CN109761257A - A kind of preparation method of the Calcium carbonate micro-nano material with multicore nested structure - Google Patents
A kind of preparation method of the Calcium carbonate micro-nano material with multicore nested structure Download PDFInfo
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- CN109761257A CN109761257A CN201910147002.6A CN201910147002A CN109761257A CN 109761257 A CN109761257 A CN 109761257A CN 201910147002 A CN201910147002 A CN 201910147002A CN 109761257 A CN109761257 A CN 109761257A
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Abstract
The invention discloses a kind of preparation methods of Calcium carbonate micro-nano material with multicore nested structure, it is spare that carbon ball template is prepared first, surfactant is dissolved in deionized water and forms solution, carbon ball template is added and forms dispersion liquid, calcium salt is dissolved in deionized water and forms solution, it is added in above-mentioned dispersion liquid, ultrasound terminates to be placed in water bath with thermostatic control, centrifuge washing and drying after stirring, 450-500 DEG C of calcining 2h will be warming up to the heating rate of 1-5 DEG C/min in air atmosphere after the grinding of obtained product, then cooled to room temperature obtains the Calcium carbonate micro-nano material with multicore nested structure.Calcium carbonate micro-nano material produced by the present invention with multicore nested structure have biggish specific surface area and more active sites, make its removal of heavy metal ions, drug loading and in terms of have a good application prospect.
Description
Technical field
The invention belongs to the synthesis technical fields of inorganic nanometer functional material, and in particular to one kind has multicore nested structure
Calcium carbonate micro-nano material preparation method.
Background technique
With the fast development of modern science and technology, the micro Nano material with core-shell structure is because of its unique property, example
Such as: small-size effect, skin effect, quantum size effect, macro quanta tunnel effect, Dielectric confinement effect feature are wide
General research, scientific circles and business circles worldwide all cause extensive pay attention to and in catalysis, energy storage, drug
Load and control release etc. are widely used.Multicore material is with its unique structure and the performance such as more shape of elaborate
Looks structure has the superiority such as higher specific surface area, more active sites, is considered as most promising micro-nano
One of material.It is made due to its complicated internal structure and the pore structure of classification for the micro Nano material of multicore nested structure
The great application potential in terms of as adsorbent.On the other hand, carbonate mineral is in removing heavy metal application, since ion is handed over
Change and surface precipitation mechanism and have and preferable remove efficiency.In addition this material hydrogen storage, in terms of also great potential.
Therefore, it is even more the target of present researcher that preparation, which has the micro Nano material of multicore nested structure,.However, since multicore is embedding
The complexity and resistance to control of this body structure of nested structure micro Nano material, the document reported both at home and abroad it at present are fewer and fewer.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of simple process, it is environmentally protective and it is low-cost have multicore
The preparation method of the Calcium carbonate micro-nano material of nested structure, this method prepare specific surface area by easy synthetic route
Greatly, selective good and good adsorption performance the Calcium carbonate micro-nano material with multicore nested structure.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of calcium carbonate with multicore nested structure
The preparation method of micro Nano material, it is characterised in that specific steps are as follows:
Step S1: taking 6g fructose to be dissolved in 50mL secondary water, and 100mL polytetrafluoroethyl-ne alkene reaction is transferred to after magnetic agitation 20min
In kettle, 180 DEG C are warming up to the rate of 5 DEG C/min and keeps 15h, then cooled to room temperature, dry system after centrifuge washing
It is spare to obtain carbon ball template;
Step S2: 2-12mmol surfactant being dissolved in 30mL deionized water and forms solution, is added after stirring 5-20min
The carbon ball template that 0.1-1g step S1 is obtained, continues ultrasound 10-50min after stirring 5-30min, and the surfactant is
SDS, PEG2000, PEG4000 or PEG6000;
Step S3: 0.01-0.1mol calcium salt being dissolved in deionized water and forms solution, is added to step S2 after stirring 5-20min
Obtained dispersion liquid continues ultrasound 10-50min after stirring 5-30min, and ultrasound terminates to be placed in 30-80 DEG C of water bath with thermostatic control,
Centrifuge washing after stirring 6-8h, then at 80 DEG C of dry 12h, the calcium salt is calcium chloride, calcium sulfate, calcium lactate or citric acid
Calcium;
Step S4: it is warming up to after the product that step S3 is obtained is ground in air atmosphere with the heating rate of 1-5 DEG C/min
450-500 DEG C of calcining 2h, then cooled to room temperature obtains the Calcium carbonate micro-nano material with multicore nested structure.
The nucleus number of multicore is 2-3 in Calcium carbonate micro-nano material of the present invention with multicore nested structure, more
Core is as made of nanometer little particle self assembly, and there is the average grain diameter of the Calcium carbonate micro-nano material of multicore nested structure to be for this
3-4μm。
Calcium carbonate micro-nano material of the present invention with multicore nested structure answering in heavy metal adsorption removal
With, this have the Calcium carbonate micro-nano material of multicore nested structure as adsorbent it is attainable to heavy metal lead ion most
Big adsorbance is 4125mg/g.
The invention has the following advantages: (1) experimentation of the present invention is simple, mild condition is environmental-friendly;(2) originally
Invention preparation cost is low, and the appearance structure that product is made is controllable, in order to increase absorption of the carbon ball to calcium salt, joined a certain amount of
Surfactant makes it be easier to self assembly generation coenocytism under calcination condition;(3) produced by the present invention to have multicore nested
The Calcium carbonate micro-nano material of structure has biggish specific surface area and more active sites, goes it in heavy metal ion
It removes, drug loading and catalyst etc. have a good application prospect.
Detailed description of the invention
Fig. 1 is the TEM figure of the Calcium carbonate micro-nano material of multicore nested structure made from the present invention implements 1.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
Step S1: taking 6g fructose to be dissolved in 50mL secondary water, and 100mL polytetrafluoroethyl-ne alkene reaction is transferred to after magnetic agitation 20min
In kettle, 180 DEG C are warming up to the rate of 5 DEG C/min and keeps 15h, then cooled to room temperature, dry system after centrifuge washing
It is spare to obtain the carbon ball template that average grain diameter is 5 μm;
Step S2: 2mM surfactant SDS being dissolved in 30mL deionized water and forms solution, and 0.1g step is added after stirring 5min
The carbon ball template that rapid S1 is obtained continues ultrasound 10min after stirring 10min;
Step S3: 0.01mol calcium chloride being dissolved in 30mL deionized water and forms solution, is added to step S2 after stirring 10min
Obtained dispersion liquid continues ultrasound 10min after stirring 10min, and ultrasound terminates to be placed in 30 DEG C of water bath with thermostatic control, after stirring 6h
Centrifuge washing, then at 80 DEG C of dry 12h;
Step S4: 450 DEG C are warming up to the heating rate of 1 DEG C/min in air atmosphere after the product that step S3 is obtained is ground
2h is calcined, then cooled to room temperature obtains the Calcium carbonate micro-nano material with multicore nested structure.
Fig. 1 is the TEM figure of the present embodiment Calcium carbonate micro-nano material obtained with multicore nested structure, as seen from the figure
The nucleus number of multicore is 3 in Calcium carbonate micro-nano material obtained with multicore nested structure, and multicore is by nanometer little particle
Made of self assembly, it is 3-4 μm that this, which has the average grain diameter of the Calcium carbonate micro-nano material of multicore nested structure, is used for inhaling
In the experiment of attached heavy metal ion, this has the Calcium carbonate micro-nano material of multicore nested structure attainable as adsorbent institute
Maximal absorptive capacity to heavy metal lead ion is 4125mg/g.
Embodiment 2
Step S1: taking 6g fructose to be dissolved in 50mL secondary water, and 100mL polytetrafluoroethyl-ne alkene reaction is transferred to after magnetic agitation 20min
In kettle, 180 DEG C are warming up to the rate of 5 DEG C/min and keeps 15h, then cooled to room temperature, dry system after centrifuge washing
It is spare to obtain the carbon ball template that average grain diameter is 5 μm;
Step S2: 4mM surfactant SDS being dissolved in 30mL deionized water and forms solution, and 0.2g step is added after stirring 5min
The carbon ball template that rapid S1 is obtained continues ultrasound 20min after stirring 10min;
Step S3: 0.025mol calcium chloride being dissolved in 30mL deionized water and forms solution, is added to step S2 after stirring 15min
Obtained dispersion liquid continues ultrasound 10min after stirring 10min, and ultrasound terminates to be placed in 40 DEG C of water bath with thermostatic control, after stirring 6h
Centrifuge washing, then at 80 DEG C of dry 12h;
Step S4: 450 DEG C are warming up to the heating rate of 1 DEG C/min in air atmosphere after the product that step S3 is obtained is ground
2h is calcined, then cooled to room temperature obtains the Calcium carbonate micro-nano material with multicore nested structure.
Embodiment 3
Step S1: taking 6g fructose to be dissolved in 50mL secondary water, and 100mL polytetrafluoroethyl-ne alkene reaction is transferred to after magnetic agitation 20min
In kettle, 180 DEG C are warming up to the rate of 5 DEG C/min and keeps 15h, then cooled to room temperature, dry system after centrifuge washing
It is spare to obtain the carbon ball template that average grain diameter is 5 μm;
Step S2: 6mM surfactant SDS being dissolved in 30mL deionized water and forms solution, and 0.4g step is added after stirring 5min
The carbon ball template that rapid S1 is obtained continues ultrasound 30min after stirring 15min;
Step S3: 0.04mol calcium sulfate being dissolved in 30mL deionized water and forms solution, is added to step S2 after stirring 10min
Obtained dispersion liquid continues ultrasound 10min after stirring 10min, and ultrasound terminates to be placed in 50 DEG C of water bath with thermostatic control, after stirring 6h
Centrifuge washing, then at 80 DEG C of dry 12h;
Step S4: 450 DEG C are warming up to the heating rate of 3 DEG C/min in air atmosphere after the product that step S3 is obtained is ground
2h is calcined, then cooled to room temperature obtains the Calcium carbonate micro-nano material with multicore nested structure.
Embodiment 4
Step S1: taking 6g fructose to be dissolved in 50mL secondary water, and 100mL polytetrafluoroethyl-ne alkene reaction is transferred to after magnetic agitation 20min
In kettle, 180 DEG C are warming up to the rate of 5 DEG C/min and keeps 15h, then cooled to room temperature, dry system after centrifuge washing
It is spare to obtain the carbon ball template that average grain diameter is 5 μm;
Step S2: 8mM Surfactant PEG 4000 being dissolved in 30mL deionized water and forms solution, is added after stirring 15min
The carbon ball template that 0.6g step S1 is obtained continues ultrasound 40min after stirring 10min;
Step S3: 0.055mol calcium lactate being dissolved in 30mL deionized water and forms solution, is added to step S2 after stirring 5min
Obtained dispersion liquid continues ultrasound 10min after stirring 10min, and ultrasound terminates to be placed in 60 DEG C of water bath with thermostatic control, and stirring 8h is simultaneously
Centrifuge washing after standing 1h, then at 80 DEG C of dry 12h;
Step S4: 500 DEG C are warming up to the heating rate of 3 DEG C/min in air atmosphere after the product that step S3 is obtained is ground
2h is calcined, then cooled to room temperature obtains the Calcium carbonate micro-nano material with multicore nested structure.
Embodiment 5
Step S1: taking 6g fructose to be dissolved in 50mL secondary water, and 100mL polytetrafluoroethyl-ne alkene reaction is transferred to after magnetic agitation 20min
In kettle, 180 DEG C are warming up to the rate of 5 DEG C/min and keeps 15h, then cooled to room temperature, dry system after centrifuge washing
It is spare to obtain the carbon ball template that average grain diameter is 5 μm;
Step S2: 10mM Surfactant PEG 2000 being dissolved in 30mL deionized water and forms solution, is added after stirring 15min
The carbon ball template that 0.8g step S1 is obtained continues ultrasound 50min after stirring 5min;
Step S3: 0.08mol calcium lactate being dissolved in 30mL deionized water and forms solution, is added to step S2 after stirring 20min
Obtained dispersion liquid continues ultrasound 50min after stirring 10min, and ultrasound terminates to be placed in 70 DEG C of water bath with thermostatic control, after stirring 8h
Centrifuge washing, then at 80 DEG C of dry 12h;
Step S4: 500 DEG C are warming up to the heating rate of 3 DEG C/min in air atmosphere after the product that step S3 is obtained is ground
2h is calcined, then cooled to room temperature obtains the Calcium carbonate micro-nano material with multicore nested structure.
Embodiment 6
Step S1: taking 6g fructose to be dissolved in 50mL secondary water, and 100mL polytetrafluoroethyl-ne alkene reaction is transferred to after magnetic agitation 20min
In kettle, 180 DEG C are warming up to the rate of 5 DEG C/min and keeps 15h, then cooled to room temperature, dry system after centrifuge washing
It is spare to obtain the carbon ball template that average grain diameter is 5 μm;
Step S2: 12mM Surfactant PEG 6000 being dissolved in 30mL deionized water and forms solution, is added after stirring 20min
The carbon ball template that 1.0g step S1 is obtained continues ultrasound 10min after stirring 30min;
Step S3: 0.1mol calcium citrate being dissolved in 30mL deionized water and forms solution, is added to step S2 after stirring 10min
Obtained dispersion liquid continues ultrasound 50min after stirring 10min, and ultrasound terminates to be placed in 80 DEG C of water bath with thermostatic control, after stirring 8h
Centrifuge washing, then at 80 DEG C of dry 12h;
Step S4: 500 DEG C are warming up to the heating rate of 5 DEG C/min in air atmosphere after the product that step S3 is obtained is ground
2h is calcined, then cooled to room temperature obtains the Calcium carbonate micro-nano material with multicore nested structure.
A kind of preparation method of the Calcium carbonate micro-nano material of multicore nested structure provided by the invention is carried out above
It is detailed to introduce embodiment and describe basic principles and main features and advantage of the invention.The technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, the present invention also has several changes and improvements, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (3)
1. a kind of preparation method of the Calcium carbonate micro-nano material with multicore nested structure, it is characterised in that specific steps are as follows:
Step S1: taking 6g fructose to be dissolved in 50mL secondary water, and 100mL polytetrafluoroethyl-ne alkene reaction is transferred to after magnetic agitation 20min
In kettle, 180 DEG C are warming up to the rate of 5 DEG C/min and keeps 15h, then cooled to room temperature, dry system after centrifuge washing
It is spare to obtain carbon ball template;
Step S2: 2-12mmol surfactant being dissolved in 30mL deionized water and forms solution, is added after stirring 5-20min
The carbon ball template that 0.1-1g step S1 is obtained, continues ultrasound 10-50min after stirring 5-30min, and the surfactant is
SDS, PEG2000, PEG4000 or PEG6000;
Step S3: 0.01-0.1mol calcium salt being dissolved in deionized water and forms solution, is added to step S2 after stirring 5-20min
Obtained dispersion liquid continues ultrasound 10-50min after stirring 5-30min, and ultrasound terminates to be placed in 30-80 DEG C of water bath with thermostatic control,
Centrifuge washing after stirring 6-8h, then at 80 DEG C of dry 12h, the calcium salt is calcium chloride, calcium sulfate, calcium lactate or citric acid
Calcium;
Step S4: it is warming up to after the product that step S3 is obtained is ground in air atmosphere with the heating rate of 1-5 DEG C/min
450-500 DEG C of calcining 2h, then cooled to room temperature obtains the Calcium carbonate micro-nano material with multicore nested structure.
2. the preparation method of the Calcium carbonate micro-nano material according to claim 1 with multicore nested structure, feature
Be: the nucleus number of multicore is 2-3 in the Calcium carbonate micro-nano material with multicore nested structure, and multicore is by nanometer
Made of little particle self assembly, it is 3-4 μm that this, which has the size of the Calcium carbonate micro-nano material of multicore nested structure,.
3. the method according to claim 1 or 2 Calcium carbonate micro-nano material obtained with multicore nested structure is in weight
Application in metal adsorption removal, this has the Calcium carbonate micro-nano material of multicore nested structure attainable as adsorbent institute
Maximal absorptive capacity to heavy metal lead ion is 4125mg/g.
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115709084A (en) * | 2022-10-24 | 2023-02-24 | 河南师范大学 | Preparation method of Fe-Mo heterojunction multi-core micro-nano material based on sexual propagation yeast regulation |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110229640A1 (en) * | 2010-03-16 | 2011-09-22 | Korea Institute Of Geoscience And Mineral Resources | Fabrication method of calcium carbonate thin film with shape-controlled finestructure pattern using additive |
CN102423698A (en) * | 2011-11-07 | 2012-04-25 | 河南师范大学 | Sewage purification agent |
CN103159278A (en) * | 2013-04-07 | 2013-06-19 | 桂林理工大学 | Method for recovering Pb<2+> from electrolytic zinc rinsing wastewater with calcium-carbonate-modified kieselguhr |
CN103708523A (en) * | 2014-01-08 | 2014-04-09 | 河南师范大学 | Calcium carbonate micro-nano material with structure of multilayered shell and multistage compound pores |
CN103771479A (en) * | 2014-01-08 | 2014-05-07 | 河南师范大学 | Porous empty-shell calcium carbonate micro-nano material with hierarchical structure |
CN106882832A (en) * | 2017-03-29 | 2017-06-23 | 河南师范大学 | A kind of preparation method of calcium carbonate ghost micro Nano material |
-
2019
- 2019-02-27 CN CN201910147002.6A patent/CN109761257A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110229640A1 (en) * | 2010-03-16 | 2011-09-22 | Korea Institute Of Geoscience And Mineral Resources | Fabrication method of calcium carbonate thin film with shape-controlled finestructure pattern using additive |
CN102423698A (en) * | 2011-11-07 | 2012-04-25 | 河南师范大学 | Sewage purification agent |
CN103159278A (en) * | 2013-04-07 | 2013-06-19 | 桂林理工大学 | Method for recovering Pb<2+> from electrolytic zinc rinsing wastewater with calcium-carbonate-modified kieselguhr |
CN103708523A (en) * | 2014-01-08 | 2014-04-09 | 河南师范大学 | Calcium carbonate micro-nano material with structure of multilayered shell and multistage compound pores |
CN103771479A (en) * | 2014-01-08 | 2014-05-07 | 河南师范大学 | Porous empty-shell calcium carbonate micro-nano material with hierarchical structure |
CN106882832A (en) * | 2017-03-29 | 2017-06-23 | 河南师范大学 | A kind of preparation method of calcium carbonate ghost micro Nano material |
Non-Patent Citations (1)
Title |
---|
邓琴等: "CaCO3 微球吸附重金属的性能机理研究", 《水处理技术》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115709084A (en) * | 2022-10-24 | 2023-02-24 | 河南师范大学 | Preparation method of Fe-Mo heterojunction multi-core micro-nano material based on sexual propagation yeast regulation |
CN115709084B (en) * | 2022-10-24 | 2024-02-06 | 河南师范大学 | Preparation method of Fe-Mo heterojunction polynuclear micro-nano material based on sexual propagation yeast regulation and control |
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