# US 11,027,259 B2 · Preparation method for hollow molybdate composite microspheres and method for catalyzing ammonia borane hydrolysis to produce hydrogen

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- Number: US 11,027,259 B2
- Document ID: US11027259B2
- Status: Granted
- Kind: B2
- Application number: 16/747,048
- Filed: 2020-01-20
- Published: 2020-05-14
- Granted: 2021-06-08
- Earliest claimed: 2017-12-05
- Assignees: Huizhou University
- Applicants: Huizhou University
- Inventors: Jinyun Liao; Dongsheng Lu; Hao Li; Dingshu Xiao
- Web page: https://patentgrep.com/patent/US11027259B2

## CPC

- B01J 23/002: {Mixed oxides other than spinels, e.g. perovskite}
- B01J 23/885: and copper
- B01J 35/397: {Egg shell like}
- B01J 35/52: Hollow spheres
- B01J 35/613: {10-100 m2/g}
- B01J 35/70: characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00)
- B01J 37/009: {Preparation by separation, e.g. by filtration, decantation, screening}
- B01J 37/031: {Precipitation}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/06: Washing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- C01B 3/06: by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents
- C01B 3/065: by reaction of inorganic compounds with hydrides
- C01G 39/00: Compounds of molybdenum
- C01G 39/006: {Compounds containing molybdenum, with or without oxygen or hydrogen, and containing two or more other elements}
- C01G 51/82: Compounds containing cobalt, with or without oxygen or hydrogen, and containing two or more other elements
- C01G 53/40: Complex oxides containing nickel and at least one other metal element
- C01G 53/82: Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
- B01J 2235/15: X-ray diffraction
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- B01J 2523/00: Constitutive chemical elements of heterogeneous catalysts
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2004/03: obtained by SEM
- C01P 2004/04: obtained by TEM, STEM, STM or AFM
- C01P 2004/16: Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
- C01P 2004/34: hollow
- C01P 2006/12: Surface area
- Y02E 60/36: Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

A method of preparing hollow molybdate composite microspheres includes steps of: (1) dissolving 1-4 mmol of MCl2 in 20 ml of water to obtain a solution A and dissolving 1-4 mmol. of molybdic acid in 20 ml of water to obtain a solution B, followed by mixing the solution A and the solution B, in which M is Co, Ni, or Cu; (2) dissolving 10-40 mmol of urea in 40 ml of water, adding the mixed solution of step (1) and stirring uniformly; (3) placing the mixed solution of step (2) into a reaction vessel and reacting at 120-160° C. for 6-12 hours; (4) suction filtrating and water washing, followed by drying in a vacuum oven at 40-60° C.; (5) calcination at 350-500° C. for 2-4 hours in a Muffle furnace.

## Claims

### Claim 1

A method for preparing hollow molybdate composite microspheres, comprising steps of:
(1) dissolving 1-4 mmol of MCl2 in 20 ml of water to obtain a solution A, and dissolving 1-4 mmol of molybdic acid in 20 ml of water to obtain a solution B, followed by mixing the solution A and the solution B to obtain a mixed solution C, in which M being at least one of Co, Ni, or Cu;
(2) dissolving 10-40 mmol of urea in 40 ml of water, adding the mixed solution C of step (1) and stirring uniformly to obtain a solution D;
(3) transferring the mixed solution D of step (2) into a reaction vessel and reacting at 120-160° C. for 6-12 hours to obtain product E;
(4) carrying out suction filtration and water washing to the product E, followed by drying in a vacuum oven at 40-60° C. to obtain a solid; and
(5) calcining the solid at 350-500° C. for 2 to 4 hours in a muffle furnace to obtain hollow molybdate composite microspheres.

### Claim 2 (depends on 1)

The method for preparing the hollow molybdate composite microspheres according to claim 1, wherein a ratio of a total mass of soluble MCl2 to a mass of molybdic acid in the step (1) is 1:1.

### Claim 3 (depends on 2)

The method for preparing the hollow molybdate composite microspheres according to claim 2, wherein in the step (2), a stirring time is 0.5-1 hour.

### Claim 4 (depends on 3)

The method for preparing the hollow molybdate composite microspheres according to claim 3, wherein in the step (3), a temperature in the vacuum oven is 40-60° C.

### Claim 5 (depends on 1)

The method for preparing the hollow molybdate composite microspheres according to claim 1, wherein in the step (2), a stirring time is 0.5-1 hour.

### Claim 6 (depends on 5)

The method for preparing the hollow molybdate composite microspheres according to claim 5, wherein in the step (3), a temperature in the vacuum oven is 40-60° C.

### Claim 7 (depends on 1)

The method for preparing the hollow molybdate composite microspheres according to claim 1, wherein in the step (3), a temperature in the vacuum oven is 40-60° C.

### Claim 8 (depends on 1)

A method for catalyzing ammonia borane hydrolysis to produce hydrogen, wherein a catalyst used in the method is the hollow molybdate composite microspheres prepared by the method of claim 1.

### Claim 9 (depends on 2)

A method for catalyzing ammonia borane hydrolysis to produce hydrogen, wherein a catalyst used in the method is the hollow molybdate composite microspheres prepared by the method of claim 2.