Methods for low energy inorganic material synthesis

Patent metadata

Field	Value
Publication number	US-12448700-B2
Application number	US-202217663694-A
Country	US
Kind code	B2
Filing date	May 17, 2022
Priority date	Dec 29, 2015
Publication date	Oct 21, 2025
Grant date	Oct 21, 2025

Abstract

The present invention relates to solvothermal vapor synthesis methods for the crystallization of a phase from a mixture of selected inorganic or organic precursors in an unsaturated vapor-phase reaction medium.

First claim

The invention claimed is:

1. A method of synthesizing an inorganic product, the method comprising:
providing one or more inorganic compound sources of reaction elements, wherein said reaction elements react to form one or more inorganic products in a sealed reaction vessel;
providing a reaction medium comprising water or an organic species or an inorganic species that forms an unsaturated phase at a predetermined temperature and non-standard state pressure;
adding the reaction elements and reaction medium to the reaction vessel;
forming an unsaturated vapor phase of the reaction medium at a predetermined temperature and non-standard state pressure, wherein the reaction vessel has a total pressure of greater than 1 atm; and
reacting the reaction elements in said unsaturated vapor phase of the reaction medium to form at least one inorganic reaction product;
wherein one or more or the temperature, unsaturated vapor pressure, and partial pressure of any gases added or produced are selected to reduce the total non-standard state change in Gibbs free energy of the chemical reaction for the formation of at least one inorganic reaction product to less than or equal to zero.

2. The method of claim 1 , wherein the reaction medium comprises water and forms unsaturated water vapor at the predetermined temperature and non-standard state pressure.

3. The method of claim 1 , wherein the reaction medium comprises at least one of unsaturated vapor of inorganic or organic species, or any mixture of organic and inorganic species.

4. The method of claim 3 , wherein the unsaturated vapor medium comprises at least one of water, ammonia, ethanol, methanol, acetone, toluene, or benzene.

5. The method of claim 1 , wherein the reaction elements are suspended above the reaction medium within the reaction vessel prior to the beginning of the reaction.

6. The method of claim 1 , wherein the amount of reaction medium added to the reaction vessel is determined using an equation of state model for the reaction of said reaction elements to form said reaction product to calculate the amount of reaction medium to be added, optionally wherein said state model is a non-ideal gas model.

7. The method of claim 1 , wherein the predetermined temperature and non-standard state pressure are subcritical.

8. The method of claim 1 , wherein the reaction vessel is a continuous reaction vessel, batch reaction vessel, or a semi-continuous reaction vessel.

9. The method of claim 1 , further comprising adding a solute to the reaction medium.

10. The method of claim 9 , wherein the concentration of the solute is between 0.1 and 80 wt % so as to lower the total pressure of the system.

11. The method of claim 1 , further comprising combining the inorganic compound sources with a soluble or insoluble catalyst salt.

12. The method of claim 11 , wherein the catalyst is a sodium salt.

13. The method of claim 12 , wherein the sodium salt is sodium chloride or sodium hydroxide.

14. The method of claim 1 , wherein the at least one inorganic reaction product has the chemical formula of A a B b C c Z z Y y X x (α) f (β) g (γ) h ·i(δ)·j(ε)·k(θ), wherein
A, B, and C are each a single or multi-elemental cation species;
Z, Y, and X are each a single or multi-elemental anion species;
A, β, and γ are each a charged molecule;
Δ, ε, θ are each a neutral molecule; and
a, b, c, d, e, f, g, h, i, j, and k are each a value equal to or greater than 0.

15. The method of claim 1 , wherein: the non-standard state change in Gibb's free energy is reduced below zero kJ/mol or wherein the non-standard state change in Gibb's free energy is equal to zero kJ/mol and/or wherein the non-standard state change in Gibb's free energy is reduced by the unsaturated vapor phase, and/or wherein the non-standard state change in Gibb's free energy is reduced by the addition of a gaseous species to the reaction vessel.

16. The method of claim 1 , wherein the non-standard state change in Gibb's free energy is reduced by the addition of a liquid or solid species to the reaction vessel.

17. The method of claim 1 , wherein the non-standard state change in Gibb's free energy is reduced by the production of a gaseous, liquid or solid species.

18. The method of claim 1 , wherein the non-standard state change in Gibb's free energy is reduced by removing a species from the reaction vessel, or by outgassing the reaction vessel.

19. The method of claim 1 , wherein the inorganic product is CaSiO 3 , Ca 6 Si 6 O 17 (OH) 2 , Ca 7 (Si 3 O) 2 CO 3 *2H 2 O, MgAl 2 O 4 , Mg 6 Al 2 CO 3 (OH) 16 *4H 2 O, Y 3 Al 5 O 12 , SrZrO 3 , ZnAl 2 O 4 , CaTiO 3 , Ba 2 Ti 9 O 20 , LiMn 2 O 4 , Li 2 MnO 3 , Co 3 O 4 , LiCoO 2 , Y 2 Ti 2 O 7 , Li 2 Mn 2 O 3 or LiV 3 O 8 .

20. The method of claim 1 , wherein the inorganic compound sources comprise:
CaCO 3 and SiO 2 ; or
Mg(OH 2 ) and Al 2 O 3 ; or
Mg(OH 2 ), CO 2 and Al 2 O 3 ; or
Y(OH) 3 and Al 2 O 3 ; or
Sr(OH) 2 and ZrO 2 ; or
ZnO and Al 2 O 3 ; or
CaCO 3 and TiO 2 ; or
BaCO 3 and TiO 2 ; or
Li 2 CO 3 and Mn 2 O 3 ; or
Li 2 CO 3 and CoO; or
Li(OH)*H 2 O and CoO; or
Y 2 O 3 and TiO 2 ; or
Li(OH)*H 2 O and MnCO 3 ; or
Li(OH)*H 2 O and V 2 O 5 .

Assignees

• Univ Rutgers

Inventors

• Riman Richard E
• Kopp Daniel

Classifications

• C04B35/22

  rich in calcium oxide {, e.g. wollastonite (C04B35/195 takes precedence)} · CPC title

• C01B33/24

  Alkaline-earth metal silicates · CPC title

• C04B2235/3225

  Yttrium oxide or oxide-forming salts thereof · CPC title

• C04B2235/604

  Pressing at temperatures other than sintering temperatures · CPC title

• C04B35/443

  Magnesium aluminate spinel · CPC title