CN114797915A - Hydroxyapatite, preparation method thereof and application of hydroxyapatite in piezoelectric catalytic degradation of organic pollutants in water - Google Patents
Hydroxyapatite, preparation method thereof and application of hydroxyapatite in piezoelectric catalytic degradation of organic pollutants in water Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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Abstract
The invention belongs to the technical field of inorganic nano materials and piezoelectric catalysis, and particularly relates to a preparation method of a calcined hydroxyapatite material and application of the calcined hydroxyapatite material in removing organic pollutants in water through piezoelectric catalysis. Preparing a precursor solution by taking anhydrous calcium chloride and sodium dihydrogen phosphate as raw materials, adjusting the pH of the precursor solution by using ethylenediamine, preparing simple hydroxyapatite through simple hydrothermal reaction, and then calcining at high temperature in inert gas to obtain the calcined hydroxyapatite. The hydroxyapatite product of the invention effectively inhibits the recombination of carriers, improves the mobility of the carriers, and simultaneously enhances the adsorption capacity of the material surface to oxygen, thereby improving the capacity of the material to generate active free radicals. The calcined hydroxyapatite can significantly improve the piezoelectric catalytic activity compared to the uncalcined hydroxyapatite. Experiments prove that the bisphenol A in the water body can be rapidly degraded under the ultrasonic condition, and the performance of the bisphenol A is obviously superior to that of uncalcined hydroxyapatite.
Description
Technical Field
The invention belongs to the technical field of inorganic nano materials and piezoelectric catalysis, and particularly relates to a preparation method of a hydroxyapatite material and application of the hydroxyapatite material in removing organic pollutants in water through piezoelectric catalysis.
Background
The shortage of water resources and the pollution of water bodies are closely related to the life of people, and are concerned. Piezoelectric catalysis is considered to be an effective means of degrading organic pollutants in water bodies. Piezoelectric catalysis can convert mechanical energy into chemical energy: under the action of external mechanical force, the surface of the piezoelectric material induces charges due to the piezoelectric effect, and the generated piezoelectric potential can induce a huge piezoelectric field; the carriers are separated and transferred to the surface of the material under the drive of an electric field, and are contacted and reacted with substances such as water, oxygen and the like, so that the organic pollutants in the water body are oxidized/reduced by the active free radicals. Unlike photocatalysis, piezo-catalysis overcomes the dependence of materials on light sources; meanwhile, mechanical energy (such as sea waves, tides, waterfalls, respiration of animal bodies, muscle movement and the like) existing in nature and life is visible everywhere, if the mechanical energy can be effectively utilized, the mechanical energy is converted into chemical energy or electric energy through the response of the piezoelectric material to the mechanical energy, and the problems of energy shortage and environmental pollution are expected to be effectively solved for human beings through a very 'green' implementation mode.
Hydroxyapatite (HAP) is a natural apatite mineral and is also the major inorganic component of human and animal bones. Researches show that the material has the advantages of environmental friendliness, high stability, good adsorbability on heavy metal ions, simple synthesis method, controllable morphology and the like, and has wide application prospects in various fields of medicine, pollution treatment, heterogeneous catalysis and the like. However, hydroxyapatite is a new piezoelectric material, and there are only few research reports on the piezoelectric catalytic performance of hydroxyapatite at present.
Disclosure of Invention
The invention aims to provide a preparation method of a hydroxyapatite material, which can realize efficient degradation of bisphenol A in a water body under an ultrasonic condition. Preparing a precursor solution by taking anhydrous calcium chloride and sodium dihydrogen phosphate as raw materials, adjusting the pH of the precursor solution by using ethylenediamine, preparing simple hydroxyapatite through simple hydrothermal reaction, and then calcining at high temperature in inert gas to obtain the calcined hydroxyapatite. The hydroxyapatite product of the invention enhances the piezoelectricity of the material, and simultaneously enhances the adsorption capacity of the surface of the material to oxygen, thereby enhancing the capacity of the material to generate active free radicals. Compared with the uncalcined hydroxyapatite, the piezoelectric catalytic activity of the calcined hydroxyapatite is obviously improved. Experiments prove that the bisphenol A in the water body can be rapidly degraded under the ultrasonic condition, and the performance of the bisphenol A is obviously superior to that of uncalcined hydroxyapatite.
In order to achieve the purpose, the specific technical scheme of the invention is as follows:
a hydroxyapatite is prepared by preparing initial hydroxyapatite from calcium salt and phosphate; then calcining to obtain the hydroxyapatite.
The method for removing organic pollutants by piezoelectricity is characterized in that the calcined hydroxyapatite is placed in an environment containing the organic pollutants to realize the removal of the organic pollutants.
In the invention, calcium salt and phosphate are used as raw materials to prepare a precursor solution, the pH of the solution is adjusted to be alkaline, and then hydroxyapatite is prepared through a hydrothermal method; and then calcining the obtained hydroxyapatite at high temperature in an inert gas atmosphere, and naturally cooling to obtain calcined hydroxyapatite serving as a piezoelectric catalyst.
The invention discloses a method for treating organic pollutants, which comprises the following steps:
1. preparing a precursor solution by taking calcium salt and phosphate as raw materials, adjusting the pH of the solution to be alkaline, and then preparing initial hydroxyapatite by a hydrothermal method; then calcining the obtained hydroxyapatite at high temperature in an inert gas atmosphere, and naturally cooling to obtain the hydroxyapatite;
2. the hydroxyapatite is added into the water solution containing the organic pollutants, and the degradation of the organic pollutants is realized under the action of ultrasonic waves.
According to the invention, the hydroxyapatite is calcined at high temperature in the inert gas atmosphere, so that the piezoelectricity of the hydroxyapatite is improved, the progress of a piezoelectric catalytic reaction is promoted, and the catalytic performance is improved.
In the technical scheme, the calcium salt can be anhydrous calcium chloride, calcium nitrate tetrahydrate and other calcium salts, and the anhydrous calcium chloride is preferred; the phosphate can be ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, etc., preferably disodium hydrogen phosphate; the alkaline solution for adjusting the pH of the solution can be sodium hydroxide aqueous solution or ethylenediamine and the like, preferably ethylenediamine; in the calcium salt and the phosphate, the molar ratio of Ca to P is 1.6-1.7, preferably 1.67; the pH value of the precursor solution can be 8-14, and preferably, the pH value = 12; the temperature of the hydrothermal reaction can be 150-200 DEG o C, preferably 200 o C; the time of the hydrothermal reaction can be 12-36 h, and preferably 24 h.
According to the technical scheme, the calcining atmosphere can be nitrogen or argon, and preferably argon; the calcining temperature is 500-900 deg.C o C, preferably 800 o C; the calcination time is 1-3 h, preferably 2 h; the heating rate can be 5-10 o C/min, preferably 5 oC /min。
According to the technical scheme, the organic pollutant is bisphenol A; the ultrasonic treatment frequency is 40-60 KHz, the power is 400-800W, preferably 45 KHz and 600W. Further, the ultrasonic treatment was carried out under a dark condition without irradiation.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the hydroxyapatite disclosed by the invention has relatively uniform nanorod morphology, and meanwhile, the cost of raw materials is low, and the preparation method is simple. The invention prepares the hydroxyapatite by a high-temperature calcination method in inert gas for the first time, and improves the piezoelectric catalytic activity of the hydroxyapatite.
Drawings
FIG. 1 is a scanning electron micrograph of Hydroxyapatite (HAP) alone according to the first embodiment.
FIG. 2 is a scanning electron micrograph of hydroxyapatite (OVHAP-2) calcined for 2 hours as described in example III.
FIG. 3 shows Raman spectra of hydroxyapatite (HAP, OVHAP-1, OVHAP-2, OVHAP-3) at different calcination times.
FIG. 4 shows XPS spectra of hydroxyapatite (HAP, OVHAP-1, OVHAP-2, OVHAP-3) at different calcination times.
FIG. 5 is a graph showing the effect of hydroxyapatite (HAP, OVHAP-1, OVHAP-2, OVHAP-3) on the degradation of bisphenol A at different calcination times.
FIG. 6 is a graph showing the cyclic effect of hydroxyapatite (OVHAP-2) calcined for 2 hours on the degradation of bisphenol A as described in example seven.
Detailed Description
The crystal structure of hydroxyapatite belongs to hexagonal system, and the piezoelectricity of the hydroxyapatite is derived from the hydroxyl radical contained in the crystal lattice along the [001 ] edge]Ferroelectric domains formed by directional ordering. In the ideal case, the hydroxyl group is at Ca 2+ The enclosed channels are arranged in a columnar mode along the direction parallel to the +/-c axis, hydroxyl groups point to the same direction in any selected single tunnel, in fact, the direction of the hydroxyl groups in adjacent tunnels can be the same or opposite, and when the directions of the hydroxyl groups in adjacent tunnels are opposite, two opposite columns of hydroxyl columns form a symmetrical center and do not have piezoelectricity. In practical situations, the arrangement of the hydroxyl dipoles is disordered macroscopically, and a non-centrosymmetric structure may exist in a local range, so that the hydroxyl dipoles can show limited piezoelectricity; in the prior art, hydroxyapatite is subjected to harsh treatment, usually a high-voltage electric field is applied externally at high temperature, so that the energy consumption is high and the operation is complex. According to the invention, pure hydroxyapatite is prepared by a simple hydrothermal method, and then the hydroxyapatite is calcined at high temperature in an inert gas atmosphere to obtain the hydroxyapatite catalyst, so that the purpose of efficiently degrading organic pollutants in a water body is realized under the condition of no need of illumination. The calcined hydroxyapatite material provided by the invention improves the separation efficiency of carriers and enhances the adsorption of oxygen on the surface of the catalyst, thereby realizing the efficient degradation of organic pollutants in water under the condition of no illumination. The invention is further described with reference to the following examples, wherein the starting materials are commercially available products, the specific preparation operations and tests are conventional techniques, and each of the piezo-catalytic degradation tests is a parallel experiment.
Example one preparation of simple Hydroxyapatite (HAP) was carried out by the following steps:
4 mmol (444 mg) of anhydrous CaCl 2 Dissolved in 20 mL of deionized water, 2.4 mmol (288)mg) anhydrous NaH 2 PO 4 Dissolving in 20 mL of deionized water, adding CaCl 2 Dropping NaH into the solution 2 PO 4 Stirring the solution for 0.5 h to obtain a uniform mixed solution, adding ethylenediamine to adjust the pH of the solution to 12, stirring the solution for 0.5 h, transferring the resulting white suspension to a 50 mL reaction kettle liner, and stirring the solution for 200 h oC And reacting for 24 hours. Taking the lower layer precipitate after the reaction is finished, washing the lower layer precipitate for three times by using deionized water and ethanol in sequence, and finally washing the lower layer precipitate at 60 DEG oC Vacuum drying for 12 h to obtain pure hydroxyapatite. FIG. 1 is a scanning electron micrograph of the initial hydroxyapatite obtained above. As can be seen from the attached figure 1, the obtained hydroxyapatite presents the shape of a nanorod and is relatively uniform, the diameter of the hydroxyapatite is about 30 nm, and the length of the hydroxyapatite is about 100 nm.
Example two calcination of hydroxyapatite (OVHAP-1) prepared for 1 hour, the specific steps are as follows:
100 mg of the hydroxyapatite obtained in the first example was weighed and transferred to a crucible, and placed in a clean tube furnace, and argon gas was first introduced for 5 min to remove the air in the furnace. Then keeping the flow rate of argon constant at 60 mL/min to 5 o Heating the mixture from room temperature to 800 ℃ at a temperature rising rate of C/min o C, and is at 800 o Calcining for 1 h at the temperature of C, naturally cooling to room temperature, and stopping ventilation to obtain calcined hydroxyapatite (OVHAP-1).
Example three calcination of hydroxyapatite (OVHAP-2) prepared for 2 hours, the specific steps are as follows:
100 mg of the hydroxyapatite obtained in the first example was weighed and transferred to a crucible, and placed in a clean tube furnace, and argon gas was first introduced for 5 min to remove the air in the furnace. Then keeping the flow rate of argon constant at 60 mL/min to 5 o Heating the mixture from room temperature to 800 ℃ at a temperature rising rate of C/min o C, and is at 800 o Calcining for 2 h at the temperature of C, naturally cooling to room temperature, and stopping ventilation to obtain calcined hydroxyapatite (OVHAP-2). FIG. 2 is a scanning electron micrograph of the calcined hydroxyapatite (OVHAP-2) obtained above, the morphology of which was transformed from the initial nanorods to coralline nanoplates.
Example four calcination of hydroxyapatite (OVHAP-3) prepared for 3 hours, the specific steps are as follows:
100 mg of the hydroxyapatite obtained in the first example was weighed and transferred to a crucible, and placed in a clean tube furnace, and argon gas was first introduced for 5 min to remove the air in the furnace. Then keeping the flow rate of argon constant at 60 mL/min to 5 o Heating the mixture at a temperature rising rate of 800 to room temperature o C, and is at 800 o Calcining for 3 h at the temperature of C, naturally cooling to room temperature, and stopping ventilation to obtain calcined hydroxyapatite (OVHAP-3).
Example five piezoelectric catalytic degradation tests of simple hydroxyapatite on bisphenol a:
10 mg of the initial hydroxyapatite obtained in the first example was taken and placed in a small beaker containing 20 mL of a bisphenol A aqueous solution having a concentration of 15 mg/L. Standing in a dark place for adsorption for 1 h, sampling 800 muL every 30 min, and filtering by a filter head (0.22μm) and injecting into a high-efficiency liquid phase sample bottle. After the adsorption for 1 h is balanced, transferring a sample into a glass test tube, placing the test tube into an ultrasonic cleaner, turning on ultrasonic in a dark place, adjusting the frequency to be 45 KHz, adjusting the power to 600W, sampling 800 muL every 6 min, filtering by using a filter head (0.22μm) to remove a catalyst, injecting into a high performance liquid sample bottle, testing the absorption curve of the sample under 290 nm ultraviolet wavelength in a mobile phase of deionized water and methanol = 30: 70 by using a high performance liquid chromatograph, recording the peak area of bisphenol A in about 6 min, recording the concentration of initial bisphenol A as 100%, and obtaining the piezoelectric catalytic degradation curve of bisphenol A.
Example six different calcination time experiments on the piezoelectric catalytic degradation of bisphenol a with hydroxyapatite:
10 mg of each of the hydroxyapatite (OVHAP-1, OVHAP-2, OVHAP-3) obtained in example two, three, and four and obtained at different calcination times was placed in a small beaker containing 20 mL of a bisphenol A aqueous solution having a concentration of 15 mg/L. Standing in a dark place for adsorption for 1 h, sampling 800 muL every 30 min, and filtering by a filter head (0.22μm) and injecting into a high-efficiency liquid phase sample bottle. After the adsorption for 1 h is balanced, transferring a sample into a glass test tube, placing the test tube into an ultrasonic cleaner, turning on ultrasonic in a dark place, adjusting the frequency to be 45 KHz, adjusting the power to 600W, sampling 800 muL every 6 min, filtering by using a filter head (0.22μm) to remove a catalyst, injecting into a high performance liquid sample bottle, testing the absorption curve of the sample under 290 nm ultraviolet wavelength in a mobile phase of deionized water and methanol = 30: 70 by using a high performance liquid chromatograph, recording the peak area of bisphenol A in about 6 min, recording the concentration of initial bisphenol A as 100%, and obtaining the piezoelectric catalytic degradation curve of bisphenol A.
FIG. 3 shows Raman spectra of hydroxyapatite (HAP, OVHAP-1, OVHAP-2, OVHAP-3) at different calcination times, and FIG. 4 shows XPS spectra of hydroxyapatite (HAP, OVHAP-1, OVHAP-2, OVHAP-3) at different calcination times. FIG. 5 is a graph showing the effect of degrading bisphenol A by HAP, OVHAP-1, OVHAP-2 and OVHAP-3. Under the action of ultrasonic wave, the removal rates of HAP, OVHAP-1, OVHAP-2 and OVHAP-3 to bisphenol A are respectively about 46%, 67%, 88% and 77% within 6 min, the degradation effect of OVHAP-2 is the best, and the removal rate can reach 100% within 18 min.
20 ml of aqueous bisphenol A solution with the concentration of 15 mg/L is used as a comparison, the apparent reaction rate constant k value of the hydroxyapatite to the degradation of the bisphenol A with different calcination time is shown in Table 1, and the OVHAP-2 has the highest k value of 0.3480 min as shown in Table 1 -1 The rate of degradation is fastest. Wherein the apparent reaction rate constant k is calculated by the following formula:
wherein t is the sonication time (min), C t And C 0 Is the concentration of bisphenol A at t and the initial concentration.
Example seven cycle experiment of 2 hour calcination of hydroxyapatite (OVHAP-2) on degradation of bisphenol A:
in the sixth example, OVHAP-2 recovered after 30 min of ultrasound was washed with deionized water and 95% ethanol in sequence, dried, and placed in a small beaker containing 20 mL of fresh 15 mg/L bisphenol A solution. Standing in a dark place for adsorption for 1 h, sampling 800 muL every 30 min, and filtering by a filter head (0.22μm) and injecting into a high-efficiency liquid phase sample bottle. After the adsorption for 1 h is balanced, transferring a sample into a glass test tube, placing the test tube into an ultrasonic cleaner, turning on ultrasonic in a dark place, adjusting the frequency to be 45 KHz, adjusting the power to 600W, sampling 800 muL every 6 min, filtering by using a filter head (0.22μm) to remove a catalyst, injecting into a high performance liquid sample bottle, testing the absorption curve of the sample under 290 nm ultraviolet wavelength in a mobile phase of deionized water and methanol = 30: 70 by using a high performance liquid chromatograph, recording the peak area of bisphenol A in about 6 min, recording the concentration of initial bisphenol A as 100%, and obtaining the piezoelectric catalytic degradation curve of bisphenol A. Repeat 5 times according to the above steps, test and record data. FIG. 4 is a statistical graph of the removal effect of OVHAP-2 piezoelectric catalyst from example four on five piezoelectric degradation experiments with five cycles of bisphenol A solution. It can be seen that in the course of five times of repeated use, the material always maintains excellent piezoelectric catalytic performance, and the final removal efficiency of bisphenol A molecules in the aqueous solution is greater than 99%. Therefore, the catalyst can be repeatedly used and has good stability.
Claims (10)
1. A preparation method of hydroxyapatite is characterized in that calcium salt and phosphate are used as raw materials to prepare initial hydroxyapatite; then calcining to obtain the hydroxyapatite.
2. The method for preparing hydroxyapatite according to claim 1, wherein a precursor solution is prepared by using calcium salt and phosphate as raw materials, the pH of the solution is adjusted to be alkaline, and then initial hydroxyapatite is prepared by hydrothermal reaction; and then calcining the initial hydroxyapatite in an inert gas atmosphere to obtain the hydroxyapatite.
3. The method for producing hydroxyapatite according to claim 2, wherein the calcium salt is a water-soluble calcium salt; a phosphate water-soluble phosphate; in the calcium salt and the phosphate, the molar ratio of Ca/P is 1.6-1.7; the pH value of the precursor solution is 8-14.
4. Method for preparing hydroxyapatite according to claim 2The method is characterized in that the temperature of the hydrothermal reaction can be 150-200 DEG o C; the time of the hydrothermal reaction can be 12-36 h; the calcining temperature is 500-900 deg.C o C; the calcination time is 1-3 h.
5. The hydroxyapatite prepared by the method for preparing hydroxyapatite according to claim 1.
6. A method for removing organic contaminants, comprising placing the hydroxyapatite of claim 5 in an environment containing organic contaminants to effect removal of the organic contaminants.
7. The piezoelectric organic pollutant removing method according to claim 6, wherein hydroxyapatite is added into the solution containing the organic pollutants to degrade the organic pollutants under the action of ultrasonic waves.
8. The piezoelectric organic contaminant removal method according to claim 7, wherein the ultrasonic treatment is performed at a frequency of 40 to 60 KHz and at a power of 400 to 800W.
9. Use of the hydroxyapatite according to claim 5 for the piezoelectric treatment of organic pollutants.
10. Use according to claim 9, wherein the piezoelectric is sonicated.
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| CN202210394066.8A CN114797915A (en) | 2022-04-15 | 2022-04-15 | Hydroxyapatite, preparation method thereof and application of hydroxyapatite in piezoelectric catalytic degradation of organic pollutants in water |
| PCT/CN2022/091237 WO2023197385A1 (en) | 2022-04-15 | 2022-05-06 | Hydroxyapatite and preparation method therefor, and application thereof in piezoelectric catalytic degradation of organic pollutant in water |
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2022
- 2022-04-15 CN CN202210394066.8A patent/CN114797915A/en active Pending
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