CN114367267B - Mesoporous composite material and preparation method and application thereof - Google Patents
Mesoporous composite material and preparation method and application thereof Download PDFInfo
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- CN114367267B CN114367267B CN202210061442.1A CN202210061442A CN114367267B CN 114367267 B CN114367267 B CN 114367267B CN 202210061442 A CN202210061442 A CN 202210061442A CN 114367267 B CN114367267 B CN 114367267B
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- rare earth
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- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- -1 rare earth metal salt Chemical class 0.000 claims abstract description 50
- 239000013335 mesoporous material Substances 0.000 claims abstract description 41
- 238000001035 drying Methods 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000008247 solid mixture Substances 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 229910052785 arsenic Inorganic materials 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 35
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002808 molecular sieve Substances 0.000 claims description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052773 Promethium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 3
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 3
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 35
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 description 22
- 239000002351 wastewater Substances 0.000 description 14
- 239000011148 porous material Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910000346 scandium sulfate Inorganic materials 0.000 description 5
- QHYMYKHVGWATOS-UHFFFAOYSA-H scandium(3+);trisulfate Chemical compound [Sc+3].[Sc+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O QHYMYKHVGWATOS-UHFFFAOYSA-H 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- 230000008265 DNA repair mechanism Effects 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 208000019423 liver disease Diseases 0.000 description 1
- 230000005976 liver dysfunction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000006540 mitochondrial respiration Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- RHVPCSSKNPYQDU-UHFFFAOYSA-H neodymium(3+);trisulfate;hydrate Chemical compound O.[Nd+3].[Nd+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RHVPCSSKNPYQDU-UHFFFAOYSA-H 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 201000007048 respiratory system cancer Diseases 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
Abstract
The invention provides a mesoporous composite material, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Firstly mixing rare earth metal salt, mesoporous material and alcohol solution, and carrying out solid-liquid separation and first drying to obtain a solid mixture; (2) And (3) carrying out second mixing on the alkali solution and the solid mixture obtained in the step (1), and carrying out second drying after solid-liquid separation to obtain the mesoporous composite material. The rare earth metal salt is reacted with the alkali solution in the mesoporous material to generate the rare earth oxide with oxygen vacancies, the rare earth oxide with oxygen vacancies and the mesoporous material form the composite material, and the mesoporous composite material with selective adsorption is obtained.
Description
Technical Field
The invention belongs to the field of water treatment, and relates to a mesoporous composite material, in particular to a mesoporous composite material, and a preparation method and application thereof.
Background
Arsenic (As) is widely available in the environment, mostly in the form of inorganic arsenic distributed in many minerals; arsenic pollution in the environment is mainly caused by pesticides with arsenide as a main component, metallurgical industry and fossil fuel combustion. In industrial production and metallurgical processes, a large amount of industrial wastewater containing heavy metal elements is discharged, wherein inorganic As can inhibit enzyme activity, inhibit cellular mitochondrial respiration and influence DNA repair mechanisms, and long-term contact of inorganic As can influence a plurality of organs in human and animal bodies, such As liver dysfunction and respiratory system cancers. Arsenic in water environment is mainly As 3+ And As 5+ In the form of weak acids or weak acid salts, most of them are soluble compounds, which are easy to migrate with water. At present, methods for treating arsenic-containing wastewater mainly comprise a precipitation method, an ion exchange method, a biological method, a membrane method, an adsorption method and the like. The precipitation method has perfect arsenic removal technology and wide application, but can generate a large amount of waste residues, cause secondary pollution and has low arsenic removal efficiency. The ion exchange method is suitable for wastewater with small treatment capacity, single composition and high recovery value, but the treatment process is complex, the cost is high, and the industrial production is difficult to realize. The biological method has strict requirements on the surrounding environment, and arsenic in water is treated by the method at present in a starting stage because arsenic has toxicity. The membrane separation method has high treatment cost and is difficult to apply on a large scale. The adsorption method is attractive because of the advantages of simplicity, easy implementation, good removal effect, capability of recycling arsenic in wastewater, no or little secondary pollution to the environment, wide source of adsorption materials, low price, reusability and the like. However, the adsorption material in the prior art has poor selectivity, and can adsorb other coexisting metal ions in water while adsorbing arsenic in water. This will increase subsequent arsenic reclamation recoveryThe processing procedure and the cost of the utilization.
CN103521197a discloses a preparation method of a light rare earth ion imprinted mesoporous molecular sieve adsorbent which can be used for absorbing and recovering rare earth ions in wastewater. According to the invention, ethyl orthosilicate is used as a silicon source to prepare mesoporous molecular sieve precursor suspension. And then coupling the rare earth imprinting ions to induce the aminosilane in the mesoporous molecular sieve precursor liquid to form a rare earth ion-aminosilane polymer-mesoporous molecular sieve compound. Finally, removing the rare earth ions in the compound to obtain the mesoporous molecular sieve adsorbent imprinted by the rare earth ions. However, the preparation method of the light rare earth ion imprinting adsorbent for treating rare earth wastewater is complex, the preparation cost is high, and the adsorption selectivity is poor.
CN104624158A discloses a preparation method of rare earth ion adsorption material and application of selective recovery adsorption rare earth ion. The invention uses maleic anhydride as raw material and mesoporous silicon with high specific surface as supporting material, and the method for preparing rare earth ion adsorption material has selective pair adsorption separation performance of rare earth ions with extremely high value. However, the rare earth ion adsorption material has poor selectivity and complex preparation method, and is difficult to popularize and use on a large scale.
CN106334537a discloses a magnetic mesoporous silica surface imprinting polymer adsorption material and a preparation method thereof. Firstly, modifying magnetic mesoporous silica by adopting a silane coupling agent, then grafting an initiator, and finally preparing the surface imprinting adsorption material by adopting a surface imprinting technology and electron-activated regeneration atom transfer radical polymerization. Similarly, the magnetic mesoporous silica surface imprinted polymer adsorption material has poor selective adsorption capability, and can adsorb other metal ions coexisting in water while adsorbing arsenic in water, so that the recycling cost of subsequent arsenic resources can be increased.
The mesoporous composite material disclosed at present has certain defects, and has the problems of complex preparation method, high preparation cost and poor selective adsorption capacity. Therefore, development of a novel mesoporous composite material and a preparation method thereof are important.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a mesoporous composite material and a preparation method and application thereof, wherein rare earth metal salt is utilized to react with alkali solution in the mesoporous material to generate rare earth oxide with oxygen vacancies, the rare earth oxide with oxygen vacancies and the mesoporous material form the composite material, and the obtained mesoporous composite material with selective adsorption effect has the advantages of high adsorption efficiency, strong selectivity and environmental protection in the preparation method, can be widely used for treating arsenic-containing wastewater, and has better application prospect.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a mesoporous composite material, the method comprising the steps of:
(1) Firstly mixing rare earth metal salt, mesoporous material and alcohol solution, and carrying out solid-liquid separation and first drying to obtain a solid mixture;
(2) And (3) carrying out second mixing on the alkali solution and the solid mixture obtained in the step (1), and carrying out second drying after solid-liquid separation to obtain the mesoporous composite material.
The invention provides a preparation method of a mesoporous composite material, which enables rare earth metal salt to react with alkali solution in the mesoporous material to generate rare earth oxide with oxygen vacancies, and the rare earth oxide with oxygen vacancies and the mesoporous material form the composite material to obtain the mesoporous composite material with selective adsorption. The mesoporous composite material has the advantages of high adsorption efficiency, strong selectivity and environment-friendly preparation method, can be widely used for treating arsenic-containing wastewater, and has good application prospect.
Preferably, the rare earth metal in the rare earth metal salt of step (1) comprises any one or a combination of at least two of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, or lutetium, and may be, for example, a combination of scandium and yttrium, a combination of yttrium and lanthanum, a combination of cerium and praseodymium, a combination of neodymium and promethium, a combination of samarium and europium, a combination of gadolinium and terbium, a combination of holmium and erbium, a combination of ytterbium and lutetium, a combination of scandium, yttrium and lanthanum, or a combination of lanthanum, cerium, praseodymium, and neodymium.
Preferably, the rare earth metal salt in step (1) includes any one or a combination of at least two of sulfate, chlorate, acetate or nitrate, and may be, for example, a combination of sulfate and chlorate, a combination of chlorate and acetate, a combination of acetate and nitrate, a combination of sulfate, chlorate and acetate, or a combination of sulfate, chlorate and acetate.
Preferably, the mesoporous material in the step (1) includes any one or a combination of at least two of a mesoporous molecular sieve, a mesoporous resin, mesoporous carbon, and carbon nanotubes, for example, a combination of a mesoporous molecular sieve and a mesoporous resin, a combination of a mesoporous resin and mesoporous carbon, a combination of mesoporous carbon and carbon nanotubes, or a combination of a mesoporous molecular sieve, a mesoporous resin, and mesoporous carbon.
Preferably, the mass ratio of the rare earth metal salt to the mesoporous material in the step (1) is 1 (1-20), for example, it may be 1:1, 1:3, 1:5, 1:7, 1:10, 1:12, 1:15, 1:17 or 1:20, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The invention limits that the mass ratio of the rare earth metal salt to the mesoporous material is 1 (1-20), when the mass ratio of the rare earth metal salt to the mesoporous material is lower, the content of the rare earth oxide with oxygen vacancy in the mesoporous composite material is lower, which is unfavorable for the adsorption of arsenic ions in the arsenic-containing wastewater, thereby leading to low arsenic removal efficiency; when the mass ratio of the rare earth metal salt to the mesoporous material is higher, excessive rare earth oxide can be generated to block the pore canal of the mesoporous material, the nano-domain limiting effect can not be displayed, and the performance of the mesoporous composite material for selectively adsorbing arsenic is reduced.
Preferably, the alcohol solution in the step (1) is a mixed solution of alcohol and water.
Preferably, the alcohol comprises any one or a combination of at least two of ethanol, methanol or propanol, for example, can be a combination of ethanol and methanol, a combination of methanol and propanol, a combination of ethanol and propanol, or a combination of ethanol, methanol and propanol.
Preferably, the volume fraction of the alcohol in the alcohol solution is 5-20v/v%, for example, 5v/v%, 7v/v%, 10v/v%, 12v/v%, 15v/v%, 17v/v% or 20v/v%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the mass of the alcohol solution is 10-100 times of the sum of the mass of the rare earth metal salt and the mass of the mesoporous material, for example, 10 times, 20 times, 30 times, 40 times, 50 times, 60 times, 70 times, 80 times, 90 times or 100 times, but the alcohol solution is not limited to the recited values, and other non-recited values in the range of the values are equally applicable; when the mass of the alcohol solution is lower than 10 times of the sum of the mass of the rare earth metal salt and the mass of the mesoporous material, the rare earth ions cannot be completely ionized to form corresponding ions to enter the pore canal of the mesoporous material, the generation of the rare earth oxide is affected, when the mass of the alcohol solution is higher than 100 times of the sum of the mass of the rare earth metal salt and the mass of the mesoporous material, the use amount of alcohol and the volume of the whole system are excessively large, the preparation cost is increased, and the rare earth ions entering the pore canal of the mesoporous material can be diluted, so that the generation of the rare earth oxide is affected.
Preferably, the first mixing of step (1) comprises sequentially performing ultrasound and first stirring.
Preferably, the time of the ultrasonic treatment is 0.1-0.5h, for example, 0.1h, 0.2h, 0.3h, 0.4h or 0.5h, but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the rotation speed of the first stirring is 100-500rpm, and the time is 2-6h.
The rotation speed of the first stirring is defined as 100 to 500rpm in the present invention, and may be, for example, 100rpm, 200rpm, 300rpm, 400rpm or 500rpm, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The time of the first stirring is defined as 2 to 6 hours in the present invention, and may be, for example, 2 hours, 3 hours, 4 hours, 5 hours or 6 hours, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the temperature of the first drying in the step (1) is 60-100 ℃ and the time is 6-12h.
The first drying temperature is defined to be 60 to 100 ℃, and may be 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, for example, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the alkaline solution of step (2) is an aqueous solution of a base; the base includes sodium hydroxide and/or potassium hydroxide.
Preferably, the mass fraction of the alkaline solution in the step (2) is 10-30wt%.
Preferably, the mass ratio of the alkaline solution to the rare earth metal salt is (3-15): 1.
Preferably, the second mixing of step (2) comprises a second agitation.
Preferably, the rotation speed of the second stirring is 100-500rpm, and the time is 2-6h.
The rotation speed of the second stirring is defined as 100 to 500rpm in the present invention, and may be, for example, 100rpm, 200rpm, 300rpm, 400rpm or 500rpm, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The second stirring time is defined to be 2-6 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours or 6 hours, but the stirring time is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the temperature of the second stirring is 60-90 ℃, for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable; the second stirring temperature in the second mixing can influence the performance of the mesoporous composite material, when the stirring temperature is low, the reaction of the alkali solution and the rare earth metal salt can be too slow to effectively generate the rare earth oxide, and when the stirring temperature is high, the reaction can be too strong to form the better rare earth oxide.
Preferably, the temperature of the second drying in the step (2) is 60-100 ℃ and the time is 6-12h.
The present invention defines that the second drying temperature is 60-100 ℃, for example 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The invention defines a second drying time of 6-12h, for example 6h, 7h, 8h, 9h, 10h, 11h or 12h, but is not limited to the values recited, and other non-recited values within this range are equally applicable.
Preferably, the drying in the step (2) is carried out to obtain a dried product, and the dried product is washed by deionized water to obtain the mesoporous composite material.
Preferably, as a preferred technical scheme of the preparation method according to the first aspect, the preparation method comprises the following steps:
(1) Mixing rare earth metal salt and mesoporous material with the mass ratio of (1-20) (20-2100) with alcohol solution, performing ultrasonic treatment for 0.1-0.5h, wherein the volume fraction of the alcohol is 5-20v/v%, stirring for 2-6h at the rotating speed of 100-500rpm, and drying for 6-12h at the temperature of 60-100 ℃ to obtain a solid mixture;
(2) Mixing the alkali solution with the mass ratio of (3-15) being 1 with the solid mixture obtained in the step (1), wherein the mass fraction of the alkali is 10-30wt%, stirring the mixture for 2-6h at the speed of 100-500rpm at the temperature of 60-90 ℃, and drying the mixture for 6-12h at the temperature of 60-100 ℃ to obtain the mesoporous composite material.
In a second aspect, the present invention provides a mesoporous composite material obtained by the preparation method of the first aspect.
In a third aspect, the present invention provides the use of a mesoporous composite as described in the second aspect for adsorption arsenic removal.
Compared with the prior art, the invention has the beneficial effects that:
the invention utilizes rare earth metal salt to react with alkali solution in mesoporous material to generate rare earth oxide with oxygen vacancy, the rare earth oxide with oxygen vacancy and mesoporous material form composite material, and the obtained mesoporous composite material with selective adsorption effect; the mesoporous composite material has the advantages of high adsorption efficiency and environment-friendly preparation method, can be widely used for treating arsenic-containing wastewater, and has large-scale industrialized production and application potential; compared with rare earth oxides produced in a commercial way, the mesoporous composite material has stronger selective adsorption effect and stronger arsenic removal effect on wastewater.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of a mesoporous composite material, which comprises the following steps:
(1) Scandium sulfate with the mass ratio of 1:10:500 and mesoporous molecular sieve MCM-48 with the aperture of 2.5-3nm are mixed with aqueous solution of ethanol with the volume fraction of 20v/v% and are ultrasonically treated for 0.4h, and then stirred for 3h at the rotating speed of 100rpm, and dried for 10h at the temperature of 80 ℃ to obtain a solid mixture;
(2) Mixing an aqueous solution of sodium hydroxide in a mass ratio of 9:1 with the solid mixture obtained in step (1), the mass fraction of sodium hydroxide being 25% by weight and rotating at 100rpm at 80 DEG C
Stirring for 3h at a high speed, and drying for 10h at 80 ℃ to obtain the mesoporous composite material.
Example 2
The embodiment provides a preparation method of a mesoporous composite material, which comprises the following steps:
(1) Mixing yttrium chloride with the mass ratio of 1:15:500 and mesoporous molecular sieve SAB-15 with the pore diameter of 5-6nm with aqueous solution of methanol, carrying out ultrasonic treatment for 0.5h, stirring for 4h at the rotating speed of 200rpm, and drying for 12h at 90 ℃ to obtain a solid mixture;
(2) Mixing an aqueous solution of potassium hydroxide with the mass ratio of 12:1 with the solid mixture obtained in the step (1), wherein the mass fraction of the potassium hydroxide is 15wt%, stirring the mixture at 60 ℃ for 4 hours at a rotating speed of 200rpm, and drying the mixture at 90 ℃ for 12 hours to obtain the mesoporous composite material.
Example 3
The embodiment provides a preparation method of a mesoporous composite material, which comprises the following steps:
(1) Mixing cerium nitrate and mesoporous molecular sieve MCM-41 with the pore diameter of 5nm in a mass ratio of 1:20:2100 with an alcohol solution, performing ultrasonic treatment for 0.1h, stirring for 5h at a rotating speed of 300rpm, and drying for 6h at 100 ℃ to obtain a solid mixture;
(2) Mixing an alkali solution with the mass ratio of 15:1 with the solid mixture obtained in the step (1), wherein the mass fraction of the alkali is 10wt%, stirring for 5 hours at 65 ℃ at the rotating speed of 300rpm, and drying for 6 hours at 100 ℃ to obtain the mesoporous composite material.
Example 4
The embodiment provides a preparation method of a mesoporous composite material, which comprises the following steps:
(1) Mixing neodymium sulfate and mesoporous carbon with the pore diameter of 3-10nm in a mass ratio of 1:5:500 with aqueous solution of propanol, performing ultrasonic treatment for 0.3h, stirring for 2h at a rotating speed of 500rpm, and drying for 9h at 70 ℃ to obtain a solid mixture;
(2) Mixing a sodium hydroxide solution with the mass ratio of 3:1 with the solid mixture obtained in the step (1), wherein the mass fraction of the sodium hydroxide is 30wt%, stirring at the temperature of 85 ℃ for 2 hours at the rotating speed of 500rpm, and drying at the temperature of 70 ℃ for 9 hours to obtain the mesoporous composite material.
Example 5
The embodiment provides a preparation method of a mesoporous composite material, which comprises the following steps:
(1) Mixing gadolinium chloride with the mass ratio of 1:1:20 and mesoporous molecular sieve SAB-3 with the pore diameter of 2.8-3.8 with aqueous solution of ethanol, and carrying out ultrasonic treatment for 0.2h, wherein the volume fraction of the ethanol is 10v/v%, stirring for 6h at the rotating speed of 400rpm, and drying for 7h at the temperature of 60 ℃ to obtain a solid mixture;
(2) Mixing a sodium hydroxide solution with the mass ratio of 6:1 with the solid mixture obtained in the step (1), wherein the mass fraction of the sodium hydroxide is 20wt%, stirring at 75 ℃ for 6 hours at a rotating speed of 400rpm, and drying at 60 ℃ for 7 hours to obtain the mesoporous composite material.
Example 6
The present example provides a method for preparing a mesoporous composite material, which is the same as example 1 except that scandium sulfate in step (1), mesoporous molecular sieve MCM-48 with aperture of 2.5-3nm, and aqueous solution of ethanol in a mass ratio of 1:0.5:500.
Example 7
The present example provides a method for preparing a mesoporous composite material, which is the same as example 1 except that scandium sulfate in step (1), mesoporous molecular sieve MCM-48 with aperture of 2.5-3nm, and aqueous solution of ethanol in a mass ratio of 1:25:500.
Example 8
The present example provides a method for preparing a mesoporous composite material, which is the same as example 1 except that scandium sulfate in step (1), mesoporous molecular sieve MCM-48 with aperture of 2.5-3nm, and aqueous solution of ethanol in a mass ratio of 1:10:80.
Example 9
The present example provides a method for preparing a mesoporous composite material, which is the same as example 1 except that scandium sulfate in step (1), mesoporous molecular sieve MCM-48 with aperture of 2.5-3nm, and aqueous solution of ethanol in a mass ratio of 1:10:1500.
Example 10
This example provides a method for preparing a mesoporous composite material, which is the same as example 1 except that in step (2), stirring is performed at 40℃and a rotational speed of 100rpm for 3 hours.
Example 11
This example provides a method for preparing a mesoporous composite material, which is the same as example 1 except that in step (2), stirring is performed at 120℃and a rotational speed of 100rpm for 3 hours.
Comparative example 1
The present example provides a method for preparing a mesoporous composite material, which is the same as example 1 except that mesoporous molecular sieve MCM-48 with aperture of 2.5-3nm in step (1) is replaced with macroporous molecular sieve USY with aperture of 60-70 nm.
Comparative example 2
The present example provides a method for preparing a mesoporous composite material, which is the same as example 1 except that mesoporous molecular sieve MCM-48 with pore diameter of 2.5-3nm in step (1) is replaced with microporous molecular sieve ZSM-5 with pore diameter of 0.5-0.6 nm.
The mesoporous composites obtained by the preparation methods of examples 1 to 11 and comparative examples 1 and 2 were tested as follows:
300mg of the mesoporous composite materials prepared in examples 1 to 11 and comparative examples 1 and 2 were weighed and placed in a conical flask, 150mL of a solution containing As, cd, co, cr and Pb and having an ion concentration of 10mg/L was added to the conical flask, the solution was sonicated in an ultrasonic cleaner for 1min, and then shaken on a constant-temperature shaking table with a shaking rate of 200rpm for 1h, the solution in the conical flask was sampled and filtered, and then the ion solubility in the solution was measured by using an ICP test, to obtain As, cd, co, cr and Pb removal rates as shown in Table 1.
TABLE 1
From the data of table 1:
(1) The mesoporous composite material with selective adsorption effect obtained in the embodiments 1-5 has the advantages of high adsorption efficiency, strong selectivity and environmental protection of the preparation method, can be widely used for treating arsenic-containing wastewater, and has good application prospect;
(2) As can be seen from comparison of examples 1 and examples 6 and 7, the mass ratio of the rare earth metal salt to the mesoporous material in the present invention affects the performance of the mesoporous composite material, and when the mass ratio of the rare earth metal salt to the mesoporous material is lower, the content of the rare earth oxide with oxygen vacancies in the mesoporous composite material is lower, which is unfavorable for adsorption of arsenic ions in arsenic-containing wastewater, thereby reducing the arsenic removal efficiency; when the mass ratio of the rare earth metal salt to the mesoporous material is higher, excessive rare earth oxide can be generated to block the pore canal of the mesoporous material, the nano-domain limiting effect can not be displayed, and the performance of selectively adsorbing arsenic of the mesoporous composite material is reduced;
(3) As can be seen from comparison of examples 1 and 8 and 9, the mass ratio of the mass of the alcohol solution to the sum of the mass of the rare earth metal salt and the mass of the mesoporous material in the invention affects the performance of the mesoporous composite material, when the mass of the alcohol solution is lower than 10 times of the sum of the mass of the rare earth metal salt and the mass of the mesoporous material, the rare earth ions cannot be completely ionized to form corresponding ions to enter the pore channels of the mesoporous material, the generation of rare earth oxide is affected, when the mass of the alcohol solution is higher than 100 times of the sum of the mass of the rare earth metal salt and the mass of the mesoporous material, the usage amount of alcohol and the volume of the whole system are excessively large, the preparation cost is increased, and the rare earth ions entering the pore channels of the mesoporous material are diluted, so that the generation of the rare earth oxide is affected;
(4) As can be seen from comparison of example 1 with examples 10 and 11, the second stirring temperature in the second mixing in the present invention affects the performance of the mesoporous composite material, and when the stirring temperature is low, the reaction between the alkali solution and the rare earth metal salt is too slow to effectively generate the rare earth oxide, and when the stirring temperature is high, the reaction is too strong to form the better rare earth oxide;
(5) As can be seen from the comparison of the embodiment 1 with the comparative examples 1 and 2, the mesoporous composite material with higher selectivity can be obtained by adopting the mesoporous material, when the mesoporous material is replaced by the microporous material, the mesoporous composite material is easy to be blocked, and when arsenic is adsorbed to a certain degree, the adsorption cannot be continued, so that the adsorption efficiency of the mesoporous composite material is low; when the mesoporous material is replaced by a macroporous material, the specific surface area of the mesoporous composite material is reduced, the contact area of the mesoporous composite material and the waste liquid containing the arsenic solution is reduced, and the adsorbed arsenic is easy to separate from the mesoporous adsorption material, so that the adsorption efficiency is reduced.
In summary, the rare earth metal salt is reacted with the alkali solution in the mesoporous material to generate the rare earth oxide with oxygen vacancy, and the rare earth oxide with oxygen vacancy and the mesoporous material form the composite material, so that the mesoporous composite material with selective adsorption effect is obtained; the mesoporous composite material has the advantages of high adsorption efficiency and environment-friendly preparation method, can be widely used for treating arsenic-containing wastewater, and has large-scale industrialized production and application potential; compared with rare earth oxides produced in a commercial way, the mesoporous composite material has stronger selective adsorption effect and stronger arsenic removal effect on wastewater.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (21)
1. The application of the mesoporous composite material is characterized in that the mesoporous composite material is used for adsorbing and removing arsenic, and the preparation method of the mesoporous composite material comprises the following steps:
(1) Firstly mixing rare earth metal salt, mesoporous material and alcohol solution, and carrying out solid-liquid separation and first drying to obtain a solid mixture; the mass ratio of the rare earth metal salt to the mesoporous material is 1 (5-20);
(2) And (3) carrying out second mixing on the alkali solution and the solid mixture obtained in the step (1), and carrying out second drying after solid-liquid separation to obtain the mesoporous composite material.
2. The use according to claim 1, wherein the rare earth metal in the rare earth metal salt of step (1) comprises any one or a combination of at least two of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, or lutetium.
3. The use according to claim 1, wherein the rare earth metal salt of step (1) comprises any one or a combination of at least two of a sulfate, a chlorate, an acetate or a nitrate.
4. The use of claim 1, wherein the mesoporous material of step (1) comprises any one or a combination of at least two of mesoporous molecular sieves, mesoporous resins, mesoporous carbon, or carbon nanotubes.
5. The use according to claim 1, wherein the alcoholic solution of step (1) is a mixture of alcohol and water.
6. The use according to claim 5, wherein the alcohol comprises any one or a combination of at least two of ethanol, methanol or propanol.
7. Use according to claim 1, characterized in that the volume fraction of alcohol in the alcohol solution is 5-20v/v%.
8. The use according to claim 1, wherein the mass of the alcoholic solution is 10-100 times the sum of the mass of the rare earth metal salt and the mass of the mesoporous material.
9. The use of claim 1, wherein the first mixing of step (1) comprises sequentially performing ultrasound and first agitation.
10. The use according to claim 9, wherein the time of the ultrasound is 0.1-0.5h.
11. The use according to claim 9, wherein the first stirring is carried out at a speed of 100-500rpm for a period of 2-6 hours.
12. The use according to claim 1, wherein the first drying in step (1) is carried out at a temperature of 60-100 ℃ for a time of 6-12 hours.
13. The use according to claim 1, wherein the alkaline solution of step (2) is an aqueous solution of a base; the base includes sodium hydroxide and/or potassium hydroxide.
14. The use according to claim 1, characterized in that the mass fraction of alkali in the alkaline solution in step (2) is 10-30wt%.
15. The use according to claim 1, wherein the mass ratio of the alkaline solution to the rare earth metal salt is (3-15): 1.
16. The use of claim 1, wherein the second mixing of step (2) comprises a second agitation.
17. The use according to claim 16, wherein the second stirring is carried out at a speed of 100-500rpm for a period of 2-6 hours.
18. The use according to claim 16, wherein the temperature of the second agitation is 60-90 ℃.
19. The use according to claim 1, wherein the second drying in step (2) is carried out at a temperature of 60-100 ℃ for a time of 6-12 hours.
20. The use according to claim 1, wherein the drying in step (2) results in a dried product, which is washed with deionized water to obtain the mesoporous composite.
21. The use according to claim 1, wherein the preparation method comprises the steps of:
(1) Mixing rare earth metal salt and mesoporous material with the mass ratio of (1-20) (20-2100) with alcohol solution, performing ultrasonic treatment for 0.1-0.5h, wherein the volume fraction of the alcohol is 5-20v/v%, stirring for 2-6h at the rotating speed of 100-500rpm, and drying for 6-12h at the temperature of 60-100 ℃ to obtain a solid mixture;
(2) Mixing the alkali solution with the mass ratio of (3-15) being 1 with the solid mixture obtained in the step (1), wherein the mass fraction of the alkali is 10-30wt%, stirring the mixture for 2-6h at the speed of 100-500rpm at the temperature of 60-90 ℃, and drying the mixture for 6-12h at the temperature of 60-100 ℃ to obtain the mesoporous composite material.
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