CN110734090A - rare earth ion doping-based α -Ag2WO4Method for preparing optical thermometer - Google Patents

rare earth ion doping-based α -Ag2WO4Method for preparing optical thermometer Download PDF

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CN110734090A
CN110734090A CN201910908344.5A CN201910908344A CN110734090A CN 110734090 A CN110734090 A CN 110734090A CN 201910908344 A CN201910908344 A CN 201910908344A CN 110734090 A CN110734090 A CN 110734090A
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rare earth
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王祥夫
余吉宏
步妍妍
颜晓红
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Nanjing Post and Telecommunication University
Nanjing University of Posts and Telecommunications
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Abstract

The invention discloses rare earth ion doping-based α -Ag2WO4The preparation method of the optical thermometer comprises the following steps of S1, S2, preparing a solution containing rare earth ions, S3, preparing a silver ion solution and a tungstate solution, S4, adding the rare earth ion solution, S5, mixing the solution to obtain a precipitate, heating the solution obtained in the S4 step and the tungstate solution obtained in the S3 step, adding the solution obtained in the S4 step into the tungstate solution under the stirring condition, keeping the temperature for time to generate a light yellow precipitate instantly, whitening the light yellow precipitate after time, centrifuging the precipitate after naturally cooling the solution to room temperature, washing the precipitate with deionized water, washing the precipitate with ethanol and drying in an oven to obtain the rare earth ion doped α -Ag2WO4And (3) powder. The preparation method is simple and convenient, and the prepared optical materialThe thermometer has high sensitivity, and the method can be used as an excellent optical thermometer.

Description

rare earth ion doping-based α -Ag2WO4Method for preparing optical thermometer
Technical Field
The invention relates to rare earth ion doping-based α -Ag2WO4Belonging to the field of preparation method of optical thermometerThe technical field of light temperature sensing.
Background
However, in many fields where direct contact is inconvenient, such as the interior of microelectronic devices, coal mines, transformation sites of high-voltage power stations, and the like, conventional thermometers have difficulty in achieving temperature measurement, and therefore, it is very urgent to research non-contact temperature sensors.
Silver tungstates are of great interest for their various applications, particularly α -Ag2WO4Many groups have studied α -Ag doped with different rare earth ions (Pr, Sm, Eu, Tb, Dy and Tm) at room temperature2WO4However, temperature on rare earth ion doped α -Ag2WO4The effect of the luminescence properties of (a) has not been investigated. In the invention, Eu doped is purposefully synthesized3+，Dy3+，Tm3+And Er3+α -Ag with adjustable ionic nano particle morphology2WO4And (4) crystals. Study Eu3+，Dy3+，Tm3+And Er3+Doped α -Ag2WO4The temperature sensing property of the obtained material was found to be α -Ag2WO4：1％Eu3+，α-Ag2WO4：2％Dy3+，α-Ag2WO4：2％T3+And α -Ag2WO4：1％Er3+The relative sensitivity of these phosphors can reach 1.84% K-1，2.53％K-1，0.46％K-1And 0.47% K-1Respectively, higher than the most phosphors reported.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides rare earth ion doping-based α -Ag2WO4The method for producing an optical thermometer of (1).
The aim of the invention is realized by the following technical scheme that rare earth ion doping-based α -Ag2WO4The method for preparing the optical thermometer comprises the following steps:
s1: selecting raw materials;
AgNO3，Na2WO4·2H2o, ethanol, Er2O3，Dy2O3，Eu2O3And Tm2O3；
S2: preparing a solution containing rare earth ions;
adding Er2O3，Dy2O3，Eu2O3And Tm2O3Respectively dissolved in dilute HNO3Transferring the product to a volumetric flask after neutralization to obtain Er (NO)3)3，Dy(NO3)3，Eu(NO3)3And Tm (NO)3)3The mixed solution of (1);
s3: preparing a silver ion solution and a tungstate solution;
weighing AgNO3And Na2WO4·2H2O, and dissolving the O in 50mL of deionized water in two beakers respectively to obtain AgNO3Solution and Na2WO4A solution;
s4: adding a rare earth ion solution;
AgNO obtained in S33Er (NO) is added into the solution3)3Or Dy (NO)3)3Or Eu (NO)3)3Or Tm (NO)3)3Obtaining a solution containing rare earth ions and silver ions;
s5: mixing the solution to obtain a precipitate;
mixing the rare earth ion-containing and silver ion solution obtained in the step S4 with Na obtained in the step S32WO4Heating the solution, adding the solution containing rare earth ions and silver ions to Na under stirring2WO4Maintaining the temperature for time to instantly generate light yellow precipitate, whitening the light yellow precipitate after time, naturally cooling the solution to room temperature, centrifuging the precipitate, washing with deionized water, washing with ethanol, and drying in oven to obtain α -Ag doped with rare earth ions2WO4And (3) powder.
Preferably, in the step S2, Er (NO)3)3，Dy(NO3)3，Eu(NO3)3And Tm (NO)3)3The concentration of the mixed solution of (3) was 0.2M.
Preferably, in the step S3, 1.97mmol of AgNO is weighed3And 1mmol of Na2WO4·2H2O。
Preferably, in the step S4, the Er (NO)3)3Or Dy (NO)3)3Or Eu (NO)3)3Or Tm (NO)3)3The solution was 50. mu.L.
Preferably, in the step of S5, the rare earth ion-containing and silver ion solution obtained in the step of S4 and Na obtained in the step of S3 are mixed2WO4The solution was heated to 90 ℃ for 5 minutes.
Preferably, in the S5 step, the solution containing rare earth ions and silver ions is added to tungsten Na with stirring2WO4In the solution, the heating temperature was 90 ℃ for 30 minutes.
Preferably, in the S5 step, the precipitate is washed with ethanol and dried in an oven at 60 ℃ for 12 hours.
Compared with the prior art, the invention adopting the technical scheme has the following technical effects:
(1) the rare earth ion prepared by the invention is doped with α -Ag2WO4The optical thermometer has good thermal stability and chemical stability.
The preparation method is simple and convenient and is suitable for industrial batch production.
(2) The rare earth ion doped α -Ag2WO4The optical thermometer has good optical properties.
(3) The invention researches Eu3+，Dy3+，Tm3+And Er3+Doped α -Ag2WO4The luminescent property at low temperature, the temperature sensing property is discovered, and Eu doped is purposefully synthesized3+，Dy3+，Tm3+And Er3+The form of the ion is adjustable α -Ag2WO4The crystal and the sensitivity of the optical thermometer is improved, for α -Ag2WO4：1％Eu3+，α-Ag2WO4：2％Dy3+，α-Ag2WO4：2％Tm3+And α -Ag2WO4：1％Er3+The relative sensitivity of these phosphors can reach 1.84% K-1，2.53％K-1，0.46％K-1And 0.47% K-1Respectively, higher than the most phosphors reported.
Drawings
FIG. 1 shows α -Ag doped with different rare earth ions according to the present invention2WO4XRD pattern of (a).
FIG. 2 shows α -Ag of the present invention2WO4：1％Eu3+，(b)α-Ag2WO4：1％Er3+，(c)α-Ag2WO4：2％Dy3+And (d) α -Ag2WO4：2％Tm3+SEM image of (d).
FIG. 3 shows α -Ag of the present invention2WO4：1％Er3+，α-Ag2WO4：1％Eu3+，α-Ag2WO4：2％Dy3+And α -Ag2WO4：2％Tm3+The ultraviolet light-visible light-infrared light diffuse reflection spectrogram.
FIG. 4 shows (a) monitoring at 615nm for α -Ag according to the present invention2WO4：1％Eu3+(b) monitoring α -Ag at 575nm2WO4：2％Dy3+(c) monitoring α -Ag at 805nm2WO4：2％Tm3+And (d) monitoring α -Ag at 530nm2WO4：2％Er3+The excitation spectrum of (1).
FIG. 5 shows α -Ag at different temperatures of (a) according to the present invention2WO4：1％Eu3+With Eu3+A temperature dependence of emission intensity corresponding to emission, (c) an emission intensity ratio of 425nm and 614nm as a fit to temperature, and (d) α -Ag2WO4：1％Eu3+Temperature relative sensitivity of excitation at 355 nm.
FIG. 6 shows α -Ag at different temperatures of (a) according to the present invention2WO4：2％Dy3+Emission spectrum of (b) and Dy3+A temperature relationship of emission intensity corresponding to emission, (c) a fit of emission to temperature with emission intensity ratios of 425nm and 575nm, and (d) α -Ag2WO4：2％Dy3+Temperature relative sensitivity of excitation at 355 nm.
FIG. 7 shows α -Ag at different temperatures of (a) according to the present invention2WO4：2％Tm3+Emission spectrum of (a), (b) and Tm3+A temperature dependence of emission intensity corresponding to emission, (c) an emission intensity ratio of 425nm and 550nm as a fit to temperature, and (d) α -Ag2WO4：2％Tm3+Temperature relative sensitivity of excitation at 355 nm.
FIG. 8 shows α -Ag at different temperatures of (a) according to the present invention2WO4：2％Er3+Emission spectrum of (a), (b) and Er3+A temperature dependence of emission intensity corresponding to emission, (c) an emission intensity ratio of 425nm and 805nm as a fit to temperature, and (d) α -Ag2WO4：1％Er3+Temperature relative sensitivity of excitation at 355 nm.
Detailed Description
Objects, advantages and features of the present invention will be illustrated and explained by the following non-limiting description of preferred embodiments. The embodiments are merely exemplary for applying the technical solutions of the present invention, and any technical solution formed by replacing or converting the equivalent thereof falls within the scope of the present invention claimed.
The invention discloses rare earth ion doping-based α -Ag2WO4The method for preparing the optical thermometer comprises the following steps:
s1: selecting raw materials;
AgNO3(99.8％，Sigma-Aldrich)，Na2WO4·2H2o (99.5%, Sigma-Aldrich), ethanol (99.99%, Sigma-Aldrich) Er2O3(99.99％，Sigma-Aldrich)，Dy2O3(99.99％，Sigma-Alldrich)，Eu2O3(99.99%, Sigma-Aldrich) and Tm2O3(99.99%, Sigma-Aldrich) was used without further purifications;
s2: preparing a solution containing rare earth ions;
adding Er2O3，Dy2O3，Eu2O3And Tm2O3Respectively dissolved in dilute HNO3Transferring to volumetric flask after neutralization to obtain ErNO3)3，Dy(NO3)3，Eu(NO3)3And Tm (NO)3)3The mixed solution of (1).
In the step S2, Er (NO)3)3，Dy(NO3)3，Eu(NO3)3And Tm (NO)3)3The concentration of the mixed solution of (3) was 0.2M
S3: preparing a silver ion solution and a tungstate solution;
carefully weigh AgNO3And Na2WO4·2H2O, and dissolving the O in 50mL of deionized water respectively in two beakers to obtain AgNO3Solution and Na2WO4A solution; in the step S3, 1.97mmol of AgNO is weighed respectively3And 1mmol of Na2WO4·2H2O。
S4: adding a rare earth ion solution;
AgNO obtained in S33Er (NO) is added into the solution3)3Or Dy (NO)3)3Or Eu (NO)3)3Or Tm (NO)3)3Obtaining a solution containing rare earth ions and silver ions; in the step S4, the Er (NO)3)3Or Dy (NO)3)3Or Eu (NO)3)3Or Tm (NO)3)3The solution was 50. mu.L.
S5: mixing the solution to obtain a precipitate;
mixing the rare earth ion-containing and silver ion solution obtained in the step S4 with Na obtained in the step S32WO4Heating the solution, adding the solution containing rare earth ions and silver ions to Na under stirring2WO4Maintaining the temperature for time to instantly generate light yellow precipitate, whitening the light yellow precipitate after time, naturally cooling the solution to room temperature, centrifuging the precipitate, washing with deionized water, washing with ethanol, and drying in oven to obtain α -Ag doped with rare earth ions2WO4And (3) powder.
In the step of S5, the rare earth ion-containing and silver ion solution obtained in the step of S4 and Na obtained in the step of S3 are mixed2WO4The solution was heated to 90 ℃ for 5 minutes. In the step S5, the solution containing rare earth ions and silver ions is added to Na with stirring2WO4In the solution, the heating temperature was 90 ℃ for 30 minutes. In the S5 step, the precipitate was washed with ethanol and dried in an oven at 60 ℃ for 12 hours.
The experimental results are as follows:
FIG. 1 shows the XRD pattern of the as-synthesized sample all patterns are a perfect match to the standard PDF card (#34-0016), which can be indexed to α -Ag2WO4Crystals, no trace of impurity phase was observed, indicating a pure orthorhombic α -Ag system2WO4Successful phase synthesis and doping of ions (Er)3+，Dy3+，Eu3+And Tm3+) Negligible effect on the phase structure.
The morphology and size distribution of the phosphor crystals are important parameters affecting the luminous fluxThe morphology of these phosphors was confirmed by SEM images, as shown in FIG. 2(a) shows α -Ag2WO4：1％Eu3+These nanoparticles have a width of about 130nm and a length of 1.3 μm when 1% mol Er is added3+Introduction of α -Ag2WO4When crystalline, with α -Ag2WO4：1％Eu3+In contrast, there was no significant difference in shape, only size.
FIG. 2(b) shows α -Ag2WO4：1％Er3+A nanocrystal morphology with a width of about 140nm and a length of 1.3 μm, FIG. 2(c) shows α -Ag2WO4：2％Dy3+Has a particle size distribution of 70nm to 350 nm. Analogous to 2% molDy3+Doping, 2% mol Tm in FIG. 2(d)3+Doped α -Ag2WO4Nanocrystals also exhibit spherical morphologies with size distributions ranging from about 70nm to 170nm thus, in the present case, high doping metal ion concentrations can induce α -Ag2WO4The morphology of the crystals changes, a phenomenon which can be explained by internal charge transfer. In general, doping can cause lattice distortion, resulting in a change in morphology.
FIG. 3 shows α -Ag2WO4：1％Er3+，α-Ag2WO4：1％Eu3+，α-Ag2WO4：2％Dy3+And α -Ag2WO4：2％Tm3+In these four samples, a strong host absorption band in the UV range of 200nm to 410nm can be observed, indicating good absorption properties in the UV region for these synthetic samples several characteristic peaks of rare earth ions can be found simultaneously, at α -Ag2WO4：2％Dy3+In the spectrum of (1), due to 4f-4f6H15/2Transition of ground state to6F5/2，6F7/2，6H7/2And6H9/2excited states are respectively Dy3+The ion has four peaks centered at 805nm, 910nm, 1105nm and 1288nm at α -Ag2WO4：2％Tm3+In the spectrum, three absorption peaks at 688nm, 798nm and 1215nm correspond to the peaks respectively3H6Ground state to3F3，3H4And3H5tm3+ transition of excited state.
FIG. 4(a) shows the emission at 615nm by monitoring, α -Ag2WO4：1％Eu3+Excitation spectrum of (1). The excitation spectrum includes a broad band in the range of 300nm to 450nm and two smaller sharp bands due to Eu3+Ion from ground state7F0To an excited state5L6(393nm) and5D2characteristic transition of (465 nm). The broad excitation band is due to WO6A combination of charge transfer of the ligand to the metal in the group and charge transfer of the Eu-O group.
α -Ag monitored at 575nm emission band2WO4：2％Dy3+The two broad bands centered at 265nm and 440nm in FIG. 4(b) can find weak bands the first two bands can be attributed to the overlap of the charge transfer band from oxygen to dysprosium and tungsten, the latter due to Dy3+Ion from ground state6H15/2To an excited state6P7/2(352nm)，4I13/2(392nm) and4I15/2typical transition of (446 nm). Ag2WO4：2％Tm3+And α -Ag2WO4：1％Eu3+Recording and monitoring of 805nm and 530nm emission, respectively, as shown in FIGS. 4(c) and 4 (d.) these spectra are similar to α -Ag2WO4：1％Eu3+And (3) sampling.
A broad band of 300nm to 450nm was observed in both spectra, which can be attributed to charge transfer from the ligand to the metal, which originates from WO6In group O2-→W6-Is/are as follows1T1→1A1Transition, at the same time, Tm3+ f-f transitions of the ion are located at 440nm and 464nm, corresponding to3F4→1D2And3H6→1G4transition and Er at 412nm3+F-f of ionsThe transition is due to a transition from4I15/2Ground state to2H9/2Transition of the excited state.
FIG. 5(a) shows α -Ag2WO4：1％Eu3+A temperature dependent emission spectrum in the range of 11K to 295K. Due to the broad band of the host lattice at 425nm and two typical Eu at 592nm and 614nm3+Emission peak corresponding to excited state5D0To the ground state7F1And7F2the 4f-4f transition of (a) can also be observed. Eu increases with temperature3+Due to the thermal quenching effect, the luminescence intensity of the host lattice shows an irregular variation with increasing temperature. In general, the temperature-dependent luminescence intensity can be described by the modified Arrhenius equation:
Figure BDA0002212942060000051
where I (T) is the normalized emission intensity at temperature K (divided by I (11K)), C is a constant, Δ Ea is the activation energy for thermal quenching, and K is the Boltzmann constant.
Equation (1) is used to fit the temperature dependent emission intensity of Eu3+ shown in figure 5 (b). From the fitting procedure, the activation energy (. DELTA.Ea) was determined to be 39.8. + -. 2.0meV, which is close to the reported values (20.1. + -. 2.5 and 33.4. + -. 1.9). The temperature-dependent emission intensity was calculated, and the ratio of the emission intensities at 425nm and 614nm showed temperature dependence. Based on the Arrhenius equation, the emission intensity ratio can be fitted through a modified equation
Figure BDA0002212942060000052
By using equation (2), the emission intensity ratio of 425nm and 614nm can be fitted in the range of 11-295K, as shown in FIG. 5 (c). The relative sensitivity Sr is an important parameter for evaluating and comparing the temperature sensing properties of the phosphors, and is defined as
α -Ag derived from formula (3)2WO4：1％Eu3+The temperature dependence of the relative sensitivity Sr of (a) is shown in fig. 5 (d). 1.84% K at 211K-1Maximum relative sensitivity of.
FIG. 6(a) shows α -Ag2WO4：2％Dy3+Temperature dependent emission spectra in the 11K to 295K range two bands at 425nm and 640nm are due to the host lattice, typically observed corresponding to all temperature ranges4F9/2→6H13/2Dy at 575nm of transitions3+Emission peak. At 11K, new Dy appears at 485nm3+Emission peak due to4F9/2→6H15/2Jump and quench with increasing temperature.
FIG. 6(b) shows Dy3+(575nm) and bulk (640nm) emission of the normalized emission intensity showing temperature dependence due to thermal quenching effect according to fitting equation (1) the activation energy (. DELTA.Ee) was obtaineda)，Dy3+And a host of 11.78 and 15.83meV, respectively FIG. 6(c) shows emission intensity ratios of 425 and 575nm in a temperature range of 11-174K, which shows temperature dependence and can be fitted by using equation (2) α -Ag is calculated by using equation (3)2WO4：2％Dy3 +The relative sensitivity Sr of (c) is shown in FIG. 6 (d). At 90K, the maximum relative sensitivity is as high as 2.53 percent K-1。
α -Ag recorded in the temperature range of 11K to 291K2WO4：2％Tm3+The emission spectrum of (a) is shown in FIG. 7 (a). In the low temperature range (11-55K), two distinct broad emission bands at 425 and 600nm can be found, which are due to host lattice emission. At the same time, a corresponding Tm can also be observed3+Two typical peak emissions of ions, which can be attributed to1G2→3H6(481nm) and3H4→3H6(805nm) transition. Emission intensities 600nm (bulk) and 805nm (Tm)3+) The temperature dependence of (a) is shown in FIG. 7 (b).
The luminous intensity assigned to shows a tendency to decrease with increasing temperature, associated with the thermal quenching effect by using the improved Arrhenius equation (1), subject and Tm3+Activation energy of (Δ E)a) Can be calculated as 7.84 and 19.7meV, respectively. Based on Tm3+The thermal quenching properties of the emission, the emission intensity ratio of 425nm/805nm (FIG. 7(c)), show a temperature dependence that can be well fitted by using equation (2). FIG. 7(d) shows the relative sensitivity obtained from equation (3) and reaches 0.46% K-1The maximum sensitivity of (c).
FIG. 8(a) depicts α -Ag at an excitation wavelength of 355nm2WO4：2％Tm3+Temperature-dependent (11-295K) emission spectrum. It can be seen from the figure that the low temperature emission spectrum (11-44K) clearly contains two distinct main emission bands centered at 425nm and 600 nm. At the same time, two emission peaks at 550nm and 660nm were observed, due to Er3+Characteristics of the ions4S3/2→4I15/2And4F9/2→4I15/24f-4f transition of (a).
New Er with increasing temperature3+The emission peak (532nm) starts to appear at 156K and is due to2H11/2The heat capacity of the energy levels increases with temperature while the other emission intensities gradually decrease due to thermal quenching fig. 8(b) shows the normalized emission intensity of the 550nm emission as a function of temperature.
By using the fitting equation (1), the activation energy (. DELTA.EE) of 15.4. + -. 2.74meV was obtaineda) Using equation (2), the parameters A, Δ E, and B were determined to be 18.1, 226.9, and 7.19, indicating α -Ag2WO4：1％Er3+Can be used as a thermometer in the low temperature range. Sensitivity was calculated by using equation (3) to reach 0.47% K-1The maximum sensitivity of (a), which is comparable to other sensors.
The rare earth ions prepared by the invention are doped with α -Ag2WO4Has good flexibility, and can be used as a spectral and optical thermometerAnd (4) sensitivity.
The invention has various embodiments, and all technical solutions formed by adopting equivalent transformation or equivalent transformation are within the protection scope of the invention.

Claims (7)

1, rare earth ion doping-based α -Ag2WO4The method for manufacturing an optical thermometer is characterized in that:
the method comprises the following steps:
s1: selecting raw materials;
AgNO3，Na2WO4·2H2o, ethanol, Er2O3，Dy2O3，Eu2O3And Tm2O3；
S2: preparing a solution containing rare earth ions;
adding Er2O3，Dy2O3，Eu2O3And Tm2O3Respectively dissolved in dilute HNO3Transferring the product to a volumetric flask after neutralization to obtain Er (NO)3)3，Dy(NO3)3，Eu(NO3)3And Tm (NO)3)3The mixed solution of (1);
s3: preparing a silver ion solution and a tungstate solution;
weighing AgNO3And Na2WO4·2H2O, and dissolving the O in 50mL of deionized water in two beakers respectively to obtain AgNO3Solution and Na2WO4A solution;
s4: adding a rare earth ion solution;
AgNO obtained in S33Er (NO) is added into the solution3)3Or Dy (NO)3)3Or Eu (NO)3)3Or Tm (NO)3)3Obtaining a solution containing rare earth ions and silver ions;
s5: mixing the solution to obtain a precipitate;
mixing the rare earth ion-containing and silver ion solution obtained in the step S4 with Na obtained in the step S32WO4Heating the solution, adding the solution containing rare earth ions and silver ions to Na under stirring2WO4Maintaining the temperature for time to instantly generate light yellow precipitate, whitening the light yellow precipitate after time, naturally cooling the solution to room temperature, centrifuging the precipitate, washing with deionized water, washing with ethanol, and drying in oven to obtain α -Ag doped with rare earth ions2WO4And (3) powder.
2. The rare earth ion-based dopings α -Ag of claim 12WO4The method for manufacturing an optical thermometer is characterized in that: in the step S2, Er (NO)3)3，Dy(NO3)3，Eu(NO3)3And Tm (NO)3)3The concentration of the mixed solution of (3) was 0.2M.
3. The rare earth ion-based dopings α -Ag of claim 12WO4The method for manufacturing an optical thermometer is characterized in that: in the step S3, 1.97mmol of AgNO is weighed respectively3And 1mmol of Na2WO4·2H2O。
4. The rare earth ion-based dopings α -Ag of claim 12WO4The method for manufacturing an optical thermometer is characterized in that: in the step S4, the Er (NO)3)3Or Dy (NO)3)3Or Eu (NO)3)3Or Tm (NO)3)3The solution was 50. mu.L.
5. The rare earth ion-based dopings α -Ag of claim 12WO4The method for manufacturing an optical thermometer is characterized in that: in the step of S5, the rare earth ion-containing and silver ion solution obtained in the step of S4 and Na obtained in the step of S3 are mixed2WO4The solution was heated to 90 ℃ for 5 minutes.
6. The rare earth ion-based dopings α -Ag of claim 12WO4The method for manufacturing an optical thermometer is characterized in that: in the step S5, the solution containing rare earth ions and silver ions is added to tungsten Na with stirring2WO4In the solution, the heating temperature was 90 ℃ for 30 minutes.
7. The rare earth ion-based dopings α -Ag of claim 12WO4The method for manufacturing an optical thermometer is characterized in that: in the S5 step, the precipitate was washed with ethanol and dried in an oven at 60 ℃ for 12 hours.
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