Synthesis of M13 clusters from aluminum and gallium mineral polymorphs

1. A method comprising:

reacting an aluminum mineral polymorph or a gallium mineral polymorph with an acid at an aluminum metal to acid molar ratio or gallium metal to acid molar ratio sufficient to produce M 13 nanoscale clusters, M 13 nano-agglomerates, or a M 13 slurry, wherein the M 13 nanoscale clusters, M 13 nano-agglomerates, or M 13 slurry comprises [M 13 (μ 3 -OH) 6 (μ 2 -OH) 18 (H 2 O) 24 ] a [X] 15a , wherein a is an integer of 1 to 4, [M 13 O 4 (OH) 24 (H 2 O) 12 )] b [X] 7b , wherein b is an integer of 1 to 4, or a mixture thereof, wherein M is Al or Ga and X is a counterion derived from the acid.

2. The method of claim 1 , wherein a or b is 1, and X is NO 3 , Cl, I, Br, F, ClO 4 , TsO, or MnO 4 .

3. The method of claim 1 , wherein the M 13 nanoscale clusters comprise [M 13 (μ 3 -OH) 6 (μ 2 -OH) 18 (H 2 O) 24 ] a [X] 15a .

4. The method of claim 1 , wherein the M 13 slurry comprises [M 13 O 4 (OH) 24 (H 2 O) 12 )] b [X] 7b .

5. The method of claim 1 , wherein the aluminum mineral polymorph is reacted with the acid and the aluminum mineral polymorph is selected from corundum, gibbsite, boehmite, diaspore, bayerite, nordstrandite, or any combination or mixture thereof.

6. The method of claim 5 , wherein the acid is nitric acid.

7. The method of claim 1 , wherein the gallium mineral polymorph is reacted with the acid and the gallium mineral polymorph is selected from Ga(O)OH, Ga 2 O 3 , Ga(OH) 3 , or any combination or mixture thereof.

8. The method of claim 7 , wherein the acid is nitric acid.

9. The method of claim 1 , wherein the acid is selected from nitric acid, sulfuric acid, selenic acid, a halide acid, a sulfonic acid, a carboxylic acid, or a mixture thereof.

10. The method of claim 1 , wherein the acid is nitric acid.

11. The method of claim 1 , wherein the aluminum metal to acid molar ratio or gallium metal to acid molar ratio is 1:0.3 mol eq of metal to acid to 1:1.3 mol. eq. of metal to acid.

12. The method of claim 11 , wherein the aluminum metal to acid molar ratio or gallium metal to acid molar ratio is 1:0.3 to 1:0.65 mol eq to produce the slurry.

13. The method of claim 12 , wherein the slurry comprises [M 13 O 4 (OH) 24 (H 2 O) 12 )] b [X] 7b .

14. The method of claim 11 , wherein the aluminum metal to acid molar ratio or gallium metal to acid molar ratio is 1:0.7 to 1:1.0 mol eq to produce the nano-agglomerates.

15. The method of claim 11 , wherein the aluminum metal to acid molar ratio or gallium metal to acid molar ratio is 1:1.15 to 1:1.3 mol eq to produce the nanoscale clusters.

16. The method of claim 15 , wherein the M 13 nanoscale clusters comprise [M 13 (μ 3 -OH) 6 (μ 2 -OH) 18 (H 2 O) 24 ] a [X] 15a .

17. The method of claim 1 , wherein the method is controlled to avoid formation of Al(NO 3 ) 3 or Ga(NO 3 ) 3 .

18. The method of claim 1 , wherein the nanoscale clusters have a dimension ranging from 1 nm to 5 nm.

19. The method of claim 1 , wherein the nano-agglomerates have a dimension ranging from 5 nm to 200 nm.

20. A method comprising:

mixing an aluminum mineral polymorph or a gallium mineral polymorph with an acid to produce a slurry; and

processing the slurry under conditions sufficient to produce an aqueous solution of M 13 (μ 3 -OH) 6 (μ 2 -OH) 18 (H 2 O) 24 (NO 3 ) 15 nanoscale clusters, wherein M is Al or Ga.

21. The method of claim 20 , wherein the gallium mineral polymorph is mixed with the acid and the gallium mineral polymorph is selected from Ga(O)OH, Ga 2 O 3 , Ga(OH) 3 , or any combination or mixture thereof.

22. The method of claim 20 , wherein the aluminum mineral polymorph is mixed with the acid and the aluminum mineral polymorph is selected from corundum, gibbsite, boehmite, diaspore, bayerite, nordstrandite, or any combination or mixture thereof.

23. The method of claim 20 , wherein the aluminum metal to acid molar ratio or gallium metal to acid molar ratio is greater than 1:0.7 mol eq.

24. The method of claim 22 , wherein the acid is nitric acid.

25. The method of claim 21 , wherein the acid is nitric acid.

26. A method comprising:

reacting a gallium mineral polymorph with an acid at a gallium metal to acid molar ratio sufficient to produce M 13 nanoscale clusters, M 13 nano-agglomerates, or a M 13 slurry, wherein M is Ga and the gallium mineral polymorph is selected from Ga(O)OH, Ga 2 O 3 , Ga(OH) 3 , or any combination or mixture thereof.

27. The method of claim 26 , wherein the acid is selected from nitric acid, sulfuric acid, selenic acid, a halide acid, a sulfonic acid, a carboxylic acid, or a mixture thereof.

28. The method of claim 26 , wherein the acid is nitric acid.

29. The method of claim 26 , wherein the nanoscale clusters have a dimension ranging from 1 nm to 5 nm.

30. The method of claim 26 , wherein the nano-agglomerates have a dimension ranging from 5 nm to 200 nm.