CN110835103B - Preparation method of cobalt-copper phosphate microspheres and application of cobalt-copper phosphate microspheres in catalyzing ammonia borane hydrolysis to produce hydrogen - Google Patents

Preparation method of cobalt-copper phosphate microspheres and application of cobalt-copper phosphate microspheres in catalyzing ammonia borane hydrolysis to produce hydrogen Download PDF

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CN110835103B
CN110835103B CN201911190956.1A CN201911190956A CN110835103B CN 110835103 B CN110835103 B CN 110835103B CN 201911190956 A CN201911190956 A CN 201911190956A CN 110835103 B CN110835103 B CN 110835103B
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copper phosphate
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冯裕发
李�浩
廖锦云
张喜斌
朱咏梅
林维敏
苏新龙
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Huizhou University
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
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    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
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    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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    • C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
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Abstract

The invention discloses a preparation method of cobalt copper phosphate microspheres, which comprises the following steps: (1) Dissolving a pH regulator, a surfactant and ultrapure water to form a solution A; (2) Dissolving soluble cobalt salt and copper salt solution in ultrapure water to prepare mixed salt solution B; (3) Slowly adding the solution B into the solution A to mix to form a solution C, and stirring for 0-1 h; (4) Slowly adding 30% of H dropwise into the solution C 3 PO 4 A solution; (5) Then transferring the mixture to a reaction kettle, reacting for 2 to 24 hours at the temperature of between 80 and 180 ℃, filtering and washing, collecting the product, and drying the product in a vacuum oven at the temperature of between 40 and 80 ℃. The invention adopts a hydrothermal synthesis method, and prepares a series of cobalt-copper phosphate microsphere catalysts by selecting, optimizing and controllably synthesizing reaction conditions. The process effectively realizes the setting of the cobalt-copper ratio in the raw materials, the whole preparation process is simple to operate, environment-friendly, very good in experimental reproducibility, low in cost, easy for industrial production and capable of producing Cu in large scale 3‑3x Co 3x (PO 4 ) 2 A phosphate salt.

Description

Preparation method of cobalt-copper phosphate microspheres and application of cobalt-copper phosphate microspheres in catalyzing ammonia borane hydrolysis to produce hydrogen
Technical Field
The invention belongs to the field of catalysis and the field of hydrogen storage materials. In particular to a preparation method of cobalt copper phosphate microspheres and application thereof in catalyzing ammonia borane hydrolysis to produce hydrogen.
Background
With the world economyThe rapid development of the method, the excessive consumption of non-renewable energy sources such as coal and petroleum, and the gradual deterioration of environmental pollution, so that the search for a renewable clean energy source has become a hot spot of scientific research. Hydrogen is of great interest because of its high heat value of combustion, no pollution of the product, etc. High-efficiency hydrogen storage and transportation are important factors which restrict the development and utilization of hydrogen energy at present. In order to solve the problems of hydrogen storage and hydrogen transportation, hydrogen production by using hydride becomes a current research hotspot. Among the numerous hydrogen storage materials, ammonia borane (NH) 3 BH 3 AB) has high hydrogen content, high hydrogen release rate, good stability and environmental protection, and is considered to be one of the potential hydrogen storage materials. However, the reaction rate is extremely slow under the condition that ammonia borane hydrolysis hydrogen production is not catalyzed by a catalyst at normal temperature, while in the previous research on catalysts, noble metal catalysts show excellent hydrogen production performance, but the noble metals are expensive, so that the industrial application of the noble metals is limited. Therefore, the research focus is to find a non-noble metal catalyst with abundant and low price for rapid hydrogen release in ammonia borane hydrolysis. The document reports that the introduction of heteroatoms (P, B, N and the like) can cause the change of an electronic structure of the catalyst in the reaction process, so that the energy required by bond breaking of the B-N bond of the ammonia borane is reduced, and the performance of the catalyst is improved.
Transition metal phosphates (Co) 3 (PO 4 ) 2 、Cu 3 (PO 4 ) 2 Etc.) the nano-material has the characteristics of special lattice structure, high specific surface area, good conductivity, complex electronic structure, etc., and has wide application in the fields of super capacitors, lithium ion batteries, electrocatalysis, photocatalysis, etc.
Chinese patent (CN 107096555A) proposes a preparation method of a cobalt carbonate composite cobalt phosphate photocatalyst, which prepares a precursor solution by cobalt nitrate, sodium carbonate and deionized water; stirring and mixing the two solutions to form a colloidal substance, and reacting sodium carbonate with cobalt nitrate in the stirring process to generate cobalt carbonate colloid; placing the cobalt carbonate colloid in a semipermeable membrane bag, washing with distilled water to remove free ions, adding the cobalt carbonate colloid into a sodium phosphate solution with a certain concentration, soaking until cobalt phosphate nano-particles are formed on the surfaces of the cobalt carbonate particles, performing solid-liquid separation, washing the solid with deionized water, and drying to obtain the cobalt carbonate composite cobalt phosphate photocatalyst. However, the preparation period is too long and the energy consumption is high, which is not beneficial to industrial application.
Chinese patent (CN 104269528A) discloses a preparation method of a cobalt phosphate powder material, which comprises the steps of obtaining cobalt phosphate by simply reacting soluble cobalt salt with soluble phosphate, adjusting the pH value of a reaction system to be neutral by using ammonia water, washing, drying, grinding and screening, and preparing the cobalt phosphate powder material, wherein the cobalt phosphate powder material prepared by the method is not uniform in shape distribution.
Therefore, the invention aims to solve the problem of developing a method which has controllable appearance, lower cost and excellent product performance and can be applied to the industrial production of phosphate compounds.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a phosphate catalyst with regular morphology, the synthesis method is simple, the conditions are mild, and the synthesized Cu 3-3x Co 3x (PO 4 ) 2 Is spherical, and has the advantages of uniform dispersion, regular appearance and the like.
The invention provides a preparation method of cobalt-copper phosphate microspheres, which comprises the following steps:
(1) Dissolving a pH regulator, a surfactant and ultrapure water to form solution A;
(2) Dissolving soluble cobalt salt or soluble copper salt or both of them in ultrapure water to prepare a mixed salt solution B;
(3) Slowly adding the solution B into the solution A to mix to form a solution C, and stirring for 0-1 h;
(4) Slowly dropwise adding 30% of H into the solution C 3 PO 4 A solution;
(5) Then transferring the mixture to a reaction kettle, reacting for 2 to 24 hours at the temperature of between 80 and 180 ℃, filtering and washing, collecting the product, and drying the product in a vacuum oven at the temperature of between 40 and 80 ℃.
Preferably, the surfactant in step (1) is one or more selected from sodium dodecyl sulfate, polyvinylpyrrolidone, cetyl trimethyl ammonium bromide and polyethylene glycol.
Preferably, the pH regulator in step (1) is one or more of urea, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water and hexamethylenetetramine.
Preferably, the soluble cobalt salt in step (2) is selected from one or more of cobalt acetate tetrahydrate, cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt chloride hexahydrate, cobalt sulfate heptahydrate and cobalt nitrate hexahydrate.
Preferably, the soluble copper salt in step (2) is selected from one or more of copper chloride dihydrate, copper sulfate pentahydrate and copper nitrate.
Preferably, the amount of phosphoric acid added in step (4) is in combination with the metal salt Co 2+ Or Cu 2+ Or the molar ratio of the two is 2/3-3.
The invention also discloses application of the cobalt-copper phosphate catalyst prepared by the method in catalyzing ammonia borane hydrolysis to produce hydrogen. In conclusion, the preparation method disclosed by the invention has the following beneficial effects:
1. the preparation method is simple, and the synthesized product is microspherical and uniformly dispersed.
2. Can flexibly adjust the proportion of cobalt and copper to synthesize the copper alloy with the chemical general formula of Cu 3-3x Co 3x (PO 4 ) 2 Cobalt copper phosphate catalyst.
3. Cu prepared by the invention 3-3x Co 3x (PO 4 ) 2 The microspheres are used for catalyzing ammonia borane hydrolysis to produce hydrogen. Exhibit excellent properties, especially Cu 0.6 Co 2.4 (PO 4 ) 2 Exhibit strong catalytic performance.
Drawings
FIG. 1 shows Cu prepared by the present invention 0.6 Co 2.4 (PO 4 ) 2 SEM picture of (g);
FIG. 2 shows Cu prepared by the present invention 0.6 Co 2.4 (PO 4 ) 2 A TEM image of (B);
FIG. 3 shows Cu prepared by the present invention 0.6 Co 2.4 (PO 4 ) 2 Mapping graph of (a);
FIG. 4 shows Cu prepared by the present invention 0.6 Co 2.4 (PO 4 ) 2 XRD pattern of (a);
FIG. 5 shows Cu prepared by the present invention 0.6 Co 2.4 (PO 4 ) 2 FT-IR diagram of (1);
FIG. 6 shows Cu with different ratios of Co and Cu prepared by the present invention 3-3x Co 3x (PO 4 ) 2 The catalyst is used for catalyzing hydrogen production performance.
Detailed Description
The foregoing summary of the invention is described in further detail below with reference to specific embodiments. It should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples. Various substitutions, alterations, modifications and the like are included in the scope of the present invention according to the common technical knowledge and the conventional means in the field without departing from the technical idea of the present invention.
Example 1
Preparing a precursor: 6.0g of urea and 0.5g of Sodium Dodecyl Sulfate (SDS) were weighed out and dissolved in 61.3mL of ultrapure water by magnetic stirring to obtain solution A, and 0.281g of CoSO was weighed out 4 ·7H 2 O was dissolved in 2.7mL of ultrapure water, and dissolved by magnetic stirring to obtain a solution B. And slowly dropwise adding the solution B into the solution A to obtain a solution C, and continuously stirring for 30min. Slowly dropwise adding 0.326gH into the solution C 3 PO 4 (30 wt%), the resulting solution was transferred to a reaction vessel and screwed down for hydrothermal reaction at 90 ℃ for 4 hours. After the reaction is finished, cooling to room temperature, carrying out suction filtration washing, collecting a product, washing for 2-3 times with ethanol, drying in a vacuum oven at 60 ℃, taking out a sample after the product is cooled to room temperature to obtain a target product Co 3 (PO 4 ) 2 。
Through determination, the Co obtained by the invention 3 (PO 4 ) 2 The appearance is spherical, and the color is dark purple.
Example 2
Preparing a precursor: 6.0g of urea and 0.5g of Sodium Dodecyl Sulfate (SDS) were dissolved in 61.3mL of ultrapure water by magnetic stirring to obtain a solutionSolution A, 0.225g of CoSO was weighed 4 ·7H 2 O and 0.050g CuSO 4 ·5H 2 O was dissolved in 2.7mL of ultrapure water, and dissolved by magnetic stirring to obtain a solution B. Slowly adding the solution B into the solution A dropwise to obtain a solution C, and continuously stirring for 30min. Slowly dropwise adding 0.326gH into the solution C 3 PO 4 (30 wt%), the resulting solution was transferred to a reaction vessel and screwed down for hydrothermal reaction at 90 ℃ for 4 hours. After the reaction is finished, cooling to room temperature, carrying out suction filtration washing, collecting the product, washing for 2-3 times with water, washing for 2-3 times with ethanol, drying at 60 ℃ in a vacuum oven, and taking out the sample after the product is cooled to room temperature to obtain the target product Cu 0.6 Co 2.4 (PO 4 ) 2 。
Through determination, the Cu obtained by the invention 0.6 Co 2.4 (PO 4 ) 2 The appearance is spherical, and the color is dark purple.
Example 3
Preparing a precursor: 6.0g of urea and 0.5g of Sodium Dodecyl Sulfate (SDS) were weighed out and dissolved in 61.3mL of ultrapure water, and the solution A was dissolved by magnetic stirring, and 0.169g of CoSO was weighed out 4 ·7H 2 O and 0.100g of CuSO 4 ·5H 2 O was dissolved in 2.7mL of ultrapure water, and dissolved by magnetic stirring to obtain a solution B. And slowly dropwise adding the solution B into the solution A to obtain a solution C, and continuously stirring for 30min. Slowly dropwise adding 0.326gH into the solution C 3 PO 4 (30 wt%), the resulting solution was transferred to a reaction vessel and screwed down for hydrothermal reaction at 90 ℃ for 4 hours. After the reaction is finished, cooling to room temperature, carrying out suction filtration washing, collecting the product, washing for 2-3 times with water, washing for 2-3 times with ethanol, drying at 60 ℃ in a vacuum oven, and taking out the sample after the product is cooled to room temperature to obtain the target product Cu 1.2 Co 1.8 (PO 4 ) 2 。
Through determination, the Cu obtained by the invention 1.2 Co 1.8 (PO 4 ) 2 The appearance is spherical, and the color is blue-violet.
Example 4
Preparing a precursor: 6.0g of urea and 0.5g of Sodium Dodecyl Sulfate (SDS) were weighed out and dissolved in 61.3mL of ultrapure water, and the solution A was dissolved by magnetic stirring, and 0.141g of CoSO was weighed out 4 ·7H 2 O and 0.125g CuSO 4 ·5H 2 O is dissolved in 2.7mL of ultrapure water, and the solution is dissolved by magnetic stirring to obtain a solution B. Slowly adding the solution B into the solution A dropwise to obtain a solution C, and continuously stirring for 30min. Slowly dropwise adding 0.326gH into the solution C 3 PO 4 (30 wt%), the resulting solution was transferred to a reaction vessel and screwed down for hydrothermal reaction at 90 ℃ for 4 hours. After the reaction is finished, cooling to room temperature, carrying out suction filtration washing, collecting the product, washing for 2-3 times with water, washing for 2-3 times with ethanol, drying at 60 ℃ in a vacuum oven, and taking out the sample after the product is cooled to room temperature to obtain the target product Cu 1.5 Co 1.5 (PO 4 ) 2 。
Through determination, the Cu obtained by the invention 1.5 Co 1.5 (PO 4 ) 2 The appearance is spherical, and the color is blue-violet.
Example 5
Preparing a precursor: 6.0g of urea and 0.5g of Sodium Dodecyl Sulfate (SDS) were weighed out and dissolved in 61.3mL of ultrapure water by magnetic stirring to obtain a solution A, and 0.225g of CoSO was weighed out 4 ·7H 2 O and 0.050gCuSO 4 ·5H 2 O is dissolved in 2.7mL of ultrapure water, and the solution is dissolved by magnetic stirring to obtain a solution B. Slowly adding the solution B into the solution A dropwise to obtain a solution C, and continuously stirring for 30min. Slowly dropwise adding 0.625gH into the solution C 3 PO 4 (30 wt%), the resulting solution was transferred to a reaction kettle and screwed down for hydrothermal reaction at 90 ℃ for 4h. After the reaction is finished, cooling to room temperature, carrying out suction filtration washing, collecting a product, washing for 2-3 times with ethanol, drying in a vacuum oven at 60 ℃, taking out a sample after the product is cooled to room temperature to obtain a target product Cu 0.6 Co 2.4 (PO 4 ) 2 。
Through determination, the Cu obtained by the invention 0.6 Co 2.4 (PO 4 ) 2 The appearance is spherical, and the color is dark purple.
Example 6
Preparing a precursor: 6.0g of urea and 0.5g of cetyltrimethylammonium bromide (CTAB) were weighed out and dissolved in 61.3mL of ultrapure water, and dissolved by magnetic stirring to obtain a solution A, and 0.225g of CoSO was weighed out 4 ·7H 2 O and 0.050gCuSO 4 ·5H 2 O solutionDissolved in 2.7mL of ultrapure water with magnetic stirring to obtain solution B. Slowly adding the solution B into the solution A dropwise to obtain a solution C, and continuously stirring for 30min. Slowly dropwise adding 0.326gH into the solution C 3 PO 4 (30 wt%), the resulting solution was transferred to a reaction vessel and screwed down for hydrothermal reaction at 90 ℃ for 4 hours. After the reaction is finished, cooling to room temperature, performing suction filtration washing to collect a product, washing for 2-3 times with water, washing for 2-3 times with ethanol, drying at 60 ℃ in a vacuum oven, cooling to room temperature, taking out a sample to obtain a target product Cu 0.6 Co 2.4 (PO 4 ) 2 。
Through determination, the Cu obtained by the invention 0.6 Co 2.4 (PO 4 ) 2 The appearance is spherical, and the color is dark purple.
Example 7
Preparing a precursor: 6.0g of hexamethylenetetramine and 0.5g of Sodium Dodecyl Sulfate (SDS) were weighed out and dissolved in 61.3mL of ultrapure water by magnetic stirring to obtain a solution A, and 0.225g of CoSO was weighed out 4 ·7H 2 O and 0.050g CuSO 4 ·5H 2 O was dissolved in 2.7mL of ultrapure water, and dissolved by magnetic stirring to obtain a solution B. Slowly adding the solution B into the solution A dropwise to obtain a solution C, and continuously stirring for 30min. Slowly dropwise adding 0.326gH into the solution C 3 PO 4 (30 wt%), the resulting solution was transferred to a reaction kettle and screwed down for hydrothermal reaction at 90 ℃ for 4h. After the reaction is finished, cooling to room temperature, carrying out suction filtration washing, collecting the product, washing for 2-3 times with water, washing for 2-3 times with ethanol, drying at 60 ℃ in a vacuum oven, and taking out the sample after the product is cooled to room temperature to obtain the target product Cu 0.6 Co 2.4 (PO 4 ) 2 。
Through determination, the Cu obtained by the invention 0.6 Co 2.4 (PO 4 ) 2 The appearance is spherical, and the color is dark purple.
Below with Cu 0.6 Co 2.4 (PO 4 ) 2 For example, the structure and properties of the composite phosphate prepared according to the present invention were analyzed and tested.
1. SEM analysis
FIG. 1 shows Cu prepared by the present invention 0.6 Co 2.4 (PO 4 ) 2 SEM image of (d). As can be seen from the scanning electron micrograph, the synthesized Cu 0.6 Co 2.4 (PO 4 ) 2 The morphology is spherical, and the particle size is about 500nm.
2. TEM analysis
FIG. 2 shows Cu prepared by the present invention 0.6 Co 2.4 (PO 4 ) 2 A TEM image of (a). As can be seen from the scanning image of the transmission electron microscope, the synthesized Cu 0.6 Co 2.4 (PO 4 ) 2 The appearance is spherical, the grain diameter is about 500nm, and the inside is a solid structure.
3. Elemental distribution test
FIG. 2 shows Cu prepared by the present invention 0.6 Co 2.4 (PO 4 ) 2 The Mapping graph shows that Cu, co, P and O elements are uniformly distributed.
4. XRD analysis
FIG. 4 shows Cu prepared by the present invention 0.6 Co 2.4 (PO 4 ) 2 XRD test of (1).
5. Infrared analysis
FIG. 5 shows Cu prepared by the present invention 0.6 Co 2.4 (PO 4 ) 2 FT-IR test of (1).
6. Testing of catalytic Hydrogen production Performance
FIG. 6 shows the preparation of Cu with different ratios of Co to Cu according to the present invention 3-3x Co 3x (PO 4 ) 2 Performance test of ammonia borane hydrolysis to hydrogen as catalyst, NH 3 BH 3 The amount was 3mmol, naOH was 20mmol and the catalyst was 5mg. Measuring Cu at 25 ℃ 3-3x Co 3x (PO 4 ) 2 Hydrogen production rate curve.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (4)

1. The application of the cobalt copper phosphate as the catalyst in catalyzing ammonia borane hydrolysis to produce hydrogen is characterized in that the preparation method of the cobalt copper phosphate microspheres comprises the following steps:
(1) Dissolving a pH regulator, a surfactant and ultrapure water to form solution A;
(2) Dissolving soluble cobalt salt and soluble copper salt in ultrapure water together to prepare a mixed salt solution B;
(3) Slowly adding the solution B into the solution A, mixing to form a solution C, and stirring for 0 to 1 hour;
(4) Slowly dropwise adding 30% of H into the solution C 3 PO 4 A solution;
(5) Transferring the mixture to a reaction kettle, reacting at 80 to 180 ℃ for 2 to 24 hours, filtering and washing, collecting a product, and drying in a vacuum oven at 40 to 80 ℃;
the surfactant in the step (1) is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and polyethylene glycol;
the amount of phosphoric acid added in the step (4) and the metal salt Co 2+ And Cu 2+ The molar ratio of (B) is 2/3 to 3.
2. The application of the cobalt copper phosphate as the catalyst to catalyzing ammonia borane to hydrolyze to produce hydrogen according to the claim 1, which is characterized in that: in the step (1), the pH regulator is one or more of urea, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water and hexamethylene tetramine.
3. The application of the cobalt copper phosphate as the catalyst to catalyzing ammonia borane hydrolysis to produce hydrogen according to claim 1 is characterized in that: in the step (2), the soluble cobalt salt is selected from one or more of cobalt acetate tetrahydrate, cobalt sulfate, cobalt nitrate, cobalt chloride hexahydrate, cobalt sulfate heptahydrate and cobalt nitrate hexahydrate.
4. The application of the cobalt copper phosphate as the catalyst to catalyzing ammonia borane hydrolysis to produce hydrogen according to claim 1 is characterized in that: the soluble copper salt in the step (2) is selected from one or more of copper chloride dihydrate, copper sulfate pentahydrate and copper nitrate.
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