CN101475589A - Preparation and use of mesoporous-macroporous structure aluminum organophosphonate material - Google Patents
Preparation and use of mesoporous-macroporous structure aluminum organophosphonate material Download PDFInfo
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- CN101475589A CN101475589A CNA2009100677270A CN200910067727A CN101475589A CN 101475589 A CN101475589 A CN 101475589A CN A2009100677270 A CNA2009100677270 A CN A2009100677270A CN 200910067727 A CN200910067727 A CN 200910067727A CN 101475589 A CN101475589 A CN 101475589A
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Abstract
The invention belongs to the field of porous material preparation, in particular to the preparation method and uses of an organic-inorganic combined material with a mesopore-macropore structure. The material is aluminium phosphate material which has a mesopore-macropore structure and different organic phosphonate groups, wherein the weight percentage of an organic phosphoric acid P is 7.55 to 19.68 weight percent. The material is directly synthesized by a hydrothermal synthesis method. The product is used for absorbing biological macromolecular lysozymes in water with better effect. The method has the advantages of simple equipment, mild synthesis conditions, easily available raw material and suitability for industrial production.
Description
Technical field
The present invention relates to the preparation of classification pore structure material, particularly a kind of preparation method and application with organic phospho acid aluminum of mesopore-macropore structure.Novel mesopore-macropore structure phosphonic acids aluminum is used for the absorption of organism in water macromole N,O-Diacetylmuramidase.
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 transmitter.CN1387942A discloses a kind of preparation method of high absorbability titanium silicate, and adopting tetraethoxy is the silicon source, and polyoxyethylene glycol (PEG-600) is an additive, stepwise synthesis a kind of titanium silicate with nano-pore structure.The strict control hydrolysis condition of this method palpus, generated time is long, complex steps, condition harshness and product hydrothermally stable type are poor.The organic-inorganic heterozygosis mesoporous material of Chu Xianing is because after organic functional group introduces inorganic hole material with step copolymerization or a grafting in recent years, not only improved the hydrothermally stable of hole material, and, also strengthened it greatly and underwater gold has been belonged to the absorption property of ion and biomolecules.CN1727061A discloses a kind of preparation method of adsorbent for heavy metal, and it is template that this method adopts non-ionic polyalcohol (Brij-76) and segmented copolymer P123, organosilane (MeO)
3SiCH
2CH
2Si (MeO)
3(MeO)
3SiCH
2CH
2CH
2SH is the silicon source, synthesizes to have large specific 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 organosilane as precursor usually, and polymkeric substance and multipolymer 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.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 only bibliographical information about the organic phosphonate porous material only is confined to the mesoporous material scope of phosphonic acids aluminium, phosphonic acids titanium or phosphonic acids vanadium at present, and employed organic phospho acid kind is very limited, as paper Chem.Mater.2003,15,3742, Chem.Mater.2005,17,337, Chem.Mater.2005,17,5521, Chem.Mater.2004,16,4359, Chem.Eur.J.2006,12,3507, Chem.Mater.2006,18,2781.The organic phospho acid aluminium hybrid material of the classification pore structure that we synthesized does not see that as yet report is arranged.And this mesopore-macropore organic phospho acid aluminium hybrid material that we will synthesize first is used for the macromolecular absorption of organism in water, and the result shows that it has bigger loading capacity to N,O-Diacetylmuramidase.
Summary of the invention
The object of the present invention is to provide a kind of organic phosphonate hybrid material and preparation method thereof, can be applied to the macromolecular absorption of organism in water with mesopore-macropore structure; Synthesis device of the present invention is simple, and is easy to operate, and condition is loose, the energy is saved in less contamination, and raw material is simple and easy to, and is with low cost.
For above-mentioned purpose, the present invention adopts aluminium secondary butylate and organic phospho acid ATMP, the synthetic organic/inorganic heterozygosis porous material of method of HEDP, the BHMTPMPA cohydrolysis in the template existence or not.
The present invention is to provide a kind of phosphonic acids aluminium mesopore-macropore preparation methods that contains different organic groups, concrete steps are as follows:
1. organic phospho acid, template, water and dissolve with ethanol are formed settled solution A, selected template is triblock copolymer F127; Can not add any template at this moment yet;
2. slowly stir down, aluminium secondary butylate is added drop-wise in the solution A, the each component mass ratio is the aluminium source: template: organic phospho acid: alcohol: water=2.46:5.0:(2.99-6.85): 30:70; The 24-48h that stirs the mixture under 0 ℃～50 ℃ changes mixture in the reactor over to, in 60 ℃～150 ℃ following crystallization 12-120h;
3. product is washed the back after filtration in room temperature-80 ℃ drying; Product extracted 96 hours or above to remove template wherein down in 78 ℃ with ethanol;
4. above-mentioned materials has bigger loading capacity to the biomacromolecule in the water as N,O-Diacetylmuramidase etc.
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 center and aluminium is with covalent bonds, difficult drop-off;
3. the material that can prepare by preparation method's modulation of control material is to the absorption property of biomacromolecule;
4. material preparation method is simple, modulation duct size under template that can be by using cheapness, easily degraded or the condition of not using template, one-step synthesis metal organic phosphonate;
5. Zhi Bei material can reuse, and it is simple to regenerate, and also can keep big loading capacity during repeated use.
Description of drawings
Fig. 1. and embodiment 1 (a, b), embodiment 2 (c), (e, sem photograph f) show that material has one dimension macropore pore passage structure for embodiment 3 (d) and embodiment 4;
Fig. 2. nitrogen adsorption-desorption isotherm and the graph of pore diameter distribution that calculates by density functional theory accordingly thereof show that this material has typical meso-hole structure;
Fig. 3 .pH is respectively 6.5,9.6, and the adsorption isothermal line of 4 pairs of N,O-Diacetylmuramidases of 11,12 o'clock embodiment shows that the sorbent material that is synthesized is 11 o'clock adsorptive capacity maximums to N,O-Diacetylmuramidase at pH.
Fig. 4. embodiment 1-4 is 11 o'clock adsorption isothermal lines to N,O-Diacetylmuramidase at pH, shows that sample BHMT-F127 is to N,O-Diacetylmuramidase loading capacity maximum among the embodiment 4.
Embodiment
Embodiment 1:
Under stirring at room, 2.99g organic phospho acid ATMP is added the mixing solutions of 30ml ethanol and 70ml water, be stirred to the solution clarification after, recording the pH value of solution value is 1.Slowly drip aluminium secondary butylate 2.46g, continue to stir 24h at a slow speed, in 80 ℃ of following crystallization 24h.Product after filtration, after the washing, drying, promptly obtain organic/inorganic heterozygosis classification hole material (ATMP-non).Sample is through XRD, TG-DSC, N
2Absorption/desorption, SEM, TEM, XPS,
27Al,
31P and
13Signs such as C MAS NMR turn out to be the organic phospho acid aluminium hybrid material with mesopore-macropore structure.Wherein, the TEM display material has irregular worm meso-porous; There are the one dimension macropore duct that is parallel to each other in a large number, diameter 800-1200nm in the SEM display material.The XRD spectra display material is the phosphonate of amorphous state; Nitrogen adsorption-desorption isotherm and corresponding density functional theory thereof calculate graph of pore diameter distribution and show that this material has typical meso-hole structure, and the BET specific surface area is 77m
2/ g; Pore volume is 0.38cm
3/ g; Mesoporous pore size is 4.3nm.Wherein P content is 19.68%, N content 2.31%.
Embodiment 2:
Under stirring at room, 2.99g organic phospho acid ATMP is added the mixing solutions of 30ml ethanol and 70ml water, add again after 5.0g F127 is stirred to the solution clarification, recording the pH value of solution value is 1.Slowly drip aluminium secondary butylate 2.46g, continue to stir 24h at a slow speed, in 80 ℃ of crystallization 24h.Product after filtration, after the washing, drying, promptly obtain organic/inorganic hybrid material (ATMP-F127).Sample is through XRD, TG-DSC, N
2Absorption/desorption, SEM, TEM, XPS,
27Al,
31P and
13Signs such as C MAS NMR turn out to be the organic phospho acid aluminium hybrid material with mesopore-macropore structure.Wherein, the TEM display material has irregular worm meso-porous; There are the one dimension macropore duct that is parallel to each other in a large number, diameter 800-1200nm in the SEM display material.The XRD spectra display material is the phosphonate of amorphous state; Nitrogen adsorption-desorption isotherm and corresponding graph of pore diameter distribution thereof show that this material has typical meso-hole structure, and the BET specific surface area is 154m
2/ g; Pore volume is 0.44cm
3/ g; Mesoporous pore size is 5.2nm.Wherein P content is 19.66%, N content 2.28%.
Embodiment 3:
Under stirring at room, 6.85g organic phospho acid BHMTPMPA is added the mixing solutions of 30ml ethanol and 70ml water, be stirred to the solution clarification after, recording the pH value of solution value is 1.Slowly drip aluminium secondary butylate 2.46g, 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 mesoporous material (BHMT-non).Sample is through XRD, TG-DSC, N
2Absorption/desorption, SEM, TEM, XPS,
27Al,
31P and
13Signs such as C MAS NMR turn out to be the organic phospho acid aluminium hybrid material with mesopore-macropore structure.Wherein, the TEM display material has irregular worm meso-porous; There are the one dimension macropore duct that is parallel to each other in a large number, diameter 800-1200nm in the SEM display material.The XRD spectra display material is the phosphonate of amorphous state; Nitrogen adsorption-desorption isotherm and corresponding graph of pore diameter distribution thereof show that this material has typical meso-hole structure, and the BET specific surface area is 60m
2/ g; Pore volume is 0.36cm
3/ g; Mesoporous pore size is 4.2nm.Wherein P content is 7.78%, N content 2.10%.
Embodiment 4:
Under stirring at room, 6.85g organic phospho acid ATMP is added the mixing solutions of 30ml ethanol and 70ml water, add again after 5.0g F127 is stirred to the solution clarification, recording the pH value of solution value is 1.Slowly drip aluminium secondary butylate 2.46g, 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 mesoporous material (BHMT-F127).Sample through XRD, TG-DSC, N2 absorption/desorption, SEM, TEM, XPS,
27Al,
31P and
13Signs such as CMAS NMR turn out to be the organic phospho acid aluminium hybrid material with mesopore-macropore structure.Wherein, the TEM display material has irregular worm meso-porous; There are the one dimension macropore duct that is parallel to each other in a large number, diameter 800-1200nm in the SEM display material.The XRD spectra display material is the phosphonate of amorphous state; Nitrogen adsorption-desorption isotherm and corresponding graph of pore diameter distribution thereof show that this material has typical meso-hole structure, and the BET specific surface area is 128m
2/ g; Pore volume is 0.42cm
3/ g; Mesoporous pore size is 5.0nm.Wherein P content is 7.55%, N content 2.08%.
Embodiment 5:
Get in fact that sample 0.020g makes sorbent material among the embodiment 4, drop into lysozyme concentration and be respectively 20,30, the pH of 60,100,150,200 μ mol/L is respectively 6.5,9.6, in 11,12 the 4g buffered soln, stirs 96h and reaches the adsorption-desorption balance, by measuring λ
MaxBefore the absorption and absorption back solution absorbency is calculated the adsorptive capacity of N,O-Diacetylmuramidase during=281.5nm, obtains the adsorption isothermal line of N,O-Diacetylmuramidase.With Lamgmuir type adsorption isotherm equation curve is carried out match, obtain maximum adsorption capacity and be in proper order: 11.80 μ mol/g (pH=11) 10.42 μ mol/g (pH=12) 9.23 μ mol/g (pH=9.6) 8.24 μ mol/g (pH=6.5).The result shows that the sorbent material that is synthesized is 11 o'clock loading capacity maximums to N,O-Diacetylmuramidase at pH.
Embodiment 6:
Get in fact that sample 0.020g makes sorbent material among the embodiment 1-4, drop into lysozyme concentration and be respectively 20,30, the pH of 60,100,150,200 μ mol/L is in 11 the 4g buffered soln, stirs 96h and reaches the adsorption-desorption balance, by measuring λ
MaxBefore the absorption and absorption back solution absorbency is calculated adsorptive capacity during=281.5nm.The result show optimal adsorption pH be 11 o'clock, sample loading capacity: ATMP-non among each embodiment (5.57 μ mol/g)＜BHMT-non (6.74 μ mol/g)＜ATMP-F127 (8.32 μ mol/g)＜BHMT-F127 (11.80 μ mol/g).The result show among the embodiment 4 sample BHMT-F127 pH be 11 o'clock to N,O-Diacetylmuramidase loading capacity maximum.
Claims (5)
1. an organic phospho acid Lu porous material is characterized in that it has the hierarchy of mesopore-macropore, combines different organic phospho acid functional group in skeleton, and wherein organic phospho acid P weight percentage is 7.55-19.68wt%; Described phosphonic acids aluminum has higher loading capacity to the biomacromolecule in the water.
2. one kind prepares the described preparation method with organic phosphonate aluminum of mesopore-macropore structure of claim 1, it is characterized in that it comprises the steps:
A), or do not add template only with organic phospho acid or organic phospho acid and water/alcohol mixed solvent formation settled solution A with organic phospho acid and water/alcohol mixed solvent and template formation settled solution A;
B) stirring slowly is added dropwise to solution A with the aluminium source down, stirs the mixture under 0-50 ℃ 24-48 hour, the gained mixture is changed in the reactor, in 60-150 ℃ of crystallization 12-120h;
C) product after filtration, washing back is in room temperature-80 ℃ drying;
D) template in the product with dehydrated alcohol in 78 ℃ down extraction 96 hours or more than, obtain the organic phospho acid aluminium of target product mesopore-macropore classification pore structure, wherein amount of alcohol added is a 1g sample 100ml ethanol.
3. according to the described preparation method of claim 2 with organic phospho acid aluminum of mesopore-macropore structure, it is characterized in that described organic phospho acid is Amino Trimethylene Phosphonic Acid ATMP, hydroxy ethylene diphosphonic acid HEDP and hexamethylene triamine pentamethylene phosphonic acids BHMTPMPA; The aluminium source is an aluminium secondary butylate; Template is triblock copolymer F127.
4. according to the preparation method of claim 2, it is characterized in that,, do not need the d step this moment as not adding template among the step a.
5. according to the preparation method of claim 2, it is characterized in that the aluminium source that adds among the step b and the mass ratio of organic phospho acid are 0.359:1-0.822:1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513069A (en) * | 2011-12-16 | 2012-06-27 | 浙江农林大学 | Method for producing hierarchically structured porous coordination polymer absorbent material |
| CN103058449A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Treatment method for aluminum phosphate molecular sieve production wastewater |
| CN104549379A (en) * | 2013-10-18 | 2015-04-29 | 中国石油化工股份有限公司 | Sulfated zirconium phosphonate solid strong acid porous material and preparation method |
| CN108067304A (en) * | 2016-11-17 | 2018-05-25 | 南京农业大学 | A kind of mesoporous function hybrid material and preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100584447C (en) * | 2007-01-23 | 2010-01-27 | 南开大学 | Organic phosphonium transition metal salt graded hole material preparing method and the application |
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2009
- 2009-01-19 CN CN2009100677270A patent/CN101475589B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058449A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Treatment method for aluminum phosphate molecular sieve production wastewater |
| CN103058449B (en) * | 2011-10-18 | 2014-03-26 | 中国石油化工股份有限公司 | Treatment method for aluminum phosphate molecular sieve production wastewater |
| CN102513069A (en) * | 2011-12-16 | 2012-06-27 | 浙江农林大学 | Method for producing hierarchically structured porous coordination polymer absorbent material |
| CN104549379A (en) * | 2013-10-18 | 2015-04-29 | 中国石油化工股份有限公司 | Sulfated zirconium phosphonate solid strong acid porous material and preparation method |
| CN104549379B (en) * | 2013-10-18 | 2017-01-18 | 中国石油化工股份有限公司 | Sulfated zirconium phosphonate solid strong acid porous material and preparation method |
| CN108067304A (en) * | 2016-11-17 | 2018-05-25 | 南京农业大学 | A kind of mesoporous function hybrid material and preparation method and application |
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