CN111659411A - Preparation and application of rare earth cerium doped iron molybdate photocatalyst - Google Patents
Preparation and application of rare earth cerium doped iron molybdate photocatalyst Download PDFInfo
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- CN111659411A CN111659411A CN202010664065.1A CN202010664065A CN111659411A CN 111659411 A CN111659411 A CN 111659411A CN 202010664065 A CN202010664065 A CN 202010664065A CN 111659411 A CN111659411 A CN 111659411A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 41
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 36
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 36
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 27
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910017354 Fe2(MoO4)3 Inorganic materials 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- 239000002957 persistent organic pollutant Substances 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910015667 MoO4 Inorganic materials 0.000 abstract description 17
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 12
- 229960000907 methylthioninium chloride Drugs 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- -1 cerium ions Chemical class 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000013032 photocatalytic reaction Methods 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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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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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8871—Rare earth metals or actinides
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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Abstract
The invention provides a preparation method and application of rare earth cerium doped iron molybdate photocatalyst, which is prepared by mixing Fe (NO)3)・9H2Dissolving O in deionized water, adding Ce (NO) at room temperature3)3To obtain Fe (NO)3)・9H2O and Ce (NO)3)3The mixed solution of (1); will be (NH)4)6Mo7O24・4H2O is dissolved in deionized water and added dropwise to Fe (NO)3)・9H2O and Ce (NO)3)3Stirring the mixed solution, adding ammonia water to adjust the pH value to 3-4, reacting for 12-13 h at 180-185 ℃, centrifugally washing and drying to obtain the rare earth cerium doped iron molybdate photocatalyst Ce-Fe2(MoO4)3. The cerium-doped iron molybdate prepared by the invention is in a uniform nano spherical structure and has a larger specific surface area; meanwhile, the doping of the rare earth element can effectively reduce the photoproduction electron-hole recombination rate of the photocatalyst, can improve the specific surface area of the photocatalyst to a certain extent, is beneficial to improving the photocatalytic efficiency, and ensures that the Ce-Fe photocatalyst is prepared by adding the rare earth element into the photocatalyst2(MoO4)3Has wide application prospect in the field of photocatalytic dye wastewater treatment.
Description
Technical Field
The invention relates to a rare earth cerium doped iron molybdate photocatalyst (Ce-Fe)2(MoO4)3) In particular to a cerium-doped iron molybdate (Ce-Fe) with a nano spherical structure2(MoO4)3) The rare earth cerium doped iron molybdate photocatalyst prepared by the preparation method is used for photocatalytic degradation of organic pollutants in dye wastewater, and belongs to the field of material preparation and the field of photocatalytic application.
Background
Iron molybdate (Fe)2(MoO4)3) Has the excellent performances of responding to ultraviolet and visible light, high specific surface energy, selectivity, strong exposed activity and the like. More noteworthy, molybdic acid in iron molybdate has catalytic performance, and iron also has catalytic performance, so that the iron molybdate and iron molybdate can achieve synergistic catalytic effect, and the catalytic performance of iron molybdate is stronger. Due to Fe2(MoO4)3The iron molybdate has excellent properties of catalysis, optics, magnetism and the like, so that the iron molybdate has wide application prospect in the fields of catalysts, magnetic materials, optical fibers and the like.
The rare earth resource reserves in China are rich, wherein the abundance of the cerium element is the highest and the most cheap, and meanwhile, the cerium element has unique 4f1，5d1，6S2The electron arrangement structure can exist stably in the form of +4 valence or +3 valence, and the valence state difference can affect the originalDue to the coordination structure of the element, the unique valence configuration of the cerium element is greatly beneficial to improving the material performance. The shape, size, specific surface area and oxygen vacancy of the material jointly influence the photocatalytic performance of the material, wherein the oxygen defect is related to the electronic structure of cerium ions, and the transition process of cerium ions with different valence states is accompanied by O2The oxygen vacancy is formed during the release and can directly participate in the reaction, so that the redox performance is shown, and meanwhile, the doping of the cerium element can effectively reduce the photo-generated electron-hole recombination rate of the photocatalyst, so that the photocatalytic performance of the cerium element can be obviously improved by doping the cerium element into the iron molybdate.
Disclosure of Invention
The invention aims to provide a preparation method and application of a rare earth cerium doped iron molybdate photocatalyst.
Rare earth cerium doped iron molybdate photocatalyst (Ce-Fe)2(MoO4)3) Preparation of
The invention discloses a preparation method of rare earth cerium doped iron molybdate photocatalyst, which is to mix Fe (NO)3)・9H2Dissolving O in deionized water, adding Ce (NO) at room temperature3)3To obtain Fe (NO)3)・9H2O and Ce (NO)3)3The mixed solution of (1); will be (NH)4)6Mo7O24・4H2O is dissolved in deionized water and added dropwise to Fe (NO)3)・9H2O and Ce (NO)3)3Continuously stirring the mixed solution for 4-6 h in a water bath at 25 ℃, adding ammonia water to adjust the pH value to 3-4, reacting for 12-13 h at 180-185 ℃, centrifugally washing, and drying at 80-85 ℃ to obtain the rare earth cerium doped iron molybdate photocatalyst Ce-Fe2(MoO4)3. Wherein, Ce (NO)3)3And Fe (NO)3)・9H2The molar ratio of O is 0.01-0.06: 1; fe (NO)3)・9H2O and (NH)4)6Mo7O24・4H2The molar ratio of O is 1: 0.2-1: 0.25.
Second, rare earth cerium doped iron molybdate (Ce-Fe)2(MoO4)3) Morphology of
1. Analysis by scanning Electron microscope
FIG. 1 shows a rare earth cerium-doped iron molybdate (Ce-Fe) prepared according to the present invention2(MoO4)3) The doping amount of Ce is 2 percent and iron molybdate (Fe)2(MoO4)3) Scanning electron micrograph (c). As can be seen in FIG. 1A, the rare earth cerium-doped iron molybdate (Ce-Fe)2(MoO4)3) Is in the form of uniform nano-particles, has larger specific surface area and particle size of 110-220 nm. As can be seen in FIG. 1B, iron molybdate (Fe)2(MoO4)3) Is nanoflowers assembled by nano sheets.
2. XRD analysis
FIG. 2 shows pure iron molybdate and rare earth cerium doped iron molybdate (Ce-Fe) prepared by the present invention2(MoO4)3): 1% -Ce, rare earth cerium doped iron molybdate (Ce-Fe)2(MoO4)3): 2% -Ce, and all diffraction peaks are consistent with the standard card PDF #35-0183 diffraction peak, which indicates that the sample is successfully synthesized. No additional diffraction peaks appeared after doping with the rare earth element cerium, indicating Fe2(MoO4)3No change in crystal structure occurs after introduction of the rare earth ions. Fe after introduction of rare earth element doping2(MoO4)3Compared with Fe without rare earth element doping2(MoO4)3Part of the peak positions are shifted, which is probably due to the incorporation of rare earth ions, replacing Fe in the catalyst crystal3+Position of (3) causing Fe2(MoO4)3The crystal lattice is deformed.
Thirdly, rare earth cerium doped iron molybdate (Ce-Fe)2(MoO4)3) Catalytic performance of
FIG. 3 shows Ce in the prepared sample3+With Fe3+The material ratio of the material is 1%, 2%, 4% and 6%, respectively, by using a photocatalytic reactor of model LY-GHX-Xe-300, a xenon lamp light source is HSX-F300 xenon lamp of Beijing Newbit technologies, Inc., and a filter at the light source to filter out ultraviolet light (lambda)<400 nm), the circulating water of the reaction device is kept at constant temperature and is continuously stirred, and the water is respectively placed in dark stripsAnd carrying out photocatalytic performance test under irradiation of visible light. From the figure, it can be found that the doping of rare earth cerium element can effectively improve Fe2(MoO4)3The catalyst material Ce-Fe2(MoO4)3The degradation capability to methylene blue is sequentially Ce-2%/Fe2(MoO4)3>Ce-1%/Fe2(MoO4)3>Ce-4%/Fe2(MoO4)3>Ce-6%/Fe2(MoO4)3>Fe2(MoO4)3. Wherein Ce-2%/Fe2(MoO4)3The photocatalytic performance of the catalyst material is the strongest, and the photocatalytic performance of the catalyst material without doped cerium is the weakest. After 4h of photocatalytic reaction, Ce-2%/Fe2(MoO4)3The degradation rate of the catalyst material to methylene blue solution reaches 95.7%, while the degradation rate of the catalyst material not doped with cerium to the methylene blue solution is only 63.29%.
In conclusion, the cerium-doped iron molybdate prepared by the invention is in a uniform nano spherical structure and has a larger specific surface area; meanwhile, the doping of the rare earth element can effectively reduce the photoproduction electron-hole recombination rate of the photocatalyst, can improve the specific surface area of the photocatalyst to a certain extent, is beneficial to improving the photocatalytic efficiency, and ensures that the Ce-Fe photocatalyst is prepared by adding the rare earth element into the photocatalyst2(MoO4)3Has wide application prospect in the field of photocatalytic dye wastewater treatment.
Drawings
FIG. 1 is a rare earth cerium doped iron molybdate Ce-Fe2(MoO4)3: 2% -Ce and iron molybdate.
Fig. 2 is an XRD pattern of a sample prepared by the present invention.
FIG. 3 is a diagram showing the photocatalytic performance of the sample prepared by the present invention for photocatalytic degradation of methylene blue.
Detailed Description
The following is a description of a rare earth cerium doped iron molybdate (Ce-Fe) of the present invention by way of specific example2(MoO4)3) The preparation and properties of (a) are further illustrated.
Example 1
1.0 mmol of Fe (NO)3)・9H2O was dissolved in 20mL of deionized water, and then 0.01mmol Ce (NO) was added at room temperature3)3To obtain Fe (NO)3)・9H2O and Ce (NO)3)3The mixed solution of (1); 0.22mmol (NH)4)6Mo7O24・4H2O was dissolved in 20mL of deionized water and added dropwise to Fe (NO) under magnetic stirring3)・9H2O and Ce (NO)3)3Continuously stirring the mixed solution in a constant-temperature water bath at 25 ℃ for 6 hours, and adding ammonia water to adjust the pH value to 4; finally transferring the mixture to a high-pressure reaction kettle with a 50mL polytetrafluoroethylene liner, reacting for 12h at 180 ℃, centrifugally washing the mixture three times by deionized water after the reaction is finished, centrifugally washing the mixture two times by absolute ethyl alcohol, and drying the mixture at 80 ℃ to obtain the rare earth cerium doped iron molybdate Ce-Fe2(MoO4)3Photocatalyst: 1% -Ce.
The catalytic performance is as follows: the prepared material is added into methylene blue solution, and after 4 hours of photocatalytic reaction, the degradation rate of the methylene blue in the solution reaches 92.85%.
Example 2
1.0 mmol of Fe (NO)3)・9H2O was dissolved in 20mL of deionized water, and then 0.02mmol Ce (NO) was added at room temperature3)3To obtain Fe (NO)3)・9H2O and Ce (NO)3)3The mixed solution of (1); 0.22mmol (NH)4)6Mo7O24・4H2O was dissolved in 20mL of deionized water and added dropwise to Fe (NO) under magnetic stirring3)・9H2O and Ce (NO)3)3Continuously stirring the mixed solution in a constant-temperature water bath at 25 ℃ for 6 hours, and adding ammonia water to adjust the pH value to 4; finally transferring the mixture to a high-pressure reaction kettle with a 50mL polytetrafluoroethylene liner, reacting for 12h at 180 ℃, centrifugally washing the mixture three times by using deionized water after the reaction is finished, centrifugally washing the mixture two times by using absolute ethyl alcohol, and drying the mixture at 80 ℃ to obtain the rare earth cerium doped iron molybdate photocatalyst Ce-Fe2(MoO4)3：2%-Ce。
The catalytic performance is as follows: the prepared material is added into methylene blue solution, and after 4 hours of photocatalytic reaction, the degradation rate of the methylene blue in the solution reaches 95.7 percent.
Example 3
1.0 mmol of Fe (NO)3)・9H2O was dissolved in 20mL deionized water and then 0.04 mmoleCe (NO) was added at room temperature3)3To obtain Fe (NO)3)・9H2O and Ce (NO)3)3The mixed solution of (1); 0.22mmol (NH)4)6Mo7O24・4H2O was dissolved in 20mL of deionized water and added dropwise to Fe (NO) under magnetic stirring3)・9H2O and Ce (NO)3)3Continuously stirring the mixed solution in a constant-temperature water bath at 25 ℃ for 6 hours, and adding ammonia water to adjust the pH value to 4; finally transferring the mixture to a high-pressure reaction kettle with a 50mL polytetrafluoroethylene liner, reacting for 12h at 180 ℃, centrifugally washing the mixture three times by using deionized water after the reaction is finished, centrifugally washing the mixture two times by using absolute ethyl alcohol, and drying the mixture at 80 ℃ to obtain the rare earth cerium doped iron molybdate photocatalyst Ce-Fe2(MoO4)3：4%-Ce。
The catalytic performance is as follows: the prepared material is added into a methylene blue solution, and after 4 hours of photocatalytic reaction, the degradation rate of the methylene blue in the solution reaches 67.39 percent.
Example 4
1.0 mmol of Fe (NO)3)・9H2O was dissolved in 20mL of deionized water, and then 0.06mmol Ce (NO) was added at room temperature3)3To obtain Fe (NO)3)・9H2O and Ce (NO)3)3The mixed solution of (1); 0.22mmol (NH)4)6Mo7O24・4H2O was dissolved in 20mL of deionized water and added dropwise to Fe (NO) under magnetic stirring3)・9H2O and Ce (NO)3)3Continuously stirring the mixed solution in a constant-temperature water bath at 25 ℃ for 6 hours, and adding ammonia water to adjust the pH value to 4; finally transferring the mixture to a high-pressure reaction kettle with a 50mL polytetrafluoroethylene liner, reacting for 12h at 180 ℃, centrifugally washing for three times by deionized water after the reaction is finished, and then using absolute ethyl alcoholCentrifugally washing twice, and then drying at 80 ℃ to obtain the rare earth cerium doped iron molybdate photocatalyst Ce-Fe2(MoO4)3：6%-Ce。
The catalytic performance is as follows: the prepared material is added into methylene blue solution, and after 4 hours of photocatalytic reaction, the degradation rate of the methylene blue in the solution reaches 65.65 percent.
Claims (6)
1. A process for preparing rare-earth Ce doped iron molybdate photocatalyst includes such steps as mixing Fe (NO)3)・9H2Dissolving O in deionized water, adding Ce (NO) at room temperature3)3To obtain Fe (NO)3)・9H2O and Ce (NO)3)3The mixed solution of (1); will be (NH)4)6Mo7O24・4H2O is dissolved in deionized water and added dropwise to Fe (NO)3)・9H2O and Ce (NO)3)3Stirring the mixed solution, adding ammonia water to adjust the pH value to 3-4, reacting for 12-13 h at 180-185 ℃, centrifugally washing and drying to obtain the rare earth cerium doped iron molybdate photocatalyst Ce-Fe2(MoO4)3。
2. The method of claim 1, wherein the preparation method comprises the following steps: the Ce (NO)3)3And Fe (NO)3)・9H2The molar ratio of O is 0.01-0.06: 1.
3. The method of claim 1, wherein the preparation method comprises the following steps: said Fe (NO)3)・9H2O and (NH)4)6Mo7O24・4H2The molar ratio of O is 1: 0.2-1: 0.25.
4. The method of claim 1, wherein the preparation method comprises the following steps: the stirring is carried out for 4-6 h under a water bath at 25 ℃.
5. The method of claim 1, wherein the preparation method comprises the following steps: the drying temperature is 80-85 ℃.
6. The rare earth cerium-doped iron molybdate photocatalyst prepared by the preparation method as claimed in claims 1 to 5 is used for photocatalytic degradation of organic pollutants in dye wastewater.
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| CN116550350A (en) * | 2023-05-14 | 2023-08-08 | 广州绿固环保科技有限公司 | Environment-friendly formaldehyde purifying agent and preparation method and application thereof |
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| CN107213904A (en) * | 2017-05-08 | 2017-09-29 | 武汉工程大学 | A kind of preparation method of high activity, the monoclinic form iron molybdate nanosheets of crystal face exposure |
| CN108295862A (en) * | 2018-02-27 | 2018-07-20 | 成都新柯力化工科技有限公司 | A kind of sheet iron molybdate photochemical catalyst and preparation method for dye wastewater treatment |
| CN111229242A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Iron-molybdenum-based catalyst for preparing formaldehyde by oxidizing cerium-doped methanol, preparation and application thereof |
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| CN107213904A (en) * | 2017-05-08 | 2017-09-29 | 武汉工程大学 | A kind of preparation method of high activity, the monoclinic form iron molybdate nanosheets of crystal face exposure |
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| CN111229242A (en) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | Iron-molybdenum-based catalyst for preparing formaldehyde by oxidizing cerium-doped methanol, preparation and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116550350A (en) * | 2023-05-14 | 2023-08-08 | 广州绿固环保科技有限公司 | Environment-friendly formaldehyde purifying agent and preparation method and application thereof |
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