CN113388645B - Batch synthesis of basic carbonate and metal oxide nano-tubes by urea enzymolysis method - Google Patents

Batch synthesis of basic carbonate and metal oxide nano-tubes by urea enzymolysis method Download PDF

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CN113388645B
CN113388645B CN202110696928.8A CN202110696928A CN113388645B CN 113388645 B CN113388645 B CN 113388645B CN 202110696928 A CN202110696928 A CN 202110696928A CN 113388645 B CN113388645 B CN 113388645B
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王荷芳
王婷
王正午
朱义州
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Abstract

A method for synthesizing a basic carbonate nanotube and a corresponding metal oxide nanotube by urea enzymolysis, which is simple and convenient and does not need a template. The method is characterized in that: synthesizing the basic carbonate nanotube under mild conditions, and calcining to obtain various biological metal oxide nanotubes. The method comprises the following steps: 1) the metal hydrochloride or nitrate, urea and enzyme are mixed evenly according to a certain proportion, the feeding ratio and the feeding speed are adjusted, and the reaction is carried out under mild conditions to obtain the basic carbonate nanotube. 2)500-1000 o And C, calcining the basic carbonate to obtain the corresponding metal oxide nanotube. The invention has the advantages and effects that: the NH with uniform appearance can be obtained by controlling the reaction time and the concentration of the urea 4 Ga(OH) 2 CO 3 Nanotube, NH 4 Al(OH) 2 CO 3 Nanotube, gallium oxide nanotube, aluminum oxide nanotube and corresponding composite nanotube. The method is simple, easy to operate, high in yield, uniform in product appearance and large in specific surface area, and is suitable for large-scale application in the aspects of serving as a catalyst, a catalyst carrier, an adsorption material and the like.

Description

Batch synthesis of basic carbonate and metal oxide nano-tube by urea enzymolysis method
Technical Field
The invention relates to a synthesis technology of a bimetal basic carbonate nanotube of Ga, Al basic carbonate, Ga-Al, Ga-Mn, Al-Mn and Al-Ti and a synthesis method of an oxide nanotube after calcination thereof.
Background
In recent years, one-dimensional nano materials, especially nanotube materials, have attracted great attention due to their advantages of excellent photoelectric properties, large specific surface area, high light utilization rate, and the like, but most nanotube synthesis methods require high-temperature processes or templating agent molecules, and have the problems of time consumption, energy consumption, low yield, and the like. The types of nanotubes that have been reported are also limited, which limits the wide range of applications for nanotubes. Therefore, the synthesis of nanotube materials by a mild and convenient method is still a hot spot of current research.
The metal basic carbonate and the metal oxide have wide application prospect in the field of catalysis, and the construction of a heterojunction and a composite catalyst is concerned. Alumina is an excellent catalyst carrier due to small biological toxicity, large specific surface area and good stability, but most of the currently reported synthesis steps of many alumina carriers are complicated, multi-step synthesis is needed, the morphology is difficult to control, and the alumina exists in a form that a catalyst is attached to the carrier, so that the alumina is not favorable for full dispersion of the catalyst. Gallium oxide is a semiconductor with stable crystal structure, strong chemical stability and thermal stability, and has excellent photocatalytic activity. The heterojunction can be constructed according to the energy band structure of gallium oxide, and the light absorption capability and the catalytic activity are enhanced, but the construction of the heterojunction needs to fully contact two phases to realize the transfer of carriers, and the general construction method needs multi-step functionalization and is difficult to fully contact. Therefore, the method has great significance for synthesizing the composite catalyst and the heterojunction nanotube with controllable shapes and uniform dispersion of the aluminum oxide and the gallium oxide in one step.
Disclosure of Invention
The invention provides a mild template-free method for synthesizing metal basic carbonate nanotubes by urea enzymolysis, and calcined products, namely various metal oxides, of the method can still keep the nanotube morphology with a large specific surface area.
The method comprises the following steps:
1) the metal hydrochloride or nitrate, urea, enzyme and the like are uniformly mixed according to a certain proportion, the feeding ratio and the feeding speed are adjusted, and the hydrothermal reaction is carried out under mild conditions to obtain the metal salt nanotube.
2）500-1000 o And C, calcining the metal alkali carbonate nanotube to obtain the corresponding metal oxide nanotube.
The invention has the advantages and effects that: by controlling the reaction time and the concentration of urea, the basic gallium carbonate (aluminum) nanotube, gallium oxide and aluminum oxide nanotube with uniform appearance can be obtained. Controlling the feeding speed and the feeding proportion, the bimetallic basic carbonate nanotube can be obtained, and the bimetallic oxide nanotube can also be obtained after calcinationThe method can be used to construct composite catalysts, e.g., Al can be constructed 2 O 3 -Mn 2 O 3 ，Al 2 O 3 -Ga 2 O 3 ，Ga 2 O 3 -Mn 2 O 3 Nanotube composite structures, and the like.
Description of the drawings:
FIG. 1 shows NH synthesized by the present invention 4 Ga(OH) 2 CO 3 Transmission electron micrograph of nanotubes showing: the synthetic material is a nanotube.
FIG. 2 is a transmission electron microscope image of a calcined synthesized gallium oxide nanotube.
FIG. 3 is a transmission electron microscope image of the synthesized alumina nanotubes after calcination.
FIG. 4 NH synthesized according to the invention 4 Ga(OH) 2 CO 3 -NH 4 Al(OH) 2 CO 3 Scanning electron microscopy of nanotubes.
[ embodiments ] of the present invention:
example 1
Synthetic NH 4 Ga(OH) 2 CO 3 A method of nanotubes. It is characterized in that NH with more uniform appearance is conveniently synthesized by a simple and mild method 4 Ga(OH) 2 CO 3 A nanotube. The method comprises the following steps:
1) dissolving gallium salt in water, adding 0.5-2.5 g urea under stirring, and stirring for 30 min.
2) Adjusting pH of the above solution to 7-8 with ammonia water, adding urease, stirring for 30 min, placing into a polytetrafluoroethylene lined reaction kettle, and adding into a reactor with 37 deg.C o C, reacting for 24 hours in an oven.
3) The precipitate obtained from the reaction was collected by centrifugation, washed with water until the supernatant was neutral, and dried under vacuum.
Example 2
Synthetic chromium-doped NH 4 Ga(OH) 2 CO 3 A method of nanotubes. The method is characterized in that the method is simple and mild, and chromium-doped NH with uniform appearance can be conveniently synthesized 4 Ga(OH) 2 CO 3 And (4) nanorods. The procedure and method were substantially the same as in example 1, except thatAdding chromium nitrate solution with corresponding proportion in the step 1 to obtain NH with different chromium doping amount 4 Ga(OH) 2 CO 3 A nanotube.
Example 3
A method for synthesizing gallium oxide nanotubes with different crystal forms. It is characterized in that the gallium oxide nano-tube with larger specific surface area is obtained. The method comprises the following steps: reacting the obtained NH 4 Ga(OH) 2 CO 3 The nanotube passes through 500-1000- o Calcining C for a certain time to obtain alpha-Ga 2 O 3 Nanotubes and beta-Ga 2 O 3 A nanotube.
Example 4
A method for synthesizing chromium-doped gallium oxide nanotubes with different crystal forms. The method is characterized in that the chromium-doped gallium oxide nanotube with larger specific surface area is obtained. Precursor of the material is doped with NH 4 Ga(OH) 2 CO 3 The synthesis of nanotubes was performed as in example 2 and the calcination procedure was as in example 3.
Example 5
Synthesis of NH 4 Al(OH) 2 CO 3 A method of nanotubes. It is characterized in that NH with uniform appearance is conveniently synthesized by a simple and mild method 4 Al(OH) 2 CO 3 A nanotube. The procedure and method were substantially the same as in example 1 except that the Ga salt added in step 1 was replaced with an Al salt.
Example 6
A method for synthesizing an alumina nanotube. It is characterized in that the alumina nano-tube with larger specific surface area is obtained. The method comprises the following steps: NH obtained by the reaction in example 5 4 Al(OH) 2 CO 3 The nanotube passes through 500-1000 o Calcining C for a period of time to obtain Al 2 O 3 A nanotube.
Example 7
Synthesis of NH 4 Ga(OH) 2 CO 3 -NH 4 Al(OH) 2 CO 3 A method of nanotubes. It is characterized in that NH with uniform appearance is conveniently synthesized by a simple and mild method 4 Ga(OH) 2 CO 3 -NH 4 Al(OH) 2 CO 3 A nanotube. The method comprises the following steps:
1) preparing a solution A: dissolving gallium salt in water, adding 0.5-2.5 g of urea while stirring, adjusting the pH of the system to 7-8 by using ammonia water, and adding urease.
2) Preparing a solution B: dissolving aluminum salt in water, and adding 0.5-2.5 g of urea while stirring.
3) And (3) filling the solution B into a separating funnel, slowly dripping the solution B into the solution A at a constant speed, keeping stirring the solution A during the dripping process for about 40 min, and keeping stirring for 30 min after the dripping is finished.
4) Putting the mixed solution into a polytetrafluoroethylene lined reaction kettle, and putting the polytetrafluoroethylene lined reaction kettle into a reactor with 37 percent of the mixed solution o C, reacting for 24 hours in an oven.
5) The precipitate obtained from the reaction was collected by centrifugation, washed with water until the supernatant was neutral, and dried under vacuum.
Example 8
Synthesis of NH 4 Al(OH) 2 CO 3 -TiO 2 A method of nanotubes. It is characterized in that NH with uniform appearance is conveniently synthesized by a simple and mild method 4 Al(OH) 2 CO 3 -TiO 2 A nanotube. The method comprises the following steps:
1) dissolving Al salt in water, adding 0.5-2.5 g urea under stirring, adjusting system pH to 7-8 with ammonia water, adding urease, and stirring for 30 min.
2) Preparing 10% v/v ethanol solution of tetrabutyl titanate, and slowly dripping the ethanol solution into the solution (1).
3) Stirring for 30 min, placing into a reaction kettle with polytetrafluoroethylene lining, and adding into a reactor with a polytetrafluoroethylene lining o C, reacting for 24 hours in an oven.
4) The precipitate obtained from the reaction was collected by centrifugation, washed with water until the supernatant was neutral, and dried under vacuum.
Example 9
Synthetic Al 2 O 3 -Mn 2 O 3 A method of nanotube. It is characterized by that it uses simple method to conveniently synthesize Al whose morphology is uniform and Al and Mn are uniformly dispersed 2 O 3 -Mn 2 O 3 A nanotube. The specific procedures and methods are essentially the same as those of example 8, exceptThe same is that 10% tetrabutyl titanate is required to replace the Mn salt in step 2, and the calcination process is added.
Example 10
Synthesis of Ga 2 O 3 -Mn 2 O 3 A method of nanotube. It is characterized by that it uses simple method to conveniently synthesize Ga with uniform appearance 2 O 3 -Mn 2 O 3 A nanotube. The procedure and method were substantially the same as in example 9, except that the aluminum salt was replaced with a gallium salt.

Claims (8)

1. A method for synthesizing basic gallium carbonate or basic aluminum carbonate salt nanotubes and corresponding metal oxide nanotubes is characterized by comprising the following steps:
1) dissolving gallium salt or aluminum salt in water, adding 0.5-2.5 g urea under stirring, and continuing stirring for 30 min;
2) adjusting pH of the above solution to 7-8 with ammonia water, adding urease for hydrolyzing urea, stirring for 30 min, placing into a polytetrafluoroethylene lined reaction kettle, and adding into a reactor with 37 deg.C o C, reacting in an oven for 24 hours;
3) collecting the precipitate obtained by centrifugation, washing the precipitate with water until the supernatant is neutral, and drying the precipitate in vacuum to obtain basic gallium carbonate salt or basic aluminum carbonate salt nanotube;
4) the basic gallium carbonate salt or the basic aluminum carbonate salt nanotube is placed in a 500-1000 o And C, respectively obtaining gallium oxide or aluminum oxide nanotubes after calcination.
2. The method of synthesizing nanotubes of claim 1, wherein: firstly adopting urea enzymolysis method 37 o The main component of the composition under C is NH 4 Ga(OH) 2 CO 3 Or NH 4 Al(OH) 2 CO 3 Then 500 times through 1000 times o And C, calcining to obtain the corresponding metal oxide nanotube.
3. The method of synthesizing nanotubes of claim 1, wherein: the length of the synthesized basic gallium carbonate or basic aluminum carbonate salt nanotube is 500-2000 nm.
4. The method of synthesizing nanotubes of claim 1, wherein: the yield of the basic gallium carbonate or basic aluminum carbonate nanotube is 50-80%.
5. Synthetic NH 4 Ga(OH) 2 CO 3 -NH 4 Al(OH) 2 CO 3 The nanotube preparation method is characterized by comprising the following steps:
1) preparing a solution A: dissolving gallium salt in water, adding 0.5-2.5 g of urea while stirring, adjusting the pH of the system to 7-8 by using ammonia water, and adding urease for urea enzymolysis;
2) preparing a solution B: dissolving aluminum salt in water, and adding 0.5-2.5 g of urea under stirring;
3) adding the solution B into a separating funnel, slowly dripping the solution B into the solution A kept stirring at a constant speed, keeping the dripping process for 40 min, and keeping stirring for 30 min after finishing dripping;
4) putting the mixed solution into a polytetrafluoroethylene lined reaction kettle, and putting the polytetrafluoroethylene lined reaction kettle into the reaction kettle to form a polytetrafluoroethylene lining o C, reacting in an oven for 24 hours;
5) the precipitate obtained from the reaction was collected by centrifugation, washed with water until the supernatant was neutral, and dried under vacuum.
6. Synthesis of NH 4 Al(OH) 2 CO 3 -TiO 2 The nanotube preparing process includes the following steps:
1) dissolving aluminum salt in water, adding 0.5-2.5 g of urea while stirring, adjusting the pH of the system to 7-8 with ammonia water, adding urease for urea enzymolysis, and stirring for 30 min;
2) preparing 10% v/v ethanol solution of tetrabutyl titanate, and slowly dripping the ethanol solution into the solution in the step 1);
3) stirring for 30 min, placing into a reaction kettle with polytetrafluoroethylene lining, and adding into a reactor with a polytetrafluoroethylene lining o C, reacting in an oven for 24 hours;
4) the obtained precipitate was collected by centrifugation, washed with water until the supernatant was neutral, and dried under vacuum.
7. ASynthesized Al 2 O 3 -Mn 2 O 3 The nanotube preparation method is characterized by comprising the following steps:
1) dissolving aluminum salt in water, adding 0.5-2.5 g of urea while stirring, adjusting the pH of the system to 7-8 with ammonia water, adding urease for urea enzymolysis, and stirring for 30 min;
2) preparing manganese salt solution, and slowly dripping the manganese salt solution into the solution in the step 1);
3) stirring for 30 min, placing into a polytetrafluoroethylene lined reaction kettle, and adding into a reactor with 37 deg.C o C, reacting in an oven for 24 hours;
4) centrifuging and collecting the obtained precipitate, washing with water until the supernatant is neutral, and vacuum drying;
5) the dried product is treated at 500-1000 o And C, calcining.
8. Synthesis of Ga 2 O 3 -Mn 2 O 3 The nanotube preparation method is characterized by comprising the following steps:
1) dissolving gallium salt in water, adding 0.5-2.5 g of urea while stirring, adjusting the pH of the system to 7-8 with ammonia water, adding urease for urea enzymolysis, and stirring for 30 min;
2) preparing manganese salt solution, and slowly dripping the manganese salt solution into the solution in the step 1);
3) stirring for 30 min, placing into a reaction kettle with polytetrafluoroethylene lining, and adding into a reactor with a polytetrafluoroethylene lining o C, reacting in an oven for 24 hours;
4) centrifuging and collecting the obtained precipitate, washing with water until the supernatant is neutral, and vacuum drying;
5) the dried product is treated at 500-1000 o And C, calcining.
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