CN110227520B - Copper-doped bismuth phosphate composite material, preparation method and application thereof - Google Patents
Copper-doped bismuth phosphate composite material, preparation method and application thereof Download PDFInfo
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- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 54
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 35
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 27
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 27
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 8
- 230000001699 photocatalysis Effects 0.000 claims description 8
- 238000007146 photocatalysis Methods 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 abstract description 14
- 238000006731 degradation reaction Methods 0.000 abstract description 14
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 10
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 7
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 7
- 230000000593 degrading effect Effects 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 17
- 238000007789 sealing Methods 0.000 description 11
- 239000010949 copper Substances 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 5
- 230000003321 amplification Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000003199 nucleic acid amplification method Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- -1 rare earth ions Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- 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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a copper-doped bismuth phosphate composite material and a preparation method thereof, wherein the preparation method comprises the following steps: s1, adding bismuth nitrate and copper nitrate into deionized water, uniformly stirring, adding sodium phosphate, and stirring for 20-50 min to obtain a reaction solution; and S2, adding a pH regulator into the reaction liquid obtained in the step S1, regulating the pH value to 4-7, then reacting at 160-200 ℃ for 20-36 h, naturally cooling to room temperature after the reaction is finished, washing, separating and drying to obtain the copper-doped bismuth phosphate composite material. The invention researches the photocatalytic degradation performance of the composite material by regulating and controlling the pH value, the reaction time and the molar ratio of reactants in the reaction process. The composite material synthesized by the invention has excellent photocatalytic degradation performance, and can be used for catalyzing and degrading methylene blue for 60min, wherein the degradation rate can reach 88%, and the degradation rate can reach 90% in 90 min. The preparation method is simple and convenient to operate and easy to realize.
Description
Technical Field
The invention belongs to the technical field of catalyst material preparation, and particularly relates to a copper-doped bismuth phosphate composite material, a preparation method and application thereof.
Background
The bismuth phosphate has special structural characteristics and high chemical stability, can be used as a photocatalyst, a luminescent matrix material, an organic reaction catalyst and the like, and has potential application prospects in the aspects of heat resistance, friction resistance and the like. Bismuth phosphate has three crystal forms: monoclinic phase, monoclinic phase monazite and hexagonal phase. The hexagonal phase bismuth phosphate is taken as a luminescent matrix material doped with rare earth ions and is paid the attention of researchers in the aspect of fluorescent powder development, and the monoclinic phase monazite structure bismuth phosphate becomes a new star in the field of photocatalysis. However, bismuth phosphate-based photocatalysts have the disadvantages of low quantum efficiency, low solar energy utilization rate and the like, and restrict the practical application of the bismuth phosphate-based photocatalysts in a photocatalytic technology. Therefore, the development of a method for doping copper with bismuth phosphate is of great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a copper-doped bismuth phosphate composite material, a preparation method and application thereof.
The first purpose of the invention is to provide a preparation method of a copper-doped bismuth phosphate composite material, which comprises the following steps:
s1, adding bismuth nitrate and copper nitrate into deionized water, stirring for 30min, then adding sodium phosphate, and stirring for 30min to obtain a reaction solution;
the molar ratio of bismuth nitrate to copper nitrate is 4: 2-4;
and S2, adding a pH regulator into the reaction liquid obtained in the step S1, regulating the pH value to 4-7, reacting at 180 ℃ for 20-36 hours, naturally cooling to room temperature after the reaction is finished, washing, separating and drying to obtain the copper-doped bismuth phosphate composite material.
Preferably, in step S1, the molar ratio of the sodium phosphate to the bismuth nitrate is 1: 1.
Preferably, in step S2, the pH adjusting agent is sodium hydroxide.
Preferably, in step S1, the molar ratio of bismuth nitrate to copper nitrate is 4: 3.
Preferably, in step S2, the reaction time is 24 h.
The second purpose of the invention is to provide the copper-doped bismuth phosphate composite material prepared by the preparation method.
The third purpose of the invention is to provide an application of the composite material in the field of photocatalysis.
Compared with the prior art, the invention has the beneficial effects that:
(1) the copper-doped bismuth phosphate composite material is synthesized by a simple hydrothermal method, the process is simple, the operation is convenient, the cost is lower, and no pollution is caused in the preparation process;
(2) the structure and performance of the copper-doped bismuth phosphate composite material synthesized by the method are further researched by regulating and controlling the pH, the reaction time and the molar ratio of reactants in the reaction process;
(3) the copper-doped bismuth phosphate composite material provided by the invention has the advantages that the photocatalytic performance is improved, the methylene blue is degraded for 60min, the degradation rate can reach 88%, the degradation time is continuously prolonged to 90min, the degradation rate can reach 90%, and the copper-doped bismuth phosphate composite material has excellent photocatalytic performance.
Drawings
FIG. 1 is an XRD pattern of a copper-doped bismuth phosphate composite prepared in examples 1 and 3 of the present invention and a bismuth phosphate catalyst prepared in comparative example 6;
FIG. 2 is a scanning electron micrograph of a copper-doped bismuth phosphate composite prepared according to example 1 of the present invention and a bismuth phosphate catalyst prepared according to comparative example 6;
wherein, FIG. 2a is a scanning electron micrograph of the bismuth phosphate catalyst prepared according to comparative example 6; FIG. 2b is a scanning electron micrograph of the copper-doped bismuth phosphate composite prepared in example 1;
FIG. 3 is a graph showing the energy spectra of the copper-doped bismuth phosphate composite prepared in example 1 of the present invention and the bismuth phosphate catalyst prepared in comparative example 6;
wherein, FIG. 3a is a spectrum diagram of the bismuth phosphate catalyst prepared in comparative example 6; FIG. 3b is an energy spectrum of the copper-doped bismuth phosphate composite prepared in example 1; (ii) a
FIG. 4 is an infrared spectrum of a copper-doped bismuth phosphate composite prepared in example 1 of the present invention and a bismuth phosphate catalyst prepared in comparative example 6;
FIG. 5 is a graph showing photocatalytic degradation performance of the composite materials prepared in examples 1 and 4 and comparative examples 2 and 3;
FIG. 6 is a graph showing photocatalytic degradation performance of the composite materials prepared in examples 1 to 3 and comparative example 1;
fig. 7 is a graph showing photocatalytic degradation performance of the composite materials prepared in examples 1 and 5 and comparative examples 4 and 5.
Detailed Description
Specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
Example 1
A preparation method of a copper-doped bismuth phosphate composite material comprises the following steps:
s1, adding bismuth nitrate and copper nitrate into 30mL of deionized water, stirring for 30min, then adding sodium phosphate, and stirring for 30min to obtain a reaction solution;
the molar ratio of the bismuth nitrate to the copper nitrate to the sodium phosphate is 4:3: 4;
s2, adding sodium hydroxide into the reaction liquid obtained in the step S1, adjusting the pH value to 7, transferring the reaction liquid to a reaction kettle, sealing the reaction kettle, reacting the reaction liquid at 180 ℃ for 24 hours, naturally cooling the reaction liquid to room temperature after the reaction is finished, washing, separating and drying the reaction liquid to obtain the copper-doped bismuth phosphate composite material.
Example 2
A preparation method of a copper-doped bismuth phosphate composite material comprises the following steps:
s1, adding bismuth nitrate and copper nitrate into 30mL of deionized water, stirring for 30min, then adding sodium phosphate, and stirring for 30min to obtain a reaction solution;
the molar ratio of the bismuth nitrate to the copper nitrate to the sodium phosphate is 1:1: 1;
s2, adding sodium hydroxide into the reaction liquid obtained in the step S1, adjusting the pH value to 7, transferring the reaction liquid to a reaction kettle, sealing the reaction kettle, reacting the reaction liquid at 180 ℃ for 24 hours, naturally cooling the reaction liquid to room temperature after the reaction is finished, washing, separating and drying the reaction liquid to obtain the copper-doped bismuth phosphate composite material.
Example 3
A preparation method of a copper-doped bismuth phosphate composite material comprises the following steps:
s1, adding bismuth nitrate and copper nitrate into 30mL of deionized water, stirring for 30min, then adding sodium phosphate, and stirring for 30min to obtain a reaction solution;
the molar ratio of the bismuth nitrate to the copper nitrate to the sodium phosphate is 2:1: 2;
s2, adding sodium hydroxide into the reaction liquid obtained in the step S1, adjusting the pH value to 7, transferring the reaction liquid to a reaction kettle, sealing the reaction kettle, reacting the reaction liquid at 180 ℃ for 24 hours, naturally cooling the reaction liquid to room temperature after the reaction is finished, washing, separating and drying the reaction liquid to obtain the copper-doped bismuth phosphate composite material.
Example 4
A preparation method of a copper-doped bismuth phosphate composite material comprises the following steps:
s1, adding bismuth nitrate and copper nitrate into 30mL of deionized water, stirring for 30min, then adding sodium phosphate, and stirring for 30min to obtain a reaction solution;
the molar ratio of the bismuth nitrate to the copper nitrate to the sodium phosphate is 4:3: 4;
s2, adding sodium hydroxide into the reaction liquid obtained in the step S1, adjusting the pH value to 4.5, transferring the reaction liquid to a reaction kettle, sealing the reaction kettle, reacting the reaction liquid at 180 ℃ for 24 hours, naturally cooling the reaction liquid to room temperature after the reaction is finished, washing, separating and drying the reaction liquid to obtain the copper-doped bismuth phosphate composite material.
Example 5
A preparation method of a copper-doped bismuth phosphate composite material comprises the following steps:
s1, adding bismuth nitrate and copper nitrate into 30mL of deionized water, stirring for 30min, then adding sodium phosphate, and stirring for 30min to obtain a reaction solution;
the molar ratio of the bismuth nitrate to the copper nitrate to the sodium phosphate is 4:3: 4;
s2, adding sodium hydroxide into the reaction liquid obtained in the step S1, adjusting the pH value to 7, transferring the reaction liquid to a reaction kettle, sealing the reaction kettle, reacting the reaction liquid at 180 ℃ for 36 hours, naturally cooling the reaction liquid to room temperature after the reaction is finished, washing, separating and drying the reaction liquid to obtain the copper-doped bismuth phosphate composite material.
Comparative example 1
A preparation method of a copper-doped bismuth phosphate composite material comprises the following steps:
s1, adding bismuth nitrate and copper nitrate into 30mL of deionized water, stirring for 30min, then adding sodium phosphate, and stirring for 30min to obtain a reaction solution;
the molar ratio of the bismuth nitrate to the copper nitrate to the sodium phosphate is 4:1: 4;
s2, adding sodium hydroxide into the reaction liquid obtained in the step S1, adjusting the pH value to 7, transferring the reaction liquid to a reaction kettle, sealing the reaction kettle, reacting the reaction liquid at 180 ℃ for 24 hours, naturally cooling the reaction liquid to room temperature after the reaction is finished, washing, separating and drying the reaction liquid to obtain the copper-doped bismuth phosphate composite material.
Comparative example 2
A preparation method of a copper-doped bismuth phosphate composite material comprises the following steps:
s1, adding bismuth nitrate and copper nitrate into 30mL of deionized water, stirring for 30min, then adding sodium phosphate, and stirring for 30min to obtain a reaction solution;
the molar ratio of the bismuth nitrate to the copper nitrate to the sodium phosphate is 4:3: 4;
s2, adding sodium hydroxide into the reaction liquid obtained in the step S1, adjusting the pH value to 9, transferring the reaction liquid to a reaction kettle, sealing the reaction kettle, reacting the reaction liquid at 180 ℃ for 24 hours, naturally cooling the reaction liquid to room temperature after the reaction is finished, washing, separating and drying the reaction liquid to obtain the copper-doped bismuth phosphate composite material.
Comparative example 3
A preparation method of a copper-doped bismuth phosphate composite material comprises the following steps:
s1, adding bismuth nitrate and copper nitrate into 30mL of deionized water, stirring for 30min, then adding sodium phosphate, and stirring for 30min to obtain a reaction solution;
the molar ratio of the bismuth nitrate to the copper nitrate to the sodium phosphate is 4:3: 4;
s2, adding concentrated nitric acid into the reaction liquid obtained in the step S1, adjusting the pH value to 1.5, transferring the reaction liquid to a reaction kettle, sealing the reaction kettle, reacting the reaction liquid at 180 ℃ for 24 hours, naturally cooling the reaction liquid to room temperature after the reaction is finished, washing, separating and drying the reaction liquid to obtain the copper-doped bismuth phosphate composite material.
Comparative example 4
A preparation method of a copper-doped bismuth phosphate composite material comprises the following steps:
s1, adding bismuth nitrate and copper nitrate into 30mL of deionized water, stirring for 30min, then adding sodium phosphate, and stirring for 30min to obtain a reaction solution;
the molar ratio of the bismuth nitrate to the copper nitrate to the sodium phosphate is 4:3: 4;
s2, adding a sodium hydroxide solution into the reaction liquid obtained in the step S1, adjusting the pH value to 7, transferring the solution into a reaction kettle, sealing the reaction kettle, reacting the reaction kettle at 180 ℃ for 6 hours, naturally cooling the reaction kettle to room temperature after the reaction is finished, washing, separating and drying the reaction kettle to obtain the copper-doped bismuth phosphate composite material.
Comparative example 5
A preparation method of a copper-doped bismuth phosphate composite material comprises the following steps:
s1, adding bismuth nitrate and copper nitrate into 30mL of deionized water, stirring for 30min, then adding sodium phosphate, and stirring for 30min to obtain a reaction solution;
the molar ratio of the bismuth nitrate to the copper nitrate to the sodium phosphate is 4:3: 4;
s2, adding sodium hydroxide into the reaction liquid obtained in the step S1, adjusting the pH value to 7, transferring the reaction liquid to a reaction kettle, sealing the reaction kettle, reacting the reaction liquid at 180 ℃ for 12 hours, naturally cooling the reaction liquid to room temperature after the reaction is finished, washing, separating and drying the reaction liquid to obtain the copper-doped bismuth phosphate composite material.
Comparative example 6
A preparation method of a bismuth phosphate catalyst comprises the following steps:
s1, adding bismuth nitrate and sodium phosphate into 30mL of deionized water, and stirring for 30min to obtain a reaction solution;
the molar ratio of the bismuth nitrate to the sodium phosphate is 1: 1;
s2, adding sodium hydroxide into the reaction liquid obtained in the step S1, adjusting the pH value to 7, transferring the reaction liquid to a reaction kettle, sealing the reaction kettle, reacting the reaction liquid at 180 ℃ for 24 hours, naturally cooling the reaction liquid to room temperature after the reaction is finished, washing, separating and drying the reaction liquid to obtain the bismuth phosphate catalyst.
FIG. 1 is an XRD pattern of the copper-doped bismuth phosphate composite materials prepared in examples 1 and 3 according to the present invention and the bismuth phosphate catalyst prepared in comparative example 6, and it can be seen from the XRD patterns that Cu can be seen in both of the composite materials prepared in examples 1 and 32+The doped peak value, the copper-doped bismuth phosphate composite materials prepared by different molar ratios of bismuth nitrate and copper nitrate show different peak widths due to different doping amounts, and when the molar ratio of bismuth nitrate to copper nitrate is 4:3, the peak width when the molar ratio of the copper ion peak value is 2:1 can be observed, so that the situation shows that the peak width is related to the crystal form of the copper-doped bismuth phosphate composite materials. In addition, compared with a pure phase catalyst, the angle of the composite material provided by the invention is obviously shifted to the left, and the peak value is reduced.
Fig. 2 is a scanning electron microscope image of the copper-doped bismuth phosphate composite prepared in example 1 of the present invention and the bismuth phosphate catalyst prepared in comparative example 6. As can be seen from fig. 2, the structure of the bismuth phosphate material before doping with copper is non-uniform rod-shaped and is distributed more dispersedly, and after doping with copper, the structure of the bismuth phosphate material becomes long rod-shaped, and some small particles are attached to the surface, and the morphology is more regular, which indicates that copper is successfully doped on the surface of the bismuth phosphate material.
Fig. 3 is a graph showing energy spectra of the copper-doped bismuth phosphate composite prepared in example 1 of the present invention and the bismuth phosphate catalyst prepared in comparative example 6. As can be seen from fig. 3, the contents of O, P, Cu, Bi, etc. are 47.02%, 15.79%, 27.34%, and 9.85%, respectively, further illustrating the successful doping of copper on the bismuth phosphate material.
Fig. 4 is an infrared spectrum of the copper-doped bismuth phosphate composite prepared in example 1 of the present invention and the bismuth phosphate catalyst prepared in comparative example 6. As can be seen from FIG. 4, the bismuth phosphate catalyst was at 2356.57cm-1、1551.28cm-1The absorption of water shows an impurity peak of 1500cm-1-750cm-1The interval is v (PO)4) 750cm of vibration absorption-1-500cm-1Interval is delta (PO)4) Vibration absorption, and the copper-doped bismuth phosphate composite material is 3404.6cm-1New doped Cu appears2+Characteristic absorption peak of (1).
The photocatalytic degradation performance of the copper-doped bismuth phosphate composite materials prepared in examples 1 to 5 and comparative examples 1 to 5 was investigated
0.1g of the composite materials prepared in examples 1 to 5 and comparative examples 1 to 5 was added to a beaker containing 5mg/L of a methylene blue solution and 100mL of the solution, and stirred for 30 minutes. Then moving the solution into a simple photocatalysis device for simulating ultraviolet light, taking 5mL of supernatant every 30min, centrifuging and measuring the absorbance of the supernatant. The maximum wavelength of methylene blue was determined to be 662nm, at which the absorbance A was determinedtWherein A is0＝0.450。
Measuring absorbance A of supernatant at room temperature with spectrophotometertThe photocatalytic degradation rate η is calculated according to the following formula:
η＝(A0-At)/A0*100％
wherein: eta is degradation rate; a. the0The absorbance of the original solution; a. thetIs the absorbance of the solution after the illumination time t.
Fig. 5 is a graph showing photocatalytic degradation performance of the composite materials prepared in examples 1 and 4 and comparative examples 2 and 3. It can be seen from fig. 5 that the change of pH during the reaction has an effect on the result of the composite material degrading methylene blue. Under strong acid and alkaline conditions, the photocatalytic performance of the composite material is relatively poor, and the growth trend of the composite material is still very slow and finally tends to be smooth along with the prolonging of degradation time. The catalytic activity is relatively high under weak acidity and neutral conditions, the amplification is obvious after the degradation is carried out for 30min, the amplification is slow along with the extension of the degradation time, and the catalyst finally tends to be stable after 120 min.
FIG. 6 is a graph showing photocatalytic degradation properties of the composite materials prepared in examples 1 to 3 and comparative example 1. As can be seen from fig. 6, the molar ratio of the amounts of bismuth nitrate and copper nitrate has an effect on the results of the composite catalyst degrading methylene blue. When the molar ratio of bismuth nitrate to copper nitrate is 4:3, the degradation rate is 30% after catalyzing for 30min, then the rapid increase is 60min to 88%, and then the increase slowly approaches to balance to 90%. When the molar ratio is 1:1, the degradation rate is 70% after catalyzing for 30min, reaches 89.8% after 90min, and tends to be stable. When the molar ratio is 2:1, the degradation rate is increased linearly and reaches 65% after 120 min. At a molar ratio of 4:1, the degradation rate increased linearly but was less than 20%.
Fig. 7 is a graph showing photocatalytic degradation performance of the composite materials prepared in examples 1 and 5 and comparative examples 4 and 5. As can be seen from fig. 7, the reaction time of the hydrothermal reaction has a certain effect on the effect of the composite material in degrading methylene blue. The longer the time, the higher the efficiency of degrading MB, the degradation rate of which tends to the linear equation and is highly consistent at 24h and 36h, the slower the amplification of which is less than 20% at 6h, the slower the amplification of which is at 12h before 90min and the increased amplification thereafter. Thus, 24h is the optimal reaction time.
It should be noted that when the following claims refer to numerical ranges, it should be understood that both ends of each numerical range and any value between the two ends can be selected, and since the steps and methods used are the same as those of the embodiments, the preferred embodiments and effects thereof are described in the present invention for the sake of avoiding redundancy, but once the basic inventive concept is known, those skilled in the art may make other changes and modifications to the embodiments. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (7)
1. The preparation method of the copper-doped bismuth phosphate composite material is characterized by comprising the following steps of:
s1, adding bismuth nitrate and copper nitrate into deionized water, stirring for 20-50 min, then adding sodium phosphate, and stirring for 20-50 min to obtain a reaction solution;
the molar ratio of bismuth nitrate to copper nitrate is 4: 2-4;
and S2, adding a pH regulator into the reaction liquid obtained in the step S1, regulating the pH value to 4-7, reacting at 160-200 ℃ for 20-36 hours, cooling to room temperature after the reaction is finished, washing, separating and drying to obtain the copper-doped bismuth phosphate composite material.
2. The method for preparing the copper-doped bismuth phosphate composite material according to claim 1, wherein in the step S1, the molar ratio of the sodium phosphate to the bismuth nitrate is 1: 1.
3. The method according to claim 1, wherein in step S2, the pH regulator is sodium hydroxide.
4. The method for preparing the copper-doped bismuth phosphate composite material according to claim 1, wherein in the step S1, the molar ratio of the bismuth nitrate to the copper nitrate is 4: 3.
5. The method for preparing the copper-doped bismuth phosphate composite material according to claim 1, wherein in the step S2, the reaction time is 24 h.
6. A copper-doped bismuth phosphate composite material prepared according to the preparation method of any one of claims 1 to 5.
7. The application of the copper-doped bismuth phosphate composite material of claim 6 in the field of photocatalysis.
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