CN102513069A - Method for producing hierarchically structured porous coordination polymer absorbent material - Google Patents
Method for producing hierarchically structured porous coordination polymer absorbent material Download PDFInfo
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- CN102513069A CN102513069A CN2011104218933A CN201110421893A CN102513069A CN 102513069 A CN102513069 A CN 102513069A CN 2011104218933 A CN2011104218933 A CN 2011104218933A CN 201110421893 A CN201110421893 A CN 201110421893A CN 102513069 A CN102513069 A CN 102513069A
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Abstract
The invention discloses a method for producing a hierarchically structured porous coordination polymer absorbent material, which comprises three steps of 1, dissolving aromatic carboxylic acid in an alkaline solution of 60 to 90 DEG C; 2, preparing a brine solution with metal ions; and 3, slowly adding the solution obtained in step 1 into the solution obtained in step 2, continuously reacting for 1 to 8 hours, suction filtering and drying after washing the mixed solution by water and then obtaining the hierarchically structured porous coordination polymer absorbent material. The coordination polymer absorbent material has mesoporous and macropores at the same time; and the aperture is 2 to 150 nanometers. The mesoporous/macropore coordination polymer absorbent material produced by the method has well application prospect in the areas of environment pollution, chromatograph, catalysis and the like; the product is dried at a high temperature of 120 to 160 DEG C and has a relatively high heat stability. The production method is good for the environment, simple and easy for implementation and low in cost.
Description
Technical field
the present invention relates to a kind of production method that is applied to the adsorbent of sewage purification, specifically are the production methods of the Coordination Polymers sorbing material of graded structure.
Background technology
are started from basic research and are produced actual needs in recent years, and the research and development with graduation mesopore/macropore material of multiple size excite wide spread interest.Become the focus of research as the mesoporous material with macroporous structure of catalyst and adsorbent; Such graduation mesopore/macropore material has possessed the various advantages that mesoporous material and large pore material possessed simultaneously; Such as, the macropore in the mesopore/macropore material helps the diffusion of reactant and product, improves the transmission of material; Eliminated limited aperture, obtained diffusion than single hole greater advantages.These advantages determined the graduation porous material to become a hot fields of porous material in nearly ten years just.
Coordination Polymers and metal organic frame material are the tridimensional structures that is connected to form through covalent bond by metal ion or metal ion bunch and organic ligand, and this type material has potential application prospect in fields such as medicine conveying, harmful substance absorption, catalysis, nonlinear optics, magnetic, atmosphere storage.In this type material, the research that concerns between the crystal structure of microporous coordination polymer and the performance very extensively.In recent years, because the development of nanometer technology and nano science, cause great concern based on Coordination Polymers morphology control synthetic, based on synthesizing of graduation porous material also causing people's attention.Document [Crystal Growth & Design; 2010,10,2451] copper nitrate or chromic nitrate and terephthalic acid (TPA) are dissolved in the dimethyl formamide; The hexane solution that will contain triethylamine then slowly joins above the above-mentioned dimethyl formamide solution; Occur blue deposition immediately at the interface of dimethyl formamide/n-hexane, collecting precipitation obtains the micropore/mesoporous material of classifying.Because the method for synthetic classify mesoporous or large pore material difficulty is used for synthetic Coordination Polymers, therefore, the synthetic report of the coordination polymerization of graduation meso/macroporous structure is less.
are part with the armaticity carboxylic acid; Adopt liquid phase dispersion precipitation therapy; Under the condition of no template and organic solvent; Utilize single water to produce Coordination Polymers, and can obtain the porous Coordination Polymers sorbing material of different-shape and pore-size distribution through changing carboxylic acid and metal ion ratio with graduation mesopore/macropore for solvent.To this,, do not find that as yet interrelated data report and product appear on the market through retrieval and market survey.
Summary of the invention
The technical problem that
the present invention will solve provides a kind of production method of hole Coordination Polymers sorbing material of graded structure.
The production method that solves this technical problem the technical scheme that is adopted and be the hole Coordination Polymers sorbing material of this graded structure follows these steps to carry out:
(1) the armaticity carboxylic acid of 5 weight portions and the alkali of 2～4 weight portions are dissolved in 60～90 ℃ of water of 100～300 weight portions;
(2) water soluble salt with 2～5 weight portion metal ion is dissolved in 20～80 weight portion normal-temperature water;
(3) will slowly join in the gained solution of step (1) through step (2) gained solution; Stir while adding; Add the continued reaction 1～8 hour that finishes, suction filtration, with dry after the water washing, promptly obtain the hole Coordination Polymers sorbing material of graded structure.
said fragrant carboxylic property acid be in the amino M-phthalic acid of isophthalic acid, terephthalic acids, 5-hydroxyl M-phthalic acid, 5-any.
said alkali be in NaOH, potassium hydroxide, sodium carbonate and the potash any.
Metal ion in
said metal ion water soluble salt be in iron ion, zinc ion, the aluminium ion any.
the invention has the beneficial effects as follows that the technical process of whole preparation method is simple, and reaction condition is gentle, and is environmentally friendly, steady quality.The hole Coordination Polymers sorbing material of the graded structure of preparing is used for adsorbing the anionic dye of dyeing waste water; The tracid light yellow adsorption capacity is surpassed 1800 milligrams/gram; Adsorption capacity to the gorgeous indigo plant of acidity surpasses 1500 milligrams/gram, the absorption property with superelevation.For environmental pollution improvement provides a kind of new sorbing material.
Description of drawings
Fig. 1 is the infrared spectrum of the sample of the embodiment of the invention 1 gained.
Fig. 2 is the sem photograph (a) and the transmission electron microscope picture (b) of the sample of the embodiment of the invention 1 gained.
Fig. 3 is the nitrogen adsorption figure (a) and pore-size distribution (b) figure of the sample of the embodiment of the invention 1 gained.
Fig. 4 is the absorption isotherm figure of the embodiment of the invention 1 gained sample to tracid light yellow.
Fig. 5 is the absorption isotherm figure of the embodiment of the invention 1 gained sample to the gorgeous indigo plant of acidity.
Fig. 6 is the embodiment of the invention 1 a gained sample in difference constantly to the adsorption capacity figure of tracid light yellow.
Fig. 7 is the embodiment of the invention 1 a gained sample in difference constantly to the adsorption capacity figure of the gorgeous indigo plant of acidity.
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The specific embodiment
Further detailed description below in conjunction with accompanying drawing and embodiment, is made to the present invention in
.Earlier each raw material and weight portion proportioning value thereof are listed in the table below by seven embodiment:
Embodiment 1 (raw material and the weight portion proportioning value thereof of embodiment 1 correspondence in the table of comparisons), undertaken by three steps:
(1) the 5-hydroxyl M-phthalic acid of 5 weight portions and the NaOH of 2.2 weight portions are dissolved in 75 ℃ of water of 250 weight portions;
(2) aluminum sulfate with 2.4 weight portions is dissolved in the 50 weight portion normal-temperature water;
(3) will slowly join in the gained solution of step (1) through step (2) gained solution; Stir while adding; Add the continued reaction 2 hours that finishes, suction filtration, with after the water washing 160 ℃ of dryings, promptly obtain the hole Coordination Polymers sorbing material of graded structure.
all the other embodiment 2-7, raw material and the weight portion proportioning value thereof of corresponding embodiment in the table gone up in contrast respectively, with embodiment 1 same procedure, divides three steps to produce and has concurrently mesoporous and macropore, and pore-size distribution is this sorbing material of 2～150nm.
What
needed explanation is that comparatively ideal temperature is 75 ℃ when being dissolved in armaticity carboxylic bronsted lowry acids and bases bronsted lowry in 60～90 ℃ of water in the step (1), the temperature in 60～90 ℃ of scopes all can, do not list one by one.After the slow adding of step (3) finishes, require to continue reaction 1～8 hour, the whether abundant consideration that responds, different material and different temperatures be to the consideration of the influence in reaction time, the consideration of production yield and efficient.The colleague technical staff can be according to producing actual needs, and decision continues the concrete time of reaction, does not also enumerate one by one.Iron content in the form, zinc, aluminum ions water soluble salt, because of the restriction that receives length and the technical staff that goes together can draw inferences about other cases from one instance understand so, each be that example is explained with a kind of salt (ferric nitrate, zinc nitrate, aluminum sulfate), no longer extensively expansion.
Among
seven kinds of embodiment, preferred with embodiment 1.
are existing to be example with embodiment 1 gained sample, and its infrared spectrogram, ESEM and transmission electron microscope picture are seen Fig. 1-2, and nitrogen adsorption and pore-size distribution are seen Fig. 3, and dyeing and printing sewage absorption situation is seen Fig. 4-7.Fig. 4 is the amount that the embodiment of the invention 1 gained sample at room temperature adsorbs tracid light yellow, when balance, with adsorption capacity equilibrium concentration is mapped, and the absorption isotherm that obtains, the adsorption capacity among the figure are represented the amount of every gram adsorbents adsorb tracid light yellow.Fig. 5 is the amount that the embodiment of the invention 1 gained sample at room temperature adsorbs acid gorgeous indigo plant, when balance, with adsorption capacity equilibrium concentration is mapped, and the absorption isotherm that obtains, the adsorption capacity among the figure are represented the amount of the acid gorgeous indigo plant of every gram adsorbents adsorb.Fig. 6 is that the 0.02 gram sample of getting the embodiment of the invention 1 gained is that 600 mg/litre, volume are that 50 milliliters tracid light yellow is at difference adsorption capacity figure constantly to initial concentration at room temperature.Fig. 7 is that to get the embodiment of the invention 1 gained 0.02 gram sample be that 500 mg/litre, volume are that 50 milliliters acid gorgeous indigo plant is at difference adsorption capacity figure constantly to initial concentration at room temperature.
use the active carbon of 0.2 commercially available gram to oppose than test as adsorbent; To volume is that 50 milliliters, the tracid light yellow and the acid gorgeous indigo plant of variable concentrations adsorb; After reaching adsorption equilibrium, saturated adsorption capacity is respectively 15 milligrams/gram and 40 milligrams/gram.By contrast, the sample of the embodiment of the invention 1 gained has the adsorption capacity of superelevation to anionic dye.
Claims (4)
1. the production method of the hole Coordination Polymers sorbing material of graded structure is characterized in that following these steps to carrying out:
(1) the armaticity carboxylic acid of 5 weight portions and the alkali of 2～4 weight portions are dissolved in 60～90 ℃ of water of 100～300 weight portions;
(2) water soluble salt with 2～5 weight portion metal ion is dissolved in 20～80 weight portion normal-temperature water;
(3) will slowly join in the gained solution of step (1) through step (2) gained solution; Stir while adding; Add the continued reaction 1～8 hour that finishes, suction filtration, with dry after the water washing, promptly obtain the hole Coordination Polymers sorbing material of graded structure.
2. the production method of the hole Coordination Polymers sorbing material of graded structure according to claim 1 is characterized in that: the armaticity carboxylic acid be in isophthalic acid, terephthalic acids, 5-hydroxyl M-phthalic acid, the amino M-phthalic acid of 5-any.
3. the production method of the hole Coordination Polymers sorbing material of graded structure according to claim 1 is characterized in that: said alkali be in NaOH, potassium hydroxide, sodium carbonate and the potash any.
4. the production method of the hole Coordination Polymers sorbing material of graded structure according to claim 1 is characterized in that: the metal ion of said metal ion water soluble salt be in iron ion, zinc ion, the aluminium ion any.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105149001A (en) * | 2015-09-30 | 2015-12-16 | 华东理工大学 | Preparing method for Co(bpd)(HIA) catalyst for degrading organic dyestuff |
| CN105845125A (en) * | 2016-05-18 | 2016-08-10 | 百度在线网络技术（北京）有限公司 | Speech synthesis method and speech synthesis device |
| CN107011525A (en) * | 2017-03-08 | 2017-08-04 | 宁波大学 | A kind of zinc metal-organic framework material and its preparation method and application |
| CN109400890A (en) * | 2017-08-18 | 2019-03-01 | 中国石化扬子石油化工有限公司 | A kind of preparation method of multi-stage porous metal-organic framework materials |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244377A (en) * | 2008-03-18 | 2008-08-20 | 西北大学 | Polymer absorbing agent and preparation thereof |
| CN101475589A (en) * | 2009-01-19 | 2009-07-08 | 南开大学 | Preparation and use of mesoporous-macroporous structure aluminum organophosphonate material |
| CN101693757A (en) * | 2009-04-03 | 2010-04-14 | 中国科学院上海硅酸盐研究所 | Hydrophilous porous phenolic resin as well as preparation method and application thereof |
| CN102002061A (en) * | 2010-11-12 | 2011-04-06 | 南开大学 | Porous copper coordination polymer material as well as preparation method and application thereof |
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2011
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244377A (en) * | 2008-03-18 | 2008-08-20 | 西北大学 | Polymer absorbing agent and preparation thereof |
| CN101475589A (en) * | 2009-01-19 | 2009-07-08 | 南开大学 | Preparation and use of mesoporous-macroporous structure aluminum organophosphonate material |
| CN101693757A (en) * | 2009-04-03 | 2010-04-14 | 中国科学院上海硅酸盐研究所 | Hydrophilous porous phenolic resin as well as preparation method and application thereof |
| CN102002061A (en) * | 2010-11-12 | 2011-04-06 | 南开大学 | Porous copper coordination polymer material as well as preparation method and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105149001A (en) * | 2015-09-30 | 2015-12-16 | 华东理工大学 | Preparing method for Co(bpd)(HIA) catalyst for degrading organic dyestuff |
| CN105845125A (en) * | 2016-05-18 | 2016-08-10 | 百度在线网络技术（北京）有限公司 | Speech synthesis method and speech synthesis device |
| CN105845125B (en) * | 2016-05-18 | 2019-05-03 | 百度在线网络技术（北京）有限公司 | Phoneme synthesizing method and speech synthetic device |
| CN107011525A (en) * | 2017-03-08 | 2017-08-04 | 宁波大学 | A kind of zinc metal-organic framework material and its preparation method and application |
| CN107011525B (en) * | 2017-03-08 | 2020-03-31 | 宁波大学 | Zinc metal organic framework material and preparation method and application thereof |
| CN109400890A (en) * | 2017-08-18 | 2019-03-01 | 中国石化扬子石油化工有限公司 | A kind of preparation method of multi-stage porous metal-organic framework materials |
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