CN113466199A - Preparation of copper nanocluster and diatomite composite fluorescent sensor for detecting hexavalent chromium ions - Google Patents
Preparation of copper nanocluster and diatomite composite fluorescent sensor for detecting hexavalent chromium ions Download PDFInfo
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- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
A preparation method and an application of a copper nanocluster and diatomite composite fluorescence sensor relate to a preparation method and an application of a copper nanocluster and diatomite composite fluorescence sensor. The method can effectively solve the problems of low detection sensitivity and high detection cost in the detection method of the heavy metal hexavalent chromium ions in the water environment. The method comprises the following steps: dissolving a copper salt in deionized water to form a mixed solution, and performing ultrasonic treatment on the mixed solution to obtain a solution A; secondly, adding the solution A into a penicillamine aqueous solution, and stirring for 1-2 hours by using a magnetic stirrer to obtain a solution B; and thirdly, adding the diatomite into the solution B, and stirring for 1-2 hours by using a magnetic stirrer to obtain the copper nanocluster and diatomite composite fluorescent sensor with the hexavalent chromium ion detection function. The invention has low cost and high detection sensitivity, and the detection limit can reach 10 mu M. The method is used in the field of detection of the heavy metal hexavalent chromium ions in the water environment.
Description
Technical Field
The invention relates to a preparation method and application of a copper nanocluster and diatomite composite fluorescence sensor.
Background
The science and technology is a double-edged sword, the science and technology are rapidly developed after 20 th century, the economic development is promoted, the living standard of people is improved, and meanwhile, people pay disastrous cost. Due to the emission of the exhaust gas of the industrial three wastes (waste gas, waste water and industrial residue), the irrigation of sewage, the use of pesticides, herbicides, fertilizers and the like and the development of mining industry, the soil, the water quality and the atmosphere are seriously polluted. Heavy metal contamination refers to environmental contamination caused by heavy metals or compounds thereof. Mainly caused by human factors such as mining, waste gas discharge, sewage irrigation, use of products with heavy metals exceeding standards and the like. The harm of heavy metal pollution to human body is mainly caused by 'three factors', carcinogenesis, disease and mutation, and the way is generally to enter human body through biological chain and biological enrichment. Heavy metal pollutants have the characteristics of no biodegradation, high toxicity, high carcinogenicity, long-term pollution, easy biological enrichment and the like, can be accumulated in animals and plants, are gradually enriched through a food chain, and cause serious harm to the environment, organisms and human health. The water environment becomes a problem of general attention of countries in the world, heavy metal pollution is an important aspect of water environment pollution, and along with the rapid development of economic level and industry and agriculture, the fact that the heavy metal pollution in the water environment is increasingly serious becomes a dispute. The heavy metal pollution has the characteristics of enrichment and high treatment difficulty, and great harm is generated to the health of human bodies, so that the method has very important significance for the research on the detection and removal of the heavy metals in the water. Hexavalent chromium compounds have strong oxidation and water solubility, have irritating and corrosive effects on skin and mucosa, and are common sensitizers, which are toxic substances to swallow. Therefore, the method has important significance for detecting the chromium ions by adopting the nano material.
Diatomaceous earth (Diatomite) is a mesoporous inorganic mineral derived from a single aquatic algae deposit, mainly composed of amorphous SiO2And (4) forming. In recent years, diatomaceous earth has been widely used as a photocatalyst carrier because of its advantages such as high porosity, large specific surface area, good heat resistance, low density, good chemical stability, and low cost. The unique ordered mesoporous structure facilitates mass transfer of reactant molecules, accessibility of active sites, and loading of active components. In addition, the abundant coordination defects and oxygen bridge defects on the surface and the formation of a large number of silicon hydroxyl bridges are beneficial to pollutant adsorption. Many scholars utilize the porous adsorption structure of diatomite as a carrier, and the diatomite and a photocatalyst cooperate to purify polluted gas, degrade organic matters in water and photo-reduce heavy metals in water. Copper is a ubiquitous element in the nature, and gradually receives attention from people due to unique properties, so that the metal copper has good conductivity and low price, and is widely applied to industrial production.
Fluorescent copper nanoclusters (CuNCs) have attracted extensive research interest due to their excellent physicochemical properties. But is stable due to its low quantum yieldThe qualitative is poor, and the application is limited. The size of metal nanoclusters, which is close to the fermi wavelength of electrons, is of great interest due to the optical properties and unique electronic structure of their molecular-like nature. In general, metal nanoclusters have specific characteristics including electronic transitions, size dependent fluorescence emission, and strong light absorption. Compared with gold and silver, copper has been widely used in industry because of its high rare earth content, low cost and high conductivity. Due to the instability of copper itself, the success in preparing nanocomposites with excellent luminescent properties and high stability has been achieved. The copper nano-cluster synthesized by adopting the template method has better stability and higher luminous efficiency, and the commonly used template is various biomolecules, such as protein, DNA, polymer and the like. For example, cysteine-protected CuNCs for detecting Al3+(ii) a Bovine Serum Albumin (BSA) -protected CuNCs were used for Pb2+ Detecting; glutathione protected CuNCs for detecting Hg in solution2+(ii) a Penicillium amine protected CuNCs for detecting Fe in solution3+. The CuNCs has good properties in ion detection, and CuNCs with more abundant properties can be synthesized and applied to detection of other ions. The photoluminescence nano composite material has wide application prospect in the fields of solar cells, light-emitting diodes, sensors, heavy metal ion detection and the like due to unique physical and chemical properties. To date, various diatomite composite materials have been reported and applied in the sensing field. Yang et al reported that CuS/Diatomite nano-composite photocatalyst can obtain higher activity of photocatalytic degradation of organic dye under simulated sunlight. Liu et al prepared a composite photocatalytic material for BiOCl/Diatomite composite photocatalytic degradation of liquid tetracycline hydrochloride and gaseous formaldehyde by a hydrothermal method. Zhanar Kubashieva et al prepared AgCl and Ag hybrid NPs/Diatomite composite material by direct immersion in silver nitrate aqueous solution. Therefore, the diatomite and the CuNCs are combined, and the design of the novel copper nanocluster and diatomite composite fluorescence sensor has important significance and can be used for detecting the heavy metal hexavalent chromium ions.
Disclosure of Invention
The invention provides a preparation method and application of a copper nanocluster and diatomite composite fluorescent sensor.
The invention discloses a preparation method of a copper nanocluster and diatomite composite fluorescence sensor, which is characterized by comprising the following steps of:
dissolving a copper salt in deionized water, and ultrasonically dissolving at room temperature to form a uniform mixed solution to obtain a solution A, wherein the volume ratio of the mole amount of the copper salt to the volume amount of the deionized water is (0.12) mmol: (12) mL;
secondly, adding the solution A obtained in the step one into a penicillamine solution, and stirring for 1-2 hours by using a magnetic stirrer to obtain a solution B;
and thirdly, adding the diatomite into the solution B in the step two to obtain the copper nano-cluster and diatomite composite fluorescent sensor with the hexavalent chromium ion detection function.
Further, in the first step, the copper salt is copper nitrate or copper sulfate.
Further, in the first step, the ultrasonic power is 60-100W.
Further, the stirring speed of the magnetic stirrer in the second step is 500 r/min-800 r/min.
Further, the stirring time of the magnetic stirrer in the third step is 1-2 h.
The copper nanocluster and diatomite composite fluorescent sensor prepared by the method is applied to detection of heavy metal hexavalent chromium ions in a water environment.
The invention can realize high-sensitivity detection of hexavalent chromium ions in the water environment, and the detection limit can reach 10 mu M.
The principle of the invention is as follows:
due to the rapid development of economy and the discharge of sewage, heavy metal Cr in water environment is caused6+The excessive standard of the Chinese herbal medicines is directly harmful to the health of human beings. Hexavalent chromium is mainly chronic toxic to humans, and it can invade the human body through the digestive tract, respiratory tract, skin and mucous membrane, accumulating in the body mainly in the liver, kidney and endocrine glands. The air entering through the respiratory tract is easily accumulated in the lungs. Excessive intake of chromium can cause poisoning. Chromium poisoning is mainly caused by the accidental inhalation of a limited amount of chromic acid or chromate, which causes extensive changes in the kidneys, liver, nervous system and bloodResulting in death. There are also cases of poisoning caused by sodium chromate absorbed by the burned wound. Prolonged occupational exposure, air pollution or exposure to chromium dust can cause skin irritation and ulceration, inflammation, necrosis of the nasal cavity and even lung cancer. When orally taken, it can cause gastrointestinal tract injury, circulatory disturbance and renal failure. The treatment method is characterized in that the turtle mixture is used for treatment after the turtle is separated from contact, and the chromium excretion amount is increased due to high sugar intake. Therefore, the preparation of the nano material capable of effectively removing the heavy metal ions in the water body has important practical significance.
The working principle of the copper nanocluster and diatomite composite fluorescent sensor for detecting hexavalent chromium in water is mainly that the prepared microstructure of the surface of the copper nanocluster and diatomite composite fluorescent sensor is beneficial to combination of the copper nanocluster and the diatomite composite fluorescent sensor to hexavalent chromium, and the copper nanoparticles are subjected to fluorescence quenching along with the fact that the hexavalent chromium and the copper nanoparticles are aggregated or the surface structure of the copper nanoparticles is changed due to the action between the hexavalent chromium and the copper nanoparticles6+The increase of the concentration gradually increases the quenching degree, thereby realizing the Cr6+The fluorescence detection of (3).
The invention has the beneficial effects that:
the method takes copper salt as a raw material, and adopts a one-pot hydrothermal method to prepare the copper nanocluster and diatomite composite fluorescent sensor. Therefore, the concentration of hexavalent chromium ions in water can be detected by using the copper nanocluster and diatomite composite fluorescence sensor.
The copper nano particles have good chemical stability, can be stably dispersed in an aqueous solution and show excellent color fluorescence, so that the copper nano cluster and diatomite composite fluorescence sensor has good stability and fluorescence performance.
The invention is synthesized by a one-pot hydrothermal method, and has the advantages of simple preparation method, low cost and wide source of raw materials and simple operation. Due to the complexation and redox reaction of copper (II) with the penicillamine (Pen) enantiomer, a pair of optically active red emitting CuNCs were successfully prepared, where Pen is both a reducing agent and a stabilizing ligand. With the increase of the concentration of hexavalent chromium ions in the water environment, the fluorescence intensity gradually decreases and linearly and controllably changes within a wider concentration range (0-50 mM), and the detection limit can reach 10 mu M. The above shows that the copper nanocluster and diatomite composite fluorescent sensor has good practicability and wide application prospect.
The copper nanocluster and diatomite composite fluorescent sensor prepared by the method is uniform in size and dispersibility, the synthesis method is simple, the raw materials are cheap and easy to obtain, the cost is low, and the prepared product is non-toxic, has good fluorescent property and has a fluorescent detection function on hexavalent chromium ions. Has wide application prospect in the fields of environment, material chemistry, and the like, such as environmental monitoring, treatment and the like.
Drawings
FIG. 1 is a scanning electron microscope image of the copper nanocluster and diatomite composite fluorescent sensor prepared in example 1;
FIG. 2 is an ultraviolet absorption spectrum, a fluorescence excitation spectrum and a fluorescence emission spectrum of the copper nanocluster and diatomite composite fluorescence sensor prepared in example 1;
FIG. 3 shows the Cu nanocluster and diatomite composite fluorescence sensor prepared in example 1 at different concentrations of Cr6+(0-50 mM) fluorescence spectrum in the presence of;
FIG. 4 shows a pair of Cr-containing nanoclusters of copper and diatomite as a fluorescence sensor prepared in example 16+Wherein, F is0The fluorescence intensity value of the blank copper nanocluster and diatomite composite fluorescence sensor, F: the fluorescence intensity value of the fluorescent composite material after each metal ion is added. Cr (chromium) component6+And other common metal ions such as Ag+，Ca2+，Cr3+，Fe2+，Fe3+，Hg2+，K+，Mg2+，Na+，Ni2+, Pb2+And Cr6+The concentrations were all 50 mM.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the preparation method of the copper nanocluster and diatomite composite fluorescent sensor is characterized by comprising the following steps of:
dissolving a copper salt in deionized water, and ultrasonically dissolving at room temperature to form a uniform mixed solution to obtain a solution A, wherein the volume ratio of the mole amount of the copper salt to the volume amount of the deionized water is (0.12) mmol: (12) mL;
secondly, adding the solution A obtained in the step one into a penicillamine solution, and stirring for 1-2 hours by using a magnetic stirrer to obtain a solution B;
and thirdly, adding the diatomite into the solution B to obtain the copper nanocluster and diatomite composite fluorescent sensor with the hexavalent chromium ion detection function.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the copper salt copper sulfate in the step one is the same as that in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the first step, the ultrasonic power is 60-100W. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the reaction temperature in step one was 25 ℃. The others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: and finishing the reaction for 2h in the step one. The other is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: the ratio of the molar weight of the copper salt to the volume of the deionized water in the first step is (0.12) mmol: (12) and (mL). The other is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and in the second step, the stirring speed of the magnetic stirrer is 500 r/min-800 r/min. The other is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: and in the second step, the stirring time of the magnetic stirrer is 1-2 h. The other is the same as one of the first to seventh embodiments.
The specific implementation method nine: the application of the copper nanocluster and diatomite composite fluorescent sensor in the detection of the heavy metal hexavalent chromium ions in the water environment is disclosed.
The following examples are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
Example 1:
firstly, 0.028189g of copper nitrate is weighed and dissolved in 12mL of deionized water, the solution is dissolved under 100W ultrasonic at room temperature to form a uniform mixed solution, the mixed solution is added into a penicillamine (3.6 mM, 12 mL) solution, and the stirring is finished for 2h on a magnetic stirrer, so that Cr-containing solution is obtained6+Fluorescent nanoparticles with detection function;
and secondly, adding 0.1g of diatomite into the solution obtained in the first step, and stirring at a high speed of 700r/min to obtain the copper nanocluster and diatomite composite fluorescent sensor with the hexavalent chromium ion detection function.
Fig. 1 is a scanning electron microscope image of the copper nanocluster and diatomite composite fluorescence sensor prepared in this example.
Fig. 2 is an ultraviolet absorption spectrum, a fluorescence excitation spectrum and a fluorescence emission spectrum of the copper nanocluster and diatomite composite fluorescence sensor prepared in the present example. The prepared fluorescence sensor has a large absorption area in an ultraviolet light area of 290-320 nm, and a central absorption peak is 315 nm. The fluorescence excitation peak is at 340nm, and the fluorescence emission peak is at 650 nm. The copper nanocluster and diatomite composite fluorescent sensor is in a milk white solution state under natural illumination, and the fluorescent sensor shows orange-red fluorescence under 365 nm ultraviolet illumination.
FIG. 3 shows the Cu nanocluster and diatomite composite fluorescence sensor prepared in example 1 at different concentrations of Cr6+(0-50 mM) fluorescence spectrum in the presence of; with Cr6+The concentration is increased, the fluorescence intensity of the nano sensor is gradually reduced, the detection limit can reach 10 mu M, and Cr can be detected6+Sensitive detection of (3).
FIG. 4 is a schematic view ofCopper nanocluster and diatomite composite fluorescent sensor pair prepared in example 16+The data map of the results of the selective assay of (1), wherein, Cr6+And other common metal ions such as Ag+，Ca2+，Cr3+，Fe2+，Fe3+，Hg2+，K+，Mg2+，Na+，Ni2+, Pb2+And Cr6+The concentration is 50 mM; as shown in FIG. 4, the fluorescence of the copper nanocluster and diatomite composite fluorescence sensor cannot be quenched by common metal ions, but when the common metal ions and Cr6+When the effect is generated, the fluorescence intensity is obviously quenched, which indicates that the effect is on Cr6+Has selective detection performance and can realize the detection of Cr6+Selective detection of (2).
Example 2:
firstly, 0.021576g of copper sulfate is weighed and dissolved in 12mL of deionized water, the solution is dissolved under 80W ultrasonic at room temperature to form a uniform mixed solution, the mixed solution is added into penicillamine (3.6 mM, 12 mL) solution, and the stirring is finished for 2h on a magnetic stirrer, so that Cr-containing solution is obtained6+Fluorescent nanoparticles with detection function;
and secondly, adding diatomite into the solution obtained in the first step, and stirring at a high speed of 700r/min to obtain the copper nanocluster and diatomite composite fluorescent sensor with the hexavalent chromium ion detection function.
The detection limit of the copper nanocluster and diatomite composite fluorescent sensor can reach 10 mu M, and Cr can be detected6+Intelligent detection of (2).
Claims (10)
1. A preparation method of a copper nanocluster and diatomite composite fluorescence sensor is characterized by comprising the following steps:
dissolving a copper salt in deionized water, and ultrasonically dissolving at room temperature to form a uniform mixed solution to obtain a solution A; wherein the volume ratio of the mole amount of the copper salt to the deionized water is (0.12) mmol: (12) mL;
secondly, adding the solution A obtained in the step one into a penicillamine solution, and stirring for 1-2 hours by using a magnetic stirrer to obtain a solution B;
and thirdly, adding the diatomite into the solution B to obtain the copper nanocluster and diatomite composite fluorescent sensor with the hexavalent chromium ion detection function.
2. The method for preparing the copper nanocluster and diatomite composite fluorescent sensor according to claim 1, wherein the method comprises the following steps: the copper salt in the first step is copper nitrate or copper sulfate.
3. The method for preparing the copper nanocluster and diatomite composite fluorescent sensor according to claim 1 or 2, wherein the method comprises the following steps: in the first step, the ultrasonic power is 60-100W.
4. The method for preparing the copper nanocluster and diatomite composite fluorescence sensor according to claim 3, wherein the method comprises the following steps: the reaction temperature in step one was 25 ℃.
5. The method for preparing the copper nanocluster and diatomite composite fluorescence sensor according to claim 4, wherein the method comprises the following steps: the ratio of the molar weight of the copper salt to the volume of the deionized water in the first step is (0.12) mmol: (12) and (mL).
6. The method for preparing the copper nanocluster and diatomite composite fluorescence sensor according to claim 5, wherein the method comprises the following steps: and in the second step, the stirring speed of the magnetic stirrer is 500 r/min-800 r/min.
7. The method for preparing the copper nanocluster and diatomite composite fluorescence sensor according to claim 6, wherein the method comprises the following steps: and in the second step, the stirring time of the magnetic stirrer is 1-2 h.
8. The method for preparing the copper nanocluster and diatomite composite fluorescence sensor according to claim 7, wherein the method comprises the following steps: in the third step, the diatomite is mixed with the solution B according to different mass ratios.
9. The method for preparing the copper nanocluster and diatomite composite fluorescence sensor according to claim 8, wherein the method comprises the following steps: in the third step, the diatomite and the solution B are magnetically stirred for 1 to 2 hours.
10. The use of the copper nanocluster and diatomite composite fluorescent sensor prepared by the method of claim 1 in detection of hexavalent chromium ions in sewage.
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