CN100584447C - Organic phosphonium transition metal salt graded hole material preparing method and the application - Google Patents
Organic phosphonium transition metal salt graded hole material preparing method and the application Download PDFInfo
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- CN100584447C CN100584447C CN200710056505A CN200710056505A CN100584447C CN 100584447 C CN100584447 C CN 100584447C CN 200710056505 A CN200710056505 A CN 200710056505A CN 200710056505 A CN200710056505 A CN 200710056505A CN 100584447 C CN100584447 C CN 100584447C
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Abstract
The invention relates to a preparation for multiporous material, especially a process for preparing organic and inorganic hetero-material with multiporous structure and application thereof. The hetero-material is a transition metal phosphonate with different organic phosphonic acid groups combined on the surface and skeleton of mesoporous and macroporous structure, wherein, the weight percent of the organic phosphonic acid P is 1% to 17%, and the transition metals can be selected from Ti salt, Al salt, Zr salt, etc. The hetero-material is directly synthesized by hydrothermal synthesis and can be used for heavy metal ion absorption with good absorption effect, the invention is provided with simple equipments and moderate synthesis conditions, and the raw materials is available, accordingly, the multiporous material preparing process is suitable for large-scale production.
Description
Technical field
The present invention relates to the preparation of multilevel hole material, particularly a kind of preparation method and application of organic phosphonium transition metal salt porous material.Novel organic-inorganic heterozygosis metal oxide and phosphonate (salt such as titanium, aluminium, zirconium) material is used for heavy metal ion adsorbed.
Background technology
Porous material, as molecular sieve etc., because its big specific surface, orderly pore passage structure is subjected to paying close attention to widely always, and is attempted being applied to research fields such as catalysis, absorption, separation and sensor.CN1387942A discloses a kind of preparation method of high adsorption titanium silicate, and adopting ethyl orthosilicate is the silicon source, and polyethylene glycol (PEG-600) is an additive, and substep has synthesized a kind of titanium silicate with nano-pore structure.This method must strictly be controlled hydrolysising condition, and generated time is long, complex steps, and condition harshness and product hydrothermally stable type are poor.The organic-inorganic heterozygosis mesoporous material of Chu Xianing has been owing to after organic functional group introduces inorganic hole material with step copolymerization or a grafting, not only improved the hydrothermally stable of hole material in recent years, and, also strengthened its counterweight Adsorption Properties for Metal Ions greatly.CN1727061A discloses a kind of preparation method of adsorbent for heavy metal, and it is the template agent that this method adopts non-ionic polyalcohol (Brij-76) and block copolymer P123, organosilan (MeO)
3SiCH
2CH
2Si (MeO)
3(MeO)
3SiCH
2CH
2CH
2SH is the silicon source, synthesizes to have Large ratio surface, and the organic/inorganic heterozygosis mesoporous material of pore structure is used for adsorption of metal ions in order, obtains result preferably.Yet the preparation of the mesopore silicon oxide of this organic-inorganic heterozygosis all is to adopt organosilan as precursor usually, and polymer and copolymer are template, and not only raw material is not easy to obtain, and costs an arm and a leg, and has also limited organic functional group and hole wall Material Selection simultaneously.And have macroporous/mesoporous hierarchical porous structure concurrently, and thicker hole wall can not only be provided, increase mechanical strength, and the hole dimension of super large effectively improves the mass transfer of fluid in the duct, increase metal ion diffusion velocity; Wherein mesoporous wall provides than Large ratio surface for the activated centre.Porous material has shown many potential character at aspects such as absorption, catalysis, ion-exchanges.Metal oxide and phosphate cellular material that phosphoric acid is modified receive much concern always, and the organic phospho acid salt material is the focus of whole world research at present especially.But at present only several pieces of aluminium oxide and vanadium oxide material of modifying about organic phospho acid all only are confined to mesoporous scope.We synthesize the metal oxide of organic phospho acid modification and the mesopore-macropore classification hole material of organic phosphonate has more superior performance in heavy metal ion adsorbed performance with to the present mesoporous and multilevel hole material of reporting of the photocatalytic activity ratio of organic dyestuff degraded.
Summary of the invention
The object of the present invention is to provide a kind of heavy metal ion adsorbed organic-inorganic heterozygosis porous material and preparation method thereof that is used for, can overcome the shortcoming of prior art, synthesis device of the present invention is simple, easy to operate, condition is loose, of low pollution, save the energy, raw material is simple and easy to, and is with low cost.And the adsorbing metal ions performance is efficient, high stable.
For above-mentioned purpose, the present invention adopts butyl titanate, aluminium secondary butylate, zirconium iso-propoxide etc. as source metal and organic phospho acid and organic phosphonate ATMP, EDTMPS, and DTPMPA, HEDP, the method for BHMTPMPA cohydrolysis is synthesized organic/inorganic heterozygosis porous material.
The present invention is to provide a kind of preparation method who contains the phosphonate radical organic/inorganic heterozygosis mesopore-macropore multilevel hole material of different organic groups, concrete steps are as follows:
1. template agent, organic phospho acid (salt), hydrochloric acid, water and ethanol dissolving are formed settled solution A, the template agent of selecting for use is polyethers copolymer such as C
16EO
10, block copolymer EO
30PO
34, P123, and polyol beta-schardinger dextrin-.
2. slowly stir down, (Ti (BuOT)) is added drop-wise in the solution A with butyl titanate, and the each component mass ratio is the titanium source: the template agent: organic phospho acid (salt): hydrochloric acid: alcohol: water=(1.702-3.404): (0-0.320): (0.997-3.060): (0-0.37): (0-20): (30-50); The 24-48h that stirs the mixture under 0 ℃～50 ℃ changes mixture in the reactor over to, in 60 ℃～90 ℃ following crystallization 12-120h;
3. product is washed the back after filtration in room temperature-80 ℃ drying;
The agent of product template with ethanol in 78 ℃ down extraction 96 hours or more than;
5. above-mentioned material is all to Pd
2+, Cu
2+, Cd
2+, Cr
2+, Zn
2+, Hg
2+, Fe
2+Etc. heavy metal ion suction-operated is preferably arranged; Especially, under the low concentration, still has very high selection adsorptivity.
Preparation method of the present invention has following advantage:
1. can select multiple cheapness, nontoxic source metal as required for use, not use any surfactant directly synthetic, help environmental protection;
2. can be by adopting the cheap easily template agent of degraded, or do not use modulation duct size and specific surface under the condition of any template agent, and a step synthesis of organo-phosphines hydrochlorate;
3. simple to operate, can in a big way, change organic phosphine content, and the position of organic phospho acid in pore structure, improve the adsorption of metal ions performance.
The present invention has following advantage:
1. Zhi Bei material has high mechanical stability and hydrothermal stability;
2. Zhi Bei material organic phospho acid adsorption site and titanium be with covalent bonds, difficult drop-off;
3. can be by the material counterweight Adsorption Properties for Metal Ions of control preparation methods modulation preparation;
4. Zhi Bei material can reuse, and it is simple to regenerate, repeat repeatedly after, absorption property is still kept.
The specific embodiment
Embodiment 1:
Under stirring at room, 1.03g organic phospho acid HEDP is added the mixed solution of 30ml ethanol and 15ml water, be stirred to the solution clarification after, slowly drip Ti (BuOT) 1.702g, continue to stir 24h at a slow speed, in 80 ℃ of crystallization 24h.Product after filtration, after the washing, drying, promptly obtain organic/inorganic heterozygosis porous material.Sample is through XRD, N
2Absorption/desorption, SEM, TEM, XPS, NMR characterize and turn out to be the organic titanium phosphonate with macroporous/mesoporous structure.The BET specific area of material is 257m
2/ g; Pore volume is 0.052cm
3/ g; Macropore diameter is 50-200nm; Mesoporous pore size is 2.44nm.Wherein P content is 16.54%.
Embodiment 2:
Adopt the preparation process of embodiment 1, add 3.06g organic phosphonate EDTMPS and 3.404g Ti (BuOT), stirring at room 24h is in 80 ℃ of crystallization 24h.The BET specific area of the material that obtains is 15m
2/ g; Pore volume is 0.074cm
3/ g; Macropore diameter is 50-1000nm; Mesoporous pore size is 2.48nm.Wherein P content is 5.38%.
Embodiment 3:
Adopt the preparation process of embodiment 2, the BET specific area of the material that the dense HCl of adding 0.37g obtains is 86m
2/ g; Pore volume is 0.074cm
3/ g; Macropore diameter is 50-2000nm; Mesoporous pore size is 3.22nm and 8.22nm.
Embodiment 4:
Adopt the preparation process of embodiment 1, ATMP 0.997g adds the mixed solution and the 1.702gTi (BuOT) of 30ml ethanol and 15ml water, stirs 24h fast, 80 ℃ of crystallization 24h.The BET specific area of the material that obtains is 132m
2/ g; Pore volume is 0.011cm
3/ g; Macropore diameter is that the mesoporous pore size of 50-1000nm is 1.47nm and 1.95nm.
Embodiment 5:
Adopt the preparation process of embodiment 1, BHMTPMPA 1.37g adds the mixed solution and the 1.702g Ti (BuOT) of 45ml ethanol and 15ml water, stirs 24h at a slow speed, 80 ℃ of crystallization 24h.The BET specific area of the material that obtains is 132m
2/ g; Pore volume is 0.13cm
3/ g; Macropore diameter is 100-500nm; Mesoporous pore size is 2.06nm.
Embodiment 6:
Adopt the preparation process of embodiment 1, ATMP1.37g adds the mixed solution of 30ml ethanol and 15ml water, adds 0.32g diblock (EO)
30(PO)
34With 1.702g Ti (BuOT), stir 24h at a slow speed, 80 ℃ of crystallization 24h.Extract 96h with the 100mL absolute ethyl alcohol in 78 ℃.The BET specific area of the material that obtains is 288m
2/ g; Pore volume is 0.19cm
3/ g; Macropore diameter is 50-1000nm; Mesoporous pore size is 1.48nm and 5.12nm.
Embodiment 7:
Adopt the preparation process of embodiment 1, BHMTPMPA1.37g adds the mixed solution of 30ml ethanol and 15ml water, adds 0.32g diblock (EO)
30(PO)
34With 1.702g Ti (BuOT), stir 24h at a slow speed, 80 ℃ of crystallization 24h.Extract 96h with the 100mL absolute ethyl alcohol in 78 ℃.The BET specific area of the material that obtains is 62m
2/ g; Pore volume is 0.15cm
3/ g; Macropore diameter is 200-1000nm; Mesoporous pore size is 20.91nm.
Embodiment 8:
Adopt the preparation process of embodiment 1, ATMP 0.997g adds the mixed solution of 30ml ethanol and 15ml water, adds 0.32g diblock (EO)
30(PO)
34With 1.702g Ti (BuOT), stir 24h fast, 80 ℃ of crystallization 24h.The BET specific area of the material that obtains is 316m
2/ g; Pore volume is 0.2312cm
3/ g; Macropore diameter is 100-1000nm; Mesoporous pore size is 1.74nm.
Embodiment 9:
Adopt the preparation process of embodiment 1, BHMTPMPA 1.37g adds the mixed solution of 45ml ethanol and 15ml water, adds 0.1135g β-CD and 1.702g Ti (BuOT), stirs 24h at a slow speed, 80 ℃ of crystallization 24h.The BET specific area of the material that obtains is 65m
2/ g; Pore volume is 0.098cm
3/ g; Macropore diameter is 200-2500nm; Mesoporous pore size is 2.45nm.
Embodiment 10:
Adopt the preparation process of embodiment 1, ATMP 1.495g adds the mixed solution of 50ml water, and the 1.23g aluminium secondary butylate stirs 24h at a slow speed, 80 ℃ of crystallization 24h.The BET specific area of the material that obtains is 93m
2/ g; Pore volume is 0.238cm
3/ g; Macropore diameter is 100-2000nm; Mesoporous pore size is 2.68nm.
Embodiment 11:
The organic/inorganic heterozygosis porous organic titanium phosphonate 0.0100g of embodiment 1,2,4,8 preparation is put into 50mL respectively contain 10,20,30ppm Pd
2+, Cu
2+, Cd
2+The aqueous solution; Stir; Centrifugal; AAS is surveyed effects of ion concentration.The results are shown in Table 1
Table 1.
Embodiment 12:
The organic/inorganic heterozygosis porous organic titanium phosphonate 0.0100g of embodiment 2 preparation is put into 50mL respectively contain 30ppm Cu
2+(Pd
2+, Cd
2+) the aqueous solution; Stir; Centrifugal; AAS is surveyed effects of ion concentration, behind hydrochloric acid flush away adion, surveys again, and adsorption experiment is 9 times repeatedly.The results are shown in subordinate list 2
Table 2.
| The absorption number of times | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| Adsorption rate (%) | 80.45 | 77.72 | 77.27 | 76.82 | 70.91 | 65.45 | 63.18 | 57.72 | 55.91 |
Embodiment 13
The organic/inorganic heterozygosis porous organic titanium phosphonate 0.0100g of embodiment 2 preparation is put into 50mL contain 30ppm Pd
2+, (Cu
2+, Cd
2+) the aqueous solution; Stir; Centrifugal.The ICP method is surveyed the ion concentration in solution and the solid.The results are shown in Table 3
Table 3.
Claims (3)
1. an organic phosphonium transition metal salt porous material is characterized in that it has mesopore-macropore classification pore structure, combines the phosphonate of different organic groups in surface and skeleton, and wherein organic phospho acid P weight percentage is 1wt%-17wt%;
Described transition metal salt is the phosphonate of titanium, zirconium, to heavy metal ion adsorbed demonstration high adsorption; Described organic phosphonium transition metal salt porous material prepares by following step:
A), or do not add the template agent only with organic phospho acid or organic phosphonate and water/alcohol mixed solvent formation settled solution A with organic phospho acid or organic phosphonate and water/alcohol mixed solvent and template agent formation settled solution A; The template agent is copolyether C
16EO
10, block copolymer EO
30PO
34, P123, and polyol beta-schardinger dextrin-;
B) stirring slowly is added dropwise to settled solution A with source metal butyl titanate, zirconium iso-propoxide down, stirs the mixture under 0-50 ℃ 24-48 hour, the gained mixture is changed in the reactor, in 60-90 ℃ of crystallization 12-120h;
C) product after filtration, washing back is in room temperature-80 ℃ drying;
D) the template agent of product with ethanol in 78 ℃ of extractions 96 hours or more than, obtain the organic phosphonium transition metal salt of target product mesopore-macropore hierarchical porous structure, wherein addition is that 1 gram product adds 100mL ethanol; When if the template agent that adds among the step a is beta-schardinger dextrin-, or when not adding the template agent, need not this extraction step.
2. according to the described a kind of organic phosphonium transition metal salt porous material of claim 1, it is characterized in that described organic phospho acid and organic phosphonate are ATMP ATMP, ethylene diamine tetra methylene phosphonic acid sodium EDTMPS, diethylenetriamine pentamethylenophosphonic acid sodium DTPMPA, hydroxy ethylene diphosphonic acid HEDP or 1,6-hexylidene triamine pentamethylene phosphonic acids BHMTPMPA.
3. a kind of organic phosphonium transition metal salt porous material according to claim 1 is characterized in that, when the source metal that adds among the step b was butyl titanate, constituent mass was than being the titanium source: organic phospho acid=0.772: 1-0.515: 1.
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