CN114345124B - Air purifying agent capable of rapidly degrading formaldehyde and preparation method thereof - Google Patents
Air purifying agent capable of rapidly degrading formaldehyde and preparation method thereof Download PDFInfo
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- CN114345124B CN114345124B CN202210042680.8A CN202210042680A CN114345124B CN 114345124 B CN114345124 B CN 114345124B CN 202210042680 A CN202210042680 A CN 202210042680A CN 114345124 B CN114345124 B CN 114345124B
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000012629 purifying agent Substances 0.000 title claims abstract description 42
- 230000000593 degrading effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 81
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 55
- 229910052742 iron Inorganic materials 0.000 claims abstract description 41
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 41
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 29
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims description 66
- 239000000843 powder Substances 0.000 claims description 55
- 239000000047 product Substances 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000000227 grinding Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 20
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 15
- 238000007873 sieving Methods 0.000 claims description 14
- 238000004729 solvothermal method Methods 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 13
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 12
- 239000008103 glucose Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 150000001844 chromium Chemical class 0.000 claims description 4
- 150000002603 lanthanum Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 210000001161 mammalian embryo Anatomy 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000003746 solid phase reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 230000001276 controlling effect Effects 0.000 description 10
- 238000011068 loading method Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000011651 chromium Substances 0.000 description 7
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- 229910052777 Praseodymium Inorganic materials 0.000 description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 4
- 239000000809 air pollutant Substances 0.000 description 3
- 231100001243 air pollutant Toxicity 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 239000013087 chromium-based metal-organic framework Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 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 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- 231100000925 very toxic Toxicity 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Abstract
The application belongs to the technical field of formaldehyde purification, and particularly relates to an air purifying agent capable of rapidly degrading formaldehyde and a preparation method thereof. The preparation method prepares Ba through solid phase reaction 2 In (1‑x‑y) Ce x Co y NbO 6 Wherein x=0.01 to 0.05 and y=0.01 to 0.05, and then preparing Ba by a coprecipitation method 2 In (1‑x‑y) Ce x Co y NbO 6 Iron and lanthanum doped chromium oxide; finally, preparing the carbon-coated Ba by a hydrothermal method 2 In (1‑x‑y) Ce x Co y NbO 6 Air purifying agent which can rapidly degrade formaldehyde and is doped with iron and lanthanum. The air purifying agent utilizes the coordination effect among the components, so that the photocatalysis capability of the air purifying agent is improved, and the oxidizing groups produced by sunlight are efficiently utilized to purify formaldehyde, so that formaldehyde is efficiently removed.
Description
Technical Field
The application belongs to the technical field of formaldehyde purification. More particularly, relates to an air purifying agent capable of rapidly degrading formaldehyde and a preparation method thereof.
Background
Formaldehyde (HCHO) is one of the major air pollutants in indoor environments, an air pollutant that severely affects indoor environments, and is very toxic. Even in formaldehyde environments of relatively low concentrations for long periods of time, the damage to humans is very serious. As one of the toxic air pollutants, HCHO has a negative impact on genetic material, respiratory tract and skin, and also strongly affects the central nervous system. Therefore, reducing the formaldehyde content at room temperature is a highly desirable problem in order to improve indoor air quality, reduce public health risks. The catalytic oxidation technology can oxidize and decompose formaldehyde into CO at a lower temperature 2 And H 2 O, which has the advantages of high waste gas treatment efficiency, no secondary pollution, low energy consumption, simple operation method and the like, is considered as the most promising method for eliminating formaldehyde.
GALVA' N et Al report more than w=0.4% Pd-Mn/Al 2 O 3 Can completely oxidize HCHO into CO at above 90 DEG C 2 And H 2 O. In evaluating the removal efficiency of HCHO from several metal oxides in a static reaction vessel.
Wang Xing the synthesis of N- (BiO) at room temperature using bismuth nitrate as a Bi source and cetyltrimethylammonium bromide as an N source 2 CO 3 . In N- (BiO) 2 CO 3 As a support, pt was deposited on its surface by impregnation. By using the novel LED energy-saving lamp as a light source, pt@N- (BiO) is inspected by a dynamic test method 2 CO 3 Catalytic oxidation formaldehyde behavior. Research shows that compared with N- (BiO) 2 CO 3 The Pt-loaded material shows higher photocatalytic activity under visible light. 2% Pt@N- (BiO) 2 CO 3 For an initial concentration of 0.72mg/m 3 The formaldehyde with the flow rate of 820mL/min can reach 65.2 percent of degradation efficiency.
You Xiaochang the doping amount of rare earth Ce element to nano Cr 2 O 3 Has certain influence on the phase and the microscopic morphology of the nano Cr along with the increase of the doping amount of Ce 2 O 3 The crystallinity of (c) decreases and the grain size becomes smaller. However, when the Ce doping amount is 2.0%, nano Cr 2 O 3 Is formed by assembling finer particles, and the particle size is increased; in addition, the doping of rare earth Ce element can lead Cr to be 2 O 3 The crystal generates lattice distortion, increases the concentration of electrons in a conduction band, improves the separation efficiency of electrons and holes, and can effectively improve nano Cr 2 O 3 When the Ce doping amount is 1.0%, nano Cr 2 O 3 The photocatalytic degradation efficiency of (2) is optimal.
CN112371108A discloses an environment-friendly formaldehyde purifying catalyst and a preparation method thereof. The purification catalyst is prepared from praseodymium and neodymium which are coated by carbon, wherein the modified load capacity of the praseodymium relative to the chromium oxide is 1-3wt%; the modified load capacity of neodymium relative to chromium oxide is 1-3 wt%, and the purifying catalyst is prepared by firstly preparing a chromium-based metal organic framework, then modifying the components by metal, then roasting, coating a carbon layer by a solvothermal method, and co-modifying by praseodymium and neodymium, thereby promoting the effective separation of photogenerated electrons and holes by utilizing the synergistic effect between the praseodymium and the neodymium, improving the photocatalytic purifying capacity of the chromium oxide, and improving the adsorption capacity of formaldehyde by coating a layer of carbon, and purifying the formaldehyde by utilizing active groups produced by the photocatalyst.
However, the formaldehyde purifying catalyst has longer purifying time, limited purifying capacity and low catalyst utilization rate, so that the development of a purifying agent capable of rapidly purifying formaldehyde and recycling is still a problem to be solved at present.
Disclosure of Invention
The application aims to overcome the defects and shortcomings of the prior art and provide an air purifying agent capable of rapidly degrading formaldehyde and a preparation method thereof.
The application aims to provide a preparation method of an air purifying agent capable of rapidly degrading formaldehyde, which is to prepare Ba through solid phase reaction 2 In (1-x-y) Ce x Co y NbO 6 Wherein x=0.01 to 0.05 and y=0.01 to 0.05, and then preparing Ba by coprecipitation 2 In (1-x-y) Ce x Co y NbO 6 Iron and lanthanum doped chromium oxide; finally, preparing the carbon-coated Ba by a hydrothermal method 2 In (1-x-y) Ce x Co y NbO 6 Air purifying agent which can rapidly degrade formaldehyde and is doped with iron and lanthanum.
The application also aims to provide an air purifying agent capable of rapidly degrading formaldehyde. The air purifying agent is carbon-coated Ba 2 In (1-x-y) Ce x Co y NbO 6 Iron and lanthanum doped chromium oxide, said Ba 2 In (1-x-y) Ce x Co y NbO 6 With iron andthe mass ratio of lanthanum doped chromium oxide is 1:0.5-0.7; the modified load capacity of the iron relative to the chromium oxide is 2-4wt%; the modified load of lanthanum relative to chromium oxide is 0.5-1.5 wt%.
The above object of the present application is achieved by the following technical scheme:
a method for preparing an air purifying agent capable of rapidly degrading formaldehyde, which comprises the following steps:
(1) Ba with purity greater than 99.0% 2 CO 3 、In 2 O 3 、Nb 2 O 5 、Ce 2 O 3 And Co 2 O 3 According to Ba 2 In (1-x-y) Ce x Co y NbO 6 Wherein, the stoichiometric ratio of x=0.01-0.05 and y=0.01-0.05 is weighed and then put into a ball milling tank for ball milling;
(2) After ball milling, carrying out vacuum drying on the obtained mixed material, grinding after drying, and sieving the ground powder;
(3) Calcining the sieved powder in a muffle furnace, granulating the obtained powder after calcining, preforming the granulated powder by a tablet press, pressing the powder into a blank under 15-20 MPa, sintering the obtained blank in the muffle furnace at 1150-1250 ℃ for 8-12h, cooling to room temperature along with the furnace, and grinding to obtain Ba 2 In (1-x-y) Ce x Co y NbO 6 ；
(4) Dissolving chromium salt, ferric salt and lanthanum salt in water to prepare solution, and then dissolving Ba 2 In (1-x-y) Ce x Co y NbO 6 Adding into the above solution, and stirring; slowly dripping an alkali solution into the solution under the stirring condition, and controlling the pH value to be 8-10; aging until precipitation is complete; washing the precipitate, drying and roasting to obtain a product B; the product B is Ba 2 In (1-x-y) Ce x Co y NbO 6 Iron and lanthanum doped chromium oxide.
(5) Dispersing the product B obtained in the step (4) and glucose in absolute ethyl alcohol, performing ultrasonic dispersion to obtain a suspension, transferring the suspension into a polytetrafluoroethylene high-pressure reaction kettle for solvothermal reaction, taking out and filtering after cooling, and performing vacuum freeze-drying to obtain a sample.
Preferably, in the step (1), the ball milling medium is absolute ethanol; the ball milling rotating speed is 200-300 rpm, and the ball milling time is 20-40min.
Preferably, in the step (2), the sieving is through a 180-220 mesh sieve; the vacuum drying condition is that the drying treatment is carried out for 8-12 hours at the temperature of 60-90 ℃.
Preferably, in the step (3), the calcination is calcination at 500 to 700 ℃ for 1 to 5 hours; the diameter of the embryo body is phi 10-15 mm, and the thickness is 2-4 mm.
Preferably, in step (4), the aging conditions are aging at 50-70 ℃ for 10-16 hours; the drying is carried out for 10 to 24 hours at the temperature of 80 to 120 ℃, and the roasting is carried out for 5 to 9 hours at the temperature of 700 to 900 ℃.
Preferably, in step (4), the Ba 2 In (1-x-y) Ce x Co y NbO 6 The mass ratio of the chromium oxide doped with iron and lanthanum is 1:0.5-0.7; the modified load capacity of the iron relative to the chromium oxide is 2-4wt%; the modified load of lanthanum relative to chromium oxide is 0.5-1.5 wt%.
Preferably, in step (4), the base is one or more of sodium carbonate, sodium hydroxide, potassium hydroxide; the chromium salt is one of chromium nitrate, chromium chloride or chromium sulfate; the ferric salt is one of ferric nitrate, ferric chloride and ferric acetate; the lanthanum salt is one of lanthanum nitrate, lanthanum acetate and lanthanum chloride.
Preferably, in the step (5), the solvothermal reaction condition is that the temperature is kept between 150 and 190 ℃ for 15 to 25 hours; the ultrasonic dispersion time is 25-35min.
Preferably, in step (5), the ratio of product B to glucose and absolute ethanol is 1mg: 20-28 mg: 12-16 mL.
The air purifying agent capable of rapidly degrading formaldehyde is prepared based on the preparation method of the air purifying agent capable of rapidly degrading formaldehyde.
The application has the following beneficial effects:
(1) Modification of Ba by Co and Ce doping 2 InNbO 6 The coordination between the two can effectively improve the Ba 2 InNbO 6 The photocatalytic performance of the air purifying agent is improved.
(2) Iron and lanthanum doped chromium oxide is deposited on Ba by coprecipitation method 2 In (1-x-y) Ce x Co y NbO 6 The surface is formed by combining chromium oxide and Ba while utilizing the synergistic effect of iron and lanthanum 2 In (1-x-y) Ce x Co y NbO 6 The heterojunction is formed, so that the effective separation of photo-generated electrons and holes is effectively improved, the effective utilization rate of sunlight is further improved, the photocatalytic capability is improved, and the air purifying agent can efficiently degrade formaldehyde.
(3) In Ba by solvothermal method 2 In (1-x-y) Ce x Co y NbO 6 The surface of chromium oxide doped with iron and lanthanum is coated with a carbon layer, formaldehyde can be adsorbed on the surface of a catalyst by utilizing the adsorption capacity of carbon to formaldehyde, and then the formaldehyde is purified by oxidizing an oxidizing group produced by a photocatalyst, so that the purification capacity of the formaldehyde is effectively improved.
(4) The preparation method disclosed by the application is simple in preparation process, low in cost, and excellent in performance of the prepared product, and is beneficial to industrial production.
In conclusion, the air purifying agent prepared by the application has excellent photocatalytic performance and good purifying capability on formaldehyde, and is an ideal material for purifying formaldehyde.
Detailed Description
The present application is further illustrated below with reference to specific examples, which are not intended to limit the application in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present application are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1
A method for preparing an air purifying agent capable of rapidly degrading formaldehyde, which comprises the following steps:
(1) Ba with purity greater than 99.0% 2 CO 3 、In 2 O 3 、Nb 2 O 5 、Ce 2 O 3 And Co 2 O 3 According to Ba 2 In 0.94 Ce 0.05 Co 0.01 NbO 6 Weighing the stoichiometric ratio of the raw materials, and then putting the raw materials into a ball milling tank for ball milling, wherein the ball milling medium is absolute ethyl alcohol; the ball milling rotating speed is 200rpm, and the ball milling time is 40min;
(2) After ball milling, vacuum drying the obtained mixture for 12 hours at 60 ℃, grinding after drying, and sieving the ground powder with a 220-mesh sieve;
(3) Calcining the sieved powder in a muffle furnace at 500 ℃ for 5 hours, granulating the obtained powder after calcining, preforming the granulated powder by a tablet press, and pressing the powder under 15MPa to obtain a blank, wherein the diameter of the blank is phi 10mm and the thickness of the blank is 2mm, sintering the obtained blank in the muffle furnace at 1150 ℃ for 12 hours, cooling to room temperature along with the furnace, and grinding to obtain Ba 2 In 0.94 Ce 0.05 Co 0.01 NbO 6 ；
(4) Dissolving chromium acetate, ferric nitrate and lanthanum acetate in water to prepare a solution, and then adding 1g of Ba 2 In 0.94 Ce 0.05 Co 0.01 NbO 6 Adding into the above solution, and stirring; slowly dropwise adding a potassium hydroxide solution with the concentration of 1mol/L into the solution under the stirring condition, and controlling the pH value to be 8; aging at 50deg.C for 16 hr until precipitation is complete; washing the precipitate, drying at 80 ℃ for 24 hours, and roasting at 700 ℃ for 9 hours to obtain a product B; the product B is Ba 2 In 0.94 Ce 0.05 Co 0.01 NbO 6 Iron and lanthanum doped chromium oxide; the Ba is 2 In 0.94 Ce 0.05 Co 0.01 NbO 6 The mass ratio of the chromium oxide doped with iron and lanthanum is 1:0.5; the modified loading of the iron relative to the chromium oxide was 2wt%; the modified load of lanthanum relative to chromium oxide is 1.5wt%;
(5) Dispersing 1mg of the product B obtained in the step (4) and 20mg of glucose in 12mL of absolute ethyl alcohol, performing ultrasonic dispersion for 25min to obtain a suspension, transferring the suspension into a polytetrafluoroethylene high-pressure reaction kettle, performing solvothermal reaction at 150 ℃ for 25h, taking out and filtering after cooling, and performing vacuum freeze drying to obtain a sample.
Example 2
A method for preparing an air purifying agent capable of rapidly degrading formaldehyde, which comprises the following steps:
(1) Ba with purity greater than 99.0% 2 CO 3 、In 2 O 3 、Nb 2 O 5 、Ce 2 O 3 And Co 2 O 3 According to Ba 2 In 0.94 Ce 0.01 Co 0.05 NbO 6 Weighing the stoichiometric ratio of the raw materials, and then putting the raw materials into a ball milling tank for ball milling, wherein the ball milling medium is absolute ethyl alcohol; the ball milling rotating speed is 300rpm, and the ball milling time is 20min;
(2) After ball milling, carrying out vacuum drying on the obtained mixed material for 8 hours at 90 ℃, grinding after drying, and sieving the ground powder with a 180-mesh sieve;
(3) Calcining the sieved powder in a muffle furnace at 700 ℃ for 1h, granulating the obtained powder, preforming the granulated powder by a tablet press, pressing the preformed powder under 20MPa to obtain a blank, wherein the diameter of the blank is phi 15mm and the thickness of the blank is 4mm, sintering the obtained blank in the muffle furnace at 1250 ℃ for 8h, cooling to room temperature along with the furnace, and grinding to obtain Ba 2 In 0.94 Ce 0.01 Co 0.05 NbO 6 ；
(4) Chromium chloride, ferric nitrate and lanthanum chloride are dissolved in water to prepare a solution, and 1g of Ba 2 In 0.94 Ce 0.01 Co 0.05 NbO 6 Adding into the above solution, and stirring; slowly dropwise adding a sodium carbonate solution with the concentration of 1mol/L into the solution under the stirring condition, and controlling the pH value to be 10; aging at 70deg.C for 10 hr until precipitation is complete; washing the precipitate, drying at 120 ℃ for 10 hours, and roasting at 900 ℃ for 5 hours to obtain a product B; the product B is Ba 2 In 0.94 Ce 0.01 Co 0.05 NbO 6 Iron and lanthanum dopedChromium oxide; the Ba is 2 In 0.94 Ce 0.01 Co 0.05 NbO 6 The mass ratio of the chromium oxide doped with iron and lanthanum is 1:0.7; the modified loading of the iron relative to the chromium oxide was 4wt%; the modified load of lanthanum relative to chromium oxide is 0.5wt%;
(5) Dispersing 1mg of the product B obtained in the step (4) and 28mg of glucose in 16mL of absolute ethyl alcohol, performing ultrasonic dispersion for 35min to obtain a suspension, transferring the suspension into a polytetrafluoroethylene high-pressure reaction kettle, performing solvothermal reaction at 190 ℃ for 15h, taking out and filtering after cooling, and performing vacuum freeze drying to obtain a sample.
Example 3
A method for preparing an air purifying agent capable of rapidly degrading formaldehyde, which comprises the following steps:
(1) Ba with purity greater than 99.0% 2 CO 3 、In 2 O 3 、Nb 2 O 5 、Ce 2 O 3 And Co 2 O 3 According to Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 Weighing the stoichiometric ratio of the raw materials, and then putting the raw materials into a ball milling tank for ball milling, wherein the ball milling medium is absolute ethyl alcohol; the ball milling rotating speed is 250rpm, and the ball milling time is 30min;
(2) After ball milling, vacuum drying the obtained mixture for 10 hours at 70 ℃, grinding after drying, and sieving the ground powder with a 200-mesh sieve;
(3) Calcining the sieved powder in a muffle furnace at 600 ℃ for 3 hours, granulating the obtained powder after calcining, preforming the granulated powder by a tablet press, and pressing the powder under 18MPa to obtain a blank, wherein the diameter of the blank is phi 12mm and the thickness of the blank is 3mm, sintering the obtained blank in the muffle furnace at 1200 ℃ for 10 hours, cooling to room temperature along with the furnace, and grinding to obtain Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 ；
(4) Chromium nitrate, ferric chloride and lanthanum nitrate are dissolved in water to prepare a solution, and 1g of Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 Adding into the above solutionStirring the solution uniformly; slowly dropwise adding a sodium hydroxide solution with the molar concentration of 1mol/L into the solution under the stirring condition, and controlling the pH value to be 9; aging at 60deg.C for 13 hr until precipitation is complete; washing the precipitate, drying at 100 ℃ for 18 hours, and roasting at 800 ℃ for 7 hours to obtain a product B; the product B is Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 Iron and lanthanum doped chromium oxide; the Ba is 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 The mass ratio of the chromium oxide doped with iron and lanthanum is 1:0.6; the modified loading of the iron relative to the chromium oxide was 3wt%; the modified load of lanthanum relative to chromium oxide was 1wt%;
(5) Dispersing 1mg of the product B obtained in the step (4) and 24mg of glucose in 14mL of absolute ethyl alcohol, performing ultrasonic dispersion for 30min to obtain a suspension, transferring the suspension into a polytetrafluoroethylene high-pressure reaction kettle for solvothermal reaction at 170 ℃ for 20h, taking out and filtering after cooling, and performing vacuum freeze drying to obtain a sample.
Comparative example 1
A method for preparing an air purifying agent capable of rapidly degrading formaldehyde, which comprises the following steps:
(1) Ba with purity greater than 99.0% 2 CO 3 、In 2 O 3 、Nb 2 O 5 And Ce (Ce) 2 O 3 According to Ba 2 In 0.94 Ce 0.06 NbO 6 Weighing the stoichiometric ratio of the raw materials, and then putting the raw materials into a ball milling tank for ball milling, wherein the ball milling medium is absolute ethyl alcohol; the ball milling rotating speed is 250rpm, and the ball milling time is 30min;
(2) After ball milling, vacuum drying the obtained mixture for 10 hours at 70 ℃, grinding after drying, and sieving the ground powder with a 200-mesh sieve;
(3) Calcining the sieved powder in a muffle furnace at 600 ℃ for 3 hours, granulating the obtained powder, preforming the granulated powder by a tablet press, and pressing the powder under 18MPa to obtain a blank, wherein the diameter of the blank is phi 12mm and the thickness of the blank is 3mm, sintering the obtained blank in the muffle furnace at 1200 ℃ for 10 hours, and cooling the blank to room temperature along with the furnaceGrinding to obtain Ba 2 In 0.94 Ce 0.06 NbO 6 ；
(4) Chromium nitrate, ferric chloride and lanthanum nitrate are dissolved in water to prepare a solution, and 1g of Ba 2 In 0.94 Ce 0.06 NbO 6 Adding into the above solution, and stirring; slowly dropwise adding a sodium hydroxide solution with the molar concentration of 1mol/L into the solution under the stirring condition, and controlling the pH value to be 9; aging at 60deg.C for 13 hr until precipitation is complete; washing the precipitate, drying at 100 ℃ for 18 hours, and roasting at 800 ℃ for 7 hours to obtain a product B; the product B is Ba 2 In 0.94 Ce 0.06 NbO 6 Iron and lanthanum doped chromium oxide; the Ba is 2 In 0.94 Ce 0.06 NbO 6 The mass ratio of the chromium oxide doped with iron and lanthanum is 1:0.6; the modified loading of the iron relative to the chromium oxide was 3wt%; the modified load of lanthanum relative to chromium oxide was 1wt%;
(5) Dispersing 1mg of the product B obtained in the step (4) and 24mg of glucose in 14mL of absolute ethyl alcohol, performing ultrasonic dispersion for 30min to obtain a suspension, transferring the suspension into a polytetrafluoroethylene high-pressure reaction kettle for solvothermal reaction at 170 ℃ for 20h, taking out and filtering after cooling, and performing vacuum freeze drying to obtain a sample.
Comparative example 2
A method for preparing an air purifying agent capable of rapidly degrading formaldehyde, which comprises the following steps:
(1) Ba with purity greater than 99.0% 2 CO 3 、In 2 O 3 、Nb 2 O 5 And Co 2 O 3 According to Ba 2 In 0.94 Co 0.06 NbO 6 Weighing the stoichiometric ratio of the raw materials, and then putting the raw materials into a ball milling tank for ball milling, wherein the ball milling medium is absolute ethyl alcohol; the ball milling rotating speed is 250rpm, and the ball milling time is 30min;
(2) After ball milling, vacuum drying the obtained mixture for 10 hours at 70 ℃, grinding after drying, and sieving the ground powder with a 200-mesh sieve;
(3) Calcining the sieved powder in a muffle furnace at 600 ℃ for 3h, granulating the obtained powder after calcination, preforming the granulated powder by a tablet press, pressing the preformed powder under 18MPa to obtain a blank, wherein the diameter of the blank is phi 12mm, the thickness of the blank is 3mm, sintering the obtained blank in a muffle furnace at 1200 ℃ for 10h, cooling to room temperature along with the furnace, and grinding to obtain Ba 2 In 0.94 Co 0.06 NbO 6 ；
(4) Chromium nitrate, ferric chloride and lanthanum nitrate are dissolved in water to prepare a solution, and 1g of Ba 2 In 0.94 Co 0.06 NbO 6 Adding into the above solution, and stirring; slowly dropwise adding a sodium hydroxide solution with the molar concentration of 1mol/L into the solution under the stirring condition, and controlling the pH value to be 9; aging at 60deg.C for 13 hr until precipitation is complete; washing the precipitate, drying at 100 ℃ for 18 hours, and roasting at 800 ℃ for 7 hours to obtain a product B; the product B is Ba 2 In 0.94 Co 0.06 NbO 6 Iron and lanthanum doped chromium oxide; the Ba is 2 In 0.94 Co 0.06 NbO 6 The mass ratio of the chromium oxide doped with iron and lanthanum is 1:0.6; the modified loading of the iron relative to the chromium oxide was 3wt%; the modified load of lanthanum relative to chromium oxide was 1wt%;
(5) Dispersing 1mg of the product B obtained in the step (4) and 24mg of glucose in 14mL of absolute ethyl alcohol, performing ultrasonic dispersion for 30min to obtain a suspension, transferring the suspension into a polytetrafluoroethylene high-pressure reaction kettle for solvothermal reaction at 170 ℃ for 20h, taking out and filtering after cooling, and performing vacuum freeze drying to obtain a sample.
Comparative example 3
A method for preparing an air purifying agent capable of rapidly degrading formaldehyde, which comprises the following steps:
(1) Ba with purity greater than 99.0% 2 CO 3 、In 2 O 3 、Nb 2 O 5 、Ce 2 O 3 And Co 2 O 3 According to Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 Weighing the stoichiometric ratio of the raw materials, and then putting the raw materials into a ball milling tank for ball milling, wherein the ball milling medium is absolute ethyl alcohol; the ball milling is turnedThe speed is 250rpm, and the ball milling time is 30min;
(2) After ball milling, vacuum drying the obtained mixture for 10 hours at 70 ℃, grinding after drying, and sieving the ground powder with a 200-mesh sieve;
(3) Calcining the sieved powder in a muffle furnace at 600 ℃ for 3 hours, granulating the obtained powder after calcining, preforming the granulated powder by a tablet press, and pressing the powder under 18MPa to obtain a blank, wherein the diameter of the blank is phi 12mm and the thickness of the blank is 3mm, sintering the obtained blank in the muffle furnace at 1200 ℃ for 10 hours, cooling to room temperature along with the furnace, and grinding to obtain Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 ；
(4) Chromium nitrate and ferric chloride are dissolved in water to prepare a solution, and then 1g of Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 Adding into the above solution, and stirring; slowly dropwise adding a sodium hydroxide solution with the molar concentration of 1mol/L into the solution under the stirring condition, and controlling the pH value to be 9; aging at 60deg.C for 13 hr until precipitation is complete; washing the precipitate, drying at 100 ℃ for 18 hours, and roasting at 800 ℃ for 7 hours to obtain a product B; the product B is Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 Iron doped chromium oxide; the Ba is 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 The mass ratio of the chromium oxide to the iron-doped chromium oxide is 1:0.6; the modified loading of the iron relative to the chromium oxide was 4wt%;
(5) Dispersing 1mg of the product B obtained in the step (4) and 24mg of glucose in 14mL of absolute ethyl alcohol, performing ultrasonic dispersion for 30min to obtain a suspension, transferring the suspension into a polytetrafluoroethylene high-pressure reaction kettle for solvothermal reaction at 170 ℃ for 20h, taking out and filtering after cooling, and performing vacuum freeze drying to obtain a sample.
Comparative example 4
A method for preparing an air purifying agent capable of rapidly degrading formaldehyde, which comprises the following steps:
(1) Ba with purity greater than 99.0% 2 CO 3 、In 2 O 3 、Nb 2 O 5 、Ce 2 O 3 And Co 2 O 3 According to Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 Weighing the stoichiometric ratio of the raw materials, and then putting the raw materials into a ball milling tank for ball milling, wherein the ball milling medium is absolute ethyl alcohol; the ball milling rotating speed is 250rpm, and the ball milling time is 30min;
(2) After ball milling, vacuum drying the obtained mixture for 10 hours at 70 ℃, grinding after drying, and sieving the ground powder with a 200-mesh sieve;
(3) Calcining the sieved powder in a muffle furnace at 600 ℃ for 3 hours, granulating the obtained powder after calcining, preforming the granulated powder by a tablet press, and pressing the powder under 18MPa to obtain a blank, wherein the diameter of the blank is phi 12mm and the thickness of the blank is 3mm, sintering the obtained blank in the muffle furnace at 1200 ℃ for 10 hours, cooling to room temperature along with the furnace, and grinding to obtain Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 ；
(4) Chromium nitrate and lanthanum nitrate are dissolved in water to prepare a solution, and then 1g Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 Adding into the above solution, and stirring; slowly dropwise adding a sodium hydroxide solution with the molar concentration of 1mol/L into the solution under the stirring condition, and controlling the pH value to be 9; aging at 60deg.C for 13 hr until precipitation is complete; washing the precipitate, drying at 100 ℃ for 18 hours, and roasting at 800 ℃ for 7 hours to obtain a product B; the product B is Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 Lanthanum doped chromium oxide; the Ba is 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 The mass ratio of the lanthanum-doped chromium oxide to the lanthanum-doped chromium oxide is 1:0.6; the modified load of lanthanum relative to chromium oxide is 4wt%;
(5) Dispersing 1mg of the product B obtained in the step (4) and 24mg of glucose in 14mL of absolute ethyl alcohol, performing ultrasonic dispersion for 30min to obtain a suspension, transferring the suspension into a polytetrafluoroethylene high-pressure reaction kettle for solvothermal reaction at 170 ℃ for 20h, taking out and filtering after cooling, and performing vacuum freeze drying to obtain a sample.
Comparative example 5
A method for preparing an air purifying agent capable of rapidly degrading formaldehyde, which comprises the following steps:
(1) Ba with purity greater than 99.0% 2 CO 3 、In 2 O 3 、Nb 2 O 5 、Ce 2 O 3 And Co 2 O 3 According to Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 Weighing the stoichiometric ratio of the raw materials, and then putting the raw materials into a ball milling tank for ball milling, wherein the ball milling medium is absolute ethyl alcohol; the ball milling rotating speed is 250rpm, and the ball milling time is 30min;
(2) After ball milling, vacuum drying the obtained mixture for 10 hours at 70 ℃, grinding after drying, and sieving the ground powder with a 200-mesh sieve;
(3) Calcining the sieved powder in a muffle furnace at 600 ℃ for 3 hours, granulating the obtained powder after calcining, preforming the granulated powder by a tablet press, and pressing the powder under 18MPa to obtain a blank, wherein the diameter of the blank is phi 12mm and the thickness of the blank is 3mm, sintering the obtained blank in the muffle furnace at 1200 ℃ for 10 hours, cooling to room temperature along with the furnace, and grinding to obtain Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 ；
(4) Dissolving chromium nitrate, ferric chloride and lanthanum nitrate in water to prepare a solution, slowly dropwise adding a sodium hydroxide solution with the molar concentration of 1mol/L into the solution under the stirring condition, and controlling the pH value to be 9; aging at 60deg.C for 13 hr until precipitation is complete; washing the precipitate, drying at 100 ℃ for 18 hours, and roasting at 800 ℃ for 7 hours to obtain the chromium oxide doped with iron and lanthanum; then mixing the Fe and La doped chromium oxide with 1g of Ba obtained in the step (3) 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 Grinding for 3h to obtain a product B, wherein the product B is Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 Iron and lanthanum doped chromium oxide; the Ba is 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 The mass ratio of the chromium oxide doped with iron and lanthanum is 1:0.6; modification of the iron with respect to chromium oxideThe loading was 3wt%; the modified load of lanthanum relative to chromium oxide was 1wt%;
(5) Dispersing 1mg of the product B obtained in the step (4) and 24mg of glucose in 14mL of absolute ethyl alcohol, performing ultrasonic dispersion for 30min to obtain a suspension, transferring the suspension into a polytetrafluoroethylene high-pressure reaction kettle for solvothermal reaction at 170 ℃ for 20h, taking out and filtering after cooling, and performing vacuum freeze drying to obtain a sample.
Comparative example 6
A method for preparing an air purifying agent capable of rapidly degrading formaldehyde, which comprises the following steps:
(1) Ba with purity greater than 99.0% 2 CO 3 、In 2 O 3 、Nb 2 O 5 、Ce 2 O 3 And Co 2 O 3 According to Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 Weighing the stoichiometric ratio of the raw materials, and then putting the raw materials into a ball milling tank for ball milling, wherein the ball milling medium is absolute ethyl alcohol; the ball milling rotating speed is 250rpm, and the ball milling time is 30min;
(2) After ball milling, vacuum drying the obtained mixture for 10 hours at 70 ℃, grinding after drying, and sieving the ground powder with a 200-mesh sieve;
(3) Calcining the sieved powder in a muffle furnace at 600 ℃ for 3 hours, granulating the obtained powder after calcining, preforming the granulated powder by a tablet press, and pressing the powder under 18MPa to obtain a blank, wherein the diameter of the blank is phi 12mm and the thickness of the blank is 3mm, sintering the obtained blank in the muffle furnace at 1200 ℃ for 10 hours, cooling to room temperature along with the furnace, and grinding to obtain Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 ；
(4) Chromium nitrate, ferric chloride and lanthanum nitrate are dissolved in water to prepare a solution, and 1g of Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 Adding into the above solution, and stirring; slowly dropwise adding a sodium hydroxide solution with the molar concentration of 1mol/L into the solution under the stirring condition, and controlling the pH value to be 9; aging at 60deg.C for 13 hr until precipitation is complete; after the precipitation is washed, the solution is washed,drying at 100deg.C for 18 hr, and calcining at 800deg.C for 7 hr to obtain air purifying agent; the air purifying agent is Ba 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 Iron and lanthanum doped chromium oxide; the Ba is 2 In 0.94 Ce 0.03 Co 0.03 NbO 6 The mass ratio of the chromium oxide doped with iron and lanthanum is 1:0.6; the modified loading of the iron relative to the chromium oxide was 3wt%; the lanthanum was modified to chromia loading of 1wt%.
The air purifying agents obtained in examples 1-3 and comparative examples 1-6 were used in experiments for photocatalytic degradation of formaldehyde, and the specific experimental procedures were as follows:
under the irradiation of room temperature visible light, the photocatalytic degradation performance of formaldehyde is evaluated by adopting a continuous flow reactor. Firstly, 80mg of environment-friendly formaldehyde purification catalyst is weighed and coated in the middle of a square plate with the length of 4cm multiplied by 4cm, and the catalyst is placed in the center of a reactor. The ratio of formaldehyde gas to air flow is regulated to obtain the formaldehyde gas with the volume concentration of 30 percent, and the air flow speed is controlled to be 1.0L/min. A 300W xenon lamp (equipped with a 420nm cutoff filter to shield ultraviolet radiation) was placed vertically on the reactor. Prior to irradiation, the sample-coated square plate was kept in the dark for 200min to reach adsorption-desorption equilibrium. After the adsorption is completed, the light source is turned on. The residual formaldehyde concentration was monitored by formaldehyde gas analyzer for 20min and 40min.
The degradation efficiency of the photocatalyst was calculated according to formula (1):
D＝(C 0 -C t )×100％/C 0 the method comprises the steps of carrying out a first treatment on the surface of the Wherein D is photocatalytic degradation efficiency,%; c (C) 0 The initial mass concentration of formaldehyde is mol/L; c (C) t The mass concentration of formaldehyde after t min of illumination is mol/L.
The specific test results are shown in Table 1:
TABLE 1 test data for examples 1-3 and comparative examples 1-6
| Formaldehyde purification rate at 20min (%) | Purification rate of formaldehyde at 40min (%) | |
| Example 1 | 75.6 | 94.2 |
| Example 2 | 74.6 | 93.7 |
| Example 3 | 76.8 | 95.3 |
| Comparative example 1 | 72.3 | 90.3 |
| Comparative example 2 | 71.9 | 89.6 |
| Comparative example 3 | 73.6 | 92.1 |
| Comparative example 4 | 74.1 | 92.9 |
| Comparative example 5 | 70.4 | 88.3 |
| Comparative example 6 | 65.4 | 82.8 |
As can be seen from the comparison of examples 1 to 3 and comparative examples 1 to 6, the air purifying agent prepared by the present application has excellent purifying ability to formaldehyde, and can effectively remove formaldehyde by using the synergistic effect between the components, and the maximum purifying rate of 40min reaches 95.3%, so that the air purifying agent of the present application is an ideal material for purifying formaldehyde.
The above examples are preferred embodiments of the present application, but the embodiments of the present application are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present application should be made in the equivalent manner, and the embodiments are included in the protection scope of the present application.
Claims (8)
1. A preparation method of an air purifying agent capable of rapidly degrading formaldehyde is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) Ba with purity greater than 99.0% 2 CO 3 、In 2 O 3 、Nb 2 O 5 、Ce 2 O 3 And Co 2 O 3 According to Ba 2 In (1-x-y) Ce x Co y NbO 6 Wherein, the stoichiometric ratio of x=0.01-0.05 and y=0.01-0.05 is weighed and then put into a ball milling tank for ball milling;
(2) After ball milling, carrying out vacuum drying on the obtained mixed material, grinding after drying, and sieving the ground powder;
(3) Calcining the sieved powder in a muffle furnace, granulating the obtained powder after calcining, preforming the granulated powder by a tablet press, pressing the powder into a blank under 15-20 MPa, sintering the obtained blank in the muffle furnace at 1150-1250 ℃ for 8-12h, and thenCooling the furnace to room temperature, grinding to obtain Ba 2 In (1-x-y) Ce x Co y NbO 6 ；
(4) Dissolving chromium salt, ferric salt and lanthanum salt in water to prepare solution, and then dissolving Ba 2 In (1-x-y) Ce x Co y NbO 6 Adding into the above solution, and stirring; slowly dripping an alkali solution into the solution under the stirring condition, and controlling the pH value to be 8-10; aging until precipitation is complete; washing the precipitate, drying and roasting to obtain a product B; the product B is Ba 2 In (1-x-y) Ce x Co y NbO 6 Iron and lanthanum doped chromium oxide;
in step (4), the Ba 2 In (1-x-y) Ce x Co y NbO 6 The mass ratio of the chromium oxide doped with iron and lanthanum is 1:0.5-0.7; the modified load capacity of the iron relative to the chromium oxide is 2-4wt%; the modified load of lanthanum relative to chromium oxide is 0.5-1.5 wt%;
(5) Dispersing the product B obtained in the step (4) and glucose in absolute ethyl alcohol, performing ultrasonic dispersion to obtain a suspension, transferring the suspension into a polytetrafluoroethylene high-pressure reaction kettle for solvothermal reaction, taking out and filtering after cooling, and performing vacuum freeze drying to obtain a sample;
in step (5), the ratio of product B to glucose and absolute ethanol is 1mg: 20-28 mg: 12-16 mL.
2. The method for preparing the air purifying agent capable of rapidly degrading formaldehyde according to claim 1, wherein the method comprises the following steps: in the step (1), the ball milling medium is absolute ethyl alcohol; the ball milling rotating speed is 200-300 rpm, and the ball milling time is 20-40min.
3. The method for preparing the air purifying agent capable of rapidly degrading formaldehyde according to claim 1, wherein the method comprises the following steps: in the step (2), the sieving is 180-220 mesh sieving; the vacuum drying condition is that the drying treatment is carried out for 8-12 hours at the temperature of 60-90 ℃.
4. The method for preparing the air purifying agent capable of rapidly degrading formaldehyde according to claim 1, wherein the method comprises the following steps: in the step (3), the calcination is carried out for 1 to 5 hours at the temperature of 500 to 700 ℃; the diameter of the embryo body is phi 10-15 mm, and the thickness is 2-4 mm.
5. The method for preparing the air purifying agent capable of rapidly degrading formaldehyde according to claim 1, wherein the method comprises the following steps: in the step (4), the aging condition is aging for 10-16 hours at 50-70 ℃; the drying is carried out for 10 to 24 hours at the temperature of 80 to 120 ℃, and the roasting is carried out for 5 to 9 hours at the temperature of 700 to 900 ℃.
6. The method for preparing the air purifying agent capable of rapidly degrading formaldehyde according to claim 1, wherein the method comprises the following steps: in the step (4), the alkali is one or more of sodium carbonate, sodium hydroxide and potassium hydroxide; the chromium salt is one of chromium nitrate, chromium chloride or chromium sulfate; the ferric salt is one of ferric nitrate, ferric chloride and ferric acetate; the lanthanum salt is one of lanthanum nitrate, lanthanum acetate and lanthanum chloride.
7. The method for preparing the air purifying agent capable of rapidly degrading formaldehyde according to claim 1, wherein the method comprises the following steps: in the step (5), the solvothermal reaction condition is that the temperature is kept between 150 and 190 ℃ for 15 to 25 hours; the ultrasonic dispersion time is 25-35min.
8. An air purifying agent capable of rapidly degrading formaldehyde, which is prepared by the method for preparing an air purifying agent capable of rapidly degrading formaldehyde according to any one of claims 1 to 7.
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