CN110871094A - Mn-doped sodium nickel phosphate photocatalytic material and preparation method thereof - Google Patents
Mn-doped sodium nickel phosphate photocatalytic material and preparation method thereof Download PDFInfo
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- CN110871094A CN110871094A CN201811000528.3A CN201811000528A CN110871094A CN 110871094 A CN110871094 A CN 110871094A CN 201811000528 A CN201811000528 A CN 201811000528A CN 110871094 A CN110871094 A CN 110871094A
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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 109
- 239000000463 material Substances 0.000 title claims abstract description 80
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011734 sodium Substances 0.000 claims abstract description 77
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 21
- 150000002696 manganese Chemical class 0.000 claims abstract description 15
- 239000011572 manganese Substances 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 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 73
- 229910052708 sodium Inorganic materials 0.000 claims description 73
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 59
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 59
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 40
- 239000013078 crystal Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 229910000159 nickel phosphate Inorganic materials 0.000 claims description 26
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 claims description 26
- 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
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 8
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 7
- 239000011565 manganese chloride Substances 0.000 claims description 7
- AXWBCVFFHYNTNE-UHFFFAOYSA-L sodium nickel(2+) carbonate Chemical compound [Ni+2].C([O-])([O-])=O.[Na+] AXWBCVFFHYNTNE-UHFFFAOYSA-L 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 230000009466 transformation Effects 0.000 claims description 2
- KJUINEFFKMYWTG-UHFFFAOYSA-N [Na].[Ni].[C] Chemical compound [Na].[Ni].[C] KJUINEFFKMYWTG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000010923 batch production Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 description 23
- 238000006731 degradation reaction Methods 0.000 description 23
- 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
- 238000002425 crystallisation Methods 0.000 description 19
- 230000008025 crystallization Effects 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 12
- 229960003405 ciprofloxacin Drugs 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
- 238000005303 weighing Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000011941 photocatalyst Substances 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
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- FPBMTPLRBAEUMV-UHFFFAOYSA-N nickel sodium Chemical compound [Na][Ni] FPBMTPLRBAEUMV-UHFFFAOYSA-N 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
- 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
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 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
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor 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
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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
-
- 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
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Abstract
The invention discloses a Mn-doped sodium nickel phosphate photocatalytic material, wherein the chemical formula of a substrate material is Na4Ni3P4O15The surface of the substrate material is doped with Mn salt; the invention also discloses a preparation method of the Mn-doped sodium nickel phosphate photocatalytic material. According to the method for preparing the metal manganese salt doped nickel sodium phosphate photocatalytic material by selecting the hydrated carbon nickel sodium, the phosphoric acid and the manganese salt, the introduction of other impurities is effectively avoided, the purity of the synthesized nickel sodium phosphate is improved, and the photocatalytic activity of the synthesized nickel sodium phosphate is also improved; by doping Mn salt on the surface of the nickel sodium phosphate, the corresponding range of the nickel sodium phosphate in ultraviolet and visible light regions is effectively widened, the structure of the nickel sodium phosphate is influenced to form lattice defects, and the separation of photo-generated electron pairs is facilitated; the method of the invention is a green reaction, does not need complex process,the control is simple, the cost is low, the batch production is easy, and the industrialization can be quickly realized.
Description
Technical Field
The invention belongs to the technical field of preparation of nickel sodium phosphate photocatalytic materials, and particularly relates to a Mn-doped 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 carbon dioxide and water in the air to be a mixture of 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 provide a Mn-doped sodium nickel phosphate photocatalytic material and a preparation method thereof, which solve the problems of high cost, high 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: a Mn-doped sodium nickel phosphate photocatalytic material has a base material with a chemical formula of Na4Ni3P4O15And the surface of the substrate material is doped with Mn salt.
The other technical scheme of the invention is realized as follows: a preparation method of Mn-doped sodium nickel phosphate photocatalytic material is realized by the following steps:
and 3, calcining the Mn-doped sodium nickel phosphate crystal mixture obtained in the step 2, and cooling to obtain the Mn-doped sodium nickel phosphate photocatalytic material.
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 molar ratio of the added manganese salt to the basic nickel carbonate containing sodium is (0.015-0.33): 1.
preferably, in the step 2, the manganese salt is at least one of manganese sulfate, manganese chloride and manganese nitrate.
Preferably, in the step 2, the stirring reaction time is 3-5 h.
Preferably, in the step 3, the calcination temperature 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;
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.
Compared with the prior art, the method for preparing the metal manganese salt doped nickel sodium phosphate photocatalytic material by selecting the hydrated carbon nickel sodium + the phosphoric acid + the manganese salt effectively avoids the introduction of other impurities, improves the purity of the synthesized nickel sodium phosphate, and simultaneously improves the photocatalytic activity of the synthesized nickel sodium phosphate; by doping Mn salt on the surface of the nickel sodium phosphate, the corresponding range of the nickel sodium phosphate in ultraviolet and visible light regions is effectively widened, the structure of the nickel sodium 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 is an SEM image of Mn-doped sodium nickel phosphate photocatalytic material obtained in example 1 of the present invention;
FIG. 2 is a graph showing a change in degradation rate of ciprofloxacin by the Mn-doped sodium nickel phosphate photocatalytic material obtained in example 1 of the present invention;
FIG. 3 is a graph showing a change in degradation rate of ciprofloxacin by the Mn-doped sodium nickel phosphate photocatalytic material obtained in example 2 of the present invention;
fig. 4 is a graph showing a degradation rate change of ciprofloxacin by the Mn-doped sodium nickel phosphate photocatalytic material obtained in example 3 of the present invention.
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 chemical formula of the base material of the Mn-doped sodium nickel phosphate photocatalytic material provided by the embodiment of the invention is Na4Ni3P4O15And the surface of the base material is loaded with Mn salt.
The embodiment of the invention also provides a preparation method of the Mn-doped sodium nickel phosphate photocatalytic material, which 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;
step 1.4, sequentially aging the crude sodium-containing basic nickel carbonate obtained in 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 sodium-containing basic nickel carbonate NaNi4(CO3)3(OH)3·3H2O。
And 2, adding manganese salt into the sodium-containing nickel phosphate solution obtained in the step 1, stirring and reacting for 3-5 h, and then concentrating and crystallizing to obtain a Mn-doped nickel sodium phosphate crystal mixture, wherein the molar ratio of the addition of the manganese salt to the sodium-containing basic nickel carbonate is (0.015-0.33): 1; the manganese salt is at least one of manganese sulfate, manganese chloride and manganese nitrate
And 3, calcining the Mn-doped sodium nickel phosphate crystal mixture obtained in the step 2 at the temperature of 300-800 ℃ for 2-10 h, and cooling to obtain the Mn-doped sodium nickel phosphate photocatalytic material.
According to the method, the hydrated carbon nickel sodium, the phosphoric acid and the manganese salt are selected to prepare the metal manganese salt doped nickel sodium phosphate photocatalytic material, so that the introduction of other impurities is effectively avoided, the purity of the synthesized nickel sodium phosphate is improved, and the photocatalytic activity of the synthesized nickel sodium phosphate is improved; by doping Mn salt on the surface of the nickel sodium phosphate, the corresponding range of the nickel sodium phosphate in ultraviolet and visible light regions is effectively widened, the structure of the nickel sodium 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, and adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for a dissolution reaction to obtain a sodium-containing nickel phosphate solution; according to a molar ratio of 0.15: 1 proportion of MnSO4And mixing MnSO4Adding the obtained sodium-containing nickel phosphate solution into the solution, stirring the solution for reaction for 4 hours, and then carrying out concentration crystallization to obtain a Mn-doped nickel sodium phosphate crystallization mixture; and calcining the obtained Mn-doped sodium nickel phosphate crystal mixture at 500 ℃ for 6 hours, and cooling to obtain the Mn-doped sodium nickel phosphate photocatalytic 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 basic nickel carbonate containing sodium andadding sodium-containing basic nickel carbonate into a phosphoric acid solution to perform a dissolution reaction to obtain a sodium-containing nickel phosphate solution; according to a molar ratio of 0.015: 1 proportion of MnSO4And mixing MnSO4Adding the obtained sodium-containing nickel phosphate solution into the solution, stirring the solution for reaction for 3 hours, and then carrying out concentration crystallization to obtain a Mn-doped nickel sodium phosphate crystallization mixture; and calcining the obtained Mn-doped sodium nickel phosphate crystal mixture at 300 ℃ for 2h, and cooling to obtain the Mn-doped sodium nickel phosphate photocatalytic material.
Experiments show that the main structural morphology of the Mn-doped sodium nickel phosphate photocatalytic material prepared in the embodiment 2 is similar to that of the embodiment 1, so that the Mn-doped sodium nickel phosphate is proved to have 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, and adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for a dissolution reaction to obtain a sodium-containing nickel phosphate solution; according to a molar ratio of 0.33: 1 proportion of MnSO4And mixing MnSO4Adding the obtained sodium-containing nickel phosphate solution into the solution, stirring the solution for reaction for 5 hours, and then carrying out concentration crystallization to obtain a Mn-doped nickel sodium phosphate crystallization mixture; and calcining the obtained Mn-doped sodium nickel phosphate crystal mixture at 800 ℃ for 10 hours, and cooling to obtain the Mn-doped sodium nickel phosphate photocatalytic material.
Experiments show that the main structural morphology of the Mn-doped sodium nickel phosphate photocatalytic material prepared in this example 3 is similar to that of example 1, and therefore it is also confirmed that the Mn-doped sodium nickel phosphate has strong photocatalytic activity and can be applied 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, and adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for a dissolution reaction to obtain a sodium-containing nickel phosphate solution; according to a molar ratio of 0.015: 1 proportion of MnCl2And mixing MnCl2Adding the obtained sodium-containing nickel phosphate solution into the solution, stirring the solution for reaction for 3 hours, and then carrying out concentration crystallization to obtain a Mn-doped nickel sodium phosphate crystallization mixture; and calcining the obtained Mn-doped sodium nickel phosphate crystal mixture at 300 ℃ for 2h, and cooling to obtain the Mn-doped sodium nickel phosphate photocatalytic material.
Experiments show that the main structural morphology, degradation rate change to cyclopropylsand and the like of the Mn-doped sodium nickel phosphate photocatalytic material prepared in this example 4 are similar to those of example 1, and therefore it is also confirmed that the Mn-doped sodium nickel phosphate has strong photocatalytic performance and can be applied 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, and adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for dissolving to obtain a sodium-containing nickel phosphate solution; according to a molar ratio of 0.33: 1 Mn (NO) is weighed3)2And Mn (NO)3)2Adding the obtained sodium-containing nickel phosphate solution into the solution, stirring the solution for reaction for 5 hours, and then carrying out concentration crystallization to obtain a Mn-doped nickel sodium phosphate crystallization mixture; and calcining the obtained Mn-doped sodium nickel phosphate crystal mixture at 800 ℃ for 10 hours, and cooling to obtain the Mn-doped sodium nickel phosphate photocatalytic material.
Experiments show that the main structural morphology, degradation rate change to cyclopropylsand and the like of the Mn-doped sodium nickel phosphate photocatalytic material prepared in example 5 are similar to those of example 1, and therefore it is also confirmed that the Mn-doped sodium nickel phosphate has strong photocatalytic performance and can be applied 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, and adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for dissolving to obtain a sodium-containing nickel phosphate solution; according to a molar ratio of 0.15: 1 proportion of MnSO4And mixing MnSO4Adding the obtained sodium-containing nickel phosphate solution into the solution, stirring the solution for reaction for 4 hours, and then carrying out concentration crystallization to obtain Mn-doped nickel sodium phosphateThe crystalline mixture of (a); and calcining the obtained Mn-doped sodium nickel phosphate crystal mixture at 500 ℃ for 6 hours, and cooling to obtain the Mn-doped sodium nickel phosphate photocatalytic material.
Experiments show that the main structural morphology, degradation rate change to cyclopropylsand and the like of the Mn-doped sodium nickel phosphate photocatalytic material prepared in this example 6 are similar to those of example 1, and therefore it is also confirmed that the Mn-doped sodium nickel phosphate has strong photocatalytic performance and can be applied 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, and adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for dissolving to obtain a sodium-containing nickel phosphate solution; according to a molar ratio of 0.33: 1 proportion of MnSO4And mixing MnSO4Adding the obtained sodium-containing nickel phosphate solution into the solution, stirring the solution for reaction for 5 hours, and then carrying out concentration crystallization to obtain a Mn-doped nickel sodium phosphate crystallization mixture; and calcining the obtained Mn-doped sodium nickel phosphate crystal mixture at 800 ℃ for 10 hours, and cooling to obtain the Mn-doped sodium nickel phosphate photocatalytic material.
Experiments show that the main structural morphology, degradation rate change to cyclopropylsand and the like of the Mn-doped sodium nickel phosphate photocatalytic material prepared in this example 7 are similar to those of example 1, and therefore it is also confirmed that the Mn-doped sodium nickel phosphate has strong photocatalytic performance and can be applied as an inorganic catalytic material.
Example 8
According to a molar ratio of 1.3: 1, respectively weighing sodium-containing basic nickel carbonate and a sulfuric acid solution, and adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for dissolving to obtain a sodium-containing nickel phosphate solution; according to a molar ratio of 0.15: 1 proportion of MnCl2And mixing MnCl2Adding the obtained sodium-containing nickel phosphate solution into the solution, stirring the solution for reaction for 4 hours, and then carrying out concentration crystallization to obtain a Mn-doped nickel sodium phosphate crystallization mixture; calcining the obtained Mn-doped sodium nickel phosphate crystal mixture at 500 ℃ for 6 hours, and cooling to obtain Mn-doped sodium nickel phosphateA photocatalytic material.
Experiments show that the main structural morphology, degradation rate change to cyclopropylsand and the like of the Mn-doped sodium nickel phosphate photocatalytic material prepared in this example 8 are similar to those of example 1, and therefore it is also confirmed that the Mn-doped sodium nickel phosphate has strong photocatalytic performance and can be applied 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, and adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for dissolving to obtain a sodium-containing nickel phosphate solution; according to a molar ratio of 0.015: 1 Mn (NO) is weighed3)2And Mn (NO)3)2Adding the obtained sodium-containing nickel phosphate solution into the solution, stirring the solution for reaction for 3 hours, and then carrying out concentration crystallization to obtain a Mn-doped nickel sodium phosphate crystallization mixture; and calcining the obtained Mn-doped sodium nickel phosphate crystal mixture at 300 ℃ for 2h, and cooling to obtain the Mn-doped sodium nickel phosphate photocatalytic material.
Experiments show that the main structural morphology, degradation rate change to cyclopropylsand and the like of the Mn-doped sodium nickel phosphate photocatalytic material prepared in example 9 are similar to those of example 1, and therefore it is also confirmed that the Mn-doped sodium nickel phosphate has strong photocatalytic performance and can be applied as an inorganic catalytic material.
Example 10
According to a molar ratio of 1.2: 1, respectively weighing sodium-containing basic nickel carbonate and a sulfuric acid solution, and adding the sodium-containing basic nickel carbonate into a phosphoric acid solution for a dissolution reaction to obtain a sodium-containing nickel phosphate solution; according to a molar ratio of 0.015: 1 proportion of MnSO4And mixing MnSO4Adding the obtained sodium-containing nickel phosphate solution into the solution, stirring the solution for reaction for 3 hours, and then carrying out concentration crystallization to obtain a Bi-loaded nickel sodium phosphate crystallization mixture; and calcining the obtained Mn-doped sodium nickel phosphate crystal mixture at 800 ℃ for 10 hours, and cooling to obtain the Mn-doped sodium nickel phosphate photocatalytic material.
Experiments show that the main structural morphology, degradation rate change to cyclopropylsand and the like of the Mn-doped sodium nickel phosphate photocatalytic material prepared in this example 10 are similar to those of example 1, and therefore it is also confirmed that the Mn-doped sodium nickel phosphate has strong photocatalytic performance and can be applied as an inorganic catalytic material.
Example of detection
1) Fig. 1 is an SEM (electron microscope scanning) image of the Mn-doped sodium nickel phosphate photocatalytic material prepared in this example 1, and it can be seen from the image that the obtained sample has good crystallinity and uniformly dispersed particles;
2) the degradation rate detection experiment of ciprofloxacin was carried out by using conventional nickel sodium phosphate (without metal loading) as a comparative example and using the Mn-doped nickel sodium phosphate photocatalytic materials obtained in examples 1 to 3 of the present invention, 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 (%) | Degradation efficiency after Mn doping (%) |
0.5 | 12 | 20.7 |
1 | 17.5 | 40.1 |
1.5 | 20 | 55.4 |
2 | 23.6 | 68.2 |
2.5 | 24.8 | 75.5 |
3 | 24.9 | 84 |
4 | 24.2 | 87.3 |
5 | 24.6 | 89 |
Table 2 comparative results of degradation rates of ciprofloxacin by the photocatalytic material obtained in example 2 and the conventional photocatalytic material
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 (%) | Degradation efficiency after Mn doping (%) |
0.5 | 11.3 | 20.8 |
1 | 18 | 36.4 |
1.5 | 22.3 | 55.1 |
2 | 23.2 | 67.2 |
2.5 | 24 | 74 |
3 | 24.7 | 83 |
4 | 24.6 | 87.8 |
5 | 24.3 | 88.2 |
Fig. 2, fig. 3, and fig. 4 are graphs showing the degradation rate change of ciprofloxacin by the Mn-doped nickel sodium phosphate photocatalytic material obtained in this example 1, example 2, and example 3, and it can be seen from table 1, table 2, and table 3, and fig. 2, fig. 3, and fig. 4 that the degradation rate of ciprofloxacin by the Mn-doped nickel sodium phosphate obtained in the present invention is better than the degradation rate of ciprofloxacin by the conventional nickel sodium phosphate, so that it is demonstrated that the Mn-doped nickel sodium phosphate obtained in the present invention has strong photocatalytic performance.
In addition, the main structural morphology of the Mn-doped sodium nickel phosphate obtained in the examples 2 to 10 is similar to that of the example 1; the degradation rate change curves of the Mn-doped sodium nickel phosphate on ciprofloxacin obtained in examples 4 to 10 are similar to those of example 1, so that SEM spectrogram analysis of the Mn-doped basic sodium nickel phosphate photocatalytic materials obtained in examples 2 to 10 is not performed again; the degradation rate of the Mn-doped sodium nickel phosphate photocatalytic materials obtained in examples 4 to 10 was not 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. The Mn-doped sodium nickel phosphate photocatalytic material is characterized in that the chemical formula of a substrate material is Na4Ni3P4O15And the surface of the substrate material is doped with Mn salt.
2. A preparation method of a Mn-doped sodium nickel phosphate photocatalytic material is characterized by comprising the following steps:
step 1, adding sodium-containing basic nickel carbonate into a phosphoric acid solution for a dissolution reaction to obtain a sodium-containing nickel phosphate solution;
step 2, adding manganese salt into the sodium-containing nickel phosphate solution obtained in the step 1, stirring for reaction, and then concentrating and crystallizing to obtain a Mn-doped nickel sodium phosphate crystal mixture;
and 3, calcining the Mn-doped sodium nickel phosphate crystal mixture obtained in the step 2, and cooling to obtain the Mn-doped sodium nickel phosphate photocatalytic material.
3. The method for preparing a Mn-doped nickel sodium phosphate photocatalytic material according to claim 2, wherein 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.
4. the method for preparing a Mn-doped sodium nickel phosphate photocatalytic material according to claim 3, wherein in the step 2, the molar ratio of the added manganese salt to the sodium-containing basic nickel carbonate is (0.015-0.33): 1.
5. the method as claimed in claim 4, wherein in step 2, the manganese salt is at least one of manganese sulfate, manganese chloride and manganese nitrate.
6. The preparation method of the Mn-doped sodium nickel phosphate photocatalytic material according to claim 5, characterized in that in the step 2, the stirring reaction time is 3-5 h.
7. The method as claimed in any one of claims 1 to 6, wherein the calcination temperature in step 3 is 300-800 ℃, and the calcination time is 2-10 h.
8. The method for preparing a Mn-doped nickel sodium phosphate photocatalytic material according to claim 7, wherein 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;
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. The method for preparing a Mn-doped sodium nickel phosphate photocatalytic material according to claim 8, characterized in that in step 1.2, the reaction temperature is 50-60 ℃ and the reaction time is 30-60 min.
10. The method for preparing a Mn-doped sodium nickel phosphate photocatalytic material according to any one of claims 9, wherein in the step 1.3, the reaction temperature is 50-60 ℃ and the reaction time is 11-30 hours.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115028213A (en) * | 2022-06-30 | 2022-09-09 | 金川集团股份有限公司 | Wide-distribution lithium-rich manganese-based positive electrode precursor and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
US20160090311A1 (en) * | 2014-09-26 | 2016-03-31 | Chung-Yuan Christian University | Method for forming Basic Nickel Carbonate |
-
2018
- 2018-08-30 CN CN201811000528.3A patent/CN110871094A/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Non-Patent Citations (3)
Title |
---|
付向辉等: ""连续工艺合成高纯碱式碳酸镍的研究"", 《电子元件与材料》 * |
姚仲鹏: "《空气净化原理、设计与应用》", 30 September 2014, 中国科学技术出版社 * |
曹丽云等: "《钨酸盐纳米材料的湿化学合成及光催化性能》", 31 December 2017, 西北工业大学出版社 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115028213A (en) * | 2022-06-30 | 2022-09-09 | 金川集团股份有限公司 | Wide-distribution lithium-rich manganese-based positive electrode precursor and preparation method thereof |
CN115028213B (en) * | 2022-06-30 | 2023-09-15 | 金川集团股份有限公司 | Wide-distribution lithium-rich manganese-based positive electrode precursor and preparation method thereof |
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