WO2023197385A1 - 一种羟基磷灰石及其制备方法与压电催化降解水中有机物污染物的应用 - Google Patents

一种羟基磷灰石及其制备方法与压电催化降解水中有机物污染物的应用 Download PDF

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WO2023197385A1
WO2023197385A1 PCT/CN2022/091237 CN2022091237W WO2023197385A1 WO 2023197385 A1 WO2023197385 A1 WO 2023197385A1 CN 2022091237 W CN2022091237 W CN 2022091237W WO 2023197385 A1 WO2023197385 A1 WO 2023197385A1
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hydroxyapatite
piezoelectric
organic pollutants
ovhap
calcined
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PCT/CN2022/091237
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English (en)
French (fr)
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路建美
李娜君
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苏州大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • 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

Definitions

  • the invention belongs to the technical fields of inorganic nanomaterials and piezoelectric catalysis, and specifically relates to a preparation method of hydroxyapatite material and its application in piezoelectric catalytic removal of organic pollutants in water.
  • Piezoelectric catalysis is considered an effective means to degrade 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 resulting piezoelectric potential can induce a huge piezoelectric field; current carrying The electrons are separated and migrated to the surface of the material driven by the electric field, where they contact and react with water, oxygen and other substances, thereby generating active free radicals to oxidize/reduce organic pollutants in the water body.
  • piezoelectric catalysis overcomes the dependence of materials on light sources; at the same time, mechanical energy existing in nature and life (such as waves, tides, waterfalls, animal breathing and muscle movement, etc.) can be found everywhere. If it can be effectively utilized, By converting piezoelectric materials into chemical energy or electrical energy in response to mechanical energy, it is expected to effectively solve the problems of energy shortage and environmental pollution for centuries through a very "green" implementation.
  • Hydroxyapatite is a natural apatite mineral and the main inorganic component of human and animal bones. Research has found that this material has many advantages such as environmental friendliness, high stability, good adsorption of heavy metal ions, simple synthesis method, and controllable morphology. It has broad application prospects in many fields such as medicine, pollution control, and heterogeneous catalysis. However, as a new piezoelectric material, hydroxyapatite has few research reports on its piezoelectric catalytic properties.
  • the object of the present invention is to provide a preparation method of hydroxyapatite material, which can achieve efficient degradation of bisphenol A in water under ultrasonic conditions.
  • the hydroxyapatite product of the present invention enhances the piezoelectricity of the material itself and at the same time enhances the adsorption capacity of oxygen on the surface of the material, thereby improving the material's ability to generate active free radicals.
  • a hydroxyapatite and its preparation method is as follows: using calcium salt and phosphate as raw materials to prepare initial hydroxyapatite; and then calcining to obtain hydroxyapatite.
  • a piezoelectric method for removing organic pollutants The above-mentioned calcined hydroxyapatite is placed in an environment containing organic pollutants to achieve the removal of organic pollutants.
  • calcium salt and phosphate are used as raw materials to prepare a precursor solution, the pH of the solution is adjusted to alkaline, and then hydroxyapatite is prepared through a hydrothermal reaction; and then the obtained hydroxyapatite is subjected to high temperature in an inert gas atmosphere. Calculate and wait for natural cooling to obtain calcined hydroxyapatite, which can be used as a piezoelectric catalyst.
  • the invention discloses a method for treating organic pollutants.
  • the steps are as follows: 1. Prepare a precursor solution using calcium salt and phosphate as raw materials, adjust the pH of the solution to alkaline, and then prepare initial hydroxyapatite through hydrothermal reaction; The obtained hydroxyapatite is calcined at high temperature in an inert gas atmosphere, and allowed to cool naturally to obtain hydroxyapatite; 2. Add hydroxyapatite to an aqueous solution containing organic pollutants, and under the action of ultrasound, realize the removal of organic pollutants. Degradation of pollutants.
  • hydroxyapatite is calcined at high temperature in an inert gas atmosphere, thereby improving its piezoelectricity, promoting the piezoelectric catalytic reaction, and improving the catalytic performance.
  • the calcium salt can be anhydrous calcium chloride, calcium nitrate tetrahydrate and other calcium salts, preferably anhydrous calcium chloride;
  • the phosphate can be ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, hydrogen phosphate Phosphates such as disodium, preferably disodium hydrogen phosphate;
  • the alkaline solution for adjusting the pH of the solution can be sodium hydroxide aqueous solution or ethylenediamine, preferably ethylenediamine; among calcium salts and phosphates, the Ca/P molar ratio is 1.6 ⁇ 1.7, preferably 1.67;
  • the temperature of the hydrothermal reaction can be 150-200 o C, preferably 200 o C;
  • the time of the hydrothermal reaction can be 12-36 h , preferably 24 h.
  • the calcining atmosphere can be nitrogen or argon, preferably argon; the calcining temperature is 500 to 900 o C, preferably 800 o C; the calcining time is 1 to 3 h, preferably 2 h; the heating rate can be 5 to 10 oC /min, preferably 5 oC /min.
  • the organic pollutant is bisphenol A; the frequency of ultrasonic treatment is 40-60 KHz, and the power is 400-800 W, preferably 45 KHz, 600 W. Furthermore, no light was used during ultrasonic treatment, and it was carried out under light-proof conditions.
  • the present invention has the following advantages compared with the prior art: the hydroxyapatite disclosed in the present invention has a relatively uniform nanorod morphology, while the raw material cost is low and the preparation method is simple. For the first time, this invention uses the method of high-temperature calcination in inert gas to prepare hydroxyapatite to improve its piezoelectric catalytic activity.
  • Figure 1 is a scanning electron microscope image of simple hydroxyapatite (HAP) described in Example 1.
  • Figure 2 is a scanning electron microscope image of hydroxyapatite (OVHAP-2) calcined for 2 hours as described in Example 3.
  • Figure 3 shows the Raman spectra of hydroxyapatite (HAP, OVHAP-1, OVHAP-2, OVHAP-3) with different calcination times.
  • Figure 4 shows the XPS spectra of hydroxyapatite (HAP, OVHAP-1, OVHAP-2, OVHAP-3) with different calcination times.
  • Figure 5 shows the effect of hydroxyapatite (HAP, OVHAP-1, OVHAP-2, OVHAP-3) degrading bisphenol A with different calcination times.
  • Figure 6 is a cycle effect diagram of bisphenol A degradation by hydroxyapatite (OVHAP-2) calcined for 2 hours as described in Example 7.
  • the crystal structure of hydroxyapatite belongs to the hexagonal crystal system, and its piezoelectricity comes from the ferroelectric domains formed by the orderly arrangement of hydroxyl groups contained in its crystal lattice along the [001] direction.
  • the hydroxyl groups are arranged in columns in the channel surrounded by Ca 2+ along the direction parallel to the ⁇ c axis.
  • the hydroxyl groups point in the same direction.
  • the hydroxyl groups may point in the same direction or in opposite directions.
  • the arrangement of hydroxyl dipoles is macroscopically disordered, and non-centrosymmetric structures may exist locally, causing them to exhibit limited piezoelectricity; the existing technology has strict requirements on hydroxyapatite.
  • the treatment usually involves applying a high-voltage electric field at high temperature, which consumes high energy and is complex to operate.
  • the present invention prepares simple hydroxyapatite through a simple hydrothermal method, and then calcines it at high temperature under an inert gas atmosphere to obtain a hydroxyapatite catalyst, which can achieve the purpose of efficiently degrading organic pollutants in water without the need for light. .
  • the calcined hydroxyapatite rice material provided by the invention improves the separation efficiency of carriers and enhances the adsorption of oxygen on the surface of the catalyst, thereby achieving efficient degradation of organic pollutants in water under no light conditions.
  • the present invention will be further described below with reference to the examples.
  • the raw materials are all commercially available products.
  • the specific preparation operations and tests are conventional techniques.
  • Each piezoelectric catalytic degradation test is a parallel experiment.
  • Example 1 Prepare simple hydroxyapatite (HAP). The specific steps are as follows: Dissolve 4 mmol (444 mg) anhydrous CaCl 2 in 20 mL deionized water, and dissolve 2.4 mmol (288 mg) anhydrous NaH 2 PO 4 In 20 mL of deionized water, drop the CaCl 2 solution into the NaH 2 PO 4 solution, stir for 0.5 h to obtain a uniform mixed solution, then add ethylenediamine to adjust the pH of the solution to 12, continue stirring for 0.5 h, and then the resulting white color The suspension was transferred to the liner of a 50 mL reactor and reacted at 200 °C for 24 h.
  • HAP simple hydroxyapatite
  • Figure 1 is a scanning electron microscope image of the initial hydroxyapatite obtained above. It can be seen from Figure 1 that the obtained hydroxyapatite has the morphology of nanorods and is relatively uniform, with a diameter of about 30 nm and a length of about 100 nm.
  • the hydroxyapatite (OVHAP-2) prepared in Example 3 was calcined for 2 hours.
  • the specific steps are as follows: weigh 100 mg of the hydroxyapatite obtained in Example 1 and transfer it to the crucible and place it in a clean tube furnace. First, argon gas was passed for 5 minutes to eliminate the air in the furnace. Then keep the argon flow rate constant at 60 mL/min, heat from room temperature to 800 o C at a temperature rise rate of 5 o C/min, and calcine at 800 o C for 2 h. After natural cooling to room temperature, stop ventilation to obtain the calcined of hydroxyapatite (OVHAP-2).
  • Figure 2 is a scanning electron microscope image of the calcined hydroxyapatite (OVHAP-2) obtained above. Its morphology changes from the initial nanorods to coral-like nanoplates.
  • the hydroxyapatite (OVHAP-3) prepared in Example 4 was calcined for 3 hours.
  • the specific steps are as follows: Weigh 100 mg of the hydroxyapatite obtained in Example 1 and transfer it to the crucible and place it in a clean tube furnace. First, argon gas was passed for 5 minutes to eliminate the air in the furnace. Then keep the argon flow rate constant at 60 mL/min, heat from room temperature to 800 ° C at a temperature rise rate of 5 ° C/min, and calcine at 800 ° C for 3 h. After natural cooling to room temperature, stop ventilation, and get Calcined hydroxyapatite (OVHAP-3).
  • Example 5 Piezoelectric catalytic degradation test of bisphenol A by simple hydroxyapatite: Take 10 mg of the initial hydroxyapatite obtained in Example 1 and place it in 20 mL of bisphenol A with a concentration of 15 mg/L. aqueous solution in a small beaker. Allow to stand for 1 hour in the dark, during which time 800 ⁇ L is sampled every 30 minutes, filtered through a filter (0.22 ⁇ m) and injected into a high-performance liquid phase sample bottle.
  • Example 6 Piezoelectric catalytic degradation experiment of bisphenol A by hydroxyapatite with different calcination times: Take the hydroxyapatite with different calcination times (OVHAP-1, OVHAP-2, OVHAP-2, 10 mg each of OVHAP-3) were placed in a small beaker containing 20 mL of bisphenol A aqueous solution with a concentration of 15 mg/L. Allow to stand for 1 hour in the dark, during which time 800 ⁇ L is sampled every 30 minutes, filtered through a filter (0.22 ⁇ m) and injected into a high-performance liquid phase sample bottle.
  • Figure 3 shows the Raman spectra of hydroxyapatite (HAP, OVHAP-1, OVHAP-2, OVHAP-3) with different calcination times.
  • Figure 4 shows the Raman spectra of hydroxyapatite (HAP, OVHAP-1, OVHAP-3) with different calcination times.
  • Figure 5 shows the effects of HAP, OVHAP-1, OVHAP-2, and OVHAP-3 degrading bisphenol A. Under the action of ultrasound, the removal rates of bisphenol A by HAP, OVHAP-1, OVHAP-2 and OVHAP-3 were approximately 46%, 67%, 88% and 77% respectively within 6 minutes. OVHAP-2 had the best degradation effect. Good, and can reach 100% removal rate within 18 minutes.
  • Table 1 lists the apparent reaction rate constant k value of hydroxyapatite for bisphenol A degradation at different calcination times. From Table 1, it can be seen that OVHAP- 2 has the highest k value of 0.3480 min -1 and the fastest degradation rate. Among them, the apparent reaction rate constant k is calculated by the following formula: .
  • t is the ultrasound time (minutes)
  • C t and C 0 are the concentration and initial concentration of bisphenol A at t.
  • Example 7 Cycle experiment on the degradation of bisphenol A by calcining hydroxyapatite (OVHAP-2) for 2 hours: The OVHAP-2 recovered after ultrasonic for 30 minutes in the above Example 6 was washed with deionized water and 95% ethanol in sequence. Dry and place in fresh 20 mL 15 mg/L bisphenol A solution in a small beaker. Allow to stand for 1 hour in the dark, during which time 800 ⁇ L is sampled every 30 minutes, filtered through a filter (0.22 ⁇ m) and injected into a high-performance liquid phase sample bottle.
  • OHPAP-2 hydroxyapatite
  • FIG. 4 is a statistical diagram of the removal effect of the OVHAP-2 piezoelectric catalyst in Example 4 for the piezoelectric degradation experiment of bisphenol A solution cycled five times. It can be seen that during the above five repeated uses, the material always maintained excellent piezoelectric catalytic performance, and the final removal efficiency of bisphenol A molecules in the aqueous solution was greater than 99%. Therefore, the catalyst can be reused and has good stability.

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Abstract

一种煅烧羟基磷灰石材料的制备方法及其在压电催化去除水中有机污染物的应用，属于无机纳米材料及压电催化技术领域。以无水氯化钙和磷酸二氢钠为原料制备前驱体溶液，用乙二胺调节前驱液pH，通过简单的水热反应制备单纯的羟基磷灰石，然后在惰性气体中高温煅烧得到煅烧的羟基磷灰石。以上羟基磷灰石产物有效地抑制了载流子的复合，提高载流子的迁移率，同时增强了材料表面对于氧气的吸附能力，从而提升了材料产生活性自由基的能力。与未煅烧的羟基磷灰石相比，煅烧的羟基磷灰石能够显著提高压电催化活性。实验证明，其能够在超声下实现对水体中双酚A的快速降解，且性能明显优于未煅烧的羟基磷灰石。

Description

一种羟基磷灰石及其制备方法与压电催化降解水中有机物污染物的应用 技术领域
本发明属于无机纳米材料及压电催化技术领域，具体涉及一种羟基磷灰石材料的制备方法及其在压电催化去除水中有机污染物的应用。
 背景技术
水资源的短缺和水体污染与人们的生活息息相关，备受关注。压电催化被认为是降解水体中有机污染物的有效手段。压电催化能够将机械能转化为化学能：在外部机械力的作用下，压电材料的表面因压电效应而感应出电荷，由此产生的压电电位可以引发巨大的压电场；载流子在电场驱动下分离并迁移至材料表面，与水、氧气等物质接触并反应，从而产生活性自由基氧化/还原水体中的有机污染物。不同于光催化，压电催化克服了材料对光源的依赖；同时自然界和生活中存在的机械能（如海浪、潮汐、瀑布、动物体的呼吸和肌肉运动等）随处可见，如果能被有效利用，通过压电材料对机械能的响应转化为化学能或电能，将有望通过非常“绿色”的实施方式为人类有效解决能源短缺和环境污染问题。
羟基磷灰石（HAP）是一种天然的磷灰石矿物，也是人体和动物骨骼的主要无机成分。研究发现，该材料具有环境友好、稳定性高、对重金属离子吸附性好、合成方法简单、形貌可控等诸多优点，在医学、污染治理、多相催化等诸多领域有着广泛的应用前景。但羟基磷灰石作为一种新兴的压电材料，目前鲜有对其压电催化性能的研究报道。
 技术问题
本发明的目的是提供一种羟基磷灰石材料的制备方法，该材料可以在超声条件下实现对水体中双酚A的高效降解。以无水氯化钙和磷酸二氢钠为原料制备前驱体溶液，用乙二胺调节前驱液pH，通过简单的水热反应制备单纯的羟基磷灰石，然后在惰性气体中高温煅烧得到煅烧的羟基磷灰石。本发明的羟基磷灰石产物增强了材料本身的压电性，同时增强了材料表面对于氧气的吸附能力，从而提升了材料产生活性自由基的能力。与未煅烧的羟基磷灰石相比，煅烧后的羟基磷灰石的压电催化活性得到了显著提升。实验证明，其能够在超声下实现对水体中双酚A的快速降解，且性能明显优于未煅烧的羟基磷灰石。
 技术解决方案
为达到上述目的，本发明具体技术方案如下：一种羟基磷灰石，其制备方法为，以钙盐、磷酸盐为原料制备初始羟基磷灰石；然后煅烧，得到羟基磷灰石。
一种压电除去有机污染物的方法，将上述煅烧的羟基磷灰置入含有有机污染物的环境中，实现有机污染物的去除。
本发明中，以钙盐、磷酸盐为原料制备前驱体溶液，调节溶液pH至碱性，然后通过水热法反应制备羟基磷灰石；然后将所得羟基磷灰石在惰性气体氛围中进行高温煅烧，待其自然冷却，得到煅烧的羟基磷灰石，作为压电催化剂。
本发明公开了有机污染物的处理方法，步骤如下：1. 以钙盐、磷酸盐为原料制备前驱体溶液，调节溶液pH至碱性，然后通过水热法反应制备初始羟基磷灰石；然后将所得羟基磷灰石在惰性气体氛围中进行高温煅烧，待其自然冷却，得到羟基磷灰石；2.将羟基磷灰石加入含有有机污染物的水溶液中，在超声作用下，实现对有机污染物的降解。
本发明通过在惰性气体氛围中对羟基磷灰石进行高温煅烧，从而提升其压电性，促进压电催化反应的进行，提升催化性能。
上述技术方案，钙盐可为无水氯化钙、四水合硝酸钙等钙盐，优选无水氯化钙；磷酸盐可为磷酸二氢铵、磷酸氢二铵、磷酸二氢钠、磷酸氢二钠等磷酸盐，优选磷酸氢二钠；调节溶液pH的碱性溶液可为氢氧化钠水溶液或乙二胺等，优选乙二胺；钙盐、磷酸盐中，Ca/P摩尔比为1.6～1.7，优选1.67；前驱体溶液pH可为8～14，优选pH=12；水热反应的温度可为150～200 oC，优选200 oC；水热反应的时间可为12～36 h，优选24 h。
上述技术方案，煅烧气氛可为氮气或氩气，优选氩气；煅烧的温度为500～900 oC，优选800 oC；煅烧时间为1～3 h，优选2 h；升温速率可为5～10 oC/min，优选5 oC/min。
上述技术方案，有机污染物为双酚A；超声处理的频率为40～60 KHz，功率为400～800 W，优选45 KHz，600 W。进一步的，超声处理时不进行光照，在避光的条件下进行。
 有益效果
由于上述技术方案的运用，本发明与现有技术相比具有下列优点：本发明公开的羟基磷灰石具有较为均一的纳米棒形貌，同时原材料成本低廉、制备方法简单。本发明首次利用在惰性气体中高温煅烧的方法制备了羟基磷灰石，提升其压电催化活性。
 附图说明
图1为实施例一中所述单纯羟基磷灰石（HAP）的扫描电镜图。
图2为实施例三中所述煅烧2小时的羟基磷灰石（OVHAP-2）的扫描电镜图。
图3为不同煅烧时间的羟基磷灰石（HAP、OVHAP-1、OVHAP-2、OVHAP-3）的拉曼谱图。
图4为不同煅烧时间的羟基磷灰石（HAP、OVHAP-1、OVHAP-2、OVHAP-3）的XPS谱图。
图5为不同煅烧时间的羟基磷灰石（HAP、OVHAP-1、OVHAP-2、OVHAP-3）降解双酚A的效果图。
图6为实施例七中所述煅烧2小时的羟基磷灰石（OVHAP-2）降解双酚A的循环效果图。
 本发明的实施方式
羟基磷灰石的晶体结构属于六方晶系，其压电性来源于其晶格中所含的羟基沿[001]方向有序排列所形成的铁电畴。在理想情况下，羟基在Ca 2+所围成的通道中沿平行于±c轴的方向成柱状排列，在任意选择的单一隧道中，羟基指向相同的方向，实际上，在相邻的隧道中，羟基的指向可能相同，也可能相反，当相邻隧道中的羟基指向相反，则相反的两列羟基柱形成了一个对称中心，不具有压电性。在实际情况中，羟基偶极子的排列在宏观上是无序的，局部范围内可能存在非中心对称结构，使其表现出有限的压电性；现有技术对羟基磷灰石进行严苛的处理，通常为高温下外加高压电场，其能耗高，操作复杂。本发明通过简单的水热法制备了单纯的羟基磷灰石，随后在惰性气体氛围下高温煅烧得到羟基磷灰石催化剂，在无需光照的条件下，实现高效降解水体中的有机污染物的目的。本发明提供的煅烧羟基磷灰石米材料提高了载流子的分离效率，增强了氧气在催化剂表面的吸附，从而在无光照条件下实现对水体中有机污染物的高效降解。下面结合实施例对本发明作进一步描述，所述原料都是市售产品，具体制备操作以及测试为常规技术，各压电催化降解试验为平行实验。
实施例一制备单纯的羟基磷灰石（HAP），具体步骤如下：将4 mmol（444 mg）无水CaCl 2溶于20 mL去离子水中，2.4 mmol（288 mg）无水NaH 2PO 4溶于20 mL去离子水中，将CaCl 2溶液滴入NaH 2PO 4溶液中，搅拌0.5 h以获得均匀的混合溶液，随后加入乙二胺调节溶液pH至12，继续搅拌0.5 h，接着将所得白色悬浮液转移至50 mL反应釜内胆中，200 oC反应24 h。反应结束后取下层沉淀，依次用去离子水和乙醇洗涤三遍，最后在60 oC下真空干燥12 h得到单纯的羟基磷灰石。附图1为上述所得的初始羟基磷灰石的扫描电镜图。从附图1中可以看出所得羟基磷灰石呈现纳米棒的形貌，且较为均一，其直径在30 nm左右 ，长度在100 nm左右。
实施例二 煅烧1小时制备的羟基磷灰石（OVHAP-1），具体步骤如下：称取实施例一中所得羟基磷灰石100 mg并转移至坩埚中，置于洁净的管式炉中，首先通氩气5 min以排除炉内空气。然后保持氩气流速恒定为60 mL/min，以5 oC/min的升温速率从室温加热至800 oC，并在800 oC下煅烧1 h，自然冷却至室温后，停止通气，得到煅烧的羟基磷灰石（OVHAP-1）。
实施例三 煅烧2小时制备的羟基磷灰石（OVHAP-2），具体步骤如下：称取实施例一中所得羟基磷灰石100 mg并转移至坩埚中，置于洁净的管式炉中，首先通氩气5 min以排除炉内空气。然后保持氩气流速恒定为60 mL/min，以5 oC/min的升温速率从室温加热至800 oC，并在800 oC下煅烧2 h，自然冷却至室温后，停止通气，得到煅烧的羟基磷灰石（OVHAP-2）。附图2为上述所得煅烧的羟基磷灰石（OVHAP-2）的扫描电镜图，其形貌由最初的纳米棒转变为珊瑚状的纳米板。
实施例四 煅烧3小时制备的羟基磷灰石（OVHAP-3），具体步骤如下：称取实施例一中所得羟基磷灰石100 mg并转移至坩埚中，置于洁净的管式炉中，首先通氩气5 min以排除炉内空气。然后保持氩气流速恒定为60 mL/min，以5 oC/min的升温速率从室温加热至至800 oC，并在800 oC下煅烧3 h，自然冷却至室温后，停止通气，得到煅烧的羟基磷灰石（OVHAP-3）。
实施例五 单纯羟基磷灰石对双酚A的压电催化降解试验：取实施例一中所得的初始羟基磷灰石10 mg，置于装有20 mL浓度为15 mg/L的双酚A水溶液的小烧杯中。避光静置吸附1 h，期间每30 min取样800 µL，经滤头（0.22 µm）过滤后注入高效液相样品瓶中。吸附1 h平衡之后，将样品转移至玻璃试管中，将试管置于超声清洁器中，避光下打开超声，频率为45 KHz，功率调至600 W，每6 min取样800 µL，经滤头（0.22 µm）过滤除去催化剂后注入高效液相样品瓶中，使用高效液相色谱仪在去离子水∶甲醇=30∶70的流动相中测试样品在290 nm紫外波长下的吸收曲线，记录在6 min左右的双酚A出峰面积，并把初始双酚A的浓度记为100 %，得到双酚A的压电催化降解曲线。
实施例六 不同煅烧时间的羟基磷灰石对双酚A的压电催化降解实验：取实施例二、三、四中所得的不同煅烧时间的羟基磷灰石（OVHAP-1、OVHAP-2、OVHAP-3）各10 mg，分别置于装有20 mL浓度为15 mg/L的双酚A水溶液的小烧杯中。避光静置吸附1 h，期间每30 min取样800 µL，经滤头（0.22 µm）过滤后注入高效液相样品瓶中。吸附1 h平衡之后，将样品转移至玻璃试管中，将试管置于超声清洁器中，避光下打开超声，频率为45 KHz，功率调至600 W，每6 min取样800 µL，经滤头（0.22 µm）过滤除去催化剂后注入高效液相样品瓶中，使用高效液相色谱仪在去离子水∶甲醇=30∶70的流动相中测试样品在290 nm紫外波长下的吸收曲线，记录在6 min左右的双酚A出峰面积，并把初始双酚A的浓度记为100 %，得到双酚A的压电催化降解曲线。
图3为不同煅烧时间的羟基磷灰石（HAP、OVHAP-1、OVHAP-2、OVHAP-3）的拉曼谱图，图4为不同煅烧时间的羟基磷灰石（HAP、OVHAP-1、OVHAP-2、OVHAP-3）的XPS谱图。图5为HAP、OVHAP-1、OVHAP-2、OVHAP-3降解双酚A的效果图。在超声作用下，6 min内HAP、OVHAP-1、OVHAP-2和OVHAP-3对双酚A的去除率分别约为46 %、67 %、88 %、77 %，OVHAP-2的降解效果最好，并且在18 min内可以达到100 %的去除率。
以20 ml 浓度为15 mg/L的双酚A水溶液作对照，表1列出了不同煅烧时间的羟基磷灰石对双酚A降解表观反应速率常数k值，由表1可知，OVHAP-2具有最高的k值0.3480 min -1，降解速率最快。其中，表观反应速率常数k由如下公式计算得出： 。
其中，t是超声时间（分钟），C t和C 0是双酚A在t时的浓度和初始浓度。
。
实施例七 煅烧2小时的羟基磷灰石（OVHAP-2）对双酚A降解的循环实验：上述实施例六中超声30 min后回收的OVHAP-2依次用去离子水和95 %乙醇洗涤，烘干，置于装有新鲜的20 mL 15 mg/L双酚A溶液的小烧杯中。避光静置吸附1 h，期间每30 min取样800 µL，经滤头（0.22 µm）过滤后注入高效液相样品瓶中。吸附1 h平衡之后，将样品转移至玻璃试管中，将试管置于超声清洁器中，避光下打开超声，频率为45 KHz，功率调至600 W，每6 min取样800 µL，经滤头（0.22 µm）过滤除去催化剂后注入高效液相样品瓶中，使用高效液相色谱仪在去离子水∶甲醇=30∶70的流动相中测试样品在290 nm紫外波长下的吸收曲线，记录在6 min左右的双酚A出峰面积，并把初始双酚A的浓度记为100 %，得到双酚A的压电催化降解曲线。依照上述步骤，重复5次，测试并记录数据。附图4是重复使用实施例四中OVHAP-2压电催化剂对双酚A溶液循环五次压电降解实验的去除效果统计图。可以看到，在上述五次重复使用过程中，材料始终保持优良的压电催化性能，水溶液中双酚A分子的最终去除效率均大于99 %。因此，该催化剂可以重复使用，具有良好的稳定性。

Claims (10)

  1. 一种羟基磷灰石的制备方法，其特征在于，以钙盐、磷酸盐为原料制备初始羟基磷灰石；然后煅烧，得到羟基磷灰石。
  2. 根据权利要求1所述羟基磷灰石的制备方法，其特征在于，以钙盐、磷酸盐为原料制备前驱体溶液，再调节溶液pH至碱性，然后通过水热法反应制备初始羟基磷灰石；然后将所述初始羟基磷灰石在惰性气体氛围中进行煅烧，得到羟基磷灰石。
  3. 根据权利要求2所述羟基磷灰石的制备方法，其特征在于，钙盐水溶性钙盐；磷酸盐水溶性磷酸盐；钙盐、磷酸盐中，Ca/P摩尔比为1.6～1.7；前驱体溶液的pH为8～14。
  4. 根据权利要求2所述羟基磷灰石的制备方法，其特征在于，水热反应的温度可为150～200 oC；水热反应的时间可为12～36 h；煅烧的温度为500～900 oC；煅烧时间为1～3 h。
  5. 根据权利要求1所述羟基磷灰石的制备方法制备的羟基磷灰石。
  6. 一种除去有机污染物的方法，其特征在于，将权利要求5所述羟基磷灰石置入含有有机污染物的环境中，实现有机污染物的去除。
  7. 根据权利要求6所述压电除去有机污染物的方法，其特征在于，将羟基磷灰石加入含有有机污染物的溶液中，在超声作用下，实现对有机污染物的降解。
  8. 根据权利要求7所述压电除去有机污染物的方法，其特征在于，超声处理的频率为40～60 KHz，功率为400～800 W。
  9. 权利要求5所述羟基磷灰石在压电处理有机污染物中的应用。
  10. 根据权利要求9所述的应用，其特征在于，压电为超声处理。
PCT/CN2022/091237 2022-04-15 2022-05-06 一种羟基磷灰石及其制备方法与压电催化降解水中有机物污染物的应用 WO2023197385A1 (zh)

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