CN105396555A - Preparation method of mesoporous print material capable of selectively adsorbing cadmium ions - Google Patents

Preparation method of mesoporous print material capable of selectively adsorbing cadmium ions Download PDF

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Publication number
CN105396555A
CN105396555A CN201510739736.5A CN201510739736A CN105396555A CN 105396555 A CN105396555 A CN 105396555A CN 201510739736 A CN201510739736 A CN 201510739736A CN 105396555 A CN105396555 A CN 105396555A
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mesoporous
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preparation
mcm
adsorption
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田大勇
彭云峰
杨爽
郑勇
吕会超
彭聪虎
贾太轩
侯绍刚
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Anyang Institute of Technology
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    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0296—Nitrates of compounds other than those provided for in 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • 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
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • 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
    • C02F2101/20—Heavy metals or heavy metal compounds

Abstract

The invention discloses a preparation method of a mesoporous print material capable of selectively adsorbing cadmium ions and belongs to the field of chemistry. The preparation method comprises the following steps: 1, dropwise adding tetraethoxysilane to a mixed solution of sodium hydroxide and cetrimonium bromide for reaction, and then processing to obtain a MCM-41 material; 2, washing the MCM-41 material; 3, adding a methanol solution to Cd(NO3)2.4H2O; 4, then adding 3-[2-(2-aminoethylamino) ethylamino] propyl-thimethoxy silane (AAAPTS) for reaction, then adding purified MCM-41, and then adding epichlorohydrin and reacting while stirring; 5, soaking for 4 hours while stirring to remove Cd<2+>; and 6, washing and drying to obtain the mesoporous print material. The mesoporous print material obtained according to the method is non-toxic and harmless, is large in adsorption capacity and strong in environmental protection property, is not soluble in water, and can be repeatedly used.

Description

A kind of preparation method of mesoporous imprinted material of selective absorption cadmium ion
Technical field
The present invention relates to a kind of preparation method of mesoporous imprinted material, particularly a kind of preparation method of mesoporous imprinted material of selective absorption cadmium ion, belongs to chemical field.
Background technology
Current traditional sorbing material is based on activated carbon, and shortcoming has following two aspects, and one is that adsorbance is little, generally at about 4mg/g; Two is lack selective, selectivity.In environment, heavy metal and organic pollution normally mix existence, under this mixing existence condition, activated carbon is better to Adsorption of Organic effect proportion metal based compound, like this in actual environment wastewater treatment, organic matter and other metal can and cadmium competitive Adsorption site, cause the single-minded selective adsorption capacity decline of cadmium, adsorption effect poor.
The porous material of mesoporous material finger-hole footpath between 2-50nm, specific area and aperture are all larger, its composition and aperture have adjustability flexibly, therefore mesoporous material adsorption selection be separated, catalysis, field has a wide range of applications in capacitance electrode and information storage, medicine and genetic engineering etc.And also very extensive in the application of field of Environment Protection, mesoporous material can Adsorption of Heavy Metals well, also can carry out modification energy to it, realize selective absorption for certain material.Ion blotting is a kind of selective stronger new material synthetic method.At present, more with research that is surface imprinted, polymer trace.The surface imprinted methods of employing such as bibliographical information Guo Meng sprouts, take silica gel as raw material, prepare cadmium ion imprinted silica gel material, maximal absorptive capacity is 30.8mg/g, Gao Baojiao etc. take silica gel as substrate, a kind of surface imprinted material adsorbing cadmium of grafting organic group preparation synthesis on silica, adsorption capacity is 0.44mmol/g, Hu Bin etc. take TEOS as coupling agent, magnetic Fe_3O_4 nanosphere is core, take CTAB as pore-foaming agent, prepare a kind of cadmium ion trace magnetic mesoporous silica gel solid phase extracting agent by surface imprinted method, adsorption capacity is about 32.5mg/g.Other surface imprinted material also has chromium, mercury, lead, cobalt plasma imprinted material.In the ion blotting material taking polymer as substrate, bibliographical information Lv Haixia etc. with methacrylic acid, 4-vinylpridine for function monomer, ethylene glycol dimethacrylate is crosslinking agent, prepare cadmium ion imprinted polymer, adsorption capacity is about 11mg/g, Zhang Huixin etc. are with Fe3O4SiO2 microballoon for carrier, and GDMA is crosslinking agent, and methacrylic acid and salicylaldoxime are the Fe3O4SiO2 microsphere polymer that monomer obtains adsorbing cadmium.Wang Limin etc. have synthesized lead ion imprinted polymer material, and also have scholar to be that cadmium ion imprinted polymer has been synthesized in function monomer preparation with methyl chitosan, adsorption capacity is about 19.6mg/g.Be that substrate is prepared in ion blotting material with mesoporous material, bibliographical information Zhao Dan etc. with mercury chloride and surfactant (softex kw) for template, N-(2 ammonia-ethyl)-3 ammonia-propyl trimethoxy silicane is function monomer, ethyl orthosilicate is crosslinking agent, the mesoporous imprinted polymer of a kind of double-template that utilized one-step method to prepare, reaches 0.199mmol/L to the adsorption capacity of mercury.The porous material of mesoporous material finger-hole footpath between 2-50nm, specific area and aperture are all larger, its composition and aperture have adjustability flexibly, therefore mesoporous material adsorption selection be separated, catalysis, field has a wide range of applications in capacitance electrode and information storage, medicine and genetic engineering etc.And also very extensive in the application of field of Environment Protection, mesoporous material can Adsorption of Heavy Metals well, also can carry out modification energy to it, realize selective absorption for certain material.Ion blotting is a kind of selective stronger new material synthetic method.At present, more with research that is surface imprinted, polymer trace.The surface imprinted methods of employing such as bibliographical information Guo Meng sprouts, take silica gel as raw material, prepare cadmium ion imprinted silica gel material, maximal absorptive capacity is 30.8mg/g, Gao Baojiao etc. take silica gel as substrate, a kind of surface imprinted material adsorbing cadmium of grafting organic group preparation synthesis on silica, adsorption capacity is 0.44mmol/g, Hu Bin etc. take TEOS as coupling agent, magnetic Fe_3O_4 nanosphere is core, take CTAB as pore-foaming agent, prepare a kind of cadmium ion trace magnetic mesoporous silica gel solid phase extracting agent by surface imprinted method, adsorption capacity is about 32.5mg/g.Other surface imprinted material also has chromium, mercury, lead, cobalt plasma imprinted material.In the ion blotting material taking polymer as substrate, bibliographical information Lv Haixia etc. with methacrylic acid, 4-vinylpridine for function monomer, ethylene glycol dimethacrylate is crosslinking agent, prepare cadmium ion imprinted polymer, adsorption capacity is about 11mg/g, Zhang Huixin etc. are with Fe3O4SiO2 microballoon for carrier, and GDMA is crosslinking agent, and methacrylic acid and salicylaldoxime are the Fe3O4SiO2 microsphere polymer that monomer obtains adsorbing cadmium.Wang Limin etc. have synthesized lead ion imprinted polymer material, and also have scholar to be that cadmium ion imprinted polymer has been synthesized in function monomer preparation with methyl chitosan, adsorption capacity is about 19.6mg/g.Be that substrate is prepared in ion blotting material with mesoporous material, bibliographical information Zhao Dan etc. with mercury chloride and surfactant (softex kw) for template, N-(2 ammonia-ethyl)-3 ammonia-propyl trimethoxy silicane is function monomer, ethyl orthosilicate is crosslinking agent, the mesoporous imprinted polymer of a kind of double-template that utilized one-step method to prepare, reaches 0.199mmol/L to the adsorption capacity of mercury.In some meetings, scholar proposes a kind of preparation method preparing cadmium ion trace mesoporous material; but have no any process technology scheme and parameter; as can be seen from above Review Study; current research focuses mostly in the surface imprinted or polymer aspect based on silica gel; these synthetic product multi-bands have organic group or Fe3O4; environment friendly is poor, the bad adaptability when environmental requirement increasingly stringent, and the final adsorbance of above-mentioned synthesis is all less than normal.
A kind of double-template mesoporous lead ion trace adsorbent that utilized one-step method to prepare; in some meetings, scholar proposes a kind of preparation method preparing cadmium ion trace mesoporous material; but have no any process technology scheme and parameter; as can be seen from above Review Study; current research focuses mostly in the surface imprinted or polymer aspect based on silica gel; these synthetic product multi-bands have organic group or Fe3O4; environment friendly is poor; the bad adaptability when environmental requirement increasingly stringent, and the final adsorbance of above-mentioned synthesis is all less than normal.
Summary of the invention
The object of the invention is to overcome the problems referred to above existed in the mesoporous imprinted material preparation of selective absorption cadmium ion in prior art, a kind of preparation method of mesoporous imprinted material of selective absorption cadmium ion is provided.
For realizing object of the present invention, have employed following technical scheme: a kind of preparation method of mesoporous imprinted material of selective absorption cadmium ion, comprises the following steps:
(1) joined at 80 DEG C by the sodium hydrate aqueous solution of 2.00mol/L in the aqueous solution of cetab and mix, be more dropwise added drop-wise in mixed solution by tetraethoxysilane, strong agitation was filtered after two hours simultaneously;
(2) by the solid distilled water of filtration and alcohol flushing, then 80 DEG C of dryings 8 hours, MCM-41 material can be obtained;
(3) gained MCM-41 material is added in the methanol solution containing hydrochloric acid and reflux, product is filtered, and rinses fully with deionized water and ethanol, then 60 DEG C of dryings 6 hours, obtain the MCM-41 material of purifying;
(4) Cd(NO is taken 3) 24H 2o is placed in reaction bulb, add methanol solution, under agitation with heating water bath 50 DEG C until solid dissolves completely, add 3-[2-(2-aminoethylamino) ethylamino] propyl-trimethoxysilane (AAAPTS) again and react the MCM-41 adding purifying after two hours, reflux heating 12 hours at 80 DEG C, and then add epoxychloropropane and under agitation heating water bath 50 DEG C reaction 4 hours;
(5) gained solid also with absolute ethanol washing, is placed in 6mol/L hydrochloric acid solution by suction filtration after cooling, and stirs lower immersion 4 hours removing Cd 2+;
(6) with the NaHCO of 0.1mol/L 3solution and distilled water are washed till solution in neutral, the drying 12 hours of 80 DEG C, obtain mesoporous ion blotting material;
Further, cetab in step (1): NaOH: the mol ratio of tetraethoxysilane is 1:2.6:8.2.
Further, in step (2), the volume ratio of distilled water and ethanol is 10:1.
Further, in step (3), reflux course is specially: the methanol solution 150ml that every 1.5gMCM-41 material adds containing 1.5ml37% hydrochloric acid refluxes.
Further, Cd(NO in step (4) 3) 24H 2the mass ratio of O and MCM-41 is 1:2.
Positive Advantageous Effects of the present invention is: the goods selective absorption cadmium ion performance that this method finally obtains significantly is improved, absorption capacity Da Keda 50mg/g, be much higher than absorbent charcoal material and the absorption capacity of the product that method obtains disclosed in other, achieve beyond thought technique effect, the cadmium ion in field of Environment Protection selective absorption sewage can be applied in, also recycle; Two be this product in environmental analysis field, mesoporous ion blotting material as the packing material of solid-phase extraction column, can realize, to the selective separation enrichment of cadmium in water, then measuring, can improve the Monitoring lower-cut of ion analysis; Three is compared with traditional sorbing material, and the mesoporous ion blotting material non-toxic that this method obtains is harmless, security is high, the feature of environmental protection is strong, water insoluble, can reuse.
Accompanying drawing explanation
Fig. 1 is the present invention's mesoporous ion blotting material X-ray diffraction.
Fig. 2 is the infrared spectrogram of the mesoporous ion blotting material of the present invention.
Fig. 3 is the transmission electron microscopy figure of the mesoporous ion blotting material of the present invention.
Fig. 4 is the component analysis curve of adsorbent of the present invention.
Fig. 5 is the adsorption test curve of the cadmium-ion solution of 50mg/L.
Fig. 6 is the adsorption test curve of the cadmium-ion solution of 500mg/L.
When Fig. 7 is different temperatures, mesoporous ion blotting material is to the adsorption effect of cadmium ion.
Fig. 8 is that different pH value cadmium-ion solution affects mesoporous ion blotting materials adsorption rate.
Fig. 9 is the adsorption capacity under different initial soln concentration conditions.
Figure 10 is that NIP and MIP adsorbs check experiment.
Figure 11 is repetition experimental result statistics.
Figure 12 is the schematic diagram comparing absorption.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, the following stated, only to preferred embodiment of the present invention, not do other forms of restriction to the present invention, any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed to the Equivalent embodiments of equal change.Everyly do not depart from the present invention program's content, any simple modification done following examples according to technical spirit of the present invention or equivalent variations, all drop in protection scope of the present invention.
The present invention with cetab (CTAB) be template, tetraethoxysilane (TEOS) for silicon source, synthesis MCM-41 material.Then mesoporous ion blotting material is obtained with 3-[2-(2-aminoethylamino) ethylamino] propyl-trimethoxysilane (AAAPTS) at methanol eddy.By XRD x ray diffraction, the phenetic analysis of infrared spectrum, transmission electron microscope and BET analyze, MCM-41 and mesoporous ion blotting material are characterized, investigate their structure and composition, prepared mesoporous ion blotting material of reaching a conclusion has feature and the basic framework feature of mesoporous silicon oxide.And carried out adsorption experiment.Result shows that this material has larger adsorbance, selective preferably.
One, the preparation of mesoporous ion blotting material
Preparation process and being specially:
1) Mesoporous silica MCM 41 is prepared
With cetab (CTAB, 1g, 2.74mmol) be template, be dissolved in 480ml distilled water, get sodium hydrate aqueous solution (2.00mol/l, 3.50ml) join at 80 degrees celsius in CTAB solution, again by tetraethoxysilane (TEOS, 5ml, 22.4mmol) be dropwise added drop-wise in surfactant solution, strong agitation was filtered after two hours simultaneously, by the distilled water of solid 200ml of filtration and the alcohol flushing of 20ml, then at electric heating constant-temperature blowing drying box with 80 degrees Celsius of dryings 8 hours, MCM-41 material can be obtained.In order to remove Surfactant CTAB, reflux in the methanol solution (150ml) that the MCM-41 material getting 1.5g synthesis adds containing 1.5ml hydrochloric acid (37%).Product is filtered, and rinses fully with deionized water and ethanol, be then put into dry 6 hours of the electric heating constant-temperature blowing drying box of 60 degrees Celsius, can obtain not containing the MCM-41 of surfactant;
2) on mesoporous silicon material, carry out ion blotting, obtain mesoporous ion blotting material
Take 2.94gCd(NO 3) 24H 2o is placed in the two-mouth bottle of 150ml, add methanol solution 80ml, under agitation with heating water bath 50 DEG C until solid dissolves completely, then 3-[2-(2-aminoethylamino) ethylamino] propyl-trimethoxysilane (AAAPTS) of 4ml is added, react and add MCM-416g after two hours, reflux heating 20 hours at 80 DEG C, and then add epoxychloropropane 3ml and under agitation heating water bath 50 DEG C reaction 4 hours.Suction filtration after cooling also removes AAAPTS with absolute ethanol washing.Gained solid is placed in the 6mol/L hydrochloric acid solution of 100ml, stirs lower immersion and remove Cd in four hours 2+.Use the NaHCO of 0.1mol/L again 3solution and distilled water are washed till solution in neutral, 80 oin the electric heating constant-temperature blowing drying box of C, drying 12 hours, obtains mesoporous ion blotting material.
two,the sign of mesoporous ion blotting material
1) X-ray diffraction analysis (XRD)
Adopt Bruker-X x ray diffractometer x to carry out the crystal phase structure of characterizing sample, with CaKa radiation, pipe pressure be 40KV, λ=1.5406A, tube current for 30mA, antiscatter slits (SS) 0.17 °; Divergent slit (DS) 0.17 °; Accept slit (RS) 0.15mm, sweep limits is 1 °-10 °, and sweep speed is 0.2 °/s, and concrete outcome as shown in Figure 1.
As can be seen from Figure 1, in 2 θ=2.5 othere is a characteristic peak at place, is 3 ~ 6 at 2 θ ohave 2 ~ 3 weak peaks, the peak shown in figure and pertinent literature comparing, the position at peak is substantially identical, and the material of illustrative experiment synthesis has the feature of mesoporous material.
2) infrared-spectrum analysis (FT-IR)
Utilize infrared spectrum analysis can identify the structural information such as type and group change of skeletal atom.This research adopts the FT-IR550 type infrared spectrometer of NicoLetMagna company to measure, and KBr compressing tablet, scanning wavelength scope is 4000-400cm -1, result is as Fig. 2.
As can be seen from Figure 2 at 3425cm -1there is a wider absworption peak left and right, and this is the stretching vibration peak of the O-H after Si-OH adsorbed water in water, at 1680cm -1peak is the flexural vibrations of O-H in water, 1125cm -1going out be the asymmetric stretching vibration of Si-O-Si.980cm -1place is the characteristic absorption peak of mesopore molecular sieve, is the flexural vibrations that the symmetrical stretching vibration of Si-OH causes.As can be seen here, prepared material has framework type bone and the hexahedron structure of mesoporous silicon oxide.
3) transmission electron microscope (TEM) is analyzed
Transmission electron microscope (TEM) analysis completes on JEOL2000 transmission electron microscope, and operating voltage is 200kV, and before sample test, ethanol dissolves and ultrasonic 5 minutes, and result is as Fig. 3.
As can be seen from Figure 3 MCM-41 has the duct of six side's symmetry arrangements.Result in conjunction with XRD can think that this material belongs to the mesoporous material on nano-scale with grain structure.
4) BET analyzes
Adopt the material of MicromeriticTriStarII3020 tester to synthesis to carry out the experiment of nitrogen adsorption desorption, in test process, analysis cell temperature is-195.8 oc, equilibration interval 10s, object is the surface area and the aperture that obtain mesoporous material, and result is as table 1.
The pore volume 6.23nm of mesoporous material as can be seen from Table 1, meet the definition requirement of mesoporous material aperture between 2-50nm, show that the material finally obtained is typical mesoporous ion blotting material, this result is infrared with above-mentioned, the sign conclusion of TEM is consistent.
Analyzed by above XRD, TEM, BET to mesoporous ion blotting material and show that the material synthesized has the feature of mesoporous silicon oxide; Infrared spectrum analysis shows that mesoporous ion blotting material possesses the framework type bone of mesoporous silicon oxide.
The determination of embodiment 3 adsorption conditions
Adopt the conditions such as the consumption of experiments of single factor investigation adsorbent, adsorption time, adsorption temp and pH on the impact of absorption property.Adsorption experiment step is as follows:
Take a certain amount of mesoporous ion blotting material and be placed in 50ml colorimetric cylinder, then the cadmium ion standard liquid 20ml of debita spissitudo is added, control suitable pH value, vibration absorption 60min under the freezing gas bath constant temperature oscillator of digital display is 180 turns/min and 25 degree Celsius with rotating speed.After having adsorbed, accurately measure 10ml solution immediately in centrifuge tube, with 3000 turns per minute, carry out centrifugal when setting-up time is 10 minutes, after centrifugal, get 5ml supernatant, Atomic absorption external standard method (AgilentAA 240) quantitative assay is carried out.Condition determination: wavelength is 228.8nm, light normal tape is 0.4nm, lamp current is 2mA, burner height is 6mm, air pressure 0.3MPa, acetylene pressure 0.09MPa, air mass flow are 6.5Lmin -1, acetylene flow is 1.0Lmin -1, flame pattern is the blue flame of oxidisability.Calculate adsorbance and adsorption rate according to adsorption liquid change in concentration before and after absorption, formula is as follows:
Adsorption capacity formula is:
Adsorption rate formula is:
In formula: during Q-adsorption equilibrium, unit mass adsorbent is to the adsorbance of adsorbate, mg/g
C othe initial concentration of solute in solution when-absorption starts, mg/L
C ethe equilibrium concentration of solute in solution during-adsorption equilibrium, mg/L
η-adsorption rate, %
The volume of solution during V-adsorption equilibrium, L
M-adsorbent amount, g
1) adsorbent amount is to the result of the test of adsorption effect:
By 10,25,50,75, the mesoporous ion blotting material of 100mg adds in 50ml colorimetric cylinder respectively, adsorbance is measured by the method for adsorption experiment method, draw capacity (Q)-adsorbent amount (G) relation curve of absorption, result is as Fig. 4:
As can be seen from Figure 4, in the scope of 10mg-100mg, along with the increase adsorption capacity of quantity of sorbent increases thereupon, when the amount of mesoporous material is 50-100g, adsorption capacity increase is not clearly.When the amount of getting mesoporous material is 50g, the amount Q of absorption is 16.6mg/g, and during adsorption equilibrium, in solution, the concentration of cadmium ion is 3.358mg/l, can show that cadmium sorption rate reaches more than 80% (cadmium solution initial concentration is 50mg/l) according to adsorption rate formula.Therefore, consider the amount of adsorbent to be decided to be 50g from economics.
2) mensuration of curve of adsorption kinetics:
Get the colorimetric cylinder of 16 50ml, by adsorption experiment method, get the cadmium-ion solution 20ml that initial concentration is 50 and 500mg/L respectively, add 50mg adsorbent and carry out adsorption experiment, the solution getting 10ml at regular intervals carries out centrifugal, measures absorbance.Scaled data also draws adsorption capacity (Q)-time (t) curve, i.e. curve of adsorption kinetics.Object is to investigate mesoporous ion blotting material to the adsorption rate of cadmium ion, determines the time needed for adsorption equilibrium and maximum adsorption capacity.As can be seen from Fig. 5 and Fig. 6 curve of adsorption kinetics, along with the increase adsorption capacity of time increases gradually, in incipient 0-50min, along with the postponement adsorption capacity of adsorption time increases sharply, continuation along with adsorption time increases the adsorption rate of adsorbent to cadmium ion and slows down gradually, after reaching 60 minutes, reach adsorption equilibrium.Therefore, choosing adsorption time is 60min.Cadmium ion initial concentration be 50 and 500mg/L solution in, during adsorption equilibrium, adsorption capacity is respectively 16.6 and 49.6mg/g, and therefore, the maximum adsorption capacity of this mesoporous material is 49.6mg/g.
3) impact of temperature:
Get the colorimetric cylinder of 18 50ml, be equally divided into three groups, often organize and add the mesoporous ion blotting material of 50mg successively, add a series of cadmium standard liquids that concentration is 0 ~ 50mg/L, then in isothermal vibration device, adsorption equilibrium is reached with isothermal vibration 60min under 15 DEG C, 25 DEG C, 35 DEG C different temperatures, take out supernatant centrifuge, measure absorbance, calculate adsorbance.Concentration of cadmium ions (Ce) relation curve during adsorption capacity (Q)-adsorption equilibrium under drafting different temperatures, during investigation different temperatures, mesoporous ion blotting material is to the adsorption effect of cadmium ion, as seen from Figure 7, when temperature is lower than 25 DEG C time, the adsorption capacity of mesoporous ion blotting material to cadmium ion reduces with the reduction of temperature; When temperature is higher than 25 DEG C time, the absorption of mesoporous ion blotting material to cadmium ion raises with the rising of temperature, but the trend raised is not clearly, and therefore selected 25 DEG C is optimal adsorption temperature.
4) impact of pH value:
The cadmium-ion solution of 20ml50mg/l is added respectively in the colorimetric cylinder of 5 50ml.Add nitric acid respectively or pH is adjusted to 2,4,6,7,8 by NaOH, survey its absorbance with Atomic Absorption Spectrometer.As can be seen from Fig. 8, the cadmium-ion solution of different pH value is larger on mesoporous ion blotting materials adsorption rate impact.As a whole, adsorption rate first presents the trend raised gradually, to about 7.2 along with the rising of pH presents the trend reduced gradually along with pH raises.Namely when pH is less than 7.2, adsorption rate raises with the rising of pH; When pH is greater than 7.2, adsorption rate reduces with the rising of pH.Because experiment condition restriction cannot accurately regulate too low pH value, but found by searching document, be adsorbed with larger inhibitory action to mesoporous material under the environment that pH is too low or too high.PH is too low, hydrogen ion meeting competitive Adsorption point position in water; PH is too high, Cd 2+with OH 2-generate Cd(OH) 2therefore precipitation is 7.0 be considered as best adsorption conditionses PH.
5) impact of different initial soln concentration:
Choose initial soln concentration from 2 ~ 500mg/L, temperature 25 DEG C, pH are 7.0, carry out adsorption experiment under adsorbent amount 50mg, adsorption time 60min condition, as shown in Figure 9, when adsorbent amount 50mg, adsorption time 60min, temperature are 25 DEG C and pH is 7, adsorption effect is best, and maximal absorptive capacity can reach 49.6mg/g.(be less than or equal under usual ambient concentration
Three, selective absorption cadmium ion result:
Get mesoporous nonionic trace (NIP, similar to mesoporous imprinted material material preparation process, just do not add cadmium ion template) the standard liquid 20ml of material 0.05g and cadmium, be placed in 8 50ml colorimetric cylinders respectively, shake under the freezing gas bath constant temperature oscillator of digital display is 180 turns/min and 20 degree Celsius with rotating speed, 0, 10, 20, 30, 50, 70, 90, get 10ml solution in centrifuge tube under 130min at every turn, with 3000 turns per minute, carry out centrifugal when setting-up time is 10 minutes, get 5ml supernatant after centrifugal to measure, as shown in Figure 10, adsorption experiment is carried out in contrast with mesoporous nonionic imprinted material (NIP), when reaching about 60min, mesoporous ion blotting material (MIP) adsorption capacity is almost 2.5 times of mesoporous nonionic imprinted material (NIP) adsorption capacity.This is because mesoporous ion blotting material wash-out Cd 2+after template, leave a lot of imprinted cavity, increase absorption surface sum binding site distribution number, thus adsorption capacity is improved.Above result shows that the selective comparatively conventional adsorbent of prepared material is good.
Four, repeated result
After mesoporous material absorption, use the hydrochloric acid solution wash-out of 10ml0.5mol/L, 40% small-power sonic oscillation about 2 minutes, pure water drip washing afterwards 3 times, vacuum drying.Then in the cadmium-ion solution of 50mg/l, repetition adsorption experiment is carried out, iterative cycles 5 times, adsorption capacity remains on 81.1%(Figure 11 of initial adsorption capacity) more than (suppose first time adsorption capacity be 100%), show that this SiO 2 mesoporous materials has good rigidity, capable of circulationly to reuse.
Five, absorption property interpretation of result
With existing sorbing material phase, ratio, the sorbing material of the preparation of this patent has that the feature of environmental protection is strong, security is high, adsorbance is large, the advantage such as to reuse capable of circulation:
One is that the material feature of environmental protection is strong, security is high.After forming materials prepared by this patent, only have the part of hydroxyl group of silica and attachment on it, nontoxic, can be used for drinking water treatment technique (Fig. 1).And (application number: 201210486758.1 in existing patent, publication number CN102989429A) material relies on the organic group of grafting on silica to adsorb cadmium, the existence of these organic radicals, certain toxicity or environmental threat may be produced, when therefore using in drinking water treatment, may risk be there is;
Two is that adsorption capacity is large, absorption property better.The absorption of the application carries out at low concentrations, and (application number: 201210486758.1) same concentration compares, higher than corresponding data with existing patent.Such as, the application cadmium ion initial concentration be 50 and 500mg/L(0.44mmol/L and 4.45mmol/L) in solution, during adsorption equilibrium adsorption capacity be respectively 16.6 and 49.6mg/g(0.148mmol/g and 0.441mmol/g), under same initial soln concentration, adsorption capacity is better than the relevant Adsorption experimental results of existing data, this may be that mesoporous material specific area is comparatively large, causes absorption property to promote.Corresponding result is as Figure 12: wherein curve is that (application number: artwork data 201210486758.1), two five-pointed star data points are this patent experimental results to existing patent.Consider that in daily water environment, concentration of cadmium ions is generally not more than 500mg/L, so initial soln concentration is the highest be set as 500mg/L.

Claims (5)

1. a preparation method for the mesoporous imprinted material of selective absorption cadmium ion, is characterized in that: comprise the following steps:
(1) joined at 80 DEG C by the sodium hydrate aqueous solution of 2.00mol/L in the aqueous solution of cetab and mix, be more dropwise added drop-wise in mixed solution by tetraethoxysilane, strong agitation was filtered after two hours simultaneously;
(2) by the solid distilled water of filtration and alcohol flushing, then 80 DEG C of dryings 8 hours, MCM-41 material can be obtained;
(3) gained MCM-41 material is added in the methanol solution containing hydrochloric acid and reflux, product is filtered, and rinses fully with deionized water and ethanol, then 60 DEG C of dryings 6 hours, obtain the MCM-41 material of purifying;
(4) Cd(NO is taken 3) 24H 2o is placed in reaction bulb, add methanol solution, under agitation with heating water bath 50 DEG C until solid dissolves completely, add 3-[2-(2-aminoethylamino) ethylamino] propyl-trimethoxysilane (AAAPTS) again and react the MCM-41 adding purifying after two hours, reflux heating 12 hours at 80 DEG C, and then add epoxychloropropane and under agitation heating water bath 50 DEG C reaction 4 hours;
(5) gained solid also with absolute ethanol washing, is placed in 6mol/L hydrochloric acid solution by suction filtration after cooling, and stirs lower immersion 4 hours removing Cd 2+;
(6) with the NaHCO of 0.1mol/L 3solution and distilled water are washed till solution in neutral, the drying 12 hours of 80 DEG C, obtain mesoporous ion blotting material.
2. the preparation method of the mesoporous imprinted material of a kind of selective absorption cadmium ion according to claim 1, is characterized in that: cetab in step (1): NaOH: the mol ratio of tetraethoxysilane is 1:2.6:8.2.
3. the preparation method of the mesoporous imprinted material of a kind of selective absorption cadmium ion according to claim 1, is characterized in that: in step (2), the volume ratio of distilled water and ethanol is 10:1.
4. the preparation method of the mesoporous imprinted material of a kind of selective absorption cadmium ion according to claim 1, is characterized in that: in step (3), reflux course is specially: the methanol solution 150ml that every 1.5gMCM-41 material adds containing 1.5ml37% hydrochloric acid refluxes.
5. the preparation method of the mesoporous imprinted material of a kind of selective absorption cadmium ion according to claim 1, is characterized in that: Cd(NO in step (4) 3) 24H 2the mass ratio of O and MCM-41 is 1:2.
CN201510739736.5A 2015-11-04 2015-11-04 Preparation method of mesoporous print material capable of selectively adsorbing cadmium ions Pending CN105396555A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107189011A (en) * 2016-12-21 2017-09-22 哈尔滨师范大学 Hollow molecules imprinted polymer, solid-phase extraction column and its preparation method and application
CN107213877A (en) * 2017-05-15 2017-09-29 华南师范大学 A kind of synthetic method of the trace mesoporous material to bisphenol-A with high selectivity
CN109012639A (en) * 2018-08-16 2018-12-18 辽宁大学 Chitosan silicon based composite material of molybdenum trace and preparation method thereof and the application in recycling rhenium
CN111514861A (en) * 2020-05-13 2020-08-11 天津工业大学 Preparation method and application of tridentate ligand heavy metal ion imprinting material
CN111729659A (en) * 2020-07-23 2020-10-02 桂林理工大学 Preparation method of MCM-41 molecular sieve surface-based Cr (VI) ion imprinted material
CN111729658A (en) * 2020-07-23 2020-10-02 桂林理工大学 Preparation method of Cr (III) ion imprinted material based on MCM-41 molecular sieve surface
CN111760561A (en) * 2020-07-23 2020-10-13 桂林理工大学 Preparation method of As (III) ion imprinted material based on MCM-41 molecular sieve surface
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CN112619617A (en) * 2020-11-04 2021-04-09 江苏大学 Preparation method and application of nanogold-based ion imprinted polymer material
CN113426427A (en) * 2021-06-23 2021-09-24 广州市疾病预防控制中心(广州市卫生检验中心、广州市食品安全风险监测与评估中心、广州医科大学公共卫生研究院) Molecularly imprinted glycosyl mesoporous silica microsphere, preparation method and application

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104258826A (en) * 2014-09-15 2015-01-07 江苏大学 Active/controllable mesoporous material ion-surface imprinted polymer as well as preparation method and application of ion-surface imprinted polymer
CN104275155A (en) * 2014-10-28 2015-01-14 武汉大学 Preparation method of novel cadmium ion imprinting magnetic mesoporous silica gel solid-phase extracting agent as well as application of preparation method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104258826A (en) * 2014-09-15 2015-01-07 江苏大学 Active/controllable mesoporous material ion-surface imprinted polymer as well as preparation method and application of ion-surface imprinted polymer
CN104275155A (en) * 2014-10-28 2015-01-14 武汉大学 Preparation method of novel cadmium ion imprinting magnetic mesoporous silica gel solid-phase extracting agent as well as application of preparation method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GUOZHEN FANG ET AL.: "Synthesis and Evaluation of an Ion-Imprinted Functionalized Sorbent for Selective Seperation of Cadmium Ion", 《SEPARATION SCIENCE AND TECHNOLOGY》 *
HONGTAO FAN ET AL.: "An ion-imprinted amino-functionalized silica gel sorbent prepared by hydrothermal assisted surface imprinting technique for selective removal of cadmium (II) from aqueous solution", 《APPLIED SURFACE SCIENCE》 *

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CN107189011A (en) * 2016-12-21 2017-09-22 哈尔滨师范大学 Hollow molecules imprinted polymer, solid-phase extraction column and its preparation method and application
CN107213877A (en) * 2017-05-15 2017-09-29 华南师范大学 A kind of synthetic method of the trace mesoporous material to bisphenol-A with high selectivity
CN107213877B (en) * 2017-05-15 2020-06-12 华南师范大学 Synthetic method of imprinted mesoporous material with high selectivity to bisphenol A
CN109012639A (en) * 2018-08-16 2018-12-18 辽宁大学 Chitosan silicon based composite material of molybdenum trace and preparation method thereof and the application in recycling rhenium
CN111514861B (en) * 2020-05-13 2022-07-05 天津工业大学 Preparation method and application of tridentate ligand heavy metal ion imprinting material
CN111514861A (en) * 2020-05-13 2020-08-11 天津工业大学 Preparation method and application of tridentate ligand heavy metal ion imprinting material
CN111729659A (en) * 2020-07-23 2020-10-02 桂林理工大学 Preparation method of MCM-41 molecular sieve surface-based Cr (VI) ion imprinted material
CN111760561A (en) * 2020-07-23 2020-10-13 桂林理工大学 Preparation method of As (III) ion imprinted material based on MCM-41 molecular sieve surface
CN111729658A (en) * 2020-07-23 2020-10-02 桂林理工大学 Preparation method of Cr (III) ion imprinted material based on MCM-41 molecular sieve surface
CN112295549A (en) * 2020-09-11 2021-02-02 中南大学 Adsorbent for selectively separating gold and preparation method and application thereof
CN112619617A (en) * 2020-11-04 2021-04-09 江苏大学 Preparation method and application of nanogold-based ion imprinted polymer material
CN112619617B (en) * 2020-11-04 2023-02-17 江苏大学 Preparation method and application of nanogold-based ion imprinted polymer material
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