CN110695370B - Copper-based nano composite material and preparation method and application thereof - Google Patents
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Abstract
The invention belongs to the field of food detection and nano material synthesis, and particularly discloses a copper-based nano composite material and a preparation method and detection application thereof. The copper-based nano composite material takes a waste egg membrane as a template; and then reducing the copper salt into copper nano particles by taking the plant extract as a reducing agent, thereby obtaining the copper nano particles. The copper-based nanocomposite material has high efficiency and sensitivity on nitrite detection, strong anti-interference capability and wide application prospect. The preparation material is easy to obtain, the requirements on the preparation process and equipment are simple, the material has no pollution to the environment, and the cost is low.
Description
Technical Field
The invention belongs to the technical field of food detection and nano materials, and particularly relates to a copper-based nano composite material, a preparation method thereof and application of the copper-based nano composite material in electrochemical detection of nitrous acid.
Background
Nitrite is a dangerous potential inorganic pollutant, widely present in the environment, food, industrial and physiological systems. Under the acidic conditions in the stomach, nitrite, when combined with secondary and tertiary amines present in food, is readily converted to carcinogenic N-nitrosamines, resulting in gastric cancer. Importantly, nitrite ions are considered to be one of the major hazardous contaminants in wastewater production from nuclear power plants. It causes corrosive behavior when dissolved in water and acts as an environmentally harmful substance for the degradation of some essential fertilizers. In addition, nitrite is often used as a food additive because it is effective in preventing food poisoning by microorganisms. Therefore, there is a need to detect and monitor nitrite concentration levels in environmental and physiological systems. Therefore, the development of sophisticated analytical techniques for studying nitrite ion determination has become critical to the environment and human health in recent years.
The problem of nitrite has attracted considerable attention and there are many methods available for detecting nitrite. Generally, methods for measuring nitrite include spectroscopic methods, gas chromatography, high performance liquid chromatography, chemical reagent methods, capillary electrophoresis, and electrochemical methods. Among them, the electrochemical method has many advantages due to its simple manufacture, rapid reaction, high sensitivity and low cost. Thus, electrochemical methods have recently attracted a great deal of attention to the development of high performance nitrite sensors.
The choice of copper nanoparticles is inspired by comparison with various noble metal (Au, ag, pd and Pt) nanoparticles and is valued for numerous applications due to their low cost, high catalytic, optical, electrical conductivity and antibacterial properties. Furthermore, the production of nanomaterials without compromising the environment or human health is of greater importance in order to provide a sustainable solution to environmental related problems.
Natural biomaterials have many fine hierarchical structures that cannot be mimicked by human techniques. These peculiar geometries and surface morphologies make biomaterials ideal templates for the synthesis of different nanomaterials with uniform size and complex structure. The eggshell membrane is an environmental waste, has a uniform microporous structure and an interwoven fiber network, and is a good template for constructing a three-dimensional nano structure. The waste eggshell membrane is fully utilized as a biological template to construct the nano material with high added value, and the requirement of current green development is met.
In conclusion, the invention utilizes the special fiber net structure of the eggshell membrane to synthesize the copper nanoparticles in situ. The unique three-dimensional structure can provide more adsorption sites and larger specific surface area for electrochemical reaction. In addition, unlike nanoparticles that are generally deactivated by aggregation, porous networks have a rigid structure such that they are not deactivated by aggregation. These excellent characteristics make it an efficient and durable electrocatalytic interface material useful for the catalytic oxidation of nitrites. Based on this, we developed an electrochemical nitrite sensor with high sensitivity and selectivity.
Disclosure of Invention
Aiming at the defects of the existing nitrite detection technology, the invention provides a copper-based nano composite material.
The invention also aims to provide the preparation method of the copper-based nano composite material, which has the advantages of easy material obtaining, simple preparation process and equipment requirements, no environmental pollution and low cost.
It is a further object of the present invention to provide the use of the above copper-based nanocomposite.
The purpose of the invention is realized by the following technical scheme:
the copper-based nano composite material for detecting nitrite is prepared by taking an eggshell membrane as a carrier and then taking plant substances as a reducing agent to reduce a copper salt solution into copper nano particles in situ.
Preferably, the copper-based nanocomposite is prepared by using an eggshell membrane as a template.
Preferably, the eggshell membrane comprises any one of an eggshell membrane, a duck eggshell membrane and a goose eggshell membrane.
Preferably, the concentration of the copper salt solution is 0.01-0.1M, preferably 0.05M.
Preferably, the concentration of the plant reducing agent extracting solution is 0.1-1 g/mL, and the plant reducing agent extracting solution is a root, stem and leaf extracting solution of cinnamomum camphora, platycladus orientalis, eucalyptus, green tea, mint or lemon.
The preparation method of the copper-based nanocomposite comprises the following specific steps:
(1) Egg shell membrane pretreatment: collecting waste egg shells, repeatedly washing the collected egg shells with clear water, soaking the collected egg shells in the clear water for 1-5 hours at room temperature, tearing off egg shell membranes from the soaked egg shells with tweezers, and washing the egg shells for later use;
(2) Preparing an eggshell membrane carrier: taking the eggshell membrane obtained in the step (1), soaking the eggshell membrane in a hydrochloric acid solution for 12-24 hours, taking out the eggshell membrane, drying the eggshell membrane, and grinding the eggshell membrane by using a grinder to obtain an eggshell membrane carrier;
(3) Copper ion adsorption: immersing the eggshell membrane carrier obtained in the step (2) into a copper salt solution, and immersing at room temperature for 12-24 h to absorb copper ions onto the eggshell membrane carrier;
(4) In-situ reduction of copper nanoparticles: soaking the eggshell membrane carrier adsorbed with the copper ions obtained in the step (3) in a plant extract at room temperature, reducing the copper ions into copper nanoparticles in situ, filtering the eggshell membrane loaded with the copper nanoparticles, and drying;
(5) Preparing the composite copper nano material loaded by the eggshell membrane: and (3) placing the eggshell membrane loaded with the copper nanoparticles dried in the step (4) in a muffle furnace to calcine at 100-300 ℃ for 2-5 h, and obtaining the copper-based nanocomposite material with the copper nanoparticles loaded with the mass percent of 0.1-3.0%.
Preferably, the soaking time in the step (4) is 24 to 48 hours.
The copper-based nanocomposite material is applied to detection of nitrite in food.
Compared with the prior art, the invention has the following beneficial effects:
1. the carrier used by the copper-based nano composite material is the waste eggshell membrane, the raw material source is wide, the cost is low, no pollution is generated, and the recycling of biological waste can be realized;
2. the copper-based nano material prepared by the invention has the advantages that the weight percentage of copper load is controlled to be 0.1-3.0%, and the nitrite can be detected to be 0.63 mu M at the lowest, thereby showing good detectability.
3. The invention has the advantages of easily obtained preparation materials, simple preparation process and equipment requirements and mild reaction conditions.
Drawings
FIG. 1 is a schematic representation of a copper-based powdery nanocomposite prepared in example 5 of the present invention;
FIG. 2 is a scanning electron microscope image of a copper-based nanocomposite prepared in example 5 of the present invention;
FIG. 3 is a cyclic voltammetry curve of the copper-based nanocomposite prepared in example 5 of the present invention for detecting nitrite.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
Example 1
A copper-based nano composite material for detecting nitrite is prepared by taking an eggshell membrane as a carrier and reducing a copper salt solution into copper nano particles in situ by using a reducing agent.
A preparation method of a copper-based nanocomposite material for nitrite detection comprises the following steps:
(1) Egg shell membrane pretreatment: collecting the waste egg shells; repeatedly washing the collected eggshells with clear water, and soaking the eggshells in the clear water for 1 hour at room temperature; tearing off the egg membrane from the soaked egg shell by using tweezers, and cleaning for later use;
(2) Preparing an eggshell membrane carrier: soaking the eggshell membrane obtained in the step (1) in a hydrochloric acid solution for 12 hours, taking out and drying, and grinding the eggshell membrane as small as possible by using a grinder to obtain an eggshell membrane carrier;
(3) Copper ion adsorption: soaking the 1 g eggshell membrane carrier obtained in the step (2) into 50 mL of 0.01M copper chloride solution, soaking 20 h at room temperature, and adsorbing copper ions onto the eggshell membrane carrier;
(4) In-situ reduction of copper nanoparticles: soaking the eggshell membrane carrier adsorbed with the copper ions obtained in the step (3) in 25 mL of 0.1 g/mL of cinnamomum camphora extracting solution at room temperature, reducing the copper ions into copper nanoparticles in situ, filtering the eggshell membrane loaded with the copper nanoparticles, and drying;
(5) Preparing the composite copper nano material loaded by the eggshell membrane: and (5) placing the eggshell membrane loaded with the copper nanoparticles dried in the step (4) in a muffle furnace to calcine at 100 ℃ for 2 h, and obtaining the composite copper nano material with the copper nanoparticles loaded with the mass percent of 0.1%.
The copper-based nano material prepared by the method is applied to nitrite detection.
The method for using the copper-based nano material for nitrite comprises the following steps:
1. taking 6 mg as the copper-based nano composite material, adding 3 mL deionized water, and carrying out ultrasonic treatment in an ultrasonic machine for 1 hour to obtain a mixed solution;
2. dripping 5 mu L of the mixed solution on the surface of the electrode, drying at room temperature, and storing the electrode in a refrigerator at 4 ℃ for later use;
3. a10 mL,0.5 mM nitrite solution was prepared and the cyclic voltammogram was measured in the electrochemical workstation.
Example 2
A copper-based nano material for nitrite detection is prepared by taking an eggshell membrane as a carrier; and reducing the copper salt solution into copper nano particles in situ by using a reducing agent.
A preparation method of a copper-based nano material for nitrite detection comprises the following steps:
(1) Egg shell membrane pretreatment: collecting waste duck egg shells; repeatedly washing the collected eggshells with clear water, and soaking the eggshells in the clear water for 2 hours at room temperature; tearing the duck egg membrane from the soaked duck egg shell by using a pair of tweezers, and cleaning for later use;
(2) Preparing an eggshell membrane carrier: taking the eggshell membrane obtained in the step (1), soaking the eggshell membrane into a hydrochloric acid solution for 14 hours, taking out and drying the eggshell membrane, and grinding the eggshell membrane by a grinder as small as possible to obtain an eggshell membrane carrier;
(3) Copper ion adsorption: soaking the 1 g eggshell membrane carrier obtained in the step (2) into 50 mL of 0.02M copper nitrate solution, soaking 22 h at room temperature, and adsorbing copper ions onto the eggshell membrane carrier;
(4) In-situ reduction of copper nanoparticles: soaking the eggshell membrane carrier adsorbed with the copper ions obtained in the step (3) in 25 mL of 0.1 g/mL of arborvitae extract at room temperature, reducing the copper ions into copper nanoparticles in situ, filtering the eggshell membrane loaded with the copper nanoparticles, and drying;
(5) Preparing the composite copper nano material loaded by the eggshell membrane: and (3) placing the eggshell membrane loaded with the copper nanoparticles dried in the step (4) in a muffle furnace to calcine at 200 ℃ for 2 h, and obtaining the composite copper nano material with the copper nanoparticles loaded with 1% by mass.
The copper-based nano material prepared by the method is applied to nitrite detection.
The method for using the copper-based nano material for nitrite comprises the following steps:
1. taking 4 mg as the prepared copper-based nano material, adding 2 mL deionized water, and carrying out ultrasonic treatment in an ultrasonic machine for 2 hours to prepare a mixed solution;
2. dripping 10 mu L of the mixed solution on the surface of the electrode, drying at room temperature, and storing the electrode in a refrigerator at 4 ℃ for later use;
3. a10 mL,0.6 mM nitrite solution was prepared and the cyclic voltammogram was measured in the electrochemical workstation.
Example 3
A copper-based nano material for detecting nitrite is prepared by taking an eggshell membrane as a carrier; and reducing the copper salt solution into copper nano particles in situ by using a reducing agent.
A preparation method of a copper-based nano material for nitrite detection comprises the following steps:
(1) Egg shell membrane pretreatment: collecting waste goose eggshells; repeatedly washing the collected goose eggshells with clear water, and soaking the collected goose eggshells in clear water for 3 hours at room temperature; tearing off the goose egg membrane from the soaked goose egg shell by using a pair of tweezers, and cleaning for later use;
(2) Preparing an eggshell membrane carrier: taking the eggshell membrane obtained in the step (1), soaking the eggshell membrane into a hydrochloric acid solution for 15 hours, taking out and drying the eggshell membrane, and grinding the eggshell membrane by a grinder as small as possible to obtain an eggshell membrane carrier;
(3) Copper ion adsorption: soaking the 1 g eggshell membrane carrier obtained in the step (2) into 50 mL of 0.02M copper sulfate solution, soaking 24 h at room temperature, and adsorbing copper ions onto the eggshell membrane carrier;
(4) In-situ reduction of copper nanoparticles: soaking the eggshell membrane carrier adsorbed with the copper ions obtained in the step (3) in 40 mL of 0.5 g/mL green tea extract at room temperature, reducing the copper ions into copper nanoparticles in situ, filtering the eggshell membrane loaded with the copper nanoparticles, and drying;
(5) Preparing the composite copper nano material loaded by the eggshell membrane: and (3) placing the eggshell membrane loaded with the copper nanoparticles dried in the step (4) in a muffle furnace to calcine at 300 ℃ for 2 h, and obtaining the composite copper nano material with the copper nanoparticles loaded with 2% by mass.
The copper-based nano material prepared by the method is applied to nitrite detection.
The method for using the copper-based nano material for nitrite comprises the following steps:
1. taking 8 mg as the prepared copper-based nano material, adding 4 mL deionized water, and carrying out ultrasonic treatment in an ultrasonic machine for 3 hours to prepare a mixed solution;
2. dripping 15 mu L of mixed liquid on the surface of the electrode, drying at room temperature, and storing the electrode in a refrigerator at 4 ℃ for later use;
3. a10 mL,0.4 mM nitrite solution was prepared and the cyclic voltammogram was measured in the electrochemical workstation.
Example 4
A copper-based nano material for nitrite detection is prepared by taking an eggshell membrane as a carrier; and reducing the copper chloride solution into copper nanoparticles in situ by using a reducing agent.
A preparation method of a copper-based nano material for nitrite detection comprises the following steps:
(1) Egg shell membrane pretreatment: collecting the waste egg shells; repeatedly washing the collected eggshells with clear water, and soaking the eggshells in the clear water for 4 hours at room temperature; tearing off the egg membrane from the soaked egg shell by using forceps, and cleaning for later use;
(2) Preparing an eggshell membrane carrier: soaking the eggshell membrane obtained in the step (1) in a hydrochloric acid solution for 16 hours, taking out and drying, and grinding the eggshell membrane as small as possible by using a grinder to obtain an eggshell membrane carrier;
(3) Copper ion adsorption: immersing the 1 g eggshell membrane carrier obtained in the step (2) into 50 mL of 0.02M copper chloride solution, immersing 18 h at room temperature, and adsorbing copper ions onto the eggshell membrane carrier;
(4) In-situ reduction of copper nanoparticles: soaking the eggshell membrane carrier adsorbed with the copper ions obtained in the step (3) in 35 mL of 0.1 g/mL mint extracting solution at room temperature, reducing the copper ions into copper nanoparticles in situ, filtering the eggshell membrane loaded with the copper nanoparticles, and drying;
(5) Preparing the composite copper nano material loaded by the eggshell membrane: and (5) placing the eggshell membrane loaded with the copper nanoparticles dried in the step (4) in a muffle furnace to calcine at 200 ℃ for 3 h, and obtaining the composite copper nano material with 1.4% of copper nanoparticles in load mass percentage.
The copper-based nano material prepared by the method is applied to nitrite detection.
The method for using the copper-based nano material for nitrite comprises the following steps:
1. 3 mg of the prepared copper-based nano material is taken, 1 mL deionized water is added, and ultrasonic treatment is carried out in an ultrasonic machine for 4 hours to prepare mixed liquid;
2. dripping 5 mu L of the mixed solution on the surface of the electrode, drying at room temperature, and storing the electrode in a refrigerator at 4 ℃ for later use;
3. a10 mL,0.3 mM nitrite solution was prepared and the cyclic voltammogram was measured in the electrochemical workstation.
Example 5
A copper-based nano material for nitrite detection is prepared by taking an eggshell membrane as a carrier; and reducing the copper salt solution into copper nano particles in situ by using a reducing agent.
A preparation method of a copper-based nano material for nitrite detection comprises the following steps:
(1) Egg shell membrane pretreatment: collecting the waste egg shells; repeatedly washing the collected eggshells with clear water, and soaking the eggshells in the clear water for 5 hours at room temperature; tearing the duck egg membrane from the soaked duck egg shell by using a pair of tweezers, and cleaning for later use;
(2) Preparing an eggshell membrane carrier: soaking the eggshell membrane obtained in the step (1) in a hydrochloric acid solution for 24 hours, taking out and drying, and grinding the eggshell membrane as small as possible by using a grinder to obtain an eggshell membrane carrier;
(3) Copper ion adsorption: soaking the 1 g eggshell membrane carrier obtained in the step (2) into 50 mL of 0.05M copper nitrate solution, soaking the carrier into 24 h at room temperature, and adsorbing copper ions onto the eggshell membrane carrier;
(4) In-situ reduction of copper nanoparticles: soaking the eggshell membrane carrier adsorbed with the copper ions obtained in the step (3) in 50 mL of 0.3 g/mL eucalyptus leaf extracting solution at room temperature, reducing the copper ions into copper nanoparticles in situ, filtering the eggshell membrane loaded with the copper nanoparticles, and drying;
(5) Preparing the composite copper nano material loaded by the eggshell membrane: and (3) placing the eggshell membrane loaded with the copper nanoparticles dried in the step (4) in a muffle furnace to calcine 5 h at 300 ℃ to obtain the composite copper nanomaterial with the copper nanoparticles loaded with the mass percentage of 3%.
The copper-based nano material prepared by the method is applied to nitrite detection.
The method for using the copper-based nano material for nitrite comprises the following steps:
1. taking 10 mg as the prepared copper-based nano material, adding 5 mL deionized water, and performing ultrasonic treatment in an ultrasonic machine for 5 hours to prepare a mixed solution;
2. dripping 10 mu L of mixed liquid on the surface of the electrode, drying at room temperature, and storing the electrode in a refrigerator at 4 ℃ for later use;
3. a10 mL,0.7 mM nitrite solution was prepared and the cyclic voltammogram was measured in the electrochemical workstation.
FIG. 2 is a scanning electron microscope image of the copper-based nanocomposite material of the present invention, from which we can see that a large amount of copper-based nanocomposite is loaded on the surface of the eggshell membrane.
FIG. 3 is a cyclic voltammetry curve of the copper-based nanocomposite for detecting nitrite in accordance with the present invention; from the figure we can see a distinct nitrite oxidation peak, indicating that the material can be used for nitrite detection.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (1)
1. The application of the copper-based nano composite material is characterized in that: the copper-based nano composite material is applied to detection of nitrite in food;
the copper-based nano composite material is prepared by taking an eggshell membrane as a carrier and then reducing a copper salt solution into copper nano particles in situ by taking a vegetable matter extracting solution as a reducing agent;
the copper-based nano composite material takes an eggshell membrane as a template; the eggshell membrane comprises any one of egg membrane, duck egg membrane and goose egg membrane; the concentration of the copper salt solution is 0.01-0.1M; the vegetable matter extracting solution is an extracting solution of cinnamomum camphora, platycladus orientalis, eucalyptus, green tea, mint or lemon, and the concentration of the vegetable matter extracting solution is 0.1-1 g/mL;
the method comprises the following specific steps:
(1) Egg shell membrane pretreatment: collecting waste egg shells, repeatedly washing the collected egg shells with clear water, soaking the collected egg shells in the clear water for 1-5 hours at room temperature, tearing off egg shell membranes from the soaked egg shells with tweezers, and washing the egg shells for later use;
(2) Preparing an eggshell membrane carrier: taking the eggshell membrane obtained in the step (1), soaking the eggshell membrane in a hydrochloric acid solution for 12-24 hours, taking out the eggshell membrane, drying the eggshell membrane, and grinding the eggshell membrane by using a grinder to obtain an eggshell membrane carrier;
(3) Copper ion adsorption: immersing the eggshell membrane carrier obtained in the step (2) into a copper salt solution, and immersing at room temperature for 12-24 h to absorb copper ions onto the eggshell membrane carrier;
(4) In-situ reduction of copper nanoparticles: soaking the eggshell membrane carrier adsorbed with the copper ions obtained in the step (3) in a plant extract at room temperature, reducing the copper ions into copper nanoparticles in situ, filtering the eggshell membrane loaded with the copper nanoparticles, and drying;
(5) Preparing the composite copper nano material loaded by the eggshell membrane: placing the eggshell membrane loaded with the copper nanoparticles dried in the step (4) in a muffle furnace to calcine at 100-300 ℃ for 2-5 h, and obtaining the copper-based nanocomposite material with the copper nanoparticles loaded with the mass percent of 0.1-3.0%;
the soaking time in the step (4) is 12 to 48 hours.
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| JP2018137049A (en) * | 2017-02-20 | 2018-08-30 | 独立行政法人国立高等専門学校機構 | Fuel cell including electrolyte membrane comprising eggshell membrane |
| CN109540866A (en) * | 2018-11-30 | 2019-03-29 | 泉州师范学院 | A kind of compound gold nano-material and preparation method thereof for Detecting Pesticide |
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