CN111690406B - Preparation method and application of optical property-adjustable molybdenum oxide quantum dots - Google Patents

Preparation method and application of optical property-adjustable molybdenum oxide quantum dots Download PDF

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CN111690406B
CN111690406B CN202010657370.8A CN202010657370A CN111690406B CN 111690406 B CN111690406 B CN 111690406B CN 202010657370 A CN202010657370 A CN 202010657370A CN 111690406 B CN111690406 B CN 111690406B
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CN111690406A (en
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曹海燕
石文兵
董文飞
陈果
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Chongqing Zengcheng Technology Co ltd
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Abstract

The invention discloses a preparation method and application of molybdenum oxide quantum dots with adjustable optical properties. The preparation method has the characteristics of rapidness and high efficiency, the particle size of the synthesized molybdenum oxide quantum dots can be controlled by controlling the microwave heating time, so that the emission wavelength of the molybdenum oxide quantum dots can be regulated, nitrogen and phosphorus elements are doped, the edge emission trap of the nano material is increased, the fluorescence emission of the nano material is expanded to a longer green light wavelength region, the molybdenum oxide quantum dots with green emission wavelength are obtained, the contents of permanganate and captopril can be detected sensitively and efficiently with low cost, and the application field of the molybdenum oxide quantum dots is expanded.

Description

Preparation method and application of optical property-adjustable molybdenum oxide quantum dots
Technical Field
The invention relates to the technical field of combination of nano materials and analytical chemistry, in particular to a preparation method and application of molybdenum oxide quantum dots with adjustable optical properties.
Background
Molybdenum oxide (MoO) x ) As a typical Transition Metal Oxide (TMO) material, the nano material becomes an exciting new material with excellent physical and chemical properties, in particular MoO x In the Near Infrared (NIR) and visible regionPromising tunable Localized Surface Plasmon Resonance (LSPR) has been expanding its range of applications due to its light collection capability on the nanometer scale. The application development of the method in the fields of catalysis, single molecule spectrum, photothermal therapy, photochromism and the like is promoted. On the other hand, when MoO x Is less than 10nm (MoO) x QDs), which exhibits excellent photoluminescence characteristics due to the influence of quantum confinement and edge effects. Due to MoO x QDs have special quantum size effect, surface effect, high reactivity and high stability of nanometer material defects, moO x QDs are considered suitable materials for optical probes. However, moO in almost all reports x QDs all exhibit strong blue emission, which may hinder their application in the fields of solar cells, light emitting devices, and biosensing. Therefore, development and preparation of MoO with long-wave luminescence x The QDs method is beneficial to improving the utilization value of the QDs and has high social requirements.
To date, fluorescent MoO's have been prepared x Methods of QDs can be divided into two categories: the top-down method comprises a microwave ultrasonic stripping method and an oxidation reaction; bottom-up processes include solvothermal processes. For the top-down approach, moO x QDs is from MoO 3 Powder or bulk MoS 2 Prepared by disintegration, the preparation process usually involves reagents harmful to the environment, and the size and the shape of the obtained nano material are often uncontrollable. The bottom-up method uses solvent heat as energy and utilizes end-capping molecules to obtain stable and excellent water-soluble MoO x QDs, however, generally have problems of high temperature, long time consumption, and the like. Thus, the development of rapid synthesis of water-soluble MoO with controllable size x The QDs method is of great significance to expand its application range.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of an optical property-adjustable molybdenum oxide quantum dot, so as to solve the problems that the size and the shape of a molybdenum oxide material prepared by the prior art are not controllable and do not have long-wave luminescence characteristics.
The invention also provides the application of the optical property-adjustable molybdenum oxide quantum dots in detection of the concentrations of permanganate and captopril, and the contents of the permanganate and the captopril can be detected with low cost and high sensitivity.
In order to solve the technical problem, the invention adopts the following technical scheme:
a preparation method of optical property adjustable molybdenum oxide quantum dots comprises the following steps:
will H 3 P(Mo 3 O 10 ) 4 ·xH 2 Adding O, glutathione and ammonia water into water, fully mixing under an ultrasonic condition to obtain a mixed solution, transferring the mixed solution into a microwave reaction kettle, carrying out microwave heating to 150-190 ℃, reacting for 2-60 min, naturally cooling, centrifuging to remove large particles, and dialyzing to remove unreacted substances to obtain the molybdenum oxide quantum dots with adjustable optical properties.
Preferably, the mixed solution is transferred to a microwave reaction kettle to be heated to 160-180 ℃ by microwave, and the reaction time is 4-40 min.
Preferably, said H 3 P(Mo 3 O 10 ) 4 ·xH 2 The molar ratio of O, glutathione to ammonia water is 1 (40-42) to (645-655). Wherein, the H 3 P(Mo 3 O 10 ) 4 ·xH 2 The molar ratio of O, glutathione and ammonia is further preferably 1.
Preferably, H in the mixed solution 3 P(Mo 3 O 10 ) 4 ·xH 2 The mass-volume ratio of O to water is 1mg: (725-1000) mL. Wherein, H in the mixed solution 3 P(Mo 3 O 10 ) 4 ·xH 2 The mass-to-volume ratio of O to water is further preferably 1mg:925mL.
The invention provides a method for measuring the concentration of permanganate by using optical property adjustable molybdenum oxide quantum dots, which is applied to measuring the concentration of permanganate and comprises the following steps:
and (3) drawing a permanganate standard curve: mixing the molybdenum oxide quantum dots with a series of permanganate standard solutions with concentration gradients, and buffering and dissolving the mixture by using carbonateFixing the volume to the same volume, measuring fluorescence intensity of the solution at excitation wavelength of 430nm and emission wavelength of 500nm, and measuring relative fluorescence intensity (I) with permanganate concentration as abscissa 0 -I)/I is a standard curve plotted on the ordinate; wherein, I 0 When the concentration of the permanganate is zero, the fluorescence intensity of the molybdenum oxide quantum dots is obtained, and I is the corresponding fluorescence intensity when the molybdenum oxide quantum dots and the permanganate with different concentrations coexist.
Preferably, the molar ratio of the molybdenum oxide to the permanganate standard solution is (1000-10): 1, and the carbonate is Na 2 CO 3 Or K 2 CO 3 The pH value of the carbonate buffer solution is 7-11.
Preferably, the concentration of the permanganate standard solution is 0. Mu.M, 0.08. Mu.M, 0.1. Mu.M, 0.5. Mu.M, 1. Mu.M, 3. Mu.M, 5. Mu.M, 7. Mu.M, 9. Mu.M, 15. Mu.M, 21. Mu.M, 23. Mu.M, 25. Mu.M, 27. Mu.M, 29. Mu.M, 31. Mu.M, 37. Mu.M, 39. Mu.M, 50. Mu.M, 70. Mu.M, 80. Mu.M, 90. Mu.M, 100. Mu.M, respectively.
Preferably, the regression equation of the standard curve is y =0.05967+0.05279x (0.08-25 μ M), R 2 =0.9973, wherein y is (I) 0 -I)/I, x is the permanganate concentration in μ M and R is the correlation coefficient.
The invention also provides a method for measuring captopril concentration by utilizing the optical property adjustable molybdenum oxide quantum dots, and the method for measuring the captopril concentration by utilizing the molybdenum oxide quantum dots comprises the following steps:
drawing a captopril standard curve: uniformly mixing a potassium permanganate solution, the molybdenum oxide quantum dots and a series of captopril standard solutions with concentration gradients to obtain a mixed solution, fixing the volume to the same volume by using a carbonate buffer solution, measuring the fluorescence intensity of the solution with the fixed volume at an excitation wavelength of 430nm and an emission wavelength of 500nm, and taking the captopril concentration as a horizontal coordinate and measuring the relative fluorescence intensity (I-I) 0 )/I 0 Drawing a standard curve for the ordinate; wherein, I 0 When the captopril concentration is zero, the fluorescence intensity of a molybdenum oxide quantum dot-potassium permanganate system is zero, and I is the fluorescence intensity corresponding to the co-existence of the molybdenum oxide quantum dot-potassium permanganate system and captopril with different concentrationsLight intensity.
Preferably, the molar ratio of the potassium permanganate to the molybdenum oxide to the captopril standard solution is 1 2 CO 3 Or K 2 CO 3 The pH value of the carbonate buffer solution is 7-11.
Preferably, the captopril standard solution has a concentration of 0. Mu.M, 0.1. Mu.M, 0.3. Mu.M, 0.5. Mu.M, 0.8. Mu.M, 1. Mu.M, 3. Mu.M, 5. Mu.M, 7. Mu.M, 11. Mu.M, 13. Mu.M, 15. Mu.M, 17. Mu.M, 21. Mu.M, 23. Mu.M, 25. Mu.M, 27. Mu.M, 31. Mu.M, respectively; the regression equation of the standard curve is y =0.02912+0.05921x (0.1-31 mu M), R 2 =0.9961, wherein y is (I-I) 0 )/I 0 X is captopril concentration in μ M, and R is a correlation coefficient.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention utilizes a microwave-assisted method to synthesize and prepare nitrogen-phosphorus-doped MoO x The QDs method can rapidly heat the reaction medium, and researches show that the particle size of the synthesized molybdenum oxide quantum dots can be controlled by controlling the microwave heating time, so that the emission wavelength of the molybdenum oxide quantum dots can be regulated and controlled; and compared with the traditional hydrothermal method, the method has the characteristics of rapidness and high efficiency.
2. The molybdenum oxide quantum dots prepared by the method are doped with nitrogen and phosphorus elements, so that the edge emission trap of the nano material is increased, the fluorescence emission of the nano material is expanded to a longer green light wavelength region, and the molybdenum oxide quantum dots with green emission wavelength are obtained.
3. The method can detect the contents of permanganate and captopril with low cost, sensitivity and high efficiency, is favorable for enriching and developing the rapid detection methods of the permanganate and captopril, and expands the application field of the molybdenum oxide quantum dots.
Drawings
FIG. 1 is a process schematic of the synthesis method of the present invention.
FIG. 2 is an electron microscope image of the nano material synthesized by the present invention under microwave irradiation for 5 min.
FIG. 3 is an electron microscope image of the nano material synthesized by the present invention under microwave irradiation for 15 min.
FIG. 4 is a graph showing the fluorescence intensity of permanganate concentrations measured using the present invention.
FIG. 5 is a graph showing the fluorescence intensity of captopril at various concentrations detected using the present invention.
FIG. 6 is a three-dimensional fluorescence spectrum of the nanomaterial synthesized by the present invention under microwave irradiation for 5 min.
FIG. 7 is a three-dimensional fluorescence spectrum of the nano-material synthesized by the present invention under microwave irradiation for 15 min.
Detailed Description
The invention will be further explained with reference to the drawings and the embodiments.
1. Preparation method of optical property-adjustable molybdenum oxide quantum dots
Referring to fig. 1, the synthesis method of the present invention comprises the following steps: h is to be 3 P(Mo 3 O 10 ) 4 ·xH 2 Adding O, glutathione and ammonia water into water, and fully mixing under an ultrasonic condition to obtain a mixed solution; then transferring the mixed solution into a microwave reaction kettle for microwave heating to 150-190 ℃ for 2-60 min; naturally cooling, centrifuging to remove large particles, dialyzing to remove unreacted substances to obtain the molybdenum oxide quantum dots with adjustable optical properties.
Example (b): will H 3 P(Mo 3 O 10 ) 4 ·xH 2 O, glutathione and ammonia were mixed well in water at a molar ratio of 1 3 P(Mo 3 O 10 ) 4 ·xH 2 925mL of water is needed to be added into O, the solution is fully mixed under ultrasonic, and then the mixture is transferred into a microwave reaction kettle to be heated and reacted for 5-40 min at 160-180 ℃, so as to obtain the molybdenum oxide quantum dots with different particle sizes, as shown in figure 2. After natural cooling, the mixture is centrifuged for 8min at 14000r/min for 2 times to remove large particles. Dialysis was then performed for 72h in a dialysis bag with a molecular cut-off of 1kD to remove unreacted materials.
Table 1 examples 1-4 molybdenum oxide quantum dots of different particle sizes were obtained under different heating conditions
Figure GDA0003929846630000041
Note: -indicates that the item was not detected.
As can be seen from Table 1, the molybdenum oxide quantum dots with different particle sizes can be obtained by changing the heating reaction time, and the emission wavelengths are also different. It can be found from the combination of fig. 2 and fig. 3 that when the microwave heating time is 15min, the particle size of the obtained molybdenum oxide quantum dot is 2.4 ± 0.7nm, and as can be seen from fig. 7, the fluorescence of the obtained molybdenum oxide quantum dot is blue. When the microwave heating time is shortened to 5min, the particle size of the molybdenum oxide quantum dots is obviously changed to reach 4.9 +/-1.2 nm by combining and comparing the graph 2 with the graph 3, the particle size of the molybdenum oxide quantum dots is increased due to the shortening of the microwave heating time, and at the moment, the fluorescence of the molybdenum oxide quantum dots is changed into green light with longer wavelength by combining the graph 6, so that the emission wavelength of the green light is regulated.
According to the invention, the particle size of the molybdenum oxide quantum dots is controlled by adjusting the microwave heating time, so that the fluorescent property of the molybdenum oxide quantum dots is regulated, the green-emitting molybdenum oxide quantum dots are obtained, the fluorescent influence of a blue background can be effectively avoided, and the application range of the green-emitting molybdenum oxide quantum dots is widened.
2. Method for measuring permanganate concentration by using optical property adjustable molybdenum oxide quantum dots
13 μ L of the raw solution molybdenum oxide quantum dots prepared in example 1 and 100 μ L of a series of concentration gradient permanganate standard solutions were taken and added into a colorimetric tube, and the volume was adjusted to 2mL with 0.025M sodium carbonate-carbonic acid buffer solution with pH =10.0, wherein the permanganate standard solution concentrations were 0 μ M,0.08 μ M,0.1 μ M,0.5 μ M,1 μ M,3 μ M,5 μ M,7 μ M,9 μ M,15 μ M,21 μ M,23 μ M,25 μ M,27 μ M,29 μ M,31 μ M,37 μ M,39 μ M,50 μ M,70 μ M,80 μ M,90 μ M, and 100 μ M, respectively. Measuring fluorescence intensity of the solution with constant volume at excitation wavelength of 430nm and emission wavelength of 500nm, and relative fluorescence intensity (I) with permanganate concentration as abscissa 0 The permanganate standard curve is plotted on the ordinate in the form of-I)/I as shown in FIG. 4.
Wherein, I 0 Is high in manganeseWhen the concentration of the acid salt is zero, the fluorescence intensity of the molybdenum oxide quantum dots, and I is the corresponding fluorescence intensity when the molybdenum oxide quantum dots and the permanganate with different concentrations coexist.
As can be seen in fig. 4, the fluorescence intensity of the molybdenum oxide quantum dots decreased with the increase of the permanganate concentration, which indicates that the molybdenum oxide quantum dots can be used for the measurement of permanganate.
When the concentration of the permanganate is in the range of 0.08-25 mu M, the regression equation of the standard curve is y =0.0246+0.0616x 2 =0.9973; wherein y is (I) 0 -I)/I, x is the permanganate concentration in μ M and R is the correlation coefficient.
3. Method for measuring captopril concentration by using optical property-adjustable molybdenum oxide quantum dots
A series of captopril standard solutions with concentration gradients and 100 μ L of 1mM potassium permanganate solution were added into a colorimetric cylinder, 13 μ L of the raw solution molybdenum oxide quantum dots prepared in example 1 were added and mixed, and then the mixture was made to volume of 2mL with 0.025m sodium carbonate-carbonic acid buffer solution with ph = 10.0. Wherein, the standard solution concentration of captopril is 0 μ M,0.1 μ M,0.3 μ M,0.5 μ M,0.8 μ M,1 μ M,3 μ M,5 μ M,7 μ M,11 μ M,13 μ M,15 μ M,17 μ M,21 μ M,23 μ M,25 μ M,27 μ M,31 μ M. Measuring fluorescence intensity of the solution with constant volume at excitation wavelength of 430nm and emission wavelength of 500nm, and taking captopril concentration as abscissa and relative fluorescence intensity (I-I) 0 )/I 0 The captopril standard curve is plotted on the ordinate as shown in figure 5.
Wherein, I 0 When the captopril concentration is zero, the fluorescence intensity of a molybdenum oxide quantum dot-potassium permanganate system is obtained, and I is the corresponding fluorescence intensity when the molybdenum oxide quantum dot-potassium permanganate system and captopril with different concentrations coexist.
As can be seen in fig. 5, the fluorescence intensity of the molybdenum oxide quantum dot-permanganate system increases with the increase of captopril concentration, which indicates that the molybdenum oxide quantum dot-permanganate system can be used for captopril determination.
When the captopril concentration is in the range of 0.1-31 μ M, the standard curve regression equation is y =0.02912+0.05921x,R 2 =0.9961; wherein y is (I-I) 0 )/I 0 X is captopril concentration in μ M, and R is a correlation coefficient.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.

Claims (9)

1. A preparation method of optical property adjustable molybdenum oxide quantum dots is characterized by comprising the following steps:
h is to be 3 P(Mo 3 O 10 ) 4 •xH 2 Adding O, glutathione and ammonia water into water, fully mixing under an ultrasonic condition to obtain a mixed solution, transferring the mixed solution into a microwave reaction kettle, heating the mixed solution to 150-190 ℃ by microwave, reacting for 2-60min, naturally cooling, centrifuging to remove large particles, and dialyzing to remove unreacted substances to obtain the molybdenum oxide quantum dots with adjustable optical properties;
said H 3 P(Mo 3 O 10 ) 4 •xH 2 The molar ratio of O, glutathione to ammonia water is 1 (40 to 42) to (645 to 655).
2. The method for preparing the optical property-adjustable molybdenum oxide quantum dot according to claim 1, wherein H in the mixed solution 3 P(Mo 3 O 10 ) 4 •xH 2 The mass-volume ratio of O to water is 1mg: (725 to 1000) mL.
3. The method for measuring the concentration of permanganate by using the molybdenum oxide quantum dots with adjustable optical properties is characterized in that the method for measuring the concentration of permanganate by using the molybdenum oxide quantum dots according to any one of claims 1 to 2 comprises the following steps:
and (3) drawing a permanganate standard curve: subjecting the molybdenum oxide quantum dots to a series of concentration gradientsMixing the permanganate standard solutions, diluting to the same volume with carbonate buffer solution, measuring fluorescence intensity of the solution with constant volume at excitation wavelength of 430nm and emission wavelength of 500nm, and measuring relative fluorescence intensity (I) with permanganate concentration as abscissa 0 -I)/I is a standard curve plotted on the ordinate; wherein, I 0 When the concentration of the permanganate is zero, the fluorescence intensity of the molybdenum oxide quantum dots is obtained, and I is the corresponding fluorescence intensity when the molybdenum oxide quantum dots and the permanganate with different concentrations coexist.
4. The method for measuring the concentration of permanganate by using the optical property-adjustable molybdenum oxide quantum dots according to claim 3, wherein the molar ratio of the molybdenum oxide quantum dots to the permanganate standard solution is (1000 to 10): 1, and the carbonate is Na 2 CO 3 Or K 2 CO 3 The pH value of the carbonate buffer solution is 7 to 11.
5. The method for measuring the concentration of permanganate in the optical property adjustable molybdenum oxide quantum dots according to claim 3, wherein the concentrations of the permanganate standard solutions are 0 μ M,0.08 μ M,0.1 μ M,0.5 μ M,1 μ M,3 μ M,5 μ M,7 μ M,9 μ M,15 μ M,21 μ M,23 μ M,25 μ M,27 μ M,29 μ M,31 μ M,37 μ M,39 μ M,50 μ M,70 μ M,80 μ M,90 μ M and 100 μ M respectively.
6. The method for measuring the concentration of permanganate in the optical property-adjustable molybdenum oxide quantum dots according to claim 3, wherein the regression equation of the standard curve is y =0.05967+0.05279x (0.08-25 μ M), R 2 =0.9973, wherein y is (I 0 -I)/IX is the permanganate concentration in μ M and R is the correlation coefficient.
7. A method for measuring captopril concentration by using optical property adjustable molybdenum oxide quantum dots, which is characterized in that the method for measuring the captopril concentration by using the molybdenum oxide quantum dots according to any one of claims 1 to 2 comprises the following steps:
drawing a captopril standard curve: uniformly mixing a potassium permanganate solution, the molybdenum oxide quantum dots and a series of captopril standard solutions with concentration gradients to obtain a mixed solution, fixing the volume to the same volume by using a carbonate buffer solution, measuring the fluorescence intensity of the solution with the fixed volume at an excitation wavelength of 430nm and an emission wavelength of 500nm, and taking the captopril concentration as a horizontal coordinate and measuring the relative fluorescence intensity (a)I-I 0 )/I 0 Drawing a standard curve for the ordinate; wherein the content of the first and second substances,I 0 when the captopril concentration is zero, the fluorescence intensity of the molybdenum oxide quantum dot-potassium permanganate system,Iis the corresponding fluorescence intensity when a molybdenum oxide quantum dot-potassium permanganate system and captopril with different concentrations coexist.
8. The method for measuring captopril concentration by using the optical property-adjustable molybdenum oxide quantum dots as claimed in claim 7, wherein the molar ratio of the potassium permanganate, the molybdenum oxide quantum dots and the captopril standard solution is 1 (0.002 to 0.6), the carbonate is Na 2 CO 3 Or K 2 CO 3 And the pH value of the carbonate buffer solution is 7 to 11.
9. The method for determining captopril concentration by using the optical property-adjustable molybdenum oxide quantum dots, as claimed in claim 7, wherein the captopril standard solution has a concentration of 0 μ M,0.1 μ M,0.3 μ M,0.5 μ M,0.8 μ M,1 μ M,3 μ M,5 μ M,7 μ M,11 μ M,13 μ M,15 μ M,17 μ M,21 μ M,23 μ M,25 μ M,27 μ M,31 μ M; the regression equation of the standard curve is y =0.02912+0.05921x (0.1-31 μ M), R 2 =0.9961, wherein y is (I-I 0 )/I 0 X is captopril concentration in μ M, and R is a correlation coefficient.
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