals containing from 1 to 22 carbon atoms, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl.

8. The cartridge of claim 1 , wherein the cartridge comprises the reactants, and the reactants.

9. The cartridge of claim 8 , wherein the ClO 2 − is in the form of at least one substance selected from the group consisting of chlorite salts.

10. The cartridge of claim 8 , wherein the ClO 2 − is in the form of at least one substance selected from the group consisting of sodium chlorite, potassium chlorite, calcium chlorite and magnesium chlorite.

11. The cartridge of claim 8 , wherein the ClO 2 − is mixed with a solid filler.

12. The cartridge of claim 8 , wherein the ClO 2 − is adsorbed on at least one substance selected from the group consisting of clay, silica, alumina and organic polymers.

13. The cartridge of claim 1 , wherein at least one of the iron porphyrin catalyst or the iron porphyrazine catalyst is adsorbed on a solid support.

14. The cartridge of claim 13 , wherein the solid support includes a substance selected from the group consisting of clay, silica, alumina, glass beads, functionalized polystyrene or organic polymers.

15. The cartridge of claim 1 comprising the source of ClO 2 − , wherein the at least one of the iron porphyrin catalyst or the iron porphyrazine catalyst and the source of ClO 2 − are separated by an interface.

16. The cartridge of claim 15 , wherein the interface is a solid material configured to allow mixing of the at least one of the iron porphyrin catalyst or the iron porphyrazine catalyst with the source of ClO 2 upon mechanical disruption of the interface.

17. The cartridge of claim 16 , wherein the mechanical disruption includes breaking of the solid material.

18. The cartridge of claim 16 , wherein the mechanical disruption includes dissolution of the solid material.

19. The cartridge of claim 1 comprising the source of ClO 2 − , wherein the housing includes a first compartment and a second compartment, and the at least one of an iron porphyrin catalyst or an iron porphyrazine catalyst is in the first compartment and the source of ClO 2 − is in the second compartment.

20. The cartridge of claim 19 , wherein at least one of the iron porphyrin catalyst or the iron porphyrazine catalyst is adsorbed on a solid support.

21. The cartridge of claim 20 , wherein the solid support includes a substance selected from the group consisting of clay, silica, alumina, glass beads, functionalized polystyrene and organic polymers.

22. The cartridge of claim 16 , wherein the source of ClO 2 − is a chlorite salt.