CN112812771A - Preparation method of graphene quantum dot sensitized europium terbium codoped layered hydroxide and product prepared by same - Google Patents
Preparation method of graphene quantum dot sensitized europium terbium codoped layered hydroxide and product prepared by same Download PDFInfo
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Abstract
The embodiment of the application provides a preparation method of a graphene quantum dot sensitized europium-terbium co-doped layered hydroxide and a product prepared by the same. The method provides a new method and a new idea for the preparation and large-scale production of the rare earth composite material with excellent optical characteristics.
Description
Technical Field
The application relates to the technical field of compound synthesis, in particular to a preparation method of graphene quantum dot sensitized europium terbium co-doped layered hydroxide and a product prepared by the same.
Background
The layered rare earth hydroxide LRHs serving as a two-dimensional inorganic hydroxide material not only has interlayer ion exchangeability, but also has a fluorescent characteristic, so that the layered rare earth hydroxide LRHs has important application in the fields of high-performance magnetic materials, light-emitting devices, fluorescent powder, catalysts, sensors, biological imaging, drug delivery and the like. The fluorescence characteristics of LRHs can be modulated by doping different kinds of rare earth elements and changing the doping proportion, however, in the laminate, rare earth ions can coordinate with hydroxyl and water molecules, the vibration of O-H bonds can greatly improve the non-radiative transition degree of the rare earth ions, and the molar absorption efficiency is reduced due to the f-f transition forbidden effect of the rare earth elements, so that the light emitting efficiency of the LRHs is low.
The light emitting efficiency of the LRHs can be effectively improved by introducing guest anions or molecules capable of transferring the energy absorbed by the LRHs to the rare earth ions between the layers of the LRHs, and the original layered structure of the LRHs cannot be damaged. The 'antenna effect' of the chromophore in the inorganic anion or organic molecule and the matching degree of the triplet state energy level and the fluorescence resonance energy level of the rare earth ion jointly determine the sensitization effect, and the selection of the sensitizer is very important for improving the LRHs luminous efficiency. Because the radiuses of the rare earth ions are very similar, a plurality of rare earth ions can be doped into the same main body together, and the interaction between the rare earth ions can enhance or weaken the luminous intensity, so that the effect of selecting proper doped ions on the luminous efficiency cannot be ignored.
The graphene quantum dot GQD is a zero-dimensional carbon nanomaterial with a 1-10-layer graphene structure and a size smaller than 100nm, has excellent luminescence characteristics, has a good sensitization effect on rare earth elements, and has a promotion effect on the improvement of luminescence efficiency due to effective energy transfer between trivalent terbium ions and trivalent europium ions.
At present, the sensitization of GQD to rare earth elements is only seen in an aqueous solution system, but because the reaction in the aqueous solution system has randomness, the structure of a product is difficult to control accurately, the product inevitably aggregates, and the obtained GQD has a multilayer structure or has larger disorder. Therefore, the development of the preparation method of the graphene quantum dot sensitized europium terbium layered hydroxide with the accurately controllable product structure is of great significance.
Disclosure of Invention
The embodiment of the application aims to provide a preparation method of graphene quantum dot sensitized europium terbium co-doped layered hydroxide and a product prepared by the same, so as to overcome the defects of the prior art.
The specific technical scheme is as follows:
the application firstly provides a preparation method of graphene quantum dot sensitized europium terbium codoped layered hydroxide, which comprises the following steps:
(1) preparation of europium terbium co-doped layered hydroxide NO3-LEuxTb1-xH;
(2) Treating the NO with an ion exchange process3-LEuxTb1-xH, synthesizing europium terbium codoped layered hydroxide CA-LEu with citrate intercalationxTb1-xH;
(3) Hydrothermal carbonization of the CA-LEuxTb1-xH, obtaining graphene quantum dot sensitized europium terbium codoped layered hydroxide GQD-LEuxTb1-xH;
Wherein x is more than or equal to 0.01 and less than or equal to 1.
Further, the step (1) comprises: tb (NO)3)3·6H2O、Eu(NO3)3·6H2O、NaNO3Dissolving HMT and hexamethylenetetramine in the exhaust water, stirring uniformly, transferring to a reaction kettle, and reacting at 80-95 DEG CCooling to room temperature for 10-15h, centrifuging, washing the solid, and drying to obtain NO3-LEuxTb1-xH。
Further, Tb (NO)3)3·6H2O and Eu (NO)3)3·6H2Total number of moles of O, NaNO3The ratio of the number of moles of (A) to the number of moles of HMT is 1:10-15: 0.5-1.5.
Further, Tb (NO)3)3·6H2O and Eu (NO)3)3·6H2The molar ratio of O is 1: 0.01-100.
Further, the step (2) comprises: adding NO3-LEuxTb1-xH and Na3C6H5O7·2H2Dissolving O in exhaust water, stirring, transferring to a reaction kettle, reacting at 80-95 deg.C for 20-30h, cooling to room temperature, centrifuging, washing the solid, and drying to obtain CA-LEuxTb1-xH。
Further, NO3-LEuxTb1-xH and Na3C6H5O7·2H2The molar ratio of O is 1: 10-15.
Further, the step (3) comprises: mixing CA-LEuxTb1-xDispersing H in exhaust water, adding ammonia water, stirring uniformly, transferring to a reaction kettle, reacting at the temperature of 150-200 ℃ for 7-10H, cooling to room temperature, centrifugally separating, washing and drying the solid to obtain GQD-LEuxTb1-xH。
Further, CA-LEuxTb1-xThe mass ratio of H to ammonia water is 0.1: 4-5.
The application also provides the graphene quantum dot sensitized europium terbium co-doped layered hydroxide prepared by the method.
The method utilizes the interlayer confinement space of the LRHs as a reactor, can accurately control the structure of the product while keeping the original structure and composition, and can prevent the GQD in the product from agglomerating. Tb in the product of the present application3+And Eu3+Effective energy transfer can occur, and the luminous efficiency is improved.
The preparation method of the graphene quantum dot sensitized europium terbium co-doped layered hydroxide provided by the application has the advantages that the prepared graphene quantum dot sensitized europium terbium co-doped layered hydroxide is high in luminous efficiency, the control of the LRHs luminous performance is expected to be realized by designing the structure of the GQD, a new method and a new thought are provided for the preparation and large-scale production of rare earth composite materials with excellent optical characteristics, and the method can be popularized to other carbon sources and different types of rare earth layered hydroxides.
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In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some examples of the present application, and other embodiments can be obtained by those skilled in the art according to the drawings.
FIG. 1 shows NO in examples 1 to 53-LEuxTb1-xThe X-ray diffraction pattern of H, wherein X is 0.01 for curve a, 0.09 for curve b, 0.5 for curve c, 0.91 for curve d, and 0.99 for curve e.
FIG. 2 shows CA-LEu of examples 1 to 5xTb1-xThe X-ray diffraction pattern of H, wherein X is 0.01 for curve a, 0.09 for curve b, 0.5 for curve c, 0.91 for curve d, and 0.99 for curve e.
FIG. 3 shows GQD-LEu of examples 1-5xTb1-xThe X-ray diffraction pattern of H, wherein X is 0.01 for curve a, 0.09 for curve b, 0.5 for curve c, 0.91 for curve d, and 0.99 for curve e.
FIG. 4 shows NO of example 23-LEu0.09Tb0.91H and GQD-LEu0.09Tb0.91H, fluorescence excitation and emission spectrum, wherein the maximum excitation wavelength is 352nm, and the maximum emission wavelength is 614 nm; wherein, a corresponds to NO3-LEu0.09Tb0.91H, b diagram corresponds to GQD-LEu0.09Tb0.91H。
FIG. 5 shows NO in examples 1 and 3 to 53-LEuxTb1-xH and GQD-LEuxTb1-xFluorescence excitation and emission spectra of H, wherein a1-a4 corresponds to NO3-LEuxTb1-xH, b1-b4 corresponds to GQD-LEuxTb1-xH, x is 0.01 in a1 and b1, 0.5 in a2 and b2, 0.91 in a3 and b3, and 0.99 in a4 and b 4.
FIG. 6 is an X-ray diffraction pattern of LEuH at different intercalation stages with 0 doping ratio of Tb in comparative example 1, wherein curve a corresponds to NO3-LeuH, curve b for CA-LeuH and curve c for GQD-LeuH.
FIG. 7 is an IR spectrum of LEuH in different intercalation stages of comparative example 1, where curve a corresponds to NO3-LeuH, curve b for CA-LeuH and curve c for GQD-LeuH.
FIG. 8 is a plot of fluorescence excitation and emission spectra of different intercalation stage LEuH of comparative example 1, with a maximum excitation wavelength of 394nm and a maximum emission wavelength of 614 nm; wherein a1 corresponds to NO3Fluorescence excitation spectrum of LEuH, a2 corresponding to NO3-fluorescence emission spectrum of LEuH; b1 corresponds to the fluorescence excitation spectrum of CA-LEuH, b2 corresponds to the fluorescence emission spectrum of CA-LEuH; c1 corresponds to the fluorescence excitation spectrum of GQD-LEuH, and c2 corresponds to the fluorescence emission spectrum of GQD-LEuH.
FIG. 9 shows NO of example 23-LEu0.09Tb0.91H and GQD-LEu0.09Tb0.91Optical photograph of H solid powder sample under irradiation of ultraviolet rays having wavelengths of 254nm and 365nm, NO in a3-LEu0.09Tb0.91Among H and b, GQD-LEu0.09Tb0.91H。
Detailed Description
To further illustrate the present application, the present application will be specifically described with reference to examples, but the scope of the present application is not limited to the specific examples. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in this application are within the scope of protection of this application.
Example 1
0.99mmol of Tb (NO) was taken3)3·6H2O, 0.01mmol of Eu (NO)3)3·6H2O, 10mmol of NaNO3Dissolving 0.5mmol of HMT in 80mL of exhaust water, stirring uniformly, transferring to a 100mL reaction kettle, reacting at 80 ℃ for 15h, cooling to room temperature, centrifuging, washing precipitate, and drying to obtain NO3-LEu0.01Tb0.99H。
0.3mmol of NO is taken3-LEu0.01Tb0.99H and 3mmol of Na3C6H5O7·2H2Dissolving O in 80mL of exhaust water, stirring uniformly, transferring to a 100mL reaction kettle, reacting at 95 ℃ for 20h, cooling to room temperature, centrifugally separating, washing precipitate, and drying to obtain CA-LEu0.01Tb0.99H。
0.1g of CA-LEu was weighed out0.01Tb0.99Dispersing H in 80mL of exhaust water, adding 4g of ammonia water, uniformly stirring, transferring to a 100mL reaction kettle, reacting at 150 ℃ for 10H, cooling to room temperature, centrifugally separating, washing and drying the solid to obtain GQD-LEu0.01Tb0.99H。
Example 2
0.91mmol of Tb (NO) was taken3)3·6H2O, 0.09mmol of Eu (NO)3)3·6H2O, 14mmol of NaNO3Dissolving 1mmol of HMT in 80mL of exhaust water, stirring uniformly, transferring to a 100mL reaction kettle, reacting at 90 ℃ for 12h, cooling to room temperature, centrifuging, washing precipitate, and drying to obtain NO3-LEu0.09Tb0.91H。
0.3mmol of NO is taken3-LEu0.09Tb0.91H and 4.5mmol of Na3C6H5O7·2H2Dissolving O in 80mL of exhaust water, stirring uniformly, transferring to a 100mL reaction kettle, reacting at 90 ℃ for 24h, cooling to room temperature, centrifugally separating, washing precipitate, and drying to obtain CA-LEu0.09Tb0.91H。
0.1g of CA-LEu was weighed out0.09Tb0.91Dispersing H in 80mL of exhaust water, adding 5g of ammonia water, stirring uniformly, and transferring to 100mReacting at 180 ℃ for 8h in an L reaction kettle, cooling to room temperature, centrifugally separating, washing and drying the solid to obtain GQD-LEu0.09Tb0.91H。
Example 3
0.5mmol of Tb (NO) was taken3)3·6H2O, 0.5mmol of Eu (NO)3)3·6H2O, 15mmol of NaNO3Dissolving 1.5mmol of HMT in 80mL of exhaust water, stirring uniformly, transferring to a 100mL reaction kettle, reacting at 80 ℃ for 15h, cooling to room temperature, centrifuging, washing precipitate, and drying to obtain NO3-LEu0.5Tb0.5H。
0.3mmol of NO is taken3-LEu0.5Tb0.5H and 4mmol of Na3C6H5O7·2H2Dissolving O in 80mL of exhaust water, stirring uniformly, transferring to a 100mL reaction kettle, reacting at 95 ℃ for 20h, cooling to room temperature, centrifugally separating, washing precipitate, and drying to obtain CA-LEu0.5Tb0.5H。
0.1g of CA-LEu was weighed out0.5Tb0.5Dispersing H in 80mL of exhaust water, adding 4.8g of ammonia water, uniformly stirring, transferring to a 100mL reaction kettle, reacting at 150 ℃ for 10H, cooling to room temperature, centrifugally separating, washing and drying the solid to obtain GQD-LEu0.5Tb0.5H。
Example 4
0.09mmol of Tb (NO) was taken3)3·6H2O, 0.91mmol of Eu (NO)3)3·6H2O, 11mmol of NaNO3Dissolving 1.2mmol of HMT in 80mL of exhaust water, stirring uniformly, transferring to a 100mL reaction kettle, reacting at 95 ℃ for 10h, cooling to room temperature, centrifuging, washing precipitate, and drying to obtain NO3-LEu0.91Tb0.09H。
0.3mmol of NO is taken3-LEu0.91Tb0.09H and 3.6mmol of Na3C6H5O7·2H2Dissolving O in 80mL of exhaust water, stirring uniformly, transferring to a 100mL reaction kettle, reacting at 80 ℃ for 30h, cooling to room temperature, centrifugally separating, washing precipitate, and dryingObtaining CA-LEu0.91Tb0.09H。
0.1g of CA-LEu was weighed out0.91Tb0.09Dispersing H in 80mL of exhaust water, adding 4.8g of ammonia water, uniformly stirring, transferring to a 100mL reaction kettle, reacting at 200 ℃ for 7H, cooling to room temperature, centrifugally separating, washing and drying the solid to obtain GQD-LEu0.91Tb0.09H。
Example 5
0.01mmol of Tb (NO) was taken3)3·6H2O, 0.99mmol of Eu (NO)3)3·6H2O, 13mmol of NaNO3Dissolving 1mmol of HMT in 80mL of exhaust water, stirring uniformly, transferring to a 100mL reaction kettle, reacting at 95 ℃ for 10h, cooling to room temperature, centrifuging, washing precipitate, and drying to obtain NO3-LEu0.99Tb0.01H。
0.3mmol of NO is taken3-LEu0.99Tb0.01H and 3.6mmol of Na3C6H5O7·2H2Dissolving O in 80mL of exhaust water, stirring uniformly, transferring to a 100mL reaction kettle, reacting at 80 ℃ for 30h, cooling to room temperature, centrifugally separating, washing precipitate, and drying to obtain CA-LEu0.99Tb0.01H。
0.1g of CA-LEu was weighed out0.99Tb0.01Dispersing H in 80mL of exhaust water, adding 4.5g of ammonia water, uniformly stirring, transferring to a 100mL reaction kettle, reacting at 200 ℃ for 7H, cooling to room temperature, centrifugally separating, washing and drying the solid to obtain GQD-LEu0.99Tb0.01H。
Comparative example 1
1mmol of Eu (NO)3)3·6H2O, 13mmol of NaNO3Dissolving 1mmol of HMT in 80mL of exhaust water, stirring uniformly, transferring to a 100mL reaction kettle, reacting at 95 ℃ for 10h, cooling to room temperature, centrifuging, washing precipitate, and drying to obtain NO3-LEuH。
0.3mmol of NO is taken3-LEuH and 3.6mmol of Na3C6H5O7·2H2Dissolving O in 80mL of exhaust water, stirring uniformly, transferring to 1And reacting for 24 hours at 90 ℃ in a 00mL reaction kettle, cooling to room temperature, centrifugally separating, washing precipitate, and drying to obtain CA-LEuH.
Weighing 0.1g of CA-LEuH, dispersing in 80mL of exhaust water, adding 4.8g of ammonia water, stirring uniformly, transferring to a 100mL reaction kettle, reacting at 160 ℃ for 8h, cooling to room temperature, performing centrifugal separation, washing and drying the solid to obtain GQD-LEuH.
FIGS. 1, 2 and 3 are LEu for nitrate, citrate and graphene quantum dot intercalation of examples 1-5, respectivelyxTb1-xThe X-ray diffraction pattern (XRD pattern) of H, X for curve a is 0.01 (example 1), X for curve b is 0.09 (example 2), X for curve c is 0.5 (example 3), X for curve d is 0.91 (example 4), and X for curve e is 0.99 (example 5). It can be seen that the precursor NO in FIG. 13-LEuxTb1-xInterlayer spacing of H (d)basal) Values 0.85-0.86nm compared to CA-LEu in FIG. 2xTb1-xD of HbasalThe value is reduced to 0.74-0.76nm, which indicates that the citrate successfully replaces nitrate to enter the interlayer; and CA-LEu in FIG. 2xTb1-xCompared with H, the (002) diffraction peak position in figure 3 shows small-amplitude movement in a large angle direction, and d is obtained after hydrothermal carbonization by adding ammonia waterbasalThe value is reduced by 0.02-0.04nm, which proves that GQD is successfully synthesized in situ by utilizing citrate between layers.
FIG. 6 is an XRD pattern of LEuH at different intercalation stages of comparative example 1, wherein curve a corresponds to NO3-LeuH, curve b for CA-LeuH and curve c for GQD-LeuH. It can be seen that3D of LEuHbasalValue 0.84nm compared with d of CA-LEuHbasalThe value decreases to 0.77nm, indicating that the citrate successfully replaces nitrate into the interlayer; compared with CA-LEuH, after adding ammonia water for hydrothermal carbonization, the (002) diffraction peak position of the curve c moves to a large angle direction by a small margin, and dbasalThe value is reduced by 0.03nm compared to CA-LEuH, demonstrating that GQD has been successfully synthesized in situ using interlaminar citrate.
FIG. 7 is an IR spectrum of 3600cm of LEuH in different intercalation stages of comparative example 1-1Nearby broad absorption bands are attributed to hydroxyl (-OH) groups on the LEuH lamellae, interlaminationWater molecule and O-H stretching vibration with water adsorbed on surface, 1630cm-1The nearby absorption bands are attributed to the bending vibration of the crystalline water and the surface-adsorbed water. Wherein NO3LEuH (curve a) at 1385cm-1The vibration absorption band of (B) is attributed to the N-O stretching vibration of nitrate, 581cm-1The absorption band is the stretching vibration of Eu-O in the laminate. In the spectrum of CA-LEuH (curve b), the characteristic absorption band of nitrate disappeared, indicating that the ion exchange reaction was complete, and 1508 and 1375cm-1The absorption bands of (A) are respectively assigned to the carboxyl (-COO) groups in the citrate radical-) Symmetry (v)s) And antisymmetry (v)as) Stretching vibration proves that citrate is successfully inserted into the LEuH layers, and the citrate between the layers is coordinated with rare earth ions in the LEuH laminate. And the expansion vibration absorption peak of Eu-O in GQD-LEuH (curve c) is shifted to high wave number relative to CA-LEuH, which proves that the conversion of interlaminar citrate to graphene quantum dots is positioned at 1520 and 1380cm-1nearby-COO-The stretching vibration peak of (1) indicates that GQD also reacts with Eu3+The coordinated form is bound between the layers of LEuH.
As can be seen from FIG. 4, NO is observed at a wavelength of 614nm3-LEu0.09Tb0.91(panel a of FIG. 4) and GQD-LEu0.09Tb0.91H (b of FIG. 4) all exhibit Eu3+The characteristic excitation spectrum of (1) is that a series of excitation peaks positioned at 270-400nm are sequentially derived from Tb from low waves to high waves3+4f of8→4f75d1And 4f8Electron transition and Eu3+4f of6Electron transition; at Tb3+At an optimum excitation wavelength of 352nm, NO3-LEu0.09Tb0.91And GQD-LEu0.09Tb0.91H also exhibits Eu3+Including at 595, 613, 651 and 700nm5D0→7FJ(J ═ 1, 2, 3, 4) transitions. This is illustrated at LEu0.09Tb0.91Middle, Tb3+And Eu3+Efficient energy transfer occurs. GQD-LEu0.09Tb0.91Excitation spectrum of H shows S of GQD at about 250nm0→S1Transition peak, and GQD-LEu0.09Tb0.91The luminous intensity of the H complex is higher than that of NO3-LEu0.09Tb0.91The double of the amount of the acid-base (GQD-LEu) is shown in FIG. 9, compared with the nitric acid-type starting material (FIG. 9, panel a)0.09Tb0.91The fluorescence emission intensity of H is significantly enhanced, especially in the deep ultraviolet region (fig. 9 b). This indicates that the interlayer GQD can effectively sensitize LEu0.09Tb0.91Eu in H3+The light emission of (1). FIG. 5 is NO3-LEuxTb1-xH and GQD-LEuxTb1-xFluorescence excitation and emission spectra of H, in which a1-a4 of FIG. 5 correspond to NO3-LEuxTb1-xH, panels b1-b4 of FIG. 5 correspond to GQD-LEuxTb1-xH, x is 0.01 (example 1) in the a1 diagram and b1 diagram of fig. 5, 0.5 (example 3) in the a2 diagram and b2 diagram of fig. 5, 0.91 (example 4) in the a3 diagram and b3 diagram of fig. 5, and 0.99 (example 5) in the a4 diagram and b4 diagram of fig. 5. It can be found that when Eu is used3+When the doping ratio of (A) is smaller, Eu is increased3+The doping ratio of (A) is favorable for improving the luminous efficiency of the LED; as the concentration increases, the Eu increases due to the continuous increase of the doping ratio3+Quenching of self-luminescence.
FIG. 8 is a plot of fluorescence excitation and emission spectra of different intercalation stage LEuH of comparative example 1, with a maximum excitation wavelength of 394nm and a maximum emission wavelength of 614 nm; among them, the a1 diagram of FIG. 8 corresponds to NO3Fluorescence excitation spectrum of LEuH, graph a2 of FIG. 8 corresponding to NO3-fluorescence emission spectrum of LEuH; FIG. 8, b1, shows fluorescence excitation spectra corresponding to CA-LEuH, and FIG. 8, b2, shows fluorescence emission spectra corresponding to CA-LEuH; FIG. 8, c1, shows the fluorescence excitation spectrum corresponding to GQD-LEuH, and fig. 8, c2, shows the fluorescence emission spectrum corresponding to GQD-LEuH. It can be seen that at a wavelength of 614nm, each sample exhibited Eu3+The characteristic excitation spectrum of (1), a series of excitation peaks at 280-400nm are derived from Eu3+4f of6Electron transitions (fig. 8, diagrams a1, b1, c 1); at a wavelength of 394nm, each sample showed Eu3+Including at 595, 613, 651 and 700nm5D0→7FJ(J ═ 1, 2, 3, 4) transitions (fig. 8, a2, b2, c 2). From the figure8, a1, b1 and c1 show that no intercalated citrate and no S of GQD are present in the excitation spectrum of the complex0→S1Transition peak, and Eu3+4f electron of (3) is lower in direct transition excitation strength than NO3A significant reduction in-LEuH, indicating that GQD between the composite layers cannot sensitize Eu3+The light emission of (1). -COO carried by citrate-Then Eu is significantly reduced3+Characteristic excitation and emission peak intensities.
Comparing fig. 4, 9 and 8, it is clear that the improvement of the luminous efficiency in the graphene quantum dot sensitized europium terbium co-doped layered hydroxide is the common effect of the interaction of europium ions and terbium ions and the GQD sensitization.
The above description is only for the preferred embodiment of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application are included in the protection scope of the present application.
Claims (9)
1. A preparation method of graphene quantum dot sensitized europium terbium codoped layered hydroxide comprises the following steps:
(1) preparation of europium terbium co-doped layered hydroxide NO3-LEuxTb1-xH;
(2) Treating the NO with an ion exchange process3-LEuxTb1-xH, synthesizing europium terbium codoped layered hydroxide CA-LEu with citrate intercalationxTb1-xH;
(3) Hydrothermal carbonization of the CA-LEuxTb1-xH, obtaining graphene quantum dot sensitized europium terbium codoped layered hydroxide GQD-LEuxTb1-xH;
Wherein x is more than or equal to 0.01 and less than or equal to 1.
2. The method for preparing the graphene quantum dot sensitized europium terbium co-doped layered hydroxide according to claim 1, wherein the step (1) comprises: tb (NO)3)3·6H2O、Eu(NO3)3·6H2O、NaNO3And HMT dissolved in exhaust gasStirring in water, transferring into a reaction kettle, reacting at 80-95 deg.C for 10-15 hr, cooling to room temperature, centrifuging, washing the solid, and drying to obtain NO3-LEuxTb1-xH。
3. The method for preparing the graphene quantum dot sensitized europium terbium co-doped layered hydroxide according to claim 2, wherein Tb (NO)3)3·6H2O and said Eu (NO)3)3·6H2Total number of moles of O, the NaNO3The ratio of the number of moles of (a) to the number of moles of HMT is from 1:10 to 15:0.5 to 1.5.
4. The method for preparing the graphene quantum dot sensitized europium terbium co-doped layered hydroxide according to claim 2 or 3, wherein Tb (NO) is3)3·6H2O and said Eu (NO)3)3·6H2The molar ratio of O is 1: 0.01-100.
5. The method for preparing the graphene quantum dot sensitized europium terbium co-doped layered hydroxide according to claim 1, wherein the step (2) comprises: the NO is added3-LEuxTb1-xH and Na3C6H5O7·2H2Dissolving O in exhaust water, stirring, transferring to a reaction kettle, reacting at 80-95 deg.C for 20-30h, cooling to room temperature, centrifuging, washing the solid, and drying to obtain CA-LEuxTb1-xH。
6. The method for preparing the graphene quantum dot sensitized europium terbium co-doped layered hydroxide according to claim 5, wherein the NO is3-LEuxTb1-xH and said Na3C6H5O7·2H2The molar ratio of O is 1: 10-15.
7. The method for preparing the graphene quantum dot sensitized europium terbium co-doped layered hydroxide according to claim 1, wherein the step (3)) The method comprises the following steps: mixing the CA-LEuxTb1-xDispersing H in exhaust water, adding ammonia water, stirring uniformly, transferring to a reaction kettle, reacting at the temperature of 150-200 ℃ for 7-10H, cooling to room temperature, centrifugally separating, washing and drying the solid to obtain GQD-LEuxTb1-xH。
8. The method for preparing the graphene quantum dot sensitized europium terbium co-doped layered hydroxide according to claim 7, wherein the CA-LEuxTb1-xThe mass ratio of H to the ammonia water is 0.1: 4-5.
9. The graphene quantum dot sensitized europium terbium co-doped layered hydroxide prepared by the method of any one of claims 1 to 8.
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