CN104907085A - Preparation method for copper sulphide-montmorillonite nano composite material - Google Patents
Preparation method for copper sulphide-montmorillonite nano composite material Download PDFInfo
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- CN104907085A CN104907085A CN201510239602.7A CN201510239602A CN104907085A CN 104907085 A CN104907085 A CN 104907085A CN 201510239602 A CN201510239602 A CN 201510239602A CN 104907085 A CN104907085 A CN 104907085A
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Abstract
The invention discloses a preparation method for a copper sulphide-montmorillonite nano composite material. The preparation method comprises the following steps: montmorillonite is dissolved in distilled water, magnetic stirring is carried out, thus montmorillonite is dispersed uniformly, and a montmorillonite suspension is obtained; a water-soluble copper salt solution is prepared and is added into the montmorillonite suspension dropwise, stirring is carried out continuously and a solution A is obtained; a hydrochloric acid solution is added in thioacetamide, and a solution B is obtained; the solution A and the solution B are placed in a sealed container, a reaction is carried out with stirring for 12-24h at a room temperature, then centrifugal washing and drying are carried out, and a copper sulphide-montmorillonite nano composite material is prepared. In the preparation method, montmorillonite is employed as carriers, the prepared copper sulphide-montmorillonite nano composite material has advantages of high purity, small size, good catalytic activity and the like, and has good peroxidase-like activity. The nano composite material has characteristics of simple stable high sensitivity high selectivity and the like when the nano composite material as a biosensor is applied for detection of hydrogen peroxide.
Description
Technical field
The present invention relates to a kind of preparation method of copper sulfide-imvite (CuS-MMT) nano composite material, belong to the preparing technical field of nano composite material.
Background technology
As the very important semiconductor nano material of one, metal sulfide semiconductor nanometer material, owing to having unique physico-chemical property and huge market application potential, is quite subject to the attention of scientific research personnel in recent years.
Copper sulfide is as a kind of important P-type semiconductor material, and its band gap width circle is between 1.2-2.0eV.In recent years, nanostructured CuS is because having the characteristics such as the little and specific area of particle diameter is large, and due to quantum size effect, skin effect and macro quanta tunnel effect, its semiconductor nanocrystal has the instrumentality of conduction electron between molecular entity and micromeritics, there is the photoelectric characteristic that its block materials is incomparable, be successfully applied to the various fields such as the high power capacity cathode material of solar cell, optical recording material, optical filter, nanotube switch, optical Limiting, gas sensor, thermoelectric-cooled material, superconductor and lithium ion battery.
But due to the easy absorption of single nano material, the shortcoming of easily reunion, cause its chemism position to be reduced, thus cause the reduction of its activity.In order to overcome this defect, sight has turned in the modification to metal sulfide by researchers.Such as, shitosan/Nano cadmium sulphide compound features has gone out the Congo red effect of higher visible light photocatalytic degradation better.
Imvite is the 2:1 type layer silicate mineral be made up of two-layer tetrahedral si-o film and one deck aluminum oxide octahedral sheet.Imvite has compared with excellent characteristics such as bigger serface, heat endurance, stronger adsorption capacity and even aperture distribution, and it is the rich reserves of imvite, widely distributed, cheap, become the focus of Material Field research, research mainly concentrates on catalyst and the field such as catalyst carrier and adsorbent.
Summary of the invention
Based on above-mentioned technical problem, the present invention adopts imvite to be prop carrier, provides a kind of preparation method of copper sulfide-Nano composite material of montmorillonite.
The technology used in the present invention solution is:
A preparation method for copper sulfide-Nano composite material of montmorillonite, comprises the following steps:
(1) choosing imvite, water-soluble mantoquita, thioacetamide and hydrochloric acid is raw material;
(2) be distributed in distilled water by imvite, magnetic agitation makes it be uniformly dispersed, and obtains montmorillonite suspension liquid;
(3) prepare water-soluble copper salting liquid, be dropwise added drop-wise in the montmorillonite suspension liquid of preparation in step (2), Keep agitation, obtains solution A;
(4) hydrochloric acid solution is joined in thioacetamide, obtain solution B;
(5) solution A and solution B are placed in airtight container simultaneously, react 12 ~ 24 hours under stirring at room temperature condition, then through centrifugal, washing, drying, obtained copper sulfide-Nano composite material of montmorillonite.
In step (1): described water-soluble mantoquita is preferably copper chloride, copper nitrate or copper acetate; Described water-soluble mantoquita and the consumption proportion of imvite are preferably 1: 3 ~ 1: 25, with parts by weight; Described water-soluble mantoquita and the mol ratio of thioacetamide are preferably 1: 6 ~ 1: 20; The mol ratio of described hydrochloric acid and thioacetamide is preferably greater than 1.2; The concentration of described hydrochloric acid solution is preferably 0.1 ~ 1mol/L.
In step (2): in described montmorillonite suspension liquid, the mass fraction of imvite is preferably 1%.
In step (3): in described water-soluble copper salting liquid, the mass fraction of mantoquita is preferably 0.5% ~ 2%.
In step (5): described baking temperature is preferably 50 ~ 80 DEG C; Described airtight container is preferably hermetically drying device or sealed reaction tank.
Advantageous Effects of the present invention is:
Compared with prior art, the present invention adopts imvite to be carrier, obtained copper sulfide-Nano composite material of montmorillonite has the advantages such as purity is high, size is little, catalytic activity is good, there is good class peroxidase activity, there is when being detected hydrogen oxide using it as colorimetric bio sensor easy, stable, highly sensitive, the selective feature such as by force.The present invention adopts one-step method to obtain product in addition, and the method has that preparation technology is simple, easy and simple to handle, cost is low, reaction condition is gentle and the advantage such as the reaction time is short.
Accompanying drawing explanation
Below in conjunction with accompanying drawing and detailed description of the invention, the invention will be further described:
Fig. 1 is the X-ray diffractogram of copper sulphide nano particles;
Fig. 2 is the X-ray diffractogram of copper sulfide-Nano composite material of montmorillonite that embodiment 1 obtains;
Fig. 3 is the transmission electron microscope picture of copper sulfide-Nano composite material of montmorillonite that embodiment 1 obtains;
Fig. 4 is the ultraviolet Absorbable rod spectrogram of differential responses system.
Detailed description of the invention
Embodiment 1
Take 0.3g imvite and be placed in beaker, add 30ml distilled water, magnetic agitation 18 hours, obtains homodisperse montmorillonite suspension liquid.Take 0.0256g copper chloride and be placed in another beaker, adding 5ml distilled water makes it dissolve completely, obtains copper chloride solution, is then dropwise added dropwise to by copper chloride solution in the montmorillonite suspension liquid under magnetic agitation condition, be added dropwise to complete rear continuation magnetic agitation 3 hours, obtain solution A.Be that the hydrochloric acid solution of 0.5mol/L joins in the thioacetamide of 0.1127g (1.5mmol) and forms solution B by 10ml concentration.Then solution A and solution B are placed in hermetically drying device simultaneously, react 24 hours under stirring at room temperature condition.Reaction terminates rear collection black precipitate, washing centrifugal with ultra-pure water, and drying obtains copper sulfide-Nano composite material of montmorillonite for 10 hours at 60 DEG C.
Test products obtained therefrom, result as shown in the figure.Fig. 1 is the X-ray diffractogram of copper sulphide nano particles, and as can be seen from Figure 1, the peak in spectrogram all corresponds to the diffraction maximum of copper sulfide; There is the characteristic peak of CuS at ° place, 2 θ=48.107 in Fig. 2, can learn that the successful load of CuS is in imvite.From Fig. 3 transmission electron microscope picture, obviously see that dark CuS particle is dispersed in imvite on the surface comparatively uniformly, more than can prove that CuS has loaded in imvite.
Embodiment 2
Take 0.3g imvite and be placed in beaker, add 30ml distilled water, magnetic agitation 18 hours, obtains homodisperse montmorillonite suspension liquid.Take 0.0127g copper chloride and be placed in another beaker, adding 5ml distilled water makes it dissolve completely, obtains copper chloride solution, is then dropwise added dropwise to by copper chloride solution in the montmorillonite suspension liquid under magnetic agitation condition, be added dropwise to complete rear continuation magnetic agitation 3 hours, obtain solution A.Be that the hydrochloric acid solution of 0.5mol/L joins in the thioacetamide of 0.1127g (1.5mmol) and forms solution B by 10ml concentration.Then solution A and solution B are placed in hermetically drying device simultaneously, react 24 hours under stirring at room temperature condition.Reaction terminates rear collection black precipitate, washing centrifugal with ultra-pure water, and drying obtains copper sulfide-Nano composite material of montmorillonite in 10 hours at 60 DEG C.
Embodiment 3
Take 0.3g imvite and be placed in beaker, add 30ml distilled water, magnetic agitation 18 hours, obtains homodisperse montmorillonite suspension liquid.Take 0.0511g copper chloride and be placed in another beaker, adding 5ml distilled water makes it dissolve completely, obtains copper chloride solution, is then dropwise added dropwise to by copper chloride solution in the montmorillonite suspension liquid under magnetic agitation condition, be added dropwise to complete rear continuation magnetic agitation 3 hours, obtain solution A.Be that the hydrochloric acid solution of 0.5mol/L joins in the thioacetamide of 0.1127g (1.5mmol) and forms solution B by 10ml concentration.Then solution A and solution B are placed in hermetically drying device simultaneously, react 20 hours under stirring at room temperature condition.Reaction terminates rear collection black precipitate, washing centrifugal with ultra-pure water, and drying obtains copper sulfide-Nano composite material of montmorillonite for 10 hours at 70 DEG C.
Embodiment 4
Take 0.3g imvite and be placed in beaker, add 30ml distilled water, magnetic agitation 18 hours, obtains homodisperse montmorillonite suspension liquid.Take 0.0767g copper chloride and be placed in another beaker, adding 5ml distilled water makes it dissolve completely, obtains copper chloride solution, is then dropwise added dropwise to by copper chloride solution in the montmorillonite suspension liquid under magnetic agitation condition, be added dropwise to complete rear continuation magnetic agitation 3 hours, obtain solution A.Be that the hydrochloric acid solution of 1mol/L joins in the thioacetamide of 0.1127g (1.5mmol) and forms solution B by 10ml concentration.Then solution A and solution B are placed in sealed reaction tank simultaneously, react 24 hours under stirring at room temperature condition.Reaction terminates rear collection black precipitate, washing centrifugal with ultra-pure water, and drying obtains copper sulfide-Nano composite material of montmorillonite for 10 hours at 65 DEG C.
On the basis of above-described embodiment, also need to illustrate as follows the present invention.
In above-described embodiment 1 ~ 4, raw materials used imvite etc. all can commercially obtain.The water-soluble mantoquita adopted in above-described embodiment also can be replaced copper nitrate or copper acetate.
The active colorimetric test of analogue enztme:
1. prepare the NaAc_HAc buffer solution A of pH=3.8;
2. the imvite taken prepared by embodiment 1 is that the copper sulphide nano particles 5.8mg of supporter is dissolved in 10ml redistilled water, makes it be uniformly dispersed, obtained solution B under ultrasound condition;
3. the hydrogen peroxide constant volume measuring 30% of 240 μ l is 10ml, is mixed with 0.25molL
-1solution C;
4. the TMB (3,3', 5,5'-tetramethyl benzidine) taking 2.4mg is dissolved in 10ml redistilled water, and being mixed with molar concentration is 0.76mmolL
-1solution D;
A: measure the cuvette that 1400 μ l A+200 μ l B+200 μ l C+200 μ l D are placed in 5ml with pipettor;
B: measure the cuvette that 1400 μ l A+200 μ l MMT (commercialization)+200 μ l C+200 μ l D are placed in 5ml with pipettor;
C: measure the cuvette that 1600 μ l A+200 μ l C+200 μ l D are placed in 5ml with pipettor;
D: measure the cuvette that 1600 μ l A+200 μ l B+200 μ l D are placed in 5ml with pipettor;
E: measure the cuvette that 1800 μ l A+200 μ l D are placed in 5ml with pipettor;
At room temperature react, observe and find: the display of liquid after one minute in a cuvette is significantly blue, and liquid color in b, c, d, e cuvette is unchanged; Liquid after ten minutes in b cuvette just can manifest slight color change, very slight color; Liquid after several hours in c cuvette can manifest slight color change, and d, e do not change all the time.
Interpretation of result: H
2o
2can be oxidized TMB produces significantly blue, as can be seen from above-mentioned experimental observations, compared to only adding the solution not adding catalysis analogue enztme in imvite and c in b, after adding copper sulfide-Nano composite material of montmorillonite in a, and H
2o
2change faster with the reaction color of TMB, illustrate that the copper sulfide-Nano composite material of montmorillonite prepared by the present invention serves good catalytic effect really, can be used as the analogue enztme of peroxidase.
Monitor five kinds of reaction systems with ultraviolet-visible spectrophotometer, result as shown in Figure 4 simultaneously.
Interpretation of result: corresponding above-mentioned colour developing change, in ultraviolet-visible spectrogram, b, c, d, e reaction system does not have obvious absworption peak, and be added with copper sulfide-Nano composite material of montmorillonite a system and have obvious absworption peak at 634nm place, further demonstrate the peroxidase activity of copper sulfide-Nano composite material of montmorillonite.
Claims (10)
1. a preparation method for copper sulfide-Nano composite material of montmorillonite, is characterized in that comprising the following steps:
(1) choosing imvite, water-soluble mantoquita, thioacetamide and hydrochloric acid is raw material;
(2) be distributed in distilled water by imvite, magnetic agitation makes it be uniformly dispersed, and obtains montmorillonite suspension liquid;
(3) prepare water-soluble copper salting liquid, be dropwise added drop-wise in the montmorillonite suspension liquid of preparation in step (2), Keep agitation, obtains solution A;
(4) hydrochloric acid solution is joined in thioacetamide, obtain solution B;
(5) solution A and solution B are placed in airtight container simultaneously, react 12 ~ 24 hours under stirring at room temperature condition, then through centrifugal, washing, drying, obtained copper sulfide-Nano composite material of montmorillonite.
2. the preparation method of a kind of copper sulfide-Nano composite material of montmorillonite according to claim 1, is characterized in that, in step (1): described water-soluble mantoquita is copper chloride, copper nitrate or copper acetate.
3. the preparation method of a kind of copper sulfide-Nano composite material of montmorillonite according to claim 1, is characterized in that, in step (1): described water-soluble mantoquita and the consumption proportion of imvite are 1: 3 ~ 1: 25, with parts by weight.
4. the preparation method of a kind of copper sulfide-Nano composite material of montmorillonite according to claim 1, is characterized in that, in step (1): described water-soluble mantoquita and the mol ratio of thioacetamide are 1: 6 ~ 1: 20.
5. the preparation method of a kind of copper sulfide-Nano composite material of montmorillonite according to claim 1, is characterized in that, in step (1): the mol ratio of described hydrochloric acid and thioacetamide is greater than 1.2.
6. the preparation method of a kind of copper sulfide-Nano composite material of montmorillonite according to claim 1, is characterized in that, in step (1): the concentration of described hydrochloric acid solution is 0.1 ~ 1mol/L.
7. the preparation method of a kind of copper sulfide-Nano composite material of montmorillonite according to claim 1, is characterized in that, in step (2): the mass fraction of imvite in described montmorillonite suspension liquid is 1%.
8. the preparation method of a kind of copper sulfide-Nano composite material of montmorillonite according to claim 1, is characterized in that, in step (3): in described water-soluble copper salting liquid, the mass fraction of mantoquita is 0.5% ~ 2%.
9. the preparation method of a kind of copper sulfide-Nano composite material of montmorillonite according to claim 1, is characterized in that, in step (5): described baking temperature is 50 ~ 80 DEG C.
10. the preparation method of a kind of copper sulfide-Nano composite material of montmorillonite according to claim 1, is characterized in that, in step (5): described airtight container is hermetically drying device or sealed reaction tank.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105403696A (en) * | 2015-12-11 | 2016-03-16 | 扬州大学 | Label-free chemiluminescent immunosensor based on nanometer mimic enzyme, and preparation and analysis methods thereof |
| CN109580607A (en) * | 2018-12-13 | 2019-04-05 | 泉州师范学院 | The preparation and its application of MXene-CuS nanocomposite |
| CN112374527A (en) * | 2020-11-16 | 2021-02-19 | 南昌航空大学 | Copper sulfide nano material with peroxidase-like characteristic and preparation method and application thereof |
| CN114377647A (en) * | 2022-01-20 | 2022-04-22 | 安徽工业大学 | Preparation method and application of modified attapulgite loaded ferrous sulfide |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105403696A (en) * | 2015-12-11 | 2016-03-16 | 扬州大学 | Label-free chemiluminescent immunosensor based on nanometer mimic enzyme, and preparation and analysis methods thereof |
| CN109580607A (en) * | 2018-12-13 | 2019-04-05 | 泉州师范学院 | The preparation and its application of MXene-CuS nanocomposite |
| CN109580607B (en) * | 2018-12-13 | 2021-06-29 | 泉州师范学院 | Preparation and application of MXene-CuS nano composite material |
| CN112374527A (en) * | 2020-11-16 | 2021-02-19 | 南昌航空大学 | Copper sulfide nano material with peroxidase-like characteristic and preparation method and application thereof |
| CN114377647A (en) * | 2022-01-20 | 2022-04-22 | 安徽工业大学 | Preparation method and application of modified attapulgite loaded ferrous sulfide |
| CN114377647B (en) * | 2022-01-20 | 2023-11-07 | 安徽工业大学 | Preparation method and application of modified attapulgite-loaded ferrous sulfide |
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Application publication date: 20150916 |