CN104694129A - Fluorescent material capable of detecting ultralow-concentration heavy metal ions and preparation method of fluorescent material - Google Patents
Fluorescent material capable of detecting ultralow-concentration heavy metal ions and preparation method of fluorescent material Download PDFInfo
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- CN104694129A CN104694129A CN201510055477.4A CN201510055477A CN104694129A CN 104694129 A CN104694129 A CN 104694129A CN 201510055477 A CN201510055477 A CN 201510055477A CN 104694129 A CN104694129 A CN 104694129A
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Abstract
The invention discloses a fluorescent material capable of detecting ultralow-concentration heavy metal ions and a preparation method of the fluorescent material. The fluorescent material is of a core-shell structure formed with CdSe quantum dot as a core and a ZnO nanomaterial as a shell, wherein the CdSe quantum dot and the ZnO nanomaterial are encapsulated together by use of mesoporous SiO2. The preparation method comprises the steps of preparation of ZnO colloidal nanorods, preparation of mercaptoacetic acid stabilized CdSe quantum dot spherical nanomaterial, preparation of ZnO/CdSe@SiO2 mesoporous core-shell structure and the like. The fluorescent material has the advantages of more accurate and reliable detection, high adsorption capability, remarkable improvement of the sensitivity and the lower limit of analytical detection and the like, and is also capable of solving the defects of dropping of quantum dot surface ligands, quantum dot accumulation and flocculation in the detection or long-term storage process, and the like; in short, the fluorescent material is especially suitable for detecting the ultralow-concentration heavy metal ions.
Description
Technical field
The present invention relates to environmental pollution and food safety monitoring field, specifically a kind of ZnO/CdSe@SiO detecting ultralow density heavy metal ion
2two luminescent quantum dot fluorescent material and preparation method thereof.
Background technology
In recent years, along with the fast development of leather processing, Electroplating Operations, chemical industry and IT industry, the heavy metal contamination that the mankind face is very severe, pesticide residue and the heavy metal contamination serious harm health of people, whole nation agricultural-food poisoning (as because having eaten drug case in remains of pesticide fruits and vegetables by mistake) occurs repeatedly, and food and Environmental safety supervision problem have caused people and paid much attention to.In the field that this and human health are closely bound up, how to research and develop accurate, quick, easy and economic analysis of material and detection method, with realize in real time and efficiently in monitoring of environmental in heavy metal ion and fruits and vegetables remains of pesticide just seem particularly urgent and important.And the material of research and development energy efficient detection ultralow density is the key realizing environmental pollution and food safety monitoring.Fluorometry equipment is simple, directly perceived, selectivity is good, real-time in-situ, highly sensitive, detectable least concentration is lower (can reach 10
-12the M order of magnitude is even lower), and detection both can be carried out in the solution, can carry out, therefore just becoming the method enjoying favor in food, medicine and environmental monitoring on interface.The key of fluorometry is not only the performance of detecting instrument, and what is more important must have quick response, high sensitivity, high reliability and Universal fluorescence probe material.Thus, the research and development of novel fluorescence probe material all get most of the attention in whole world scientific research and industrial field.CdX(X=S, Se and Te) the very outstanding fluorescent characteristic of quantum dot is that its fluorescence disturbs had extremely sensitive response to external world.Because the surface of quantum dot is generally all modified with sulfydryl, amine, phosphoric acid, carboxylic acid or other part, so it can pass through electrostatic interaction, hydrogen bond or covalent effect absorption foreign ion and molecule, its surface properties is caused to change, produce the response such as Fluorescence Increasing or cancellation, Fluorescent peal blue shift or red shift, this is because: the foreign matter that (1) quantum dot surface adsorbs likely becomes transfer transport center, thus causes quantum dot fluorescence cancellation; (2) foreign matter of quantum dot surface also likely passivation quantum dot surface, causes quantum dot surface defect to reduce, causes Fluorescence Increasing; (3) also likely change the iso-electric point of quantum dot after quantum dot surface absorption foreign matter, quantum dot is assembled, thus fluorescence intensity declines, Fluorescent peal red shift.Detection method conventional is at present general all using single quantum dot as probe, indicates the concentration level of detected material with the change of quantum dot fluorescence intensity absolute value.But the change of single fluorescence intensity easily causes larger error, and also there is permanent stability difference, surface ligand and easily to come off wretched insufficiencies such as causing analytical results distortion in single quantum dot.
Summary of the invention
Technical problem to be solved by this invention is to propose a kind of detection more accurately and reliably, high adsorption capacity, fluorescent material of the sensitivity of analyzing and testing and the detected ultralow density heavy metal ion of lower limit and preparation method thereof can be significantly improved, it can effectively solve, and quantum dot surface part comes off, quantum dot shortcoming such as gathering, flocculation in detection or prolonged storage.
For solving the problems of the technologies described above, a kind of fluorescent material detecting ultralow density heavy metal ion of the present invention is core by CdSe quantum dot, the nucleocapsid structure that ZnO nano material forms for shell, then through mesoporous SiO
2the two is packaged together.
Above-mentioned a kind of fluorescent material detecting ultralow density heavy metal ion, described ZnO nano material is club shaped structure.
Above-mentioned a kind of fluorescent material detecting ultralow density heavy metal ion, described is ball-like structure by CdSe quantum dot.
A kind of preparation method detecting the fluorescent material of ultralow density heavy metal ion of the present invention, comprises the following steps:
I. the gluey nanometer rod of making ZnO;
II. prepare the spherical nano material of the stable CdSe quantum dot of Thiovanic acid;
III. making ZnO/CdSe SiO
2mesoporous type nucleocapsid structure.
Above-mentioned a kind of preparation method detecting the fluorescent material of ultralow density heavy metal ion, described step I comprises following process: dissolve 15 grams of zinc acetates (70 DEG C are back to zinc acetate solid particulate and dissolve completely) by 60 ml methanol, 8 grams of potassium hydroxide are dissolved in 32 ml methanol, sodium hydroxide solution is added in acetic acid zinc solution, high-speed stirring (stir speed (S.S.) 2000rpm), present white colloidal in reaction system, colloid 60 DEG C of slakings 72 are little of 80 hours; Colloid is through centrifugation (centrifugation rate is 2000rpm), and for several times, 40 DEG C of vacuum-drying 24 hours, obtains corynebacterium nano-ZnO to deionized water wash.
Above-mentioned a kind of preparation method detecting the fluorescent material of ultralow density heavy metal ion, described step II comprises following process: be dispersed in 50 ml deionized water by 0.12 gram of Thiovanic acid and 0.229 gram of chloride hydrate cadmium, with the sodium hydroxide solution of 1.5M, the pH value of system is adjusted to 9, and logical nitrogen 30-40 minute, obtain reaction system 1.; 0.268 gram of selenium powder is dissolved in NaBH
42. the NaHSe solution of obtained anaerobic, obtain reaction system; To the reaction system under high-speed stirring state 1. in add rapidly reaction system 2., and heat (85 DEG C) backflow 2 to 3 hours, add 50 to 70 milliliters of dehydrated alcohols, separate out light yellow CdSe and precipitate, centrifugation goes out throw out and repeatedly rinses through ethanol, and product is placed in vacuum drier.
Above-mentioned a kind of preparation method detecting the fluorescent material of ultralow density heavy metal ion, described step III comprises following process: in clean 100 milliliters of Erlenmeyer flasks, add 1 ml deionized water, 50 milliliters of dehydrated alcohols, 1.8 milliliters of ammoniacal liquor and 200 microlitre tetraethyl silicate respectively, be heated to 40 DEG C, stir 15 minutes; By 0.009 gram of CdSe, 0.035 gram of ZnO nanorod and 0.1 gram of cetyl trimethylammonium bromide ultrasonic disperse in 10 ml deionized water, and join and above-mentionedly hold in the Erlenmeyer flask of ethyl silicate solution, 40 DEG C are stirred 3 to 12 hours, and the ternary nano component formed is SiO from outside to inside respectively
2shell, ZnO nanorod and CdSe quantum dot, unnecessary quantum dot and cetyl trimethylammonium bromide is removed through centrifugation, deionized water supersound washing, the surface avoiding cetyl trimethylammonium bromide to stick to material affects its photoluminescent property, final fluorescent material of the present invention.
The present invention is owing to have employed technique scheme, and it is by building two luminous mesoporous type fluorescent probe, ZnO/CdSe@SiO
2quantum dot and detected material are had an effect and are produced fluorescence response, and another kind of inert fluorescent component (ZnO nanorod) fluorescence in testing process is interference-free, plays the function of reference.Therefore, this kind of two Illuminant nanometer structure can indicate the level of detected material with the change of fluorescence ratio, which eliminate the aforementioned drawback of single quantum dot fluorescence probe, than more accurate and reliable as index with the change of single fluorescence absolute strength.And, SiO
2by fixing for quantum dot therein, this by effectively solving that quantum dot surface part comes off, quantum dot shortcoming such as gathering, flocculation in detection or prolonged storage.In addition, due to the mesoporous characteristic on surface, the two Illuminant nanometer structure of the present invention has strong adsorptive power, and analyte is easy in quantum dot surface enrichment, thus significantly improve sensitivity and the lower limit of analyzing and testing, be particularly useful for the heavy metal ion copper, mercury, the lead that detect ultra-low limit concentration.
Accompanying drawing explanation
Fig. 1 is the ZnO/CdSe@SiO prepared by the present invention
2x-ray powder diffraction (XRD) collection of illustrative plates;
Fig. 2 is the transmission electron microscope picture of the ZnO prepared by the present invention;
Fig. 3 is the scanning electron microscope (SEM) photograph of the ZnO prepared by the present invention;
Fig. 4 is the ZnO/CdSe@SiO prepared by the present invention
2transmission electron microscope picture;
Fig. 5 is the ZnO/CdSe@SiO prepared by the present invention
2scanning electron microscope (SEM) photograph;
Fig. 6 is the ZnO/CdSe@SiO prepared by the present invention
2with ZnO@SiO
2ultraviolet-visible absorption spectroscopy figure;
Fig. 7 is the ZnO/CdSe@SiO prepared by the present invention
2with ZnO@SiO
2fluorescence spectrum figure;
Fig. 8 is that material of the present invention is to the fluorescence intensity spectrogram shown after the enrichment of the cupric ion of different concns;
Fig. 9 is that material of the present invention is to the fluorescence intensity spectrogram shown after the enrichment of the mercury ion of different concns;
Figure 10 is that material of the present invention is to the fluorescence intensity spectrogram shown after the enrichment of the lead ion of different concns.
Embodiment
A kind of fluorescent material detecting ultralow density heavy metal ion of the present invention be by ZnO nanorod and CdSe nanocrystalline through Nano-meter SiO_2
2the ZnO/CdSe@SiO of the nucleocapsid structure that encapsulating is formed
2two luminescent quantum dot fluorescent material.It take CdSe quantum dot as core, and ZnO nano material is shell, then through mesoporous SiO
2the two is packaged together.Its X-ray powder diffraction (XRD) collection of illustrative plates as shown in Figure 1.It is made by following steps:
I. the gluey nanometer rod of making ZnO: dissolve 15 grams of zinc acetates (70 DEG C are back to zinc acetate solid particulate and dissolve completely) by 60 ml methanol, 8 grams of potassium hydroxide are dissolved in 32 ml methanol, sodium hydroxide solution is added in acetic acid zinc solution, high-speed stirring (stir speed (S.S.) 2000rpm), present white colloidal in reaction system, colloid 60 DEG C of slakings 72 are little of 80 hours; Colloid is through centrifugation (centrifugation rate is 2000rpm), and for several times, 40 DEG C of vacuum-drying 24 hours, obtain corynebacterium nano-ZnO, its transmission electron microscope picture and scanning electron microscope (SEM) photograph are respectively as shown in Figures 2 and 3 for deionized water wash.
II. prepare the CdSe quantum dot that Thiovanic acid is stable: be dispersed in 50 ml deionized water by 0.12 gram of Thiovanic acid and 0.229 gram of chloride hydrate cadmium, with the sodium hydroxide solution of 1.5M, the pH value of system is adjusted to 9, and logical nitrogen 30-40 minute, obtain reaction system 1.; 0.268 gram of selenium powder is dissolved in the NaHSe solution that NaBH4 obtains anaerobic, obtains reaction system 2.; To the reaction system under high-speed stirring state 1. in add rapidly reaction system 2., and heat (under 85 DEG C of temperature condition) backflow 2 to 3 hours, add 50 to 70 milliliters of dehydrated alcohols, separate out light yellow CdSe and precipitate, centrifugation goes out throw out and repeatedly rinses through ethanol, and product is placed in vacuum drier;
III. making ZnO/CdSe SiO
2mesoporous type nucleocapsid structure: in clean 100 milliliters of Erlenmeyer flask, add 1 ml deionized water, 50 milliliters of dehydrated alcohols, 1.8 milliliters of ammoniacal liquor and 200 microlitre tetraethyl silicate respectively, be heated to 40 DEG C, stir 15 minutes; By 0.009 gram of CdSe, 0.035 gram of ZnO nanorod and 0.1 gram of cetyl trimethylammonium bromide ultrasonic disperse in 10 ml deionized water, and join and above-mentionedly hold in the Erlenmeyer flask of ethyl silicate solution, stir 3 to 12 hours at 40 DEG C of temperature, the ternary nano component formed is SiO from outside to inside respectively
2shell, ZnO nanorod and CdSe quantum dot, unnecessary quantum dot and cetyl trimethylammonium bromide is removed through centrifugation, deionized water supersound washing, the surface avoiding cetyl trimethylammonium bromide to stick to material affects its photoluminescent property, final fluorescent material of the present invention, respectively as shown in Figure 4 and Figure 5, ultraviolet-visible absorption spectroscopy and fluorescence spectrum are respectively as shown in Figure 6 and Figure 7 for its transmission electron microscope picture and scanning electron microscope (SEM) photograph.
Fluorescent material of the present invention for the fluorescence response of the cupric ion of different concns, mercury ion and lead ion by following three experimental verifications.
Test 1 ZnO/CdSe@SiO
2fluorescence response to the cupric ion of different concns:
By 0.05 gram of ZnO/CdSe@SiO
2composite nano materials is dispersed in 20 milliliters of dehydrated alcohols, and ultrasonic disperse forms stable colloidal solution, and configuration concentration is respectively 10
-5, 10
-6, 10
-7, 10
-8, 10
-9the dehydrated alcohol dispersion system of cupric ion.Get the ZnO/CdSe@SiO of 250 μ L
2colloidal solution is placed in clean Erlenmeyer flask, is settled to 10mL respectively with the dehydrated alcohol dispersion liquid of the cupric ion of different concns.Then by mixed system room temperature ageing 12 hours, with the photoluminescent property of molecular fluorescence spectroscopy instrument detection system.As shown in Figure 8, fluorescence spectrum figure shows, in the cupric ion system of series concentration, its burst of ultraviolel intensity keeps stable, and due to ZnO/CdSe SiO
2the fluorescence intensity of system is caused to strengthen because of the difference of copper ion concentration or weaken, especially when the concentration of cupric ion is respectively 10
-5, 10
-6time, the fluorescence intensity of system weakens, and when the concentration of cupric ion is 10
-7, 10
-8with 10
-9time, the fluorescence intensity of system strengthens on the contrary.This phenomenon shows that cupric ion is by ZnO/CdSe@SiO
2strong adsorption and change ZnO/CdSe@SiO
2surface characteristic and its fluorescence intensity, owing to failing to react with cupric ion, its fluorescence intensity does not change nanometer rod, therefore relative to the fluorescent probe of single-shot light, in two luminescence system, the fluorescence intensity ratio of ZnO and CdSe can reflect the concentration of heavy metal copper ion, especially can reflect the subtle change of heavy metal copper ionic concn, namely can realize the detection of the heavy metal copper ion of ultralow detectability.
Test 2 ZnO/CdSe@SiO2 to the fluorescence response of the mercury ion of different concns:
By 0.05 gram of ZnO/CdSe@SiO
2composite nano materials is dispersed in 20 milliliters of dehydrated alcohols, and ultrasonic disperse forms stable colloidal solution, and configuration concentration is respectively 10
-5, 10
-6, 10
-7, 10
-8, 10
-9the dehydrated alcohol dispersion system of mercury ion.Get the ZnO/CdSe@SiO of 250 μ L
2colloidal solution is placed in clean Erlenmeyer flask, is settled to 10mL respectively with the dehydrated alcohol dispersion liquid of the mercury ion of different concns.Then by mixed system room temperature ageing 12 hours, with the photoluminescent property of molecular fluorescence spectroscopy instrument detection system.As shown in Figure 9, fluorescence spectrum figure shows, in the mercury ion system of series concentration, its burst of ultraviolel intensity keeps stable, and due to ZnO/CdSe SiO
2the fluorescence intensity of system is caused to strengthen because of the difference of ion concentration of mercury or weaken, especially when the concentration of mercury ion is respectively 10
-5, 10
-6with 10
-7time, the fluorescence intensity of system weakens, and when the concentration of mercury ion is 10
-8with 10
-9time, the fluorescence intensity of system strengthens on the contrary.This phenomenon shows that mercury ion is by ZnO/CdSe@SiO
2strong adsorption and change ZnO/CdSe@SiO
2surface characteristic and its fluorescence intensity, owing to failing to react with mercury ion, its fluorescence intensity does not change nanometer rod, therefore relative to the fluorescent probe of single-shot light, in two luminescence system, the fluorescence intensity ratio of ZnO and CdSe can reflect the concentration of metal mercury ions, especially can reflect the subtle change of metal mercury ions concentration, namely can realize the detection of the metal mercury ions of ultralow detectability.
Test 3 ZnO/CdSe@SiO2 to the fluorescence response of the lead ion of different concns:
By 0.05 gram of ZnO/CdSe@SiO
2composite nano materials is dispersed in 20 milliliters of dehydrated alcohols, and ultrasonic disperse forms stable colloidal solution, and configuration concentration is respectively 10
-5, 10
-6, 10
-7, 10
-8, 10
-9the dehydrated alcohol dispersion system of lead ion.Get the ZnO/CdSe@SiO of 250 μ L
2colloidal solution is placed in clean Erlenmeyer flask, is settled to 10mL respectively with the dehydrated alcohol dispersion liquid of the lead ion of different concns.Then by mixed system room temperature ageing 12 hours, with the photoluminescent property of molecular fluorescence spectroscopy instrument detection system.As shown in Figure 10, fluorescence spectrum figure shows, in the lead ion system of series concentration, its burst of ultraviolel intensity keeps stable, and due to ZnO/CdSe SiO
2the fluorescence intensity of system is caused to strengthen because of the reduction of plumbum ion concentration, when the concentration of lead ion is respectively 10
-5, 10
-6, 10
-7, 10
-8, 10
-9during reduction, the fluorescence intensity of system strengthens successively.This phenomenon shows that lead ion is by ZnO/CdSe@SiO
2strong adsorption and change ZnO/CdSe@SiO
2surface characteristic and its fluorescence intensity, owing to failing to react with lead ion, its fluorescence intensity does not change nanometer rod, therefore relative to the fluorescent probe of single-shot light, in two luminescence system, the fluorescence intensity ratio of ZnO and CdSe can reflect the concentration of heavy metal lead ion, especially can reflect the subtle change of heavy metal lead ionic concn, namely can realize the detection of the heavy metal lead ion of lower detectability and ultralow detectability.
Claims (7)
1. can detect a fluorescent material for ultralow density heavy metal ion, it is characterized in that, it is core by CdSe quantum dot, and ZnO nano material is the nucleocapsid structure of shell composition, then through mesoporous SiO
2the two is packaged together.
2. a kind of fluorescent material detecting ultralow density heavy metal ion as claimed in claim 1, it is characterized in that, described ZnO nano material is club shaped structure.
3. a kind of fluorescent material detecting ultralow density heavy metal ion as claimed in claim 1 or 2, it is characterized in that, described is ball-like structure by CdSe quantum dot.
4. can detect a preparation method for the fluorescent material of ultralow density heavy metal ion as claimed in claim 1, it is characterized in that, it comprises the following steps:
I. the gluey nanometer rod of making ZnO;
II. prepare the spherical nano material of the stable CdSe quantum dot of Thiovanic acid;
III. making ZnO/CdSe SiO
2mesoporous type nucleocapsid structure.
5. a kind of preparation method detecting the fluorescent material of ultralow density heavy metal ion as claimed in claim 4, it is characterized in that, described step I comprises following process: dissolve 15 grams of zinc acetates by 60 ml methanol, is back to zinc acetate solid particulate and dissolves completely under 70 DEG C of conditions; Be dissolved in 32 ml methanol by 8 grams of potassium hydroxide, added by sodium hydroxide solution in acetic acid zinc solution, high-speed stirring, stir speed (S.S.) 2000rpm, present white colloidal in reaction system, colloid slaking 72 under 60 DEG C of conditions is little of 80 hours; Colloid is through centrifugation, and centrifugation rate is 2000rpm, and for several times, under 40 DEG C of conditions, vacuum-drying 24 hours, obtains corynebacterium nano-ZnO to deionized water wash.
6. a kind of preparation method detecting the fluorescent material of ultralow density heavy metal ion as described in claim 4 or 5, it is characterized in that, described step II comprises following process: be dispersed in 50 ml deionized water by 0.12 gram of Thiovanic acid and 0.229 gram of chloride hydrate cadmium, with the sodium hydroxide solution of 1.5M, the pH value of system is adjusted to 9, and logical nitrogen 30-40 minute, obtain reaction system 1.; 0.268 gram of selenium powder is dissolved in NaBH
42. the NaHSe solution of obtained anaerobic, obtain reaction system; To the reaction system under high-speed stirring state 1. in add rapidly reaction system 2., and under 85 DEG C of conditions reflux 2 to 3 hours, add 50 to 70 milliliters of dehydrated alcohols, separate out light yellow CdSe and precipitate, centrifugation goes out throw out and repeatedly rinses through ethanol, and product is placed in vacuum drier.
7. a kind of preparation method detecting the fluorescent material of ultralow density heavy metal ion as described in claim 4 or 5, it is characterized in that, described step III comprises following process: in clean 100 milliliters of Erlenmeyer flasks, add 1 ml deionized water, 50 milliliters of dehydrated alcohols, 1.8 milliliters of ammoniacal liquor and 200 microlitre tetraethyl silicate respectively, be heated to 40 DEG C, stir 15 minutes; By 0.009 gram of CdSe, 0.035 gram of ZnO nanorod and 0.1 gram of cetyl trimethylammonium bromide ultrasonic disperse in 10 ml deionized water, and join and above-mentionedly hold in the Erlenmeyer flask of ethyl silicate solution, 40 DEG C are stirred 3 to 12 hours, and the ternary nano component formed is SiO from outside to inside respectively
2shell, ZnO nanorod and CdSe quantum dot, unnecessary quantum dot and cetyl trimethylammonium bromide is removed through centrifugation, deionized water supersound washing, the surface avoiding cetyl trimethylammonium bromide to stick to material affects its photoluminescent property, final fluorescent material of the present invention.
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| CN111781179A (en) * | 2020-07-02 | 2020-10-16 | 南宁师范大学 | Method for detecting organophosphorus pesticide based on target response hydrogel and mobile phone kit |
| CN112500847A (en) * | 2020-11-16 | 2021-03-16 | 武汉理工大学 | Cadmium ion probe based on quantum dot fluorescence resonance energy transfer system and preparation method thereof |
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Application publication date: 20150610 |