CN115814822B - Hydroxyapatite-based photocatalyst with full spectral response capability, and preparation method and application thereof - Google Patents
Hydroxyapatite-based photocatalyst with full spectral response capability, and preparation method and application thereof Download PDFInfo
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 109
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 88
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 82
- 230000003595 spectral effect Effects 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 28
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
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- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
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- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a hydroxyapatite-based photocatalyst with full spectral response capability, a preparation method and application thereof, wherein the photocatalyst is prepared from CaCl 2 And (NH) 4 ) 2 HPO 4 The photocatalyst is prepared by modifying saccharide molecules on the surface of hydroxyapatite by a coprecipitation method and calcining the saccharide-modified hydroxyapatite, wherein the photocatalyst has a rod-shaped structure, and graphite carbon is coated on the surface of the saccharide-modified hydroxyapatite. The photocatalyst has the advantages of uniform shape and size, large specific surface area, stable property, simple and environment-friendly preparation method steps, capability of full spectral response, great improvement of photocatalytic activity and good application prospect in photocatalytic degradation of organic pollutants.
Description
Technical Field
The invention belongs to the field of inorganic photocatalytic nano materials, and particularly relates to a hydroxyapatite-based photocatalyst with full spectral response capability, and a preparation method and application thereof.
Background
With the rapid development of economic globalization, the problems of energy consumption and environmental pollution are increasingly aggravated, and how to solve the energy crisis and environmental pollution becomes one of the challenges facing human beings in common. The photocatalysis technology is used as a green technology capable of converting and utilizing sunlight into electric energy, chemical energy and the like, and plays an increasingly important role in the fields of relieving energy crisis, solving environmental pollution and the like.
Since the 70 s of the last century, tiO was found 2 After having photocatalytic activity, the photocatalytic technology has attracted attention. But due to TiO 2 The band gap of the light-emitting diode is wider, ultraviolet light can be only utilized, and generated photo-generated electron-hole pairs are easy to recombine, so that the photocatalytic activity of the light-emitting diode is influenced. To overcome these shortcomings, various photocatalysts have been developed. However, the use of solar spectrum by these photocatalysts is mainly focused on ultraviolet light or visible light, and most photocatalysts are constructed based on semiconductor materials. There are few methods of research on environmentally friendly insulator materials that are widely available in nature.
Hydroxyapatite (HAp) is used as an insulator material widely existing in nature, is a main inorganic substance of animal bones, and has great application prospect in the biomedical field and the aspect of removing environmental pollutants due to the advantages of good biocompatibility, ion exchange capacity and the like.
However, hydroxyapatite is a nano material with a wide band gap, and has low solar light utilization efficiency. Therefore, in order to improve the utilization efficiency of hydroxyapatite for sunlight, a great deal of modification studies have been carried out on the hydroxyapatite by researchers. If researchers have prepared hydroxyapatite photocatalysts with ultraviolet light response by surface modification (appl. Catalyst. B: environ.2007,69, 164-170.) there are also researchers who have been doped by ions (e.g. Ti) 4+ 、Fe 3+ 、V 5+ ) The method of (2) provides hydroxyapatite with catalytic properties of ultraviolet or visible light (j.mol. Catalyst. A: chem.2012,360,54-60, mate.lett.2014, 137,256-259, j.photo. Photo. A: chem.2015,311, 30-34.). Recently, there have been studiesThe hydroxyapatite and Ag are synthesized by a multi-step synthesis method 3 PO 4 Or g-C 3 N 4 The photocatalytic performance of the hydroxyapatite can be effectively enhanced by compounding semiconductor materials (appl. Catalyst. B: environ.2015,179,29-36, appl. Catalyst. B: environ.2019,245, 662-671). Although these modification methods can improve the light absorption performance of the hydroxyapatite, most of these catalysts can only use ultraviolet light or visible light, cannot effectively use near infrared light, and have low catalytic performance, so that practical application of the hydroxyapatite is limited.
Disclosure of Invention
Aiming at the problems that the hydroxyapatite-based catalyst in the prior art cannot effectively utilize near infrared light, has low catalytic performance and the like, the invention aims to provide the hydroxyapatite-based photocatalyst with full spectral response capability, and the preparation method and the application thereof. According to the invention, saccharide molecules are modified on the surface of hydroxyapatite (HAp) by a coprecipitation method, and then the saccharide-modified HAp is calcined to obtain the oxygen vacancy hydroxyapatite/graphite carbon (OV-HAp/GC) photocatalyst with full spectral response, so that the preparation process flow is simplified, and meanwhile, the rapidity and the high efficiency of the OV-HAp/GC photocatalyst in full-spectrum photocatalytic degradation of environmental pollutants are realized.
In order to achieve the aim, the invention provides a hydroxyapatite-based photocatalyst with full spectral response capability, which is prepared by calcining carbohydrate-modified hydroxyapatite in an inert atmosphere, wherein the photocatalyst is in a rod-shaped structure, graphite carbon is coated on the surface of the carbohydrate-modified hydroxyapatite, and the carbohydrate-modified hydroxyapatite is prepared by the following steps of: 3:14 to 70 CaCl 2 、(NH 4 ) 2 HPO 4 The organic saccharide is prepared by coprecipitation method.
Further, the photocatalyst is formed by calcining carbohydrate-modified hydroxyapatite for 1-5 hours under the constant temperature condition of 350-800 ℃ in an inert atmosphere, has a rod-shaped structure, has the length of about 30-50nm and the width of about 10-20nm, is coated on the surface of the carbohydrate-modified hydroxyapatite (OV-HAp) by Graphite Carbon (GC),the light absorption range is effectively widened to the near infrared region. The nanometer particles with regular shape and uniform size have good specific surface area (more than or equal to 45.7 m) 2 And/g), the contact area with the target pollutant is favorably enhanced, and a powerful guarantee is provided for photocatalytic degradation.
The invention also provides a preparation method of the hydroxyapatite-based photocatalyst with full spectral response capability, which comprises the following steps:
(1) Preparation of saccharide-modified hydroxyapatite
CaCl is added with 2 And (NH) 4 ) 2 HPO 4 Uniformly mixing the solutions to obtain a mixed solution, regulating the pH value of the mixed solution to 2-6, adding the mixed solution into an alkaline organic saccharide solution with the pH value of 9-13 under the stirring condition, standing for 4-12 h to enable solid sediment to be fully settled, washing and separating to obtain a solid product, and drying the solid product to obtain saccharide-modified hydroxyapatite;
wherein CaCl 2 ：(NH 4 ) 2 HPO 4 : the molar ratio of organic saccharides is 5:3: 14-70.
(2) Preparation of hydroxyapatite-based photocatalyst
And (3) grinding the carbohydrate-modified hydroxyapatite obtained in the step (1) uniformly, and calcining for 1-5 hours under the constant temperature condition of 350-800 ℃ in an inert atmosphere to obtain the oxygen vacancy hydroxyapatite/graphite carbon photocatalyst with full spectral response, namely the hydroxyapatite-based photocatalyst with full spectral response capability.
The main function of the step (1) is to prepare the carbohydrate-modified hydroxyapatite (HAp) by a coprecipitation method. The invention uses (NH) 4 ) 2 HPO 4 As a reactant for preparing the hydroxyapatite, caCl is used 2 As a reactant for preparing calcium of hydroxyapatite, organic saccharides are used as a modifier, and the method specifically comprises the following steps:
s11, will (NH) 4 ) 2 HPO 4 Solution and CaCl 2 After the solution is uniformly mixed, HC is reusedl, adjusting the pH value of the solution to 2-6 to obtain a mixed solution;
s12, adding a strong alkaline solution to adjust the pH value of the organic saccharide solution to 9-13 to obtain an alkaline organic saccharide solution;
and S13, adding the mixed solution obtained in the step S11 into the alkaline organic saccharide solution obtained in the step S12, standing until the solid precipitate is fully settled, washing and separating to obtain a solid product, and drying the solid product to obtain the saccharide-modified hydroxyapatite.
The preparation method of the hydroxyapatite-based photocatalyst with full spectral response capability has the advantage that the hydrolysis of phosphate radical in the solution is related to the pH value of the solution. The degree of hydrolysis at different pH values is different and the product is different. Thus, the pH is an important influencing factor for the synthesis of hydroxyapatite. The pH affects the form of phosphate present in the solution and also affects the solubility of HAp, thus affecting the supersaturation of ions during synthesis, affecting the relative magnitudes of nucleation rate and the rate of directional alignment of crystals, and ultimately affecting the n (Ca)/n (P) and crystal integrity of the product. In step S11 and step S12, the pH of the solution is adjusted to 2 to 6 and the pH of the solution is adjusted to 9 to 13, respectively, so that a saccharide-modified HAp having stable properties can be obtained.
Further, in step S13, the purpose of standing is to fully settle the solid precipitate, and on the basis of achieving full settlement of the solid precipitate, a person skilled in the art can adjust the standing time according to the actual situation, and the usual standing time is 4-12 hours, so that the purpose of fully settling the solid precipitate can be achieved.
In the preparation method of the hydroxyapatite-based photocatalyst with full spectral response capability, in the step (1), the organic saccharide is used as a modifier, and small molecular organic saccharides commonly used in the art can be used, including but not limited to at least one of monosaccharides, disaccharides and trisaccharides. Further, at least one of glucose, sucrose, fructose and maltose is preferably employed, but not limited thereto.
The above preparation method of the hydroxyapatite-based photocatalyst with full spectral response capability, wherein in the step (1), washing, separating and drying treatments are all conventional in the art. And (3) removing the residual reaction liquid on the surface of the solid product by washing, separating to obtain the solid product, and drying to obtain the product. In the invention, deionized water and absolute ethyl alcohol are used for washing until the washing liquid is neutral, the washing times are generally 3-5 times, and then centrifugal separation is carried out for several times to obtain a solid product, wherein the centrifugal separation times can be determined according to practical conditions and have no special requirements, and the solid product is dried in a blast drying oven at 60-110 ℃, and the drying temperature is generally 100 ℃.
In the preparation method of the hydroxyapatite-based photocatalyst with full spectral response capability, in the step (2), inert gases which are conventional in the art can be adopted as the inert atmosphere, including but not limited to nitrogen and argon.
In the above method for preparing a hydroxyapatite-based photocatalyst having a full spectral response capability, in the step (2), the temperature is raised from room temperature to 350 to 800 ℃, preferably at a rate of 2.0 to 10.0 ℃/min.
In the preparation method of the hydroxyapatite-based photocatalyst with full spectral response capability, in the step (2), the calcination temperature is preferably 450-750 ℃, and the calcination time is preferably 1-3 h.
The invention also provides application of the hydroxyapatite-based photocatalyst with full spectral response capability in photocatalytic degradation of organic pollutants. The photocatalyst shows excellent full-spectrum photocatalytic performance in photocatalytic degradation of organic pollutants, and takes tetracycline degradation as an example, the OV-HAp/GC photocatalyst has the degradation efficiency of 87.0%,73.0% and 96.8% on tetracycline under visible light, near infrared light and full spectrum respectively, and has the degradation efficiency of 81.4% on tetracycline under real sunlight, so that the photocatalyst shows extremely excellent full-spectrum photocatalytic performance and has important practical significance in removing organic pollutants in water.
Compared with the prior art, the hydroxyapatite-based photocatalyst with full spectral response capability, and the preparation method and application thereof have the following beneficial effects:
1. the hydroxyapatite-based photocatalyst with full spectral response, namely the oxygen vacancy hydroxyapatite/graphite carbon (OV-HAp/GC) photocatalyst, can be prepared by a coprecipitation-calcination method, is simple in steps, easy to operate and control, green and environment-friendly, can be synthesized in a large scale, and is easy to realize industrial production.
2. The hydroxyapatite-based photocatalyst with full spectral response prepared by the method of the invention is characterized in that Graphite Carbon (GC) is coated on the surface of hydroxyapatite (OV-HAp) stone modified by saccharides, and the hydroxyapatite-based photocatalyst has a rod-shaped structure (the length is about 30-50nm, the width is about 10-20 nm), uniform morphology and size and larger specific surface area (more than or equal to 45.7 m) 2 And/g), the product has stable property, is beneficial to enhancing the contact area between OV-HAp/GC and target pollutants, provides powerful guarantee for photocatalytic degradation, and has good application prospect.
3. The hydroxyapatite-based photocatalyst with full spectral response prepared by the method has the light absorption range of more than 945nm, has full spectral response capacity, and greatly improves the photocatalytic activity. In addition, the photocatalyst has good photocatalytic activity under actual sunlight, so that the hydroxyapatite-based photocatalyst is expected to be used for full-spectrum photocatalytic degradation of organic pollutants in an actual environment.
4. The hydroxyapatite-based photocatalyst with full spectral response prepared by the method has good light absorption capacity in a near infrared region, and has strong tissue penetration capacity of near infrared light, so that the hydroxyapatite-based photocatalyst is also expected to be used for biomedical antibacterial or antitumor treatment.
Drawings
FIG. 1 is a process flow diagram of a method of preparing a hydroxyapatite-based photocatalyst having full spectral response capabilities of the present invention;
FIG. 2 is an X-ray diffraction pattern and a Raman spectrum of the OV-HAp/GC prepared in example 11, the GC prepared in comparative example 1, and the OV-HAp prepared in comparative example 2;
FIG. 3 is a TEM spectrum of OV-HAp/GC prepared in example 11, GC prepared in comparative example 1 and OV-HAp prepared in comparative example 2, wherein graphs (A) to (C) are GC prepared in comparative example 1, graphs (D) to (F) are OV-HAp prepared in comparative example 2, and graphs (G) to (I) are OV-HAp/GC prepared in example 11;
FIG. 4 shows the OV-HAp/GC prepared in example 11, the GC prepared in comparative example 1 and the N of the OV-HAp prepared in comparative example 2 2 -adsorption-desorption drawing;
FIG. 5 is an ultraviolet-visible diffuse reflectance graph of the OV-HAp/GC prepared in example 8 and example 11 and the OV-HAp prepared in comparative example 2;
FIG. 6 is a graph of electrochemical impedance spectra and photocurrent response of OV-HAp/GC prepared in example 11, GC prepared in comparative example 1, and OV-HAp prepared in comparative example 2;
FIG. 7 is a graph showing photocatalytic degradation effects of OV-HAp/GC prepared in example 11, OV-HAp prepared in comparative example 1, and GC prepared in comparative example 2 on tetracycline under visible light, near infrared light, full spectrum, and sunlight, respectively.
Detailed Description
In order to clearly and fully describe the technical solutions of the various embodiments of the invention, reference should be made to the accompanying drawings, it is apparent that the described embodiments are only some embodiments of the invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden on the person of ordinary skill in the art based on the embodiments of the present invention, are within the scope of the present invention.
The process flow of the preparation method of the hydroxyapatite-based photocatalyst with full spectral response capability is shown in figure 1, and from the process flow, the photocatalyst is obtained by combining organic saccharides (glucose in the following embodiment) on the surface of hydroxyapatite (HAp), and then calcining the surface of the hydroxyapatite-based photocatalyst in the corresponding temperature and inert gas atmosphere, so that the hydroxyapatite-based photocatalyst with full spectral response capability, namely the hydroxyapatite-based photocatalyst with full spectral response capability, is obtained.
Example 1
The preparation method of the hydroxyapatite-based photocatalyst with full spectral response capability provided by the embodiment comprises the following steps:
(1) Preparation of glucose-modified HAp
The glucose modified HAp was prepared as follows:
s11, 10mmol CaCl 2 And 6mmol (NH) 4 ) 2 HPO 4 Respectively dissolving in 100ml deionized water, ultrasonic treating until the solution becomes clear, and then (NH) 4 ) 2 HPO 4 Dropwise adding the solution into CaCl 2 Uniformly mixing the solutions, regulating the pH value of the solution to 3.5 by using a dilute HCl solution with the concentration of 0.1mol/L to obtain a mixed solution, and marking the mixed solution as a solution A;
s12, respectively dissolving 5g of anhydrous glucose (28 mmol) and 37.5mmol of NaOH in 50ml of deionized water, respectively carrying out ultrasonic treatment on the glucose and the NaOH until the solutions become clear, and then uniformly mixing the glucose and the NaOH to obtain an alkaline glucose solution which is marked as a solution B;
and S13, adding the solution A obtained in the step S11 into the solution B obtained in the step S12, standing for 8 hours to enable the solid precipitate to be fully settled, washing with deionized water and absolute ethyl alcohol for 3 times in sequence, centrifugally separating for 3 times, and drying in a blast drying oven at 100 ℃ to obtain glucose modified HAp, and marking as a product I.
(2) Preparation of HAp-based photocatalyst
And (3) uniformly grinding the product I obtained in the step (1), transferring the ground product I into a tube furnace, introducing Ar, purging for 10min, then raising the temperature of the tube furnace from room temperature to 450 ℃ at a speed of 5 ℃/min, and calcining at the constant temperature for 2h to obtain the OV-HAp/GC photocatalyst with full spectral response, namely the HAp-based photocatalyst with full spectral response capability.
Examples 2 to 5
Examples 2 to 5 differ from example 1 only in the amount of glucose added, and specific amounts are shown in Table 1.
TABLE 1 preparation of OV-HAp/GC with different glucose ratios
| Examples | Anhydrous CaCl 2 (mmol) | (NH 4 ) 2 HPO 4 (mmol) | NaOH(mmol) | Anhydrous dextrose (g) |
| Example 1 | 10.0 | 6.0 | 37.5 | 5 |
| Example 2 | 10.0 | 6.0 | 37.5 | 10 |
| Example 3 | 10.0 | 6.0 | 37.5 | 15 |
| Example 4 | 10.0 | 6.0 | 37.5 | 20 |
| Example 5 | 10.0 | 6.0 | 37.5 | 25 |
Example 6
The preparation method of the hydroxyapatite-based photocatalyst with full spectral response capability provided by the embodiment comprises the following steps:
(1) Preparation of saccharide-modified hydroxyapatite
The preparation method of the carbohydrate-modified hydroxyapatite comprises the following steps:
s11, 10mmol CaCl 2 And 6mmol (NH) 4 ) 2 HPO 4 Respectively dissolving in 100ml deionized water, ultrasonic treating until the solution becomes clear, and then (NH) 4 ) 2 HPO 4 Dropwise adding the solution into CaCl 2 Uniformly mixing the solutions, regulating the pH value of the solutions to 3.5 by using a dilute HCl solution to obtain a mixed solution, and marking the mixed solution as a solution A;
s12, respectively dissolving 10g of anhydrous glucose (56 mmol) and 37.5mmol of NaOH in 50ml of deionized water, respectively carrying out ultrasonic treatment on the glucose and the NaOH until the solutions become clear, and then uniformly mixing the glucose and the NaOH to obtain an alkaline glucose solution which is marked as a solution B;
and S13, adding the solution A obtained in the step S11 into the solution B obtained in the step S12, standing for 8 hours to enable the solid precipitate to be fully settled, washing with deionized water and absolute ethyl alcohol for 3 times in sequence, centrifugally separating for 3 times, and drying in a blast drying oven at 100 ℃ to obtain the carbohydrate-modified hydroxyapatite, which is recorded as a product I.
(2) Preparation of hydroxyapatite-based photocatalyst
Grinding the product I obtained in the step (1) uniformly, transferring the ground product I into a tube furnace, and introducing N 2 Purging for 10min, then raising the temperature of the tube furnace from room temperature to 550 ℃ at a speed of 5 ℃/min, and calcining for 1h at constant temperature at the temperature to obtain the OV-HAp/GC photocatalyst with full spectral response, namely the hydroxyapatite-based photocatalyst with full spectral response capability.
Examples 7 to 10
Examples 7 to 10 differ from example 6 only in the calcination time, and the specific parameters are shown in Table 2.
TABLE 2 preparation of OV-HAp/GC at different calcination times
| Examples | Atmosphere of gas | Rate of temperature rise (. Degree.C/min) | Calcination temperature (. Degree. C.) | Calcination time (h) |
| Example 6 | N 2 | 5.0 | 550 | 1 |
| Example 7 | N 2 | 5.0 | 550 | 2 |
| Example 8 | N 2 | 5.0 | 550 | 3 |
| Example 9 | N 2 | 5.0 | 550 | 4 |
| Example 10 | N 2 | 5.0 | 550 | 5 |
Example 11
The preparation method of the hydroxyapatite-based photocatalyst with full spectral response capability provided by the embodiment comprises the following steps:
(1) Preparation of saccharide-modified hydroxyapatite
The preparation method of the carbohydrate-modified hydroxyapatite comprises the following steps:
s11, 10mmol CaCl 2 And 6mmol (NH) 4 ) 2 HPO 4 Respectively dissolving in 100ml deionized water, ultrasonic treating until the solution becomes clear, and then (NH) 4 ) 2 HPO 4 Dropwise adding the solution into CaCl 2 Uniformly mixing the solutions, regulating the pH value of the solutions to 3.5 by using a dilute HCl solution to obtain a mixed solution, and marking the mixed solution as a solution A;
s12, respectively dissolving 10g of anhydrous glucose (56 mmol) and 37.5mmol of NaOH in 50ml of deionized water, respectively carrying out ultrasonic treatment on the glucose and the NaOH until the solutions become clear, and then uniformly mixing the glucose and the NaOH to obtain an alkaline glucose solution which is marked as a solution B;
and S13, adding the solution A obtained in the step S11 into the solution B obtained in the step S12, standing for 8 hours to enable the solid precipitate to be fully settled, washing with deionized water and absolute ethyl alcohol for 3 times in sequence, centrifugally separating for 3 times, and drying in a blast drying oven at 100 ℃ to obtain the carbohydrate-modified hydroxyapatite, which is recorded as a product I.
(2) Preparation of hydroxyapatite-based photocatalyst
And (3) uniformly grinding the product I obtained in the step (1), transferring the ground product I into a tube furnace, introducing Ar, purging for 10min, then raising the temperature of the tube furnace from room temperature to 450 ℃ at a speed of 10 ℃/min, and calcining at the constant temperature for 3h to obtain the OV-HAp/GC photocatalyst with full spectral response, namely the hydroxyapatite-based photocatalyst with full spectral response capability.
Examples 12 to 16
Examples 12 to 16 differ from example 11 only in the calcination temperature, and the specific parameters are shown in Table 3.
TABLE 3 preparation of OV-HAp/GC at different calcination temperatures
| Examples | Atmosphere of gas | Rate of temperature rise (. Degree.C/min) | Calcination temperature (. Degree. C.) | Calcination time (h) |
| Example 11 | Ar | 5.0 | 450 | 3 |
| Example 12 | Ar | 5.0 | 350 | 3 |
| Example 13 | Ar | 5.0 | 550 | 3 |
| Example 14 | Ar | 5.0 | 650 | 3 |
| Example 15 | Ar | 5.0 | 750 | 3 |
| Example 16 | Ar | 5.0 | 800 | 3 |
Examples 17 to 19
Examples 17 to 19 were different from example 11 in terms of only organic saccharides, and specific parameters are shown in Table 4.
TABLE 4 preparation of OV-HAp/GC using different organic saccharides
Comparative example 1
The comparative example provides a preparation method of a graphite carbon material, comprising the following steps:
10.0g of anhydrous glucose is placed in a tube furnace, ar is introduced to purge for 10min, then the temperature of the tube furnace is raised to 550 ℃ from room temperature at a heating rate of 5 ℃/min, and the calcination is carried out for 3h at the constant temperature, so that a black powder product, namely a graphite carbon material, is obtained and is recorded as GC.
Comparative example 2
The comparative example provides a preparation method of a hydroxyapatite-based photocatalyst, comprising the following steps:
(1) Preparation of glucose-modified HAp
The glucose modified HAp was prepared as follows:
s11, 10mmol CaCl 2 And 6mmol (NH) 4 ) 2 HPO 4 Respectively dissolving in 100ml deionized water, ultrasonic treating until the solution becomes clear, and then (NH) 4 ) 2 HPO 4 Dropwise adding the solution into CaCl 2 Uniformly mixing the solutions, regulating the pH value of the solutions to 3.5 by using a dilute HCl solution to obtain a mixed solution, and marking the mixed solution as a solution A;
s12, respectively dissolving 15g of anhydrous glucose and 37.5mmol of NaOH in 50ml of deionized water, respectively carrying out ultrasonic treatment on the glucose and the NaOH until the solution becomes clear, and then uniformly mixing the glucose and the NaOH to obtain an alkaline glucose solution which is marked as a solution B;
and S13, adding the solution A obtained in the step S11 into the solution B obtained in the step S12, standing for 4 hours, washing with deionized water and absolute ethyl alcohol for 3 times in sequence, centrifugally separating for 3 times, and drying in a blast drying oven at 100 ℃ to obtain glucose modified HAp, and marking as a product I.
(2) Preparation of HAp-based photocatalyst
And (3) uniformly grinding the product I obtained in the step (1), transferring the ground product I into a tube furnace, and then raising the temperature of the tube furnace from room temperature to 550 ℃ at a speed of 5 ℃/min in an air atmosphere, and calcining the product I at the constant temperature for 3 hours to obtain a grey product which is marked as OV-HAp.
Performance comparison analyses were performed on a part of the OV-HAp/GC prepared in example and the GC prepared in comparative example 1 and the OV-HAp prepared in comparative example 2 as follows.
Structural analysis
The OV-HAp/GC material prepared in example 11, the GC material prepared in comparative example 1 and the OV-HAp material prepared in comparative example 2 were subjected to X-ray diffraction analysis and Raman spectrum analysis, and the analysis results are shown in FIG. 2. As can be seen from fig. 2 (a), GC shows a diffraction peak of graphitic carbon at 2θ=22.6 ° (fig. 2 (a) is an interpolation chart), OV-HAp and OV-HAp/GC both detect characteristic diffraction peaks of HAp (JCPDS 09-0432), and OV-HAp/GC also shows characteristic peaks of GC, indicating that GC, OV-HAp and OV-HAp/GC were successfully prepared. Furthermore, as can be seen from FIG. 2 (B), only GC and OV-HAp/GC were carried out at 1333.2cm -1 And 1606cm -1 Two strong raman signals, corresponding to amorphous and ordered carbons of graphitic carbon, respectively, appear nearby, further demonstrating the successful preparation of the photocatalyst.
(II) morphology analysis
The GC prepared in comparative example 1 and the OV-HAp material prepared in comparative example 2, and the OV-HAp/GC material prepared in example 11 were subjected to morphological analysis using a Transmission Electron Microscope (TEM), and the results are shown in FIG. 3. The GC materials prepared in comparative example 1 are shown in FIGS. 3 (A) to (C), and GC is a layered structure. The OV-HAp material prepared in comparative example 2, as shown in FIGS. 3 (D) to (F), had a rod-like structure as a whole and was relatively nonuniform in size. The OV-HAp/GC material prepared in example 11 has a rod-like structure as shown in FIGS. 3 (G) to (I), the length and width of the material are about 30 nm to about 50nm and about 10 nm to about 20nm, and the GC (graphitic carbon) is coated on the surface of the OV-HAp (hydroxyapatite) and has uniform morphology and size.
(III) adsorption analysis
N was used for the OV-HAp/GC material prepared in example 11, the GC material prepared in comparative example 1, and the OV-HAp material prepared in comparative example 2 2 Characterization of adsorption-desorption, as shown in FIG. 4, shows that the specific surface area of OV-HAp/GC prepared in example 11 reaches 45.7m 2 /g, higher than the GC material prepared in comparative example 1 (0.73 m 2 Per g) and OV-HAp material (30.9 m) prepared in comparative example 2 2 Specific surface area per g). The larger specific surface area can provide more reaction sites, is beneficial to enhancing the contact area between the reaction sites and pollutants, and is beneficial to subsequent photocatalytic degradation.
(IV) spectral response and electrochemical response analysis
To verify that the prepared materials had full spectral response, the OV-HAp/GC materials prepared in example 8 and example 11 and the OV-HAp material prepared in comparative example 2 were characterized by using an ultraviolet-visible diffuse reflection technique, and as shown in FIG. 5, it can be seen from the results that the light absorption range of the materials of the OV-HAp prepared in comparative example 2 was 945nm, and the light absorption ranges of the OV-HAp/GC prepared in example 8 and example 11 were both more than 945nm (in the near infrared region), indicating that the prepared materials had full spectral response (absorption from the ultraviolet region to the near infrared region).
The separation ability of photo-generated electron-hole pairs is one of the main factors affecting the photocatalytic activity. Therefore, in order to examine the photo-electron separation ability of the prepared materials, the OV-HAp/GC material prepared in example 11, the GC material prepared in comparative example 1 and the OV-HAp material prepared in comparative example 2 were subjected to electrochemical impedance spectroscopy (fig. 6 (a)) and photocurrent response (fig. 6 (B)), and as a result, as shown in fig. 6, it can be seen from fig. 6 (a) that the radius of the circular arc of OV-HAp/GC is the smallest, which suggests that OV-HAp/GC can effectively separate photo-generated electron-hole pairs. The greatest photocurrent of OV-HAp/GC can be seen in fig. 6 (B), further illustrating that OV-HAp/GC is effective in suppressing photo-electron hole pair recombination, thereby producing a greater photocurrent. This ensures that the full spectrum HAp-based photocatalyst prepared has good photocatalytic activity.
In conclusion, the OV-HAp/GC prepared by the method provided by the invention has relatively uniform size, good specific surface area and full spectrum response capability, and is expected to be used for degrading pollutants in the environment of full spectrum photocatalysis.
Application example
The OV-HAp/GC photocatalyst material prepared in the application example 11 is applied to full spectrum photocatalytic degradation of tetracycline. The OV-HAp/GC photocatalyst was used in an amount of 25mg and Tetracycline (TC) in an amount of 50mL (concentration: 20 mg/L), and before illumination, adsorption-desorption was equilibrated for 30 minutes under dark conditions, and then a 300W xenon lamp equipped with filters of different wavelengths (400 nm and 800nm filters were used as visible light and near infrared light, respectively) was turned on to illuminate, and condensed water was introduced, 2mL of the reaction solution was taken at intervals, and subjected to centrifugal separation, and then absorbance was measured at 357nm with an ultraviolet-visible absorption spectrophotometer. Finally, the photocatalytic degradation efficiency (eta) is calculated according to the following formula:
wherein C is 0 For the initial concentration of tetracycline, C t The concentration of tetracycline at time t.
The results are shown in FIG. 7, and the OV-HAp/GC material prepared in example 11 was optimal for the degradation of tetracycline in all of visible light (A), near infrared light (B), full spectrum (C) and sunlight (D) as compared to the GC prepared in comparative example 1 and the OV-HAp prepared in comparative example 2.
The photocatalytic degradation performance of the OV-HAp/GC photocatalyst prepared by the invention on tetracycline under different wavelength light sources is compared and analyzed with that of the photocatalyst reported in the prior art, and is shown in table 5. As shown in Table 5, compared with the reported materials, the OV-HAp/GC photocatalyst provided by the invention has good photocatalytic activity under the irradiation of visible light, near infrared light and full spectrum light, and has good photocatalytic activity under the actual sunlight, so that the photocatalyst has good application prospect in the actual wastewater treatment.
Table 5 OV-HAp/GC comparison of the photocatalytic degradation Properties of the photocatalyst to Tetracycline with reported photocatalysts at different wavelength light sources
Note that: (1) -indicating that the original document does not provide relevant experimental data;
(2) The light emitted by the Xe lamp is a full spectrum continuous light source;
(3) The visible light is obtained by adding a 400nm optical filter on an emergent light path of the Xe lamp;
(4) The near infrared light is obtained by adding an 800nm optical filter on an emergent light path of the Xe lamp;
(5) The photodegradation experiment corresponding to the sunlight is completed under the irradiation of outdoor natural light.
In conclusion, the OV-HAp/GC photocatalyst with full spectral response is successfully synthesized by a method which is simple and easy to implement, mild in reaction condition and capable of being prepared in large batch, and the photocatalyst shows good photocatalytic performance under visible light, near infrared light, full spectrum and solar spectrum and is expected to be used for catalytic degradation of actual samples under real sunlight.
Those of ordinary skill in the art will recognize that the embodiments described herein are for the purpose of aiding the reader in understanding the principles of the present invention and should be understood that the scope of the invention is not limited to such specific statements and embodiments. Those of ordinary skill in the art can make various other specific modifications and combinations from the teachings of the present disclosure without departing from the spirit thereof, and such modifications and combinations remain within the scope of the present disclosure.
Claims (10)
1. The preparation method of the hydroxyapatite-based photocatalyst with full spectral response capability is characterized by comprising the following steps of:
(1) Preparation of saccharide-modified hydroxyapatite
CaCl is added with 2 And (NH) 4 ) 2 HPO 4 Uniformly mixing the solutions to obtain a mixed solution, regulating the pH value of the mixed solution to 2-6, adding the mixed solution into an alkaline organic saccharide solution with the pH value of 9-13 under the stirring condition, standing for 4-12 hours to enable solid sediment to be fully settled, washing and separating to obtain a solid product, and drying the solid product to obtain saccharide-modified hydroxyapatite;
wherein CaCl 2 ：(NH 4 ) 2 HPO 4 : the molar ratio of organic saccharides is 5:3: 14-70 parts;
(2) Preparation of hydroxyapatite-based photocatalyst
Grinding the carbohydrate-modified hydroxyapatite obtained in the step (1) uniformly, and calcining for 1-5 hours under the constant temperature condition of 350-800 ℃ in an inert atmosphere to obtain an oxygen vacancy hydroxyapatite/graphite carbon photocatalyst with full spectral response, namely a hydroxyapatite-based photocatalyst with full spectral response capability; the photocatalyst has a rod-shaped structure, and graphite carbon is coated on the surface of the carbohydrate-modified hydroxyapatite.
2. The method for preparing a hydroxyapatite based photocatalyst having a full spectrum response capability according to claim 1, wherein the step (1) specifically comprises the steps of:
s11, will (NH) 4 ) 2 HPO 4 Solution and CaCl 2 After the solutions are uniformly mixed, adjusting the pH value of the solutions to 2-6 by using an HCl solution to obtain a mixed solution;
s12, adding a strong alkaline solution to adjust the pH value of the organic saccharide solution to 9-13, so as to obtain an alkaline organic saccharide solution;
and S13, adding the mixed solution obtained in the step S11 into the alkaline organic saccharide solution obtained in the step S12, standing until the solid precipitate is fully settled, washing and separating to obtain a solid product, and drying the solid product to obtain the saccharide-modified hydroxyapatite.
3. The method for preparing a hydroxyapatite based photocatalyst having a full spectrum response capability according to claim 1, wherein in the step (1), the organic saccharide is at least one of monosaccharide, disaccharide and trisaccharide.
4. A method for preparing a hydroxyapatite based photocatalyst having full spectral response capability according to claim 3, wherein: the organic saccharide includes at least one of glucose, sucrose, fructose and maltose.
5. The method for preparing the hydroxyapatite based photocatalyst with full spectrum response capability according to claim 1, wherein in the step (1), deionized water and absolute ethyl alcohol are used for washing for 3-5 times, then centrifugal separation is carried out, and a solid product is obtained and is dried in a blast drying oven at 60-110 ℃.
6. The method for preparing a hydroxyapatite based photocatalyst having a full spectrum response capability according to claim 1 wherein in said step (2), said inert atmosphere is a nitrogen or argon atmosphere.
7. The method for preparing a hydroxyapatite based photocatalyst with full spectrum response capability according to any one of claims 1 to 6, wherein in the step (2), the temperature is raised to 350 to 800 ℃ at a heating rate of 2.0 to 10.0 ℃/min.
8. The method for preparing a hydroxyapatite based photocatalyst with full spectrum response capability according to any one of claims 1 to 6, wherein in the step (2), the calcination temperature is 450 to 750 ℃ and the calcination time is 1 to 3 hours.
9. A hydroxyapatite-based photocatalyst having a full spectral response capability prepared by the method of any one of claims 1-8.
10. Use of the hydroxyapatite based photocatalyst having full spectral response capability of claim 9 in photocatalytic degradation of organic contaminants.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148966A (en) * | 2015-07-10 | 2015-12-16 | 中北大学 | Carbon quantum dot grafted hydroxyapatite photocatalysis material preparation method |
| CN114057173A (en) * | 2021-09-13 | 2022-02-18 | 曲阜师范大学 | Method for synthesizing hydroxyapatite with large specific surface area by using seed crystal |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105148966A (en) * | 2015-07-10 | 2015-12-16 | 中北大学 | Carbon quantum dot grafted hydroxyapatite photocatalysis material preparation method |
| CN114057173A (en) * | 2021-09-13 | 2022-02-18 | 曲阜师范大学 | Method for synthesizing hydroxyapatite with large specific surface area by using seed crystal |
Non-Patent Citations (2)
| Title |
|---|
| Preparation and thermal stability analysis of hydroxyapatite derived from the precipitation process and microwave irradiation method;Zhengwen Yang etal.;《Materials Letters》;第58卷;3586–3590 * |
| Zhengwen Yang etal..Preparation and thermal stability analysis of hydroxyapatite derived from the precipitation process and microwave irradiation method.《Materials Letters》.2004,第58卷3586–3590. * |
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