CN113559915A - Silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst and preparation method and application thereof - Google Patents
Silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst and preparation method and application thereof Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000002131 composite material Substances 0.000 title claims abstract description 112
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 92
- 239000010439 graphite Substances 0.000 title claims abstract description 80
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 80
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 56
- 239000004332 silver Substances 0.000 title claims abstract description 56
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 100
- 239000000843 powder Substances 0.000 claims abstract description 56
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 44
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011259 mixed solution Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
- 239000010452 phosphate Substances 0.000 claims abstract description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004065 wastewater treatment Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000006012 monoammonium phosphate Substances 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 27
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 26
- 239000007787 solid Substances 0.000 description 25
- 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 description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 230000001699 photocatalysis Effects 0.000 description 18
- 229910000161 silver phosphate Inorganic materials 0.000 description 18
- 230000000694 effects Effects 0.000 description 16
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 16
- 229940019931 silver phosphate Drugs 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- 238000000227 grinding Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 10
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- 229910052799 carbon Inorganic materials 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
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- 229960000907 methylthioninium chloride Drugs 0.000 description 5
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
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- 241000237502 Ostreidae Species 0.000 description 3
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- 230000015556 catabolic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
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- 239000006228 supernatant Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 241000237852 Mollusca Species 0.000 description 1
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- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
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- 235000015170 shellfish Nutrition 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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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
- B01J27/24—Nitrogen compounds
-
- 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
- B01J27/1817—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 copper, silver or gold
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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Abstract
The invention provides a silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst, and a preparation method and application thereof, and relates to the technical field of photocatalysts. The preparation method comprises the steps of reacting oyster shell powder with an acid solution, mixing a mixed solution A obtained by the reaction with a phosphate radical-containing solution and graphite-phase carbon nitride, carrying out hydrothermal reaction to obtain a hydroxyapatite-graphite-phase carbon nitride composite carrier, mixing a carrier turbid solution formed by the hydroxyapatite-graphite-phase carbon nitride composite carrier and water with a silver nitrate solution, standing, separating and drying to obtain the silver phosphate-hydroxyapatite-graphite-phase carbon nitride composite photocatalyst.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst and a preparation method and application thereof.
Background
With the development of economy and society, the water body environment pollution is increasingly serious, and the treatment of the water body environment pollutants arouses the high attention of people. Organic matter pollution of water in China is not optimistic, persistent organic pollutants seriously threaten physical and psychological health of human bodies, the residual period of the persistent organic pollutants in the environment is extremely long, and environmental pollution treatment is an urgent task. At present, common chemical methods for treating water pollutants comprise a coagulation method, a neutralization method, an oxidation-reduction method, an ion exchange method and the like. The traditional methods have the defects of high cost, poor effect, easy secondary pollution and the like. The photocatalytic degradation technology developed along with the appearance of new materials can utilize inexhaustible solar energy to degrade pollutants, and is considered as an effective means for solving the pollution problem.
Over the past decades, TiO2And semiconductor photocatalysts such as ZnO and the like have received wide attention due to application in the aspects of environmental purification and solar energy conversion. But conventional TiO2The intrinsic energy band (Eg ≈ 3.2 eV) of the photocatalytic material can only absorb and utilize ultraviolet light, and the energy of the ultraviolet light only accounts for 5% of the energy of the whole sunlight, so that the further industrial application of the photocatalytic material is limited to a certain extent.
Silver-based materials are widely used in many fields as excellent inorganic antimicrobial agents, and are also important inorganic photosensitizer materials. The silver material has narrow band gap, is acted by the surface plasma resonance effect of the material, has fast separation of photo-generated electrons, can generate fast coupling of electrons and holes, and has high photocatalytic activity. The subject group of the leaf golden flower discovers Ag for the first time3PO4The characteristics of decomposing water and degrading organic dye under illumination prove that the silver phosphate has excellent photocatalytic degradation activity. But Ag3PO4Has the disadvantages of photosensitivity and instability. So how to solve Ag3PO4The problem of instability and the further improvement of the photocatalytic activity become the hot spots of the current research.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst.
The second purpose of the invention is to provide a silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst, which is prepared by adopting the preparation method.
The third purpose of the invention is to provide an application of the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a preparation method of a silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst, which comprises the following steps:
(a) mixing oyster shell powder and an acid solution for reaction, and separating to obtain a mixed solution A;
adjusting the pH value of a mixed solution B formed by the mixed solution A and a phosphate radical-containing solution to be alkaline, then mixing the mixed solution B with graphite-phase carbon nitride to perform hydrothermal reaction, separating and drying a hydrothermal reaction product to obtain a hydroxyapatite-graphite-phase carbon nitride composite carrier; wherein the weight ratio of the oyster shell powder to the graphite-phase carbon nitride is (3-4): 1;
(b) mixing a hydroxyapatite-graphite phase carbon nitride composite carrier with water to obtain a carrier turbid liquid;
and mixing the silver nitrate solution with the carrier turbid solution, standing, separating and drying to obtain the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst.
Further, on the basis of the above technical solution of the present invention, the acid solution includes any one or a combination of at least two of acetic acid, hydrochloric acid, or nitric acid;
the mass concentration of the acid solution is 5-15%.
Further, on the basis of the above technical scheme of the present invention, in the step (a), the weight volume ratio of the oyster shell powder to the acid solution is (1-5) g: (40-200) mL.
Further, on the basis of the above technical solution of the present invention, in the step (a), the phosphate group-containing solution includes diammonium hydrogen phosphate or ammonium dihydrogen phosphate;
the molar ratio of the calcium element in the mixed solution A to the phosphorus element in the phosphate radical-containing solution is (1.65-1.70): 1.
further, on the basis of the above technical scheme of the present invention, in the step (a), the pH value of the mixed solution B is adjusted to 9-10 by using alkali.
Further, on the basis of the above technical scheme of the present invention, in the step (a), the mass ratio of the oyster shell powder to the graphite-phase carbon nitride is (3.2-3.5): 1.
further, on the basis of the above technical scheme of the present invention, in the step (a), the temperature of the hydrothermal reaction is 140-.
Further, on the basis of the above technical scheme of the present invention, in the step (b), the weight ratio of the silver nitrate in the silver nitrate solution to the hydroxyapatite-graphite phase carbon nitride composite carrier in the carrier turbid solution is (1-3): 1.
the invention also provides a silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst, which is prepared by adopting the preparation method of the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst.
The invention also provides application of the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst in the field of photocatalysis.
Compared with the prior art, the invention has the following technical effects:
(1) the invention provides a preparation method of a silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst, which comprises the steps of firstly reacting oyster shell powder with an acid solution, then mixing a mixed solution A obtained by the reaction with a phosphate radical-containing solution and graphite phase carbon nitride, and then carrying out hydrothermal reaction to obtain a hydroxyapatite-graphite phase carbon nitride composite carrier, mixing a carrier turbid solution formed by the hydroxyapatite-graphite phase carbon nitride composite carrier and water with a silver nitrate solution, standing, separating and drying to obtain the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst. The preparation method is simple in process and convenient to operate, and the prepared composite photocatalyst is prepared by introducing hydroxyapatite and graphite-phase carbon nitride, so that silver phosphate is widely distributed in two materials, the defect that the silver phosphate is easily decomposed when visible light is used is overcome, the band gap width is increased, the stability and the photocatalytic performance of the composite photocatalyst are greatly improved, the production cost is low, the problem of recycling marine resources is solved, and the preparation method has a wide application prospect.
(2) The invention provides a silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst, which is prepared by adopting the preparation method. The composite photocatalyst is prepared by compounding silver phosphate, hydroxyapatite and graphite-phase carbon nitride, wherein the silver phosphate is widely distributed in the hydroxyapatite and graphite-phase carbon nitride, so that the defect that the silver phosphate is easily decomposed by visible light is overcome, the band gap width is increased, the stability and the photocatalytic performance of the composite photocatalyst are greatly improved, the production cost is low, the problem of ocean resource recycling is solved, and the composite photocatalyst has a wide application prospect.
(3) The invention also provides an application of the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst, and the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst has a good application prospect in the fields of wastewater treatment and the like in view of the advantages of the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is an XRD chart of the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst provided in embodiments 1 to 3 of the present invention;
fig. 2 is a scanning electron microscope image of the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst provided in embodiment 2 of the present invention;
FIG. 3 is a graph showing the catalytic effect of the composite photocatalyst provided in each example of the present invention and the comparative example.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but those skilled in the art will understand that the following embodiments and examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. Those who do not specify the conditions are performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
According to a first aspect of the present invention, there is provided a preparation method of a silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst, comprising the following steps:
(a) mixing oyster shell powder and an acid solution for reaction, and separating to obtain a mixed solution A;
adjusting the pH value of a mixed solution B formed by the mixed solution A and a phosphate radical-containing solution to be alkaline, then mixing the mixed solution B with graphite-phase carbon nitride to perform hydrothermal reaction, separating and drying a hydrothermal reaction product to obtain a hydroxyapatite-graphite-phase carbon nitride composite carrier; wherein the weight ratio of the oyster shell powder to the graphite-phase carbon nitride is (3-4): 1;
(b) mixing a hydroxyapatite-graphite phase carbon nitride composite carrier with water to obtain a carrier turbid liquid;
and mixing the silver nitrate solution with the carrier turbid solution, standing, separating and drying to obtain the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst.
Specifically, the oyster shell powder in the step (a) of the invention is mainly prepared by crushing oyster shell which is a marine waste. Oyster shell is the shell of oyster commonly known as oyster and oyster, belonging to the phylum mollusca, class bivalves, order pearl oyster, and is a common marine shellfish aquatic animal. The invention adopts oyster shell powder as a raw material to react with the phosphate radical-containing solution for preparing Hydroxyapatite (HAP), can realize the resource utilization of the oyster shell which is a marine waste, and can also reduce the production cost.
Graphite phase carbon nitride (g-C)3N4) Has the characteristics of good chemical stability, thermal stability, easy modification and the like. In the invention, the good chemical stability and photosensitive activity of the graphite phase carbon nitride are mainly utilized, and the specific source of the graphite phase carbon nitride is not particularly limited and can be purchased or prepared by self.
In the preparation process, the oyster shell powder is firstly mixed with an acid solution to react, so that calcium ions in the oyster shell powder are fully dissolved into the solution. In the mixed solution B formed by mixing the mixed solution a and the phosphate radical-containing solution, a part of the acid solution remains to make the pH value acidic, which is not favorable for obtaining the product hydroxyapatite, so the pH value of the mixed solution B needs to be adjusted to be alkaline to obtain the hydroxyapatite.
And then the mixed solution B is mixed with graphite-phase carbon nitride and then transferred to a hydrothermal reactor for hydrothermal reaction, so that the generated hydroxyapatite is compounded with the graphite-phase carbon nitride to form the hydroxyapatite-graphite-phase carbon nitride composite carrier. The graphite-phase carbon nitride can be directly added into the mixed solution B in a powder form, or can be mixed with water firstly and then added into the mixed solution B in a graphite-phase carbon nitride solution form after ultrasonic treatment. By means of ultrasound, finer and more homogeneous products can be obtained.
It should be noted that, in the experiment, the inventor finds that the relative amount of the oyster shell powder and the graphite-phase carbon nitride has a significant influence on the photocatalytic effect of the final composite photocatalyst, and only when the mass ratio of the oyster shell powder to the graphite-phase carbon nitride is (3-4): 1, good technical effect can be achieved only within a specific numerical range, and when the mass ratio of the two exceeds the numerical range, the photocatalytic effect of the composite photocatalyst is obviously reduced.
The typical but non-limiting mass ratio of oyster shell powder to graphite-phase carbon nitride is 3: 1. 3.1: 1. 3.2: 1. 3.33: 1. 3.4: 1. 3.5: 1. 3.6: 1. 3.7: 1. 3.8: 1. 3.9: 1 or 4.0: 1.
in the step (b), mixing the silver nitrate solution with the carrier turbid solution containing the hydroxyapatite-graphite phase carbon nitride composite carrier, standing, and enabling calcium ions in the hydroxyapatite and silver ions in the solution to generate ion exchange reaction, so that the silver nitrate is converted into silver phosphate and loaded on the hydroxyapatite-graphite phase carbon nitride composite carrier, and further the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst is obtained.
In the present invention, "-" represents "and" in which the hydroxyapatite-graphite phase carbon nitride composite carrier means a carrier formed by compositing hydroxyapatite and graphite phase carbon nitride, and the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst means a photocatalyst formed by compositing silver phosphate, hydroxyapatite and graphite phase carbon nitride.
The invention provides a preparation method of a silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst, which comprises the steps of firstly reacting oyster shell powder with an acid solution, then mixing a mixed solution A obtained by the reaction with a phosphate radical-containing solution and graphite phase carbon nitride, and then carrying out hydrothermal reaction to obtain a hydroxyapatite-graphite phase carbon nitride composite carrier, mixing a carrier turbid solution formed by the hydroxyapatite-graphite phase carbon nitride composite carrier and water with a silver nitrate solution, standing, separating and drying to obtain the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst. The preparation method is simple in process and convenient to operate, and the prepared composite photocatalyst is prepared by introducing hydroxyapatite and graphite-phase carbon nitride, so that silver phosphate is widely distributed in two materials, the defect that the silver phosphate is easily decomposed when visible light is used is overcome, the band gap width is increased, the stability and the photocatalytic performance of the composite photocatalyst are greatly improved, the production cost is low, the problem of recycling marine resources is solved, and the preparation method has a wide application prospect.
As an alternative embodiment of the present invention, the acid solution includes an acid solution including any one or a combination of at least two of acetic acid, hydrochloric acid, or nitric acid;
the mass concentration of the acid solution is 5-15%. Typical but not limiting mass concentrations of the acid solution are 5%, 6%, 8%, 10%, 12%, 14% or 15%.
As an alternative embodiment of the invention, the weight volume ratio of the oyster shell powder to the acid solution is (1-5) g: (40-200) mL.
Typical but not limiting mass-to-volume ratios of oyster shell powder to acid solution are 1 g: 40mL, 1 g: 60mL, 1 g: 80 mL, 1 g: 100 mL, 1 g: 120 mL, 1 g: 150 mL, 1 g: 180 mL, 1 g: 200 mL, 2 g: 40mL, 2 g: 60mL, 2 g: 80 mL, 2 g: 100 mL, 2 g: 120 mL, 2 g: 150 mL, 2 g: 180 mL, 2 g: 200 mL, 4 g: 40mL, 4 g: 60mL, 4 g: 80 mL, 4 g: 100 mL, 4 g: 120 mL, 4 g: 150 mL, 4 g: 180 mL, 4 g: 200 mL, 5 g: 40mL, 5 g: 60mL, 5 g: 80 mL, 100 mL of 5g, 120 mL of 5g, 150 mL of 5g, 180 mL of 5g or 200 mL of 5 g.
As an alternative embodiment of the present invention, in step (a), the phosphate-containing solution comprises diammonium hydrogen phosphate or ammonium dihydrogen phosphate.
The molar ratio of the calcium element in the mixed solution A to the phosphorus element in the solution containing the phosphate radical is (1.65-1.70): 1, preferably 1.67: 1.
in an alternative embodiment of the present invention, in step (a), the pH of mixed liquor B is adjusted to 9 to 10 with an alkali.
After conditioning mixture B with a base, mixture B typically has, but not limited to, a pH of 9, 9.5, or 10.
As an alternative embodiment of the present invention, in the step (a), the weight ratio of the oyster shell powder to the graphite-phase carbon nitride is (3.2-3.5): 1.
the composite catalyst has better catalytic effect by further limiting the mass ratio of the oyster shell powder to the graphite-phase carbon nitride.
As an alternative embodiment of the present invention, in step (a), the temperature of the hydrothermal reaction is 140-. The typical but not limiting temperature of the hydrothermal reaction is 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃, and the typical but not limiting time of the hydrothermal reaction is 4h, 5h, 6h, 7h or 8 h.
As an alternative embodiment of the present invention, in the step (b), the weight ratio of the silver nitrate in the silver nitrate solution to the hydroxyapatite-graphite phase carbon nitride composite carrier in the carrier turbid solution is (1-3): 1.
the typical but non-limiting weight ratio of silver nitrate to hydroxyapatite-graphite phase carbon nitride composite carrier is 1: 1. 1.5: 1. 2: 1. 2.5: 1 or 3: 1.
according to the second aspect of the invention, the invention also provides a silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst, which is prepared by adopting the preparation method of the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst.
The composite photocatalyst is prepared by compounding silver phosphate, hydroxyapatite and graphite-phase carbon nitride, wherein the silver phosphate is widely distributed in the hydroxyapatite and graphite-phase carbon nitride, so that the defect that the silver phosphate is easily decomposed by visible light is overcome, the band gap width is increased, the stability and the photocatalytic performance of the composite photocatalyst are greatly improved, the production cost is low, the problem of ocean resource recycling is solved, and the composite photocatalyst has a wide application prospect.
According to the third aspect of the invention, the application of the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst in the field of wastewater treatment is also provided.
In view of the advantages of the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst, the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst has a good application prospect in the fields of wastewater treatment and the like.
The present invention will be further described with reference to specific examples and comparative examples.
Example 1
The embodiment provides a preparation method of a silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst, which comprises the following steps:
(a) preparation of hydroxyapatite-graphite phase carbon nitride composite carrier
The preparation method of the oyster shell powder comprises the following steps: cleaning and drying oyster shell, and grinding into powder with average particle size of 200 mesh.
The preparation method of the graphite phase carbon nitride comprises the following steps: and grinding the urea solid into powder, transferring the powder into a crucible, putting the crucible into a muffle furnace, reacting for 8 hours at 550 ℃ to obtain porous light yellow solid, and grinding to obtain graphite-phase carbon nitride powder.
0.25g of graphite-phase carbon nitride was mixed with 50mL of water and subjected to ultrasonic treatment to obtain a carbon nitride solution.
The above 1.0g of oyster shell powder and 40mL of acetic acid solution (volume fraction: 10%) were mixed to effect a reaction, the reaction was carried out overnight, and the overnight placed solution was suction-filtered to obtain a mixed solution A.
To the mixture a, 20mL (NH) was added dropwise at a molar ratio of Ca/P =1.67 under vigorous stirring with a magnetic stirrer4)2HPO4Adding the solution (0.3 mol/L) dropwise, adjusting the pH of the solution to 9-10 by using ammonia water, and adding the carbon nitride solution after ultrasonic treatmentAnd after uniformly stirring, transferring the mixed solution into a stainless steel hydrothermal reaction kettle, putting the stainless steel hydrothermal reaction kettle into a constant-temperature drying oven to react for 6 hours at 160 ℃, separating a hydrothermal reaction product, washing the hydrothermal reaction product for the second time, centrifuging the hydrothermal reaction product, and drying the obtained powdery product at 100 ℃ to obtain the hydroxyapatite-graphite phase carbon nitride composite carrier.
(b) Mixing 0.5g of hydroxyapatite-graphite phase carbon nitride composite carrier with water to obtain carrier turbid liquid;
dissolving 1.5g of silver nitrate solid in deionized water (SDS), slowly dripping into the stirred carrier turbid liquid, after the dripping is finished, continuously stirring, standing for 10-14 h, performing suction filtration to obtain a solid, washing with water for three times, washing with absolute ethyl alcohol for three times, and drying at 100 ℃ to obtain the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst.
Example 2
This example provides a method for preparing a silver phosphate-hydroxyapatite-graphite-phase carbon nitride composite photocatalyst, which is the same as in example 1 except that the amount of graphite-phase carbon nitride used in step (a) is changed from 0.25g to 0.3 g.
Example 3
The embodiment provides a preparation method of a silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst, which comprises the following steps:
(a) preparation of hydroxyapatite-graphite phase carbon nitride composite carrier
The preparation method of the oyster shell powder comprises the following steps: cleaning and drying oyster shell, and grinding into powder with average particle size of 100 mesh.
The preparation method of the graphite phase carbon nitride comprises the following steps: and grinding the urea solid into powder, transferring the powder into a crucible, putting the crucible into a muffle furnace, reacting for 10 hours at 550 ℃ to obtain porous light yellow solid, and grinding to obtain graphite-phase carbon nitride powder.
0.33g of graphite-phase carbon nitride was mixed with 60mL of water and subjected to ultrasonic treatment to obtain a carbon nitride solution.
The above 1.0g of oyster shell powder and 40mL of acetic acid solution (volume fraction: 10%) were mixed to effect a reaction, the reaction was carried out overnight, and the overnight placed solution was suction-filtered to obtain a mixed solution A.
To the mixture a, 20mL (NH) was added dropwise at a molar ratio of Ca/P =1.68 under vigorous stirring with a magnetic stirrer4)2HPO4And (3) dropwise adding the solution (0.3 mol/L), adjusting the pH value of the solution to 9-10 by using ammonia water, adding the carbon nitride solution after ultrasonic treatment, stirring uniformly, transferring the mixed solution into a stainless steel hydrothermal reaction kettle, putting the stainless steel hydrothermal reaction kettle into a constant-temperature drying oven, reacting for 8 hours at 160 ℃, separating a hydrothermal reaction product, washing for the second time, centrifuging, and drying the obtained powdery product at 100 ℃ to obtain the hydroxyapatite-graphite phase carbon nitride composite carrier.
(b) Mixing 0.8 g of hydroxyapatite-graphite phase carbon nitride composite carrier with water to obtain carrier turbid liquid;
dissolving 1.6 g of silver nitrate solid in deionized water (SDS), slowly dripping into the stirred carrier turbid liquid, after the dripping is finished, continuously stirring, standing for 10-14 h, performing suction filtration to obtain a solid, washing with water for three times, washing with absolute ethyl alcohol for three times, and drying at 100 ℃ to obtain the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst.
Comparative example 1
The comparative example provides a preparation method of a silver phosphate-hydroxyapatite composite photocatalyst, which comprises the following steps:
(a) preparation of hydroxyapatite Carrier
The preparation method of the oyster shell powder comprises the following steps: cleaning and drying oyster shell, and grinding into powder with average particle size of 200 mesh.
The above 1.0g of oyster shell powder and 40mL of acetic acid solution (volume fraction: 10%) were mixed to effect a reaction, the reaction was carried out overnight, and the overnight placed solution was suction-filtered to obtain a mixed solution A.
To the mixture a, 20mL (NH) was added dropwise at a molar ratio of Ca/P =1.67 under vigorous stirring with a magnetic stirrer4)2HPO4Adding the solution (0.3 mol/L) dropwise, adjusting the pH value of the solution to 9-10 by using ammonia water, transferring the solution into a stainless steel hydrothermal reaction kettle, putting the solution into a constant-temperature drying oven to react for 6 hours at 160 ℃, separating, washing and centrifuging a hydrothermal reaction product, and drying the obtained powdery product at 100 DEG CObtaining the hydroxyapatite carrier.
(b) Mixing 0.5g of hydroxyapatite carrier with water to obtain a carrier turbid solution;
dissolving 1.5g of silver nitrate solid in deionized water (SDS), slowly dripping into the stirred carrier turbid liquid, after the dripping is finished, continuously stirring, standing for 10-14 h, performing suction filtration to obtain a solid, washing with water for three times, washing with absolute ethyl alcohol for three times, and drying at 100 ℃ to obtain the silver phosphate-hydroxyapatite composite photocatalyst.
Comparative example 2
The comparative example provides a preparation method of a silver nitrate-graphite phase carbon nitride composite photocatalyst, which comprises the following steps:
(a) preparation of graphite phase carbon nitride carrier
The preparation method of the graphite phase carbon nitride comprises the following steps: and grinding the urea solid into powder, transferring the powder into a crucible, putting the crucible into a muffle furnace, reacting for 8 hours at 550 ℃ to obtain porous light yellow solid, and grinding to obtain the graphite-phase carbon nitride carrier.
(b) Mixing 0.5g of graphite-phase carbon nitride carrier with water to obtain carrier turbid liquid;
dissolving 1.5g of silver nitrate solid in deionized water (SDS), slowly dripping into the stirred carrier turbid liquid, after the dripping is finished, continuously stirring, standing for 10-14 h, performing suction filtration to obtain a solid, washing with water for three times, washing with absolute ethyl alcohol for three times, and drying at 100 ℃ to obtain the silver nitrate-graphite phase carbon nitride composite photocatalyst.
Comparative example 3
This comparative example provides a method for preparing a hydroxyapatite-graphite phase carbon nitride composite photocatalyst, which is the same as in example 1 except that the step (b) is not performed.
Comparative example 4
The comparative example provides a preparation method of a graphite-phase carbon nitride composite photocatalyst, which comprises the following steps:
and grinding the urea solid into powder, transferring the powder into a crucible, putting the crucible into a muffle furnace, reacting for 8 hours at 550 ℃ to obtain porous light yellow solid, and grinding to obtain graphite-phase carbon nitride powder.
Comparative example 5
The comparative example provides a preparation method of a silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst, which comprises the following steps:
(a) preparation of hydroxyapatite Carrier
The preparation method of the oyster shell powder comprises the following steps: cleaning and drying oyster shell, and grinding into powder with average particle size of 200 mesh.
The above 1.0g of oyster shell powder and 40mL of acetic acid solution (volume fraction: 10%) were mixed to effect a reaction, the reaction was carried out overnight, and the overnight placed solution was suction-filtered to obtain a mixed solution A.
To the mixture a, 20mL (NH) was added dropwise at a molar ratio of Ca/P =1.67 under vigorous stirring with a magnetic stirrer4)2HPO4Adding the solution (0.3 mol/L) dropwise, adjusting the pH value of the solution to 9-10 by using ammonia water, transferring the solution into a stainless steel hydrothermal reaction kettle, putting the stainless steel hydrothermal reaction kettle into a constant-temperature drying oven to react for 6 hours at 160 ℃, separating, washing and centrifuging a hydrothermal reaction product, and drying the obtained powdery product at 100 ℃ to obtain the hydroxyapatite carrier.
The preparation method of the graphite phase carbon nitride comprises the following steps: and grinding the urea solid into powder, transferring the powder into a crucible, putting the crucible into a muffle furnace, reacting for 8 hours at 550 ℃ to obtain porous light yellow solid, and grinding to obtain graphite-phase carbon nitride powder.
0.25g of graphite-phase carbon nitride was mixed with 50mL of water and subjected to ultrasonic treatment to obtain a carbon nitride solution.
(b) Mixing 0.5g of hydroxyapatite carrier, carbon nitride solution and water to obtain carrier turbid liquid;
dissolving 1.5g of silver nitrate solid in deionized water (SDS), slowly dripping into the stirred carrier turbid liquid, after the dripping is finished, continuously stirring, standing for 10-14 h, performing suction filtration to obtain a solid, washing with water for three times, washing with absolute ethyl alcohol for three times, and drying at 100 ℃ to obtain the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst.
Comparative example 6
The comparative example provides a preparation method of a silver phosphate-hydroxyapatite-carbon dot composite photocatalyst, which comprises the following steps:
(a) preparation of hydroxyapatite-carbon dot composite carrier
The preparation method of the oyster shell powder comprises the following steps: cleaning and drying oyster shell, and grinding into powder with average particle size of 200 mesh.
The preparation method of the carbon dots comprises the following steps: and (3) taking citric acid as a carbon source, adding the carbon source according to 30% of the volume of the closed container, heating to 180 ℃, and preserving heat for 10 hours to prepare the carbon dots.
0.25g of carbon dots was mixed with 50mL of water, and subjected to ultrasonic treatment to obtain a carbon dot solution.
The above 1.0g of oyster shell powder and 40mL of acetic acid solution (volume fraction: 10%) were mixed to effect a reaction, the reaction was carried out overnight, and the overnight placed solution was suction-filtered to obtain a mixed solution A.
To the mixture a, 20mL (NH) was added dropwise at a molar ratio of Ca/P =1.67 under vigorous stirring with a magnetic stirrer4)2HPO4And (3) dropwise adding the solution (0.3 mol/L), adjusting the pH value of the solution to 9-10 by using ammonia water, adding the carbon dot solution after ultrasonic treatment, stirring uniformly, transferring the mixed solution into a stainless steel hydrothermal reaction kettle, putting the stainless steel hydrothermal reaction kettle into a constant-temperature drying oven, reacting for 6 hours at 160 ℃, separating a hydrothermal reaction product, washing for the second time, centrifuging, and drying the obtained powdery product at 100 ℃ to obtain the hydroxyapatite-carbon dot composite carrier.
(b) Mixing 0.5g of hydroxyapatite-carbon dot composite carrier with water to obtain a carrier turbid solution;
dissolving 1.5g of silver nitrate solid in deionized water (SDS), slowly dripping the silver nitrate solid into the stirred carrier turbid liquid, continuously stirring the mixture after the dripping is finished, standing the mixture for 10 to 14 hours, performing suction filtration to obtain solid, washing the solid with water for three times and absolute ethyl alcohol for three times, and drying the solid at 100 ℃ to obtain the silver phosphate-hydroxyapatite-carbon dot composite photocatalyst.
Comparative example 7
This comparative example provides a method for producing a silver phosphate-hydroxyapatite-graphite-phase carbon nitride composite photocatalyst, which is the same as in example 1 except that the amount of graphite-phase carbon nitride used in step (a) was changed from 0.25g to 0.2 g.
Comparative example 8
This comparative example provides a method for producing a silver phosphate-hydroxyapatite-graphite-phase carbon nitride composite photocatalyst, which is the same as in example 1 except that the amount of graphite-phase carbon nitride used in step (a) was changed from 0.25g to 0.6 g.
To further verify the technical effects of the respective examples and comparative examples, the following experiments were carried out.
Experimental example 1
Taking examples 1 to 3 as a representative example, XRD detection was performed on the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst provided in examples 1 to 3, as shown in fig. 1.
As can be seen from the figure, the peak shapes of the three composite photocatalysts are basically consistent, wherein Ag appears at 20.9 degrees, 29.7 degrees, 33.3 degrees, 36.6 degrees and the like3PO4The characteristic diffraction peaks of the composite photocatalyst are the characteristic diffraction peaks of hydroxyapatite at the positions of 26.2 degrees, 32.3 degrees and the like, the weak peaks of the composite photocatalyst at the positions of 27-28 degrees are the characteristic diffraction peaks of graphite-phase carbon nitride, and the chemical compositions of the composite photocatalyst are silver phosphate, hydroxyapatite and graphite-phase carbon nitride.
Taking example 2 as a representative example, the morphology of the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst provided in example 2 is subjected to electron microscope scanning, and is specifically shown in fig. 2.
As can be seen from the figure, the composite photocatalyst presents a nano rod-shaped structure, the length of the rod is between 40 nm and 120nm, and the width of the rod is about 20 nm. The appearance of the composite photocatalyst is regular, and the three components are uniformly dispersed in the material without obvious agglomeration.
Experimental example 2 analysis of catalytic Activity
The photocatalytic performance of the photocatalysts provided by the embodiments and the comparative examples is detected, that is, under the condition of visible light irradiation, different photocatalysts with the same mass are added to degrade methylene blue solution with the same volume and the same concentration, and the specific detection method is as follows:
0.3g of photocatalyst was put into 250mL of methylene blue solution (10 mg/L), stirred for 20min in the absence of light, sampled with an aspirator, added into a centrifuge tube, centrifuged for 4min, and the supernatant was taken. The absorbance was measured at a wavelength of 664nm, and the absorbance at this time was designated as A0 and the concentration was C0. Meanwhile, a visible light source (xenon lamp) is started for photocatalytic degradation, and samples are taken every 20min within the following 2 h. After centrifugation, the supernatant was subjected to UV-visible spectrophotometer to determine the absorbance At of the methylene blue solution, and the concentration was recorded as Ct. The photocatalytic degradation effect of the catalyst sample on the methylene blue solution is evaluated and is expressed by Ct/C0. The smaller the Ct/C0 value, the better the catalytic effect.
The result of the photocatalytic performance test is shown in fig. 3, and it can be seen from the graph that the composite photocatalysis provided by the embodiments of the present invention has better degradation effect on methylene blue under illumination than the comparative examples.
The photocatalyst in the embodiment 2 has the strongest catalytic effect, wherein the degradation rate reaches 94% when the photocatalyst is illuminated for 60min, and the degradation rate reaches 97% when the photocatalyst is illuminated for 80 min. When the mass ratio of the oyster shell powder to the graphite-phase carbon nitride is beyond the numerical range defined by the invention (such as comparative example 7 and comparative example 8), the photocatalytic effect of the composite photocatalyst is obviously reduced. This also shows that good technical effects can be achieved only when the mass ratio of oyster shell powder to graphite-phase carbon nitride is limited within a specific numerical range.
The photocatalysts provided by the comparative examples 1-4 are not compounded by silver phosphate, hydroxyapatite and graphite phase carbon nitride at the same time, and as can be seen from the figure, the photocatalytic effects of the comparative examples 1-4 are obviously lower than those of the examples.
The preparation method of the composite photocatalyst provided by the comparative example 5 is slightly different from the preparation method of the invention, but the performance of the composite photocatalyst is obviously reduced, so that the adding time of the graphite phase carbon nitride has a great influence on the photocatalytic effect of the composite photocatalyst.
The composite photocatalyst of comparative example 6 is compounded with silver phosphate, hydroxyapatite and carbon dots, and as can be seen from the figure, the composite photocatalyst also has a better photocatalytic effect, but the effect is not as good as that of the composite photocatalyst provided by the embodiments of the present invention.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst is characterized by comprising the following steps:
(a) mixing oyster shell powder and an acid solution for reaction, and separating to obtain a mixed solution A;
adjusting the pH value of a mixed solution B formed by the mixed solution A and a phosphate radical-containing solution to be alkaline, then mixing the mixed solution B with graphite-phase carbon nitride to perform hydrothermal reaction, separating and drying a hydrothermal reaction product to obtain a hydroxyapatite-graphite-phase carbon nitride composite carrier; wherein the weight ratio of the oyster shell powder to the graphite-phase carbon nitride is (3-4): 1;
(b) mixing a hydroxyapatite-graphite phase carbon nitride composite carrier with water to obtain a carrier turbid liquid;
and mixing the silver nitrate solution with the carrier turbid solution, standing, separating and drying to obtain the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst.
2. The method according to claim 1, wherein in the step (a), the acid solution comprises any one or a combination of at least two of acetic acid, hydrochloric acid or nitric acid;
the mass concentration of the acid solution is 5-15%.
3. The preparation method according to claim 2, wherein in the step (a), the weight-volume ratio of the oyster shell powder to the acid solution is (1-5) g: (40-200) mL.
4. The method of claim 1, wherein in step (a), the phosphate-containing solution comprises diammonium hydrogen phosphate or monoammonium phosphate;
the molar ratio of the calcium element in the mixed solution A to the phosphorus element in the phosphate radical-containing solution is (1.65-1.70): 1.
5. the method according to claim 1, wherein in the step (a), the pH of the mixed solution B is adjusted to 9 to 10 with an alkali.
6. The method according to claim 1, wherein in the step (a), the weight ratio of oyster shell powder to graphite-phase carbon nitride is (3.2-3.5): 1.
7. the preparation method as claimed in claim 1, wherein the temperature of the hydrothermal reaction in step (a) is 140 ℃ and 180 ℃ and the time of the hydrothermal reaction is 4-8 h.
8. The method according to any one of claims 1 to 7, wherein in step (b), the weight ratio of the silver nitrate in the silver nitrate solution to the hydroxyapatite-graphite phase carbon nitride composite carrier in the carrier cloud is (1-3): 1.
9. a silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst, which is characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. The use of the silver phosphate-hydroxyapatite-graphite phase carbon nitride composite photocatalyst of claim 9 in the field of wastewater treatment.
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