CN114345124A - 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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- CN114345124A CN114345124A CN202210042680.8A CN202210042680A CN114345124A CN 114345124 A CN114345124 A CN 114345124A CN 202210042680 A CN202210042680 A CN 202210042680A CN 114345124 A CN114345124 A CN 114345124A
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 202
- 239000012629 purifying agent Substances 0.000 title claims abstract description 39
- 230000000593 degrading effect Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 70
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 31
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000000498 ball milling Methods 0.000 claims description 66
- 239000000843 powder Substances 0.000 claims description 49
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- 239000000047 product Substances 0.000 claims description 33
- 238000001354 calcination Methods 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000000227 grinding Methods 0.000 claims description 23
- 238000011068 loading method Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 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
- 238000004729 solvothermal method Methods 0.000 claims description 14
- 238000006243 chemical reaction 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
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 12
- 229910000421 cerium(III) oxide Inorganic materials 0.000 claims description 11
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 238000009777 vacuum freeze-drying 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
- 238000007873 sieving Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 150000001844 chromium Chemical class 0.000 claims description 4
- 150000002603 lanthanum Chemical class 0.000 claims description 4
- 229910021555 Chromium Chloride Inorganic materials 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
- 150000002505 iron Chemical class 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
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000003746 solid phase reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 9
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 239000000809 air pollutant Substances 0.000 description 3
- 231100001243 air pollutant Toxicity 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 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
- 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
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 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
- 239000012459 cleaning agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method 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
- 238000007146 photocatalysis Methods 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
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- 231100000419 toxicity 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
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention belongs to the technical field of formaldehyde purification, and particularly relates to an air purifying agent capable of quickly degrading formaldehyde and a preparation method thereof. The preparation method prepares Ba through solid-phase reaction2In(1‑x‑y)CexCoyNbO6Wherein x is 0.01-0.05 and y is 0.01-0.05, and then preparing Ba by a coprecipitation method2In(1‑x‑y)CexCoyNbO6@ iron and lanthanum doped chromium oxide; finally preparing the carbon-coated Ba by a hydrothermal method2In(1‑x‑y)CexCoyNbO6@ iron and lanthanum doped chromium oxide air purifiers that can rapidly degrade formaldehyde. The air purifying agent utilizes the coordination effect among the components, thereby improving the photocatalytic energy of the air purifying agentAnd oxidizing radicals generated by sunlight are utilized to purify formaldehyde efficiently, so that formaldehyde is removed efficiently.
Description
Technical Field
The invention 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 main air pollutants in indoor environment, is an air pollutant which seriously affects indoor environment, and has great toxicity. Even if the formaldehyde is in a low-concentration formaldehyde environment for a long time, the harm to the human body is very serious. As one of the toxic air pollutants, HCHO has negative effects on genetic material, respiratory tract and skin, and also strongly affects the central nervous system. Therefore, in order to improve indoor air quality and reduce public health risks, the reduction of formaldehyde content at room temperature is an urgent problem to be solved. The catalytic oxidation technology can make the formaldehyde lowerOxidative decomposition to CO at temperature2And H2O, therefore, has advantages of high efficiency of waste gas treatment, no secondary pollution, low energy consumption, simple operation method, etc., and is considered as the most promising method for eliminating formaldehyde.
Wangxing et al studied the synthesis of N- (BiO) at room temperature using bismuth nitrate as Bi source and cetyl trimethyl ammonium bromide as N source2CO3. With N- (BiO)2CO3For the support, Pt was deposited on its surface by an impregnation method. Pt @ N- (BiO) is investigated by a dynamic test method by using a novel LED energy-saving lamp as a light source2CO3Catalytic oxidation of formaldehyde. Research shows that compared with N- (BiO)2CO3And the material loaded with Pt shows higher photocatalytic activity under visible light. 2% Pt @ N- (BiO)2CO3For the initial concentration of 0.72mg/m3And the formaldehyde with the flow rate of 820mL/min can reach the degradation efficiency of 65.2 percent.
The doping amount of rare earth Ce element to nano Cr is studied2O3The phase and the micro-morphology of the alloy have certain influence, and the nano Cr has certain influence along with the increase of the doping amount of Ce2O3The crystallinity of (2) is reduced and the crystal grain size becomes small. However, when the doping amount of Ce is 2.0 percent, the nano Cr2O3The microscopic morphology of the particles is changed and is formed by assembling finer particles, and the particle size of the particles is increased; in addition, the doping of rare earth Ce element can lead Cr2O3The crystal generates lattice distortion, the electron concentration in a conduction band is increased, the separation efficiency of electrons and holes is improved, and the nano Cr can be effectively improved2O3When the doping amount of Ce is 1.0 percent, the nano Cr2O3The photocatalytic degradation efficiency is optimal.
CN112371108A discloses an environment-friendly formaldehyde purification catalyst and a preparation method thereof. The purifying catalyst is carbon-coated praseodymium and neodymium co-modified chromium oxide, and the modified load capacity of the praseodymium relative to the chromium oxide is 1-3 wt%; the modified load capacity of neodymium relative to chromium oxide is 1-3 wt%, the purification catalyst is prepared by preparing a chromium-based metal organic framework, then performing metal modification on a component, then roasting, coating a carbon layer by a solvothermal method, co-modifying through praseodymium and neodymium, and promoting effective separation of photoproduction electrons and holes by utilizing synergistic action between the two, so that the photocatalytic purification capacity of chromium oxide is improved, the adsorption capacity of the chromium oxide on formaldehyde is improved by coating a layer of carbon, and formaldehyde is purified by utilizing active groups produced by the photocatalyst, so that the purification catalyst is an ideal material for formaldehyde purification.
However, the formaldehyde purification catalyst has long purification time, limited purification capacity and low catalyst utilization rate, so that the continuous development of a purifying agent which can rapidly purify formaldehyde and can be recycled is still a problem to be solved at present.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings of the prior art and provides an air purifying agent capable of quickly degrading formaldehyde and a preparation method thereof.
The invention aims to provide a preparation method of an air purifying agent capable of quickly degrading formaldehyde, which prepares Ba by solid-phase reaction2In(1-x-y)CexCoyNbO6Wherein x is 0.01-0.05 and y is 0.01-0.05, and then preparing Ba by coprecipitation2In(1-x-y)CexCoyNbO6@ iron and lanthanum doped chromium oxide; finally preparing the carbon-coated Ba by a hydrothermal method2In(1-x-y)CexCoyNbO6@ iron and lanthanum doped chromium oxide air purifiers that can rapidly degrade formaldehyde.
The invention also aims to provide an air purifying agent capable of rapidly degrading formaldehyde. The air isThe cleaning agent is carbon-coated Ba2In(1-x-y)CexCoyNbO6@ iron and lanthanum doped chromium oxide, said Ba2In(1-x-y)CexCoyNbO6The mass ratio of the chromium oxide to the iron-and lanthanum-doped chromium oxide is 1: 0.5-0.7; the modified loading capacity of the iron relative to the chromium oxide is 2-4 wt%; the modified loading amount of lanthanum relative to chromium oxide is 0.5-1.5 wt%.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of an air purifying agent capable of rapidly degrading formaldehyde comprises the following steps:
(1) ba with purity more than 99.0%2CO3、In2O3、Nb2O5、Ce2O3And Co2O3According to Ba2In(1-x-y)CexCoyNbO6Weighing x is 0.01-0.05 and y is 0.01-0.05 in a stoichiometric ratio, and then placing the weighed materials into a ball milling tank for ball milling;
(2) after the ball milling is finished, carrying out vacuum drying on the obtained mixed material, grinding the dried mixed material, and sieving the ground powder;
(3) calcining the sieved powder in a muffle furnace, granulating the calcined powder, preforming the granulated powder by a tablet press, pressing the preformed powder into a blank under the pressure of 15 MPa-20 MPa, sintering the blank in the muffle furnace at the temperature of 1150-1250 ℃ for 8-12h, cooling the blank to room temperature along with the furnace, and grinding to obtain Ba2In(1-x-y)CexCoyNbO6；
(4) Dissolving chromium salt, iron salt and lanthanum salt in water to prepare solution, and then dissolving Ba2In(1-x-y)CexCoyNbO6Adding 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 the precipitation is complete; washing the precipitate, drying and roasting to obtain a product B; the product B is Ba2In(1-x-y)CexCoyNbO6@ iron and lanthanum doped chromium oxide.
(5) And (4) 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 to a polytetrafluoroethylene high-pressure reaction kettle for solvothermal reaction, cooling, taking out, filtering, and performing vacuum freeze drying to obtain a sample.
Preferably, in the step (1), the ball milling medium is absolute ethyl alcohol; the ball milling speed is 200-300 rpm, and the ball milling time is 20-40 min.
Preferably, in the step (2), the sieving is performed by sieving with a 180-220 mesh sieve; the vacuum drying condition is drying treatment at 60-90 ℃ for 8-12 h.
Preferably, in the step (3), the calcination is carried out at 500-700 ℃ for 1-5 h; the diameter of the blank is phi 10-15 mm, and the thickness of the blank is 2-4 mm.
Preferably, in the step (4), the aging condition is aging at 50-70 ℃ for 10-16 h; the drying is drying for 10-24 hours at 80-120 ℃, and the roasting is roasting for 5-9 hours at 700-900 ℃.
Preferably, in the step (4), said Ba2In(1-x-y)CexCoyNbO6The mass ratio of the chromium oxide to the iron-and lanthanum-doped chromium oxide is 1: 0.5-0.7; the modified loading capacity of the iron relative to the chromium oxide is 2-4 wt%; the modified loading amount of lanthanum relative to chromium oxide is 0.5-1.5 wt%.
Preferably, 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.
Preferably, in the step (5), the reaction condition of solvothermal reaction is that the temperature is kept at 150-190 ℃ for 15-25 h; the ultrasonic dispersion time is 25-35 min.
Preferably, in step (5), the ratio of the product B to glucose and absolute ethanol is 1 mg: 20-28 mg: 12-16 mL.
The air purifying agent capable of quickly degrading formaldehyde is prepared by the preparation method of the air purifying agent capable of quickly degrading formaldehyde.
The invention has the following beneficial effects:
(1) ba modified by doping with cobalt and cerium2InNbO6The coordination between the two can effectively improve Ba2InNbO6The photocatalytic performance of the air purifying agent is improved.
(2) Depositing iron and lanthanum doped chromium oxide on Ba by coprecipitation2In(1-x-y)CexCoyNbO6The surface of the material is prepared by using the synergistic effect of iron and lanthanum and simultaneously leading chromium oxide and Ba to react2In(1-x-y)CexCoyNbO6The heterojunction is formed, so that the effective separation of photo-generated electrons and holes is effectively improved, the effective utilization rate of sunlight is improved, the photocatalytic capacity is improved, and the air purifying agent can efficiently degrade formaldehyde.
(3) By solvothermal method on Ba2In(1-x-y)CexCoyNbO6The carbon layer is coated on the surface of the iron and lanthanum doped chromium oxide, formaldehyde can be adsorbed on the surface of the catalyst by utilizing the adsorption capacity of carbon to formaldehyde, and then the formaldehyde is oxidized and purified by utilizing the oxidizing groups generated by the photocatalyst, so that the purification capacity of the formaldehyde is effectively improved.
(4) The preparation method is simple in preparation process and low in cost, and the prepared product is excellent in performance and beneficial to industrial production.
In conclusion, the air purifying agent prepared by the invention has excellent photocatalytic performance and good purifying capacity for formaldehyde, and is an ideal material for purifying formaldehyde.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
A preparation method of an air purifying agent capable of rapidly degrading formaldehyde comprises the following steps:
(1) ba with purity more than 99.0%2CO3、In2O3、Nb2O5、Ce2O3And Co2O3According to Ba2In0.94Ce0.05Co0.01NbO6Weighing the components according to the stoichiometric ratio, and then placing the components into a ball milling tank for ball milling, wherein a ball milling medium is absolute ethyl alcohol; the ball milling speed is 200rpm, and the ball milling time is 40 min;
(2) after the ball milling is finished, the obtained mixed material is dried for 12 hours in vacuum at the temperature of 60 ℃, grinding is carried out after drying, and the ground powder is sieved by a 220-mesh sieve;
(3) calcining the sieved powder in a muffle furnace at 500 ℃ for 5h, granulating the obtained powder after calcination, preforming the granulated powder by a tablet press, pressing the preformed powder under 15MPa to obtain a blank body, wherein the diameter of the blank body is phi 10mm, the thickness of the blank body is 2mm, sintering the obtained blank body in the muffle furnace at 1150 ℃ for 12h, cooling the blank body to room temperature along with the furnace, and grinding to obtain Ba2In0.94Ce0.05Co0.01NbO6；
(4) Dissolving chromium acetate, ferric nitrate and lanthanum acetate in water to prepare solution, and then dissolving 1g of Ba2In0.94Ce0.05Co0.01NbO6Adding into the above solution, and stirring; slowly dripping 1mol/L potassium hydroxide solution into the solution under the condition of stirring, and controlling the pH value to be 8; aging at 50 deg.C for 16h until precipitation is complete; washing the precipitate, drying at 80 deg.C for 24 hr, and calcining at 700 deg.C for 9 hr to obtain product B; the product B is Ba2In0.94Ce0.05Co0.01NbO6@ iron and lanthanum doped chromium oxide; said Ba2In0.94Ce0.05Co0.01NbO6Chromium oxide doped with iron and lanthanumThe mass ratio of (A) to (B) is 1: 0.5; the modified loading of iron relative to chromium oxide was 2 wt%; the modified loading of lanthanum relative to chromium oxide was 1.5 wt%;
(5) and (3) 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 for 25h at 150 ℃, cooling, taking out, filtering, and performing vacuum freeze drying to obtain a sample.
Example 2
A preparation method of an air purifying agent capable of rapidly degrading formaldehyde comprises the following steps:
(1) ba with purity more than 99.0%2CO3、In2O3、Nb2O5、Ce2O3And Co2O3According to Ba2In0.94Ce0.01Co0.05NbO6Weighing the components according to the stoichiometric ratio, and then placing the components into a ball milling tank for ball milling, wherein a ball milling medium is absolute ethyl alcohol; the ball milling speed is 300rpm, and the ball milling time is 20 min;
(2) after the ball milling is finished, carrying out vacuum drying on the obtained mixed material for 8 hours at 90 ℃, grinding the dried mixed material, 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 after calcination, preforming the granulated powder by a tablet press, pressing the preformed powder under 20MPa to obtain a blank body, wherein the diameter of the blank body is phi 15mm, the thickness of the blank body is 4mm, sintering the obtained blank body in the muffle furnace at 1250 ℃ for 8h, cooling the blank body to room temperature along with the furnace, and grinding to obtain Ba2In0.94Ce0.01Co0.05NbO6；
(4) Chromium chloride, ferric nitrate and lanthanum chloride are dissolved in water to prepare a solution, and then 1g of Ba is added2In0.94Ce0.01Co0.05NbO6Adding into the above solution, and stirring; slowly dripping sodium carbonate solution with the concentration of 1mol/L into the solution under the stirring condition, and controlling the pH value to be 10; toPrecipitating completely, and aging at 70 deg.C for 10 hr; washing the precipitate, drying at 120 deg.C for 10 hr, and calcining at 900 deg.C for 5 hr to obtain product B; the product B is Ba2In0.94Ce0.01Co0.05NbO6@ iron and lanthanum doped chromium oxide; said Ba2In0.94Ce0.01Co0.05NbO6The mass ratio of the iron-doped chromium oxide to the lanthanum-doped chromium oxide is 1: 0.7; the modified loading of iron relative to chromium oxide was 4 wt%; the modified loading of lanthanum relative to chromium oxide was 0.5 wt%;
(5) and (3) 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, then transferring the suspension into a polytetrafluoroethylene high-pressure reaction kettle, performing solvothermal reaction for 15h at 190 ℃, cooling, taking out, filtering, and performing vacuum freeze drying to obtain a sample.
Example 3
A preparation method of an air purifying agent capable of rapidly degrading formaldehyde comprises the following steps:
(1) ba with purity more than 99.0%2CO3、In2O3、Nb2O5、Ce2O3And Co2O3According to Ba2In0.94Ce0.03Co0.03NbO6Weighing the components according to the stoichiometric ratio, and then placing the components into a ball milling tank for ball milling, wherein a ball milling medium is absolute ethyl alcohol; the ball milling speed is 250rpm, and the ball milling time is 30 min;
(2) after the ball milling is finished, the obtained mixed material is dried for 10 hours in vacuum at 70 ℃, grinding is carried out after drying, and the ground powder is sieved by 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 under 18MPa to prepare a blank, wherein the diameter of the blank is phi 12mm, the thickness of the blank is 3mm, sintering the obtained blank in the muffle furnace at 1200 ℃ for 10h, cooling to room temperature along with the furnace, and grinding to obtain Ba2In0.94Ce0.03Co0.03NbO6；
(4) Chromium nitrate, ferric chloride and lanthanum nitrate are dissolved in water to prepare solution, and then 1g of Ba is added2In0.94Ce0.03Co0.03NbO6Adding into the above solution, and stirring; slowly and 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 60 deg.C for 13 hr until precipitation is complete; washing the precipitate, drying at 100 deg.C for 18 hr, and calcining at 800 deg.C for 7 hr to obtain product B; the product B is Ba2In0.94Ce0.03Co0.03NbO6@ iron and lanthanum doped chromium oxide; said Ba2In0.94Ce0.03Co0.03NbO6The mass ratio of the iron-doped chromium oxide to the lanthanum-doped chromium oxide is 1: 0.6; the modified loading of iron relative to chromium oxide was 3 wt%; the modified loading of lanthanum relative to chromium oxide was 1 wt%;
(5) and (3) 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, then transferring the suspension into a polytetrafluoroethylene high-pressure reaction kettle, performing solvothermal reaction for 20h at 170 ℃, cooling, taking out, filtering, and performing vacuum freeze drying to obtain a sample.
Comparative example 1
A preparation method of an air purifying agent capable of rapidly degrading formaldehyde comprises the following steps:
(1) ba with purity more than 99.0%2CO3、In2O3、Nb2O5And Ce2O3According to Ba2In0.94Ce0.06NbO6Weighing the components according to the stoichiometric ratio, and then placing the components into a ball milling tank for ball milling, wherein a ball milling medium is absolute ethyl alcohol; the ball milling speed is 250rpm, and the ball milling time is 30 min;
(2) after the ball milling is finished, the obtained mixed material is dried for 10 hours in vacuum at 70 ℃, grinding is carried out after drying, and the ground powder is sieved by a 200-mesh sieve;
(3) calcining the sieved powder in a muffle furnace at 600 ℃ for 3h to obtain the powderGranulating the obtained powder, preforming the granulated powder by a tablet press, pressing the preformed powder under 18MPa to prepare a blank body, sintering the blank body in a muffle furnace at 1200 ℃ for 10h, cooling the blank body to room temperature along with the furnace, and grinding to obtain Ba2In0.94Ce0.06NbO6；
(4) Chromium nitrate, ferric chloride and lanthanum nitrate are dissolved in water to prepare solution, and then 1g of Ba is added2In0.94Ce0.06NbO6Adding into the above solution, and stirring; slowly and 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 60 deg.C for 13 hr until precipitation is complete; washing the precipitate, drying at 100 deg.C for 18 hr, and calcining at 800 deg.C for 7 hr to obtain product B; the product B is Ba2In0.94Ce0.06NbO6@ iron and lanthanum doped chromium oxide; said Ba2In0.94Ce0.06NbO6The mass ratio of the iron-doped chromium oxide to the lanthanum-doped chromium oxide is 1: 0.6; the modified loading of iron relative to chromium oxide was 3 wt%; the modified loading of lanthanum relative to chromium oxide was 1 wt%;
(5) and (3) 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, then transferring the suspension into a polytetrafluoroethylene high-pressure reaction kettle, performing solvothermal reaction for 20h at 170 ℃, cooling, taking out, filtering, and performing vacuum freeze drying to obtain a sample.
Comparative example 2
A preparation method of an air purifying agent capable of rapidly degrading formaldehyde comprises the following steps:
(1) ba with purity more than 99.0%2CO3、In2O3、Nb2O5And Co2O3According to Ba2In0.94Co0.06NbO6Weighing the components according to the stoichiometric ratio, and then placing the components into a ball milling tank for ball milling, wherein a ball milling medium is absolute ethyl alcohol; the ball milling speed is 250rpm, and the ball milling time is 30 min;
(2) after the ball milling is finished, the obtained mixed material is dried for 10 hours in vacuum at 70 ℃, grinding is carried out after drying, and the ground powder is sieved by 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 under 18MPa to prepare a blank, wherein the diameter of the blank is phi 12mm, the thickness of the blank is 3mm, sintering the obtained blank in the muffle furnace at 1200 ℃ for 10h, cooling to room temperature along with the furnace, and grinding to obtain Ba2In0.94Co0.06NbO6；
(4) Chromium nitrate, ferric chloride and lanthanum nitrate are dissolved in water to prepare solution, and then 1g of Ba is added2In0.94Co0.06NbO6Adding into the above solution, and stirring; slowly and 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 60 deg.C for 13 hr until precipitation is complete; washing the precipitate, drying at 100 deg.C for 18 hr, and calcining at 800 deg.C for 7 hr to obtain product B; the product B is Ba2In0.94Co0.06NbO6@ iron and lanthanum doped chromium oxide; said Ba2In0.94Co0.06NbO6The mass ratio of the iron-doped chromium oxide to the lanthanum-doped chromium oxide is 1: 0.6; the modified loading of iron relative to chromium oxide was 3 wt%; the modified loading of lanthanum relative to chromium oxide was 1 wt%;
(5) and (3) 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, then transferring the suspension into a polytetrafluoroethylene high-pressure reaction kettle, performing solvothermal reaction for 20h at 170 ℃, cooling, taking out, filtering, and performing vacuum freeze drying to obtain a sample.
Comparative example 3
A preparation method of an air purifying agent capable of rapidly degrading formaldehyde comprises the following steps:
(1) ba with purity more than 99.0%2CO3、In2O3、Nb2O5、Ce2O3And Co2O3According to Ba2In0.94Ce0.03Co0.03NbO6Weighing the components according to the stoichiometric ratio, and then placing the components into a ball milling tank for ball milling, wherein a ball milling medium is absolute ethyl alcohol; the ball milling speed is 250rpm, and the ball milling time is 30 min;
(2) after the ball milling is finished, the obtained mixed material is dried for 10 hours in vacuum at 70 ℃, grinding is carried out after drying, and the ground powder is sieved by 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 under 18MPa to prepare a blank, wherein the diameter of the blank is phi 12mm, the thickness of the blank is 3mm, sintering the obtained blank in the muffle furnace at 1200 ℃ for 10h, cooling to room temperature along with the furnace, and grinding to obtain Ba2In0.94Ce0.03Co0.03NbO6；
(4) Dissolving chromium nitrate and ferric chloride in water to prepare solution, and then dissolving 1g of Ba2In0.94Ce0.03Co0.03NbO6Adding into the above solution, and stirring; slowly and 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 60 deg.C for 13 hr until precipitation is complete; washing the precipitate, drying at 100 deg.C for 18 hr, and calcining at 800 deg.C for 7 hr to obtain product B; the product B is Ba2In0.94Ce0.03Co0.03NbO6@ iron doped chromium oxide; said Ba2In0.94Ce0.03Co0.03NbO6The mass ratio of the iron-doped chromium oxide to the iron-doped chromium oxide is 1: 0.6; the modified loading of iron relative to chromium oxide was 4 wt%;
(5) and (3) 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, then transferring the suspension into a polytetrafluoroethylene high-pressure reaction kettle, performing solvothermal reaction for 20h at 170 ℃, cooling, taking out, filtering, and performing vacuum freeze drying to obtain a sample.
Comparative example 4
A preparation method of an air purifying agent capable of rapidly degrading formaldehyde comprises the following steps:
(1) ba with purity more than 99.0%2CO3、In2O3、Nb2O5、Ce2O3And Co2O3According to Ba2In0.94Ce0.03Co0.03NbO6Weighing the components according to the stoichiometric ratio, and then placing the components into a ball milling tank for ball milling, wherein a ball milling medium is absolute ethyl alcohol; the ball milling speed is 250rpm, and the ball milling time is 30 min;
(2) after the ball milling is finished, the obtained mixed material is dried for 10 hours in vacuum at 70 ℃, grinding is carried out after drying, and the ground powder is sieved by 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 under 18MPa to prepare a blank, wherein the diameter of the blank is phi 12mm, the thickness of the blank is 3mm, sintering the obtained blank in the muffle furnace at 1200 ℃ for 10h, cooling to room temperature along with the furnace, and grinding to obtain Ba2In0.94Ce0.03Co0.03NbO6；
(4) Chromium nitrate and lanthanum nitrate are dissolved in water to prepare a solution, and then 1g of Ba is added2In0.94Ce0.03Co0.03NbO6Adding into the above solution, and stirring; slowly and 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 60 deg.C for 13 hr until precipitation is complete; washing the precipitate, drying at 100 deg.C for 18 hr, and calcining at 800 deg.C for 7 hr to obtain product B; the product B is Ba2In0.94Ce0.03Co0.03NbO6@ lanthanum doped chromium oxide; said Ba2In0.94Ce0.03Co0.03NbO6The mass ratio of the lanthanum-doped chromium oxide to the lanthanum-doped chromium oxide is 1: 0.6; the modified loading of lanthanum relative to chromium oxide was 4 wt%;
(5) and (3) 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, then transferring the suspension into a polytetrafluoroethylene high-pressure reaction kettle, performing solvothermal reaction for 20h at 170 ℃, cooling, taking out, filtering, and performing vacuum freeze drying to obtain a sample.
Comparative example 5
A preparation method of an air purifying agent capable of rapidly degrading formaldehyde comprises the following steps:
(1) ba with purity more than 99.0%2CO3、In2O3、Nb2O5、Ce2O3And Co2O3According to Ba2In0.94Ce0.03Co0.03NbO6Weighing the components according to the stoichiometric ratio, and then placing the components into a ball milling tank for ball milling, wherein a ball milling medium is absolute ethyl alcohol; the ball milling speed is 250rpm, and the ball milling time is 30 min;
(2) after the ball milling is finished, the obtained mixed material is dried for 10 hours in vacuum at 70 ℃, grinding is carried out after drying, and the ground powder is sieved by 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 under 18MPa to prepare a blank, wherein the diameter of the blank is phi 12mm, the thickness of the blank is 3mm, sintering the obtained blank in the muffle furnace at 1200 ℃ for 10h, cooling to room temperature along with the furnace, and grinding to obtain Ba2In0.94Ce0.03Co0.03NbO6；
(4) Dissolving chromium nitrate, ferric chloride and lanthanum nitrate in water to prepare a solution, slowly dripping a sodium hydroxide solution with the molar concentration of 1mol/L into the solution under the condition of stirring, and controlling the pH value to be 9; aging at 60 deg.C for 13 hr until precipitation is complete; washing the precipitate, drying at 100 deg.C for 18 hr, and calcining at 800 deg.C for 7 hr to obtain iron and lanthanum doped chromium oxide; then mixing the iron and lanthanum doped chromium oxide with 1g of Ba obtained in the step (3)2In0.94Ce0.03Co0.03NbO6Grinding for 3h to obtain a product B, wherein the product B is Ba2In0.94Ce0.03Co0.03NbO6@ iron and lanthanum doped chromium oxide; said Ba2In0.94Ce0.03Co0.03NbO6The mass ratio of the iron-doped chromium oxide to the lanthanum-doped chromium oxide is 1: 0.6; the modified loading of iron relative to chromium oxide was 3 wt%; the modified loading of lanthanum relative to chromium oxide was 1 wt%;
(5) and (3) 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, then transferring the suspension into a polytetrafluoroethylene high-pressure reaction kettle, performing solvothermal reaction for 20h at 170 ℃, cooling, taking out, filtering, and performing vacuum freeze drying to obtain a sample.
Comparative example 6
A preparation method of an air purifying agent capable of rapidly degrading formaldehyde comprises the following steps:
(1) ba with purity more than 99.0%2CO3、In2O3、Nb2O5、Ce2O3And Co2O3According to Ba2In0.94Ce0.03Co0.03NbO6Weighing the components according to the stoichiometric ratio, and then placing the components into a ball milling tank for ball milling, wherein a ball milling medium is absolute ethyl alcohol; the ball milling speed is 250rpm, and the ball milling time is 30 min;
(2) after the ball milling is finished, the obtained mixed material is dried for 10 hours in vacuum at 70 ℃, grinding is carried out after drying, and the ground powder is sieved by 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 under 18MPa to prepare a blank, wherein the diameter of the blank is phi 12mm, the thickness of the blank is 3mm, sintering the obtained blank in the muffle furnace at 1200 ℃ for 10h, cooling to room temperature along with the furnace, and grinding to obtain Ba2In0.94Ce0.03Co0.03NbO6；
(4) Chromium nitrate, ferric chloride and lanthanum nitrate are dissolved in water to prepare solution, and then 1g of Ba is added2In0.94Ce0.03Co0.03NbO6Adding into the above solution, and stirring; slowly and 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 60 deg.C for 13 hr until precipitation is complete; washing the precipitate, drying at 100 deg.C for 18 hr, and calcining at 800 deg.C for 7 hr to obtain air purifying agent; the air purifying agent is Ba2In0.94Ce0.03Co0.03NbO6@ iron and lanthanum doped chromium oxide; said Ba2In0.94Ce0.03Co0.03NbO6The mass ratio of the iron-doped chromium oxide to the lanthanum-doped chromium oxide is 1: 0.6; the modified loading of iron relative to chromium oxide was 3 wt%; the modified loading of lanthanum relative to chromium oxide was 1 wt%.
The air purifiers obtained in examples 1-3 and comparative examples 1-6 are used in the experiment of degrading formaldehyde by photocatalysis, and the specific experimental steps are as follows:
the photocatalytic degradation performance of formaldehyde was evaluated by using a continuous flow reactor under visible light irradiation at room temperature. 80mg of environment-friendly formaldehyde purification catalyst is weighed and coated in the middle of a square plate with the thickness of 4cm multiplied by 4cm, and the catalyst is placed in the center of a reactor. The proportion of the formaldehyde gas and the air flow is adjusted to obtain the formaldehyde gas with the volume concentration of 30 percent and the flow rate of the air flow is controlled to be 1.0L/min. A300W xenon lamp (equipped with a 420nm cut-off filter to shield ultraviolet radiation) was placed vertically on the reactor. Prior to irradiation, the sample coated square plates were kept in the dark for 200min to reach the adsorption-desorption equilibrium. And after the adsorption is finished, switching on a light source. The concentration of residual formaldehyde at 20min and 40min was monitored by a formaldehyde gas analyzer.
The degradation efficiency of the photocatalyst was calculated according to formula (1):
D＝(C0-Ct)×100％/C0(ii) a In the formula, D represents the photocatalytic degradation efficiency,%; c0Is the initial mass concentration of formaldehyde, mol/L; ctThe mass concentration of formaldehyde after t min of illumination is mol/L.
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 ratio (%) 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 |
Through comparison of the above examples 1-3 with comparative examples 1-6, it can be seen that the air purifying agent prepared by the present application has excellent purifying ability for formaldehyde, can effectively remove formaldehyde by utilizing the synergistic effect between the components, and has a maximum purifying rate of 95.3% in 40min, so that the air purifying agent of the present application is an ideal material for purifying formaldehyde.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of an air purifying agent capable of quickly degrading formaldehyde is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) ba with purity more than 99.0%2CO3、In2O3、Nb2O5、Ce2O3And Co2O3According to Ba2In(1-x-y)CexCoyNbO6Weighing x is 0.01-0.05 and y is 0.01-0.05 in a stoichiometric ratio, and then placing the weighed materials into a ball milling tank for ball milling;
(2) after the ball milling is finished, carrying out vacuum drying on the obtained mixed material, grinding the dried mixed material, and sieving the ground powder;
(3) sieving the mixtureCalcining the powder in a muffle furnace, granulating the calcined powder, preforming the granulated powder by a tablet press, pressing the preformed powder into a blank under the pressure of 15 MPa-20 MPa, sintering the blank in the muffle furnace at the temperature of 1150-1250 ℃ for 8-12h, cooling the blank to room temperature along with the furnace, and grinding to obtain Ba2In(1-x-y)CexCoyNbO6；
(4) Dissolving chromium salt, iron salt and lanthanum salt in water to prepare solution, and then dissolving Ba2In(1-x-y)CexCoyNbO6Adding 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 the precipitation is complete; washing the precipitate, drying and roasting to obtain a product B; the product B is Ba2In(1-x-y)CexCoyNbO6@ iron and lanthanum doped chromium oxide.
(5) And (4) 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 to a polytetrafluoroethylene high-pressure reaction kettle for solvothermal reaction, cooling, taking out, filtering, and performing vacuum freeze drying to obtain a sample.
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 speed is 200-300 rpm, and the ball milling time is 20-40 min.
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 carried out by sieving with a 180-220 mesh sieve; the vacuum drying condition is drying treatment at 60-90 ℃ for 8-12 h.
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 at 500-700 ℃ for 1-5 h; the diameter of the blank is phi 10-15 mm, and the thickness of the blank 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 at 50-70 ℃ for 10-16 h; the drying is drying for 10-24 hours at 80-120 ℃, and the roasting is roasting for 5-9 hours at 700-900 ℃.
6. The method for preparing the air purifying agent capable of rapidly degrading formaldehyde according to claim 1 or 5, wherein the method comprises the following steps: in the step (4), the Ba2In(1-x-y)CexCoyNbO6The mass ratio of the chromium oxide to the iron-and lanthanum-doped chromium oxide is 1: 0.5-0.7; the modified loading capacity of the iron relative to the chromium oxide is 2-4 wt%; the modified loading amount of lanthanum relative to chromium oxide is 0.5-1.5 wt%.
7. The method for preparing the air purifying agent capable of rapidly degrading formaldehyde according to claim 6, 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.
8. 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 reaction condition of solvothermal reaction is that the temperature is kept at 150-190 ℃ for 15-25 h; the ultrasonic dispersion time is 25-35 min.
9. 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 step (5), the ratio of the product B to glucose and absolute ethanol is 1 mg: 20-28 mg: 12-16 mL.
10. An air purifying agent capable of rapidly degrading formaldehyde prepared by the method for preparing an air purifying agent capable of rapidly degrading formaldehyde according to any one of claims 1 to 9.
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