CN110871095A - WO (WO)3Loaded nickel sodium phosphate photocatalytic material and preparation method thereof - Google Patents
WO (WO)3Loaded nickel sodium phosphate photocatalytic material and preparation method thereof Download PDFInfo
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- CN110871095A CN110871095A CN201811000540.4A CN201811000540A CN110871095A CN 110871095 A CN110871095 A CN 110871095A CN 201811000540 A CN201811000540 A CN 201811000540A CN 110871095 A CN110871095 A CN 110871095A
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- carbonate
- sodium phosphate
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- HKFSHRPNWRVLKE-UHFFFAOYSA-K sodium nickel(2+) phosphate Chemical compound [Na+].[Ni++].[O-]P([O-])([O-])=O HKFSHRPNWRVLKE-UHFFFAOYSA-K 0.000 title claims abstract description 180
- 239000000463 material Substances 0.000 title claims abstract description 89
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011734 sodium Substances 0.000 claims abstract description 50
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000001354 calcination Methods 0.000 claims abstract description 37
- 238000002425 crystallisation Methods 0.000 claims abstract description 29
- 230000008025 crystallization Effects 0.000 claims abstract description 29
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 24
- 238000011068 loading method Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000010992 reflux Methods 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 16
- AXWBCVFFHYNTNE-UHFFFAOYSA-L sodium nickel(2+) carbonate Chemical compound [Ni+2].C([O-])([O-])=O.[Na+] AXWBCVFFHYNTNE-UHFFFAOYSA-L 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 59
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 58
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 58
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 46
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 46
- 229910052708 sodium Inorganic materials 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 23
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 20
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 20
- 238000004090 dissolution Methods 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 230000009466 transformation Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 14
- 230000007547 defect Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 description 24
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 22
- 230000015556 catabolic process Effects 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 238000005303 weighing Methods 0.000 description 20
- 238000007146 photocatalysis Methods 0.000 description 13
- 229960003405 ciprofloxacin Drugs 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 10
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 7
- 239000004576 sand Substances 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000010923 batch production Methods 0.000 description 2
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 2
- FPBMTPLRBAEUMV-UHFFFAOYSA-N nickel sodium Chemical compound [Na][Ni] FPBMTPLRBAEUMV-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- KJUINEFFKMYWTG-UHFFFAOYSA-N [Na].[Ni].[C] Chemical compound [Na].[Ni].[C] KJUINEFFKMYWTG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
Abstract
The invention discloses a WO3The chemical formula of the base material of the supported nickel sodium phosphate photocatalytic material is Na4Ni3P4O15The surface of the base material is loaded with WO3(ii) a The present invention also discloses the WO3A preparation method of a loaded nickel sodium phosphate photocatalytic material. The invention prepares the sodium nickel phosphate by selecting hydrated sodium nickel carbonate and phosphoric acid for concentration and crystallization and then sequentially calcining the hydrated sodium nickel carbonate and the phosphoric acid, and then prepares the sodium nickel phosphate by adding the WO3Directly mixing with sodium nickel phosphate, sequentially refluxing with ethanol, separating solid and liquid, and calcining again to obtain WO3The method for loading the nickel sodium phosphate photocatalytic material effectively avoids the introduction of other impurities, improves the purity of the synthesized nickel sodium phosphate, and simultaneously improves the photocatalytic activity of the nickel sodium phosphate; by loading WO on the surface of sodium nickel phosphate3The corresponding range of the sodium nickel phosphate in ultraviolet light and visible light regions is effectively widened, the structure of the sodium nickel phosphate is influenced to form lattice defects, and the separation of photo-generated electron pairs is facilitated.
Description
Technical Field
The invention belongs to the technical field of preparation of nickel sodium phosphate photocatalytic materials, and particularly relates to a WO3A loaded nickel sodium phosphate photocatalytic material and a preparation method thereof.
Background
The photocatalytic technology is a basic nanotechnology which was born in the 70 th century, and in mainland China we will use the common term photocatalyst as a name for photocatalyst. The typical natural photocatalyst is the chlorophyll which is commonly seen in the plants, and promotes the carbon dioxide and the water in the air to be oxygen and carbohydrate in the photosynthesis of the plants. The photocatalyst can be used in a plurality of advanced fields such as environmental purification, self-cleaning materials, advanced new energy, cancer medical treatment, high-efficiency antibiosis and the like.
Numerous materials are available worldwide as photocatalysts, including titanium dioxide (TiO)2) Zinc oxide (ZnO), tin oxide (SnO)2) Zirconium dioxide (ZrO)2) And various oxide sulfide semiconductors such as cadmium sulfide (CdS). Cadmium sulfide (CdS) and zinc oxide (ZnO) are used as photocatalyst materials, but because the chemical properties of the cadmium sulfide (CdS) and the zinc oxide (ZnO) are unstable, the cadmium sulfide (CdS) and the zinc oxide (ZnO) can be dissolved by light during photocatalysis, and dissolved harmful metal ions have certain biological toxicity, so developed countries rarely use the cadmium sulfide (CdS) and the zinc oxide (ZnO) as civil photocatalytic materials at present, wherein titanium dioxide is more applied, but the band gap of the titanium dioxide determines that the titanium dioxide is difficult to realize photocatalysis under the condition of visible light; therefore, it is still a great challenge to find a photocatalytic material which is low in cost, safe, nontoxic, good in stability and easy to recycle.
Disclosure of Invention
In view of the above, the main object of the present invention is to provideFor a WO3The loaded nickel sodium phosphate photocatalytic material and the preparation method thereof solve the problems of high cost, large toxicity and poor photocatalytic effect in the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows: WO (WO)3The chemical formula of the base material of the supported nickel sodium phosphate photocatalytic material is Na4Ni3P4O15The surface of the base material is loaded with WO3。
WO (WO)3The preparation method of the loaded nickel sodium phosphate photocatalytic material is realized by the following steps:
Preferably, in the step 1, the molar ratio of the basic nickel carbonate containing sodium to the phosphoric acid in the phosphoric acid solution is (1.0-1.3): 1.
preferably, in the step 2, the temperature of the primary calcination is 500-800 ℃, and the time of the primary calcination is 5-6 h.
Preferably, in said step 3, said WO3The molar ratio of the addition amount of the sodium carbonate to the basic nickel carbonate containing sodium is (0.015-0.33): 1.
preferably, in the step 3, ethanol at 75-80 ℃ is selected for refluxing for 2-4 times.
Preferably, in the step 4, the temperature of the secondary calcination is 300-.
Preferably, in the step 1, the specific preparation method of the basic nickel carbonate containing sodium is as follows:
step 1.1, simultaneously adding a sodium carbonate solution with the concentration of 180-300 g/L and a nickel sulfate solution with the concentration of 60-100 g/L into a reactor, and obtaining basic nickel carbonate slurry after adjusting the pH value of a flow control system of the sodium carbonate solution and the nickel sulfate solution to be 8.2-8.3 and reacting for 20-25 h at 50-60 ℃ in the feeding process, wherein the flow of the sodium carbonate solution is 100-1000L/h and the flow of the nickel sulfate solution is 100-1000L/h in the feeding process;
step 1.2, stopping adding the sodium carbonate solution and the nickel sulfate solution into the reactor, and controlling the crystal form transformation of the basic nickel carbonate in the basic nickel carbonate slurry obtained in the step 1.1 by adjusting the reaction temperature and the reaction time to obtain hydrated sodium nickel carbonate seed crystals;
step 1.3, adding the sodium carbonate solution and the nickel sulfate solution into the reactor again, wherein the pH value of a flow control system of the sodium carbonate solution and the nickel sulfate solution is adjusted to be 8.5-8.8 in the feeding process, and the growth of the hydrated nickel carbonate crystal seed obtained in the step 1.2 is controlled by adjusting the reaction temperature and the reaction time to obtain a crude sodium-containing basic nickel carbonate product;
step 1.4, sequentially aging the crude sodium-containing basic nickel carbonate product obtained in the step 1.3 for 0.5-3 h, washing, drying and screening to obtain sodium-containing basic nickel carbonate NaNi4(CO3)3(OH)3·3H2O。
Preferably, in the step 1.2, the reaction temperature is 50-60 ℃, and the reaction time is 30-60 min.
Preferably, in the step 1.3, the reaction temperature is 50-60 ℃ and the reaction time is 11-30 h.
Preferably, the washing in the step 1.4 adopts pure water, the temperature of the pure water is 70-85 ℃, and the conductivity of the pure water is less than or equal to 100 mu s/m.
Preferably, the drying temperature in the step 1.4 is 95-105 ℃, and the drying time is 2-3 h; and screening by adopting a 200-400-mesh sieve.
Compared with the prior art, the method prepares the sodium nickel phosphate by selecting the hydrated sodium nickel carbonate and the phosphoric acid for concentration and crystallization and then sequentially calcining the hydrated sodium nickel carbonate and the phosphoric acid, and then prepares the WO3Directly mixing with sodium nickel phosphate, sequentially refluxing with ethanol, separating solid and liquid, and calcining again to obtain WO3The method for loading the nickel sodium phosphate photocatalytic material effectively avoids the introduction of other impurities, improves the purity of the synthesized nickel sodium phosphate, and simultaneously improves the photocatalytic activity of the nickel sodium phosphate; by loading WO on the surface of sodium nickel phosphate3The corresponding range of the sodium nickel phosphate in ultraviolet light and visible light regions is effectively widened, the structure of the sodium nickel phosphate is influenced to form lattice defects, and the separation of photo-generated electron pairs is facilitated; the method disclosed by the invention is a green reaction, does not need a complex process, is simple to control, is low in cost, is easy for batch production, and can quickly realize industrialization.
Drawings
FIG. 1 shows WO obtained in example 1 of the present invention3SEM picture of the supported nickel sodium phosphate photocatalytic material;
FIG. 2 shows WO obtained in example 1 of the present invention3A degradation rate change curve diagram of the loaded nickel sodium phosphate photocatalytic material on ciprofloxacin;
FIG. 3 shows WO obtained in example 2 of the present invention3A degradation rate change curve diagram of the loaded nickel sodium phosphate photocatalytic material on ciprofloxacin;
FIG. 4 shows WO obtained in example 3 of the present invention3A degradation rate change curve diagram of the loaded nickel sodium phosphate photocatalytic material on ciprofloxacin;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a WO3Supported nickel sodium phosphate photocatalytic material, and chemical of substrate material thereofIs of the formula Na4Ni3P4O15The surface of the base material is loaded with WO3。
The embodiment of the invention also provides a WO3The preparation method of the loaded nickel sodium phosphate photocatalytic material is realized by the following steps:
the specific preparation method of the basic nickel carbonate containing sodium comprises the following steps:
step 1.1, simultaneously adding a sodium carbonate solution with the concentration of 180-300 g/L and a nickel sulfate solution with the concentration of 60-100 g/L into a reactor, adjusting the flow rate of the sodium carbonate solution to be 100-1000L/h and the flow rate of the nickel sulfate solution to be 100-1000L/h in the feeding process, so as to control the pH value of a system to be 8.2-8.3, and reacting for 20-25 h at the temperature of 60-90 ℃ to obtain basic nickel carbonate;
step 1.2, stopping adding a sodium carbonate solution and a nickel sulfate solution into the reactor, reacting the basic nickel carbonate obtained in the step 1.1 at 50-60 ℃ for 30-60 min, and feeding the basic nickel carbonate after the reaction is stopped to cause the surface energy of the product to change, so as to obtain hydrated nickel sodium carbonate crystal seeds;
step 1.3, adding a sodium carbonate solution and a nickel sulfate solution into the reactor again, controlling the pH value of the system to be 8.5-8.8, reacting hydrated sodium nickel carbonate crystal seeds for 11-30 h at 50-60 ℃, promoting the growth of crystal nuclei, and obtaining a sodium-containing basic nickel carbonate crude product;
and step 1.4, sequentially aging the crude sodium-containing basic nickel carbonate obtained in the step 1.3 for 0.5-3 h, washing with pure water with the conductivity of less than or equal to 100 mu s/m and the temperature of 70-85 ℃, drying at 95-105 ℃ for 2-3 h, and finally screening with a 200-400-mesh sieve to obtain the sodium-containing basic nickel carbonate.
in the step 3, the step of,adding WO into the nickel sodium phosphate obtained in the step 23Uniformly mixing, refluxing for 2-4 times by using 75-80 ℃ ethanol, and performing solid-liquid separation to obtain WO3In admixture with sodium nickel phosphate, wherein WO3The molar ratio of the addition amount of the sodium carbonate to the basic nickel carbonate containing sodium is (0.015-0.33): 1;
The invention prepares the sodium nickel phosphate by selecting hydrated sodium nickel carbonate and phosphoric acid for concentration and crystallization and then sequentially calcining the hydrated sodium nickel carbonate and the phosphoric acid, and then prepares the sodium nickel phosphate by adding the WO3Directly mixing with sodium nickel phosphate, sequentially refluxing with ethanol, separating solid and liquid, and calcining again to obtain WO3The method for loading the nickel sodium phosphate photocatalytic material effectively avoids the introduction of other impurities, improves the purity of the synthesized nickel sodium phosphate, and simultaneously improves the photocatalytic activity of the nickel sodium phosphate; by loading WO on the surface of sodium nickel phosphate3The corresponding range of the sodium nickel phosphate in ultraviolet light and visible light regions is effectively widened, the structure of the sodium nickel phosphate is influenced to form lattice defects, and the separation of photo-generated electron pairs is facilitated; the method disclosed by the invention is a green reaction, does not need a complex process, is simple to control, is low in cost, is easy for batch production, and can quickly realize industrialization.
Example 1
According to a molar ratio of 1.2: 1, respectively weighing sodium-containing basic nickel carbonate and a sulfuric acid solution, adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for a dissolution reaction, and then performing concentration crystallization to obtain a crystallization mixture of nickel sodium phosphate; calcining the obtained crystallized mixture of the nickel sodium phosphate at 600 ℃ for 6 hours to obtain nickel sodium phosphate; according to a molar ratio of 0.15: 1 weighing WO3And WO3Adding the obtained sodium nickel phosphate into the mixture, uniformly mixing, refluxing for 3 hours by using ethanol at the temperature of 80 ℃, and then carrying out solid-liquid separation to obtain WO3A mixture with sodium nickel phosphate; further subjecting the WO obtained above to a reaction at 400 deg.C3Calcining the mixture with sodium nickel phosphate for 11h, and cooling to obtain WO3Loaded nickel sodium phosphate photocatalystAnd (4) melting the material.
The specific preparation method of the basic nickel carbonate containing sodium comprises the following steps:
simultaneously adding a sodium carbonate solution with the concentration of 180g/L and a nickel sulfate solution with the concentration of 60g/L into a reactor, adjusting the flow rate of the sodium carbonate solution to be 100-1000L/h and the flow rate of the nickel sulfate solution to be 100-1000L/h in the feeding process, thereby controlling the pH value of the system to be 8.2, and reacting for 25h at the temperature of 60 ℃ to obtain basic nickel carbonate; stopping adding a sodium carbonate solution and a nickel sulfate solution into the reactor, reacting the obtained basic nickel carbonate at 55 ℃ for 45min, and feeding the basic nickel carbonate after the reaction is stopped to cause the surface energy of the product to change, thereby obtaining hydrated nickel sodium carbonate crystal seeds; adding a sodium carbonate solution and a nickel sulfate solution into the reactor again, controlling the pH value of the system to be 8.6, and enabling the hydrated carbon nickel sodium seed crystal to react for 25 hours at 55 ℃ to promote the growth of crystal nuclei to obtain a basic nickel carbonate crude product containing sodium; and (3) sequentially aging the obtained crude product of the basic nickel carbonate containing sodium for 1.5h, washing by using pure water with the conductivity of less than or equal to 100 mu s/m and the temperature of 80 ℃, drying for 2h at 100 ℃, and finally screening by using a 200-400-mesh sieve to obtain the basic nickel carbonate containing sodium.
Note: the following examples all use the sodium-containing nickel hydroxycarbonate obtained under the reaction conditions and therefore no specific preparation of the sodium-containing nickel hydroxycarbonate is set forth hereinafter
Example 2
According to a molar ratio of 1: 1, respectively weighing sodium-containing basic nickel carbonate and a sulfuric acid solution, adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for a dissolution reaction, and then performing concentration crystallization to obtain a crystallization mixture of nickel sodium phosphate; calcining the obtained crystallized mixture of the nickel sodium phosphate at 500 ℃ for 5 hours to obtain nickel sodium phosphate; according to a molar ratio of 0.015: 1 weighing WO3And WO3Adding the obtained sodium nickel phosphate into the mixture, uniformly mixing, refluxing for 2 hours by using ethanol at the temperature of 75 ℃, and then carrying out solid-liquid separation to obtain WO3A mixture with sodium nickel phosphate; further subjecting the WO obtained above to a reaction at 300 deg.C3Calcining the mixture with sodium nickel phosphate for 10 hours, and then cooling to obtain WO3Loaded sodium nickel phosphateA photocatalytic material.
As can be seen from experiments, the WO prepared and obtained in example 23The loaded nickel sodium phosphate photocatalytic material has the main structural morphology similar to that of example 1, so that the WO is also proved3The loaded sodium nickel phosphate has strong photocatalysis and can be used as an inorganic catalytic material.
Example 3
According to a molar ratio of 1.3: 1, respectively weighing sodium-containing basic nickel carbonate and a sulfuric acid solution, adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for a dissolution reaction, and then performing concentration crystallization to obtain a crystallization mixture of nickel sodium phosphate; calcining the obtained crystallized mixture of the nickel sodium phosphate at 800 ℃ for 6 hours to obtain nickel sodium phosphate; according to a molar ratio of 0.33: 1 weighing WO3And WO3Adding the obtained sodium nickel phosphate into the mixture, uniformly mixing, refluxing for 4 hours by using ethanol at the temperature of 80 ℃, and then carrying out solid-liquid separation to obtain WO3A mixture with sodium nickel phosphate; further subjecting the WO obtained above to a temperature of 500 deg.C3Calcining the mixture with sodium nickel phosphate for 12 hours, and then cooling to obtain WO3And (3) loading the nickel sodium phosphate photocatalytic material.
As can be seen from experiments, the WO prepared and obtained in example 33The loaded nickel sodium phosphate photocatalytic material has the main structural morphology similar to that of example 1, so that the WO is also proved3The loaded sodium nickel phosphate has strong photocatalysis and can be used as an inorganic catalytic material.
Example 4
According to a molar ratio of 1.2: 1, respectively weighing sodium-containing basic nickel carbonate and a sulfuric acid solution, adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for a dissolution reaction, and then performing concentration crystallization to obtain a crystallization mixture of nickel sodium phosphate; calcining the obtained crystallized mixture of the nickel sodium phosphate at 600 ℃ for 6 hours to obtain nickel sodium phosphate; according to a molar ratio of 0.015: 1 weighing WO3And WO3Adding the obtained sodium nickel phosphate into the mixture, uniformly mixing, refluxing for 2 hours by using ethanol at the temperature of 75 ℃, and then carrying out solid-liquid separation to obtain WO3With sodium nickel phosphate(ii) a Further subjecting the WO obtained above to a reaction at 300 deg.C3Calcining the mixture with sodium nickel phosphate for 10 hours, and then cooling to obtain WO3And (3) loading the nickel sodium phosphate photocatalytic material.
As can be seen from experiments, the WO prepared and obtained in example 43The main structural morphology, the degradation rate change of the loaded nickel sodium phosphate photocatalytic material on the cyclopropane sand and the like of the loaded nickel sodium phosphate photocatalytic material are similar to those of the example 1, so that the WO is also proved3The loaded sodium nickel phosphate has strong photocatalysis and can be used as an inorganic catalytic material.
Example 5
According to a molar ratio of 1.2: 1, respectively weighing sodium-containing basic nickel carbonate and a sulfuric acid solution, adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for a dissolution reaction, and then performing concentration crystallization to obtain a crystallization mixture of nickel sodium phosphate; calcining the obtained crystallized mixture of the nickel sodium phosphate at 600 ℃ for 6 hours to obtain nickel sodium phosphate; according to a molar ratio of 0.33: 1 weighing WO3And WO3Adding the obtained sodium nickel phosphate into the mixture, uniformly mixing, refluxing for 4 hours by using ethanol at the temperature of 80 ℃, and then carrying out solid-liquid separation to obtain WO3A mixture with sodium nickel phosphate; further subjecting the WO obtained above to a temperature of 500 deg.C3Calcining the mixture with sodium nickel phosphate for 12 hours, and then cooling to obtain WO3And (3) loading the nickel sodium phosphate photocatalytic material.
As can be seen from experiments, the WO prepared and obtained in example 53The main structural morphology, the degradation rate change of the loaded nickel sodium phosphate photocatalytic material on the cyclopropane sand and the like of the loaded nickel sodium phosphate photocatalytic material are similar to those of the example 1, so that the WO is also proved3The loaded sodium nickel phosphate has strong photocatalysis and can be used as an inorganic catalytic material.
Example 6
According to a molar ratio of 1: 1, respectively weighing sodium-containing basic nickel carbonate and a sulfuric acid solution, adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for a dissolution reaction, and then performing concentration crystallization to obtain a crystallization mixture of nickel sodium phosphate; calcining the obtained crystallized mixture of the nickel sodium phosphate at 500 ℃ for 5 hours to obtain nickel sodium phosphate; according to the frictionThe molar ratio is 0.15: 1 weighing WO3And WO3Adding the obtained sodium nickel phosphate into the mixture, uniformly mixing, refluxing for 3 hours by using ethanol at the temperature of 80 ℃, and then carrying out solid-liquid separation to obtain WO3A mixture with sodium nickel phosphate; further subjecting the WO obtained above to a reaction at 400 deg.C3Calcining the mixture with sodium nickel phosphate for 11h, and cooling to obtain WO3And (3) loading the nickel sodium phosphate photocatalytic material.
As can be seen from experiments, the WO prepared and obtained in example 63The main structural morphology, the degradation rate change of the loaded nickel sodium phosphate photocatalytic material on the cyclopropane sand and the like of the loaded nickel sodium phosphate photocatalytic material are similar to those of the example 1, so that the WO is also proved3The loaded sodium nickel phosphate has strong photocatalysis and can be used as an inorganic catalytic material.
Example 7
According to a molar ratio of 1: 1, respectively weighing sodium-containing basic nickel carbonate and a sulfuric acid solution, adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for a dissolution reaction, and then performing concentration crystallization to obtain a crystallization mixture of nickel sodium phosphate; calcining the obtained crystallized mixture of the nickel sodium phosphate at 500 ℃ for 5 hours to obtain nickel sodium phosphate; according to a molar ratio of 0.33: 1 weighing WO3And WO3Adding the obtained sodium nickel phosphate into the mixture, uniformly mixing, refluxing for 4 hours by using ethanol at the temperature of 80 ℃, and then carrying out solid-liquid separation to obtain WO3A mixture with sodium nickel phosphate; further subjecting the WO obtained above to a temperature of 500 deg.C3Calcining the mixture with sodium nickel phosphate for 12 hours, and then cooling to obtain WO3And (3) loading the nickel sodium phosphate photocatalytic material.
As can be seen from experiments, WO prepared and obtained in example 73The main structural morphology, the degradation rate change of the loaded nickel sodium phosphate photocatalytic material on the cyclopropane sand and the like of the loaded nickel sodium phosphate photocatalytic material are similar to those of the example 1, so that the WO is also proved3The loaded sodium nickel phosphate has strong photocatalysis and can be used as an inorganic catalytic material.
Example 8
According to a molar ratio of 1.3: 1, respectively weighing basic nickel carbonate containing sodium and sulfuric acid solution, and adding basic carbonic acid containing sodiumAdding nickel into a phosphoric acid solution for dissolution reaction, and then performing concentration crystallization to obtain a crystallization mixture of nickel sodium phosphate; calcining the obtained crystallized mixture of the nickel sodium phosphate at 800 ℃ for 6 hours to obtain nickel sodium phosphate; according to a molar ratio of 0.15: 1 weighing WO3And WO3Adding the obtained sodium nickel phosphate into the mixture, uniformly mixing, refluxing for 3 hours by using ethanol at the temperature of 80 ℃, and then carrying out solid-liquid separation to obtain WO3A mixture with sodium nickel phosphate; further subjecting the WO obtained above to a reaction at 400 deg.C3Calcining the mixture with sodium nickel phosphate for 11h, and cooling to obtain WO3And (3) loading the nickel sodium phosphate photocatalytic material.
As can be seen from experiments, the WO prepared and obtained in example 83The main structural morphology, the degradation rate change of the loaded nickel sodium phosphate photocatalytic material on the cyclopropane sand and the like of the loaded nickel sodium phosphate photocatalytic material are similar to those of the example 1, so that the WO is also proved3The loaded sodium nickel phosphate has strong photocatalysis and can be used as an inorganic catalytic material.
Example 9
According to a molar ratio of 1.3: 1, respectively weighing sodium-containing basic nickel carbonate and a sulfuric acid solution, adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for a dissolution reaction, and then performing concentration crystallization to obtain a crystallization mixture of nickel sodium phosphate; calcining the obtained crystallized mixture of the nickel sodium phosphate at 800 ℃ for 6 hours to obtain nickel sodium phosphate; according to a molar ratio of 0.015: 1 weighing WO3And WO3Adding the obtained sodium nickel phosphate into the mixture, uniformly mixing, refluxing for 2 hours by using ethanol at the temperature of 75 ℃, and then carrying out solid-liquid separation to obtain WO3A mixture with sodium nickel phosphate; further subjecting the WO obtained above to a reaction at 300 deg.C3Calcining the mixture with sodium nickel phosphate for 10 hours, and then cooling to obtain WO3And (3) loading the nickel sodium phosphate photocatalytic material.
As can be seen from experiments, WO prepared in example 93The main structural morphology, the degradation rate change of the loaded nickel sodium phosphate photocatalytic material on the cyclopropane sand and the like of the loaded nickel sodium phosphate photocatalytic material are similar to those of the example 1, so that the WO is also proved3The loaded sodium nickel phosphate has strong photocatalysis and can be used as an inorganic catalystThe material is used.
Example 10
According to a molar ratio of 1.2: 1, respectively weighing sodium-containing basic nickel carbonate and a sulfuric acid solution, adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for a dissolution reaction, and then performing concentration crystallization to obtain a crystallization mixture of nickel sodium phosphate; calcining the obtained crystallized mixture of the nickel sodium phosphate at 800 ℃ for 6 hours to obtain nickel sodium phosphate; according to a molar ratio of 0.15: 1 weighing WO3And WO3Adding the obtained sodium nickel phosphate into the mixture, uniformly mixing, refluxing for 3 hours by using ethanol at the temperature of 80 ℃, and then carrying out solid-liquid separation to obtain WO3A mixture with sodium nickel phosphate; further subjecting the WO obtained above to a temperature of 500 deg.C3Calcining the mixture with sodium nickel phosphate for 12 hours, and then cooling to obtain WO3And (3) loading the nickel sodium phosphate photocatalytic material.
As can be seen from experiments, the WO prepared in this example 103The main structural morphology, the degradation rate change of the loaded nickel sodium phosphate photocatalytic material on the cyclopropane sand and the like of the loaded nickel sodium phosphate photocatalytic material are similar to those of the example 1, so that the WO is also proved3The loaded sodium nickel phosphate has strong photocatalysis and can be used as an inorganic catalytic material.
Example of detection
1) FIG. 1 shows WO prepared in example 13An SEM image (electron microscope scanning image) of the loaded nickel sodium phosphate photocatalytic material shows that the obtained sample has good crystallinity and uniformly dispersed particles;
2) WO obtained in examples 1 to 3 of the present invention were used as comparative examples with conventional sodium nickel phosphate (no metal supported) and3the supported nickel sodium phosphate photocatalytic material is used for carrying out degradation rate detection experiments on ciprofloxacin, and the detection results are shown in the following tables 1, 2 and 3:
TABLE 1 degradation rate of ciprofloxacin by the photocatalytic material obtained in example 1 and the conventional photocatalytic material
| Illumination time (h) | Degradation efficiency of sodium Nickel phosphate (%) | Loaded WO3Efficiency of after-degradation (%) |
| 0.5 | 11.6 | 20.4 |
| 1 | 17.1 | 38.5 |
| 1.5 | 20.2 | 55.1 |
| 2 | 22.4 | 66.7 |
| 2.5 | 23.6 | 75.8 |
| 3 | 24.4 | 82.4 |
| 4 | 24.8 | 86.6 |
| 5 | 24.5 | 87.9 |
Table 2 comparative results of degradation rates of ciprofloxacin by the photocatalytic material obtained in example 2 and the conventional photocatalytic material
| Illumination time (h) | Degradation efficiency of sodium Nickel phosphate (%) | Loaded WO3Efficiency of after-degradation (%) |
| 0.5 | 11.3 | 20.1 |
| 1 | 17.5 | 38 |
| 1.5 | 18.8 | 56.1 |
| 2 | 21.6 | 66 |
| 2.5 | 23.7 | 77.4 |
| 3 | 24.8 | 81 |
| 4 | 25 | 85.4 |
| 5 | 24.3 | 87.1 |
Table 3 comparative results of degradation rates of ciprofloxacin by the photocatalytic material obtained in example 3 and the conventional photocatalytic material
| Illumination time (h) | Degradation efficiency of sodium Nickel phosphate (%) | Loaded WO3Efficiency of after-degradation (%) |
| 0.5 | 11 | 20.7 |
| 1 | 17.6 | 38.4 |
| 1.5 | 21.1 | 54.2 |
| 2 | 23.2 | 66.3 |
| 2.5 | 24 | 75.1 |
| 3 | 24.8 | 83.1 |
| 4 | 25.1 | 86.4 |
| 5 | 24.6 | 87.2 |
FIGS. 2, 3 and 4 show the WO obtained in example 1, example 2 and example 33A graph of the degradation rate change of the supported nickel sodium phosphate photocatalytic material on ciprofloxacin can be seen from the above tables 1, 2 and 3, and the figures 2, 3 and 4, and the WO obtained by the invention3The degradation rate of the supported sodium nickel phosphate to the ciprofloxacin is better than that of the conventional sodium nickel phosphate to the ciprofloxacin, so that the WO obtained by the invention is illustrated3The loaded sodium nickel phosphate has strong photocatalysis.
In addition, WO obtained as a result of examples 2 to 103The loaded sodium nickel phosphate has the main structural appearance similar to that of the embodiment 1; WO obtained in examples 4 to 103The degradation rate profile of ciprofloxacin by loading sodium nickel phosphate is similar to that of example 1, therefore, the WO obtained in examples 2 to 10 is not repeated here3Carrying out SEM spectrogram analysis on the loaded basic nickel sodium phosphate photocatalytic material; WO obtained in examples 4 to 10 is not repeated3The degradation rate of the supported nickel sodium phosphate photocatalytic material is analyzed.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.
Claims (10)
1. WO (WO)3The supported nickel sodium phosphate photocatalytic material is characterized in that the chemical formula of the base material is Na4Ni3P4O15The surface of the base material is loaded with WO3。
2. WO (WO)3The preparation method of the supported nickel sodium phosphate photocatalytic material is characterized by comprising the following steps of:
step 1, adding sodium-containing basic nickel carbonate into a phosphoric acid solution for dissolution reaction, and then performing concentration crystallization to obtain a crystallization mixture of nickel sodium phosphate;
step 2, carrying out primary calcination on the crystalline compound of the nickel sodium phosphate obtained in the step 1 to obtain nickel sodium phosphate;
step 3, adding WO into the nickel sodium phosphate obtained in the step 23After being mixed evenly, the mixture is refluxed by ethanol and then subjected to solid-liquid separation to obtain WO3A mixture with sodium nickel phosphate;
step 4, for the WO obtained in the step 33The mixture of the catalyst and sodium nickel phosphate is calcined for the second time and then cooled to obtain WO3And (3) loading the nickel sodium phosphate photocatalytic material.
3. A WO according to claim 23The preparation method of the supported nickel sodium phosphate photocatalytic material is characterized in that in the step 1, the molar ratio of the basic nickel carbonate containing sodium to phosphoric acid in a phosphoric acid solution is (1.0-1.3): 1.
4. a WO according to claim 33The preparation method of the supported nickel sodium phosphate photocatalytic material is characterized in that in the step 2, the temperature of primary calcination is 500-800 ℃, and the time of the primary calcination is 5-6 hours.
5. A WO according to claim 43Supported nickel sodium phosphate photocatalysisA method for producing a material, characterized in that, in the step 3, the WO3The molar ratio of the addition amount of the sodium carbonate to the basic nickel carbonate containing sodium is (0.015-0.33): 1.
6. a WO according to claim 53The preparation method of the loaded nickel sodium phosphate photocatalytic material is characterized in that in the step 3, ethanol with the temperature of 75-80 ℃ is selected for refluxing for 2-4 times when the ethanol is refluxed.
7. A WO according to any of claims 1 to 63The preparation method of the supported nickel sodium phosphate photocatalytic material is characterized in that in the step 4, the temperature of the secondary calcination is 300-500 ℃, and the time of the secondary calcination is 10-12 hours.
8. A WO according to claim 73The preparation method of the supported nickel sodium phosphate photocatalytic material is characterized in that in the step 1, the specific preparation method of the sodium-containing basic nickel carbonate is as follows:
step 1.1, simultaneously adding a sodium carbonate solution with the concentration of 180-300 g/L and a nickel sulfate solution with the concentration of 60-100 g/L into a reactor, and obtaining basic nickel carbonate slurry after adjusting the pH value of a flow control system of the sodium carbonate solution and the nickel sulfate solution to be 8.2-8.3 and reacting for 20-25 h at 50-60 ℃ in the feeding process, wherein the flow of the sodium carbonate solution is 100-1000L/h and the flow of the nickel sulfate solution is 100-1000L/h in the feeding process;
step 1.2, stopping adding the sodium carbonate solution and the nickel sulfate solution into the reactor, and controlling the crystal form transformation of the basic nickel carbonate in the basic nickel carbonate slurry obtained in the step 1.1 by adjusting the reaction temperature and the reaction time to obtain hydrated sodium nickel carbonate seed crystals;
step 1.3, adding the sodium carbonate solution and the nickel sulfate solution into the reactor again, wherein the pH value of a flow control system of the sodium carbonate solution and the nickel sulfate solution is adjusted to be 8.5-8.8 in the feeding process, and the growth of the hydrated nickel carbonate crystal seed obtained in the step 1.2 is controlled by adjusting the reaction temperature and the reaction time to obtain a crude sodium-containing basic nickel carbonate product;
step 1.4, sequentially aging the crude sodium-containing basic nickel carbonate product obtained in the step 1.3 for 0.5-3 h, washing, drying and screening to obtain sodium-containing basic nickel carbonate NaNi4(CO3)3(OH)3·3H2O。
9. A WO according to claim 83The preparation method of the supported nickel sodium phosphate photocatalytic material is characterized in that in the step 1.2, the reaction temperature is 50-60 ℃, and the reaction time is 30-60 min.
10. A WO as claimed in any one of claims 93The preparation method of the supported nickel sodium phosphate photocatalytic material is characterized in that in the step 1.3, the reaction temperature is 50-60 ℃, and the reaction time is 11-30 hours.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| US20160090311A1 (en) * | 2014-09-26 | 2016-03-31 | Chung-Yuan Christian University | Method for forming Basic Nickel Carbonate |
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| US20160090311A1 (en) * | 2014-09-26 | 2016-03-31 | Chung-Yuan Christian University | Method for forming Basic Nickel Carbonate |
| CN104888819A (en) * | 2015-06-18 | 2015-09-09 | 苏州德捷膜材料科技有限公司 | Preparation and photocatalytic application of Na4Ni3P4O15 photocatalyst |
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