CN101890338A - Nano-SiO2 adsorption material and preparation method and application thereof - Google Patents
Nano-SiO2 adsorption material and preparation method and application thereof Download PDFInfo
- Publication number
- CN101890338A CN101890338A CN 201010242232 CN201010242232A CN101890338A CN 101890338 A CN101890338 A CN 101890338A CN 201010242232 CN201010242232 CN 201010242232 CN 201010242232 A CN201010242232 A CN 201010242232A CN 101890338 A CN101890338 A CN 101890338A
- Authority
- CN
- China
- Prior art keywords
- nanometer sio
- sorbing material
- preparation
- aminopropyl
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a nano-SiO2 adsorption material. The preparation method comprises the following step: using nano-SiO2, aminopropyl alkyl and -CO-C6H4-CH2P+(C6H5)3Br- to perform a chemical reaction and prepare the nano-SiO2 adsorption material through covalent linkage. The preparation method is simple, the conditions are mild, and product can be used to separate/concentrate trace Cr2O7<2-> in the environment. The nano-SiO2 adsorption material of the invention has the advantages of high adsorption efficiency, easy operation, no secondary pollution and the like.
Description
Technical field
The present invention relates to a kind of material modifiedly, relate in particular to a kind of nanometer SiO that adopts the modification of organic functions reagent
2Sorbing material and this preparation methods, the sorbing material that makes can be used for environment trace Cr
2O
7 2-Separation/enrichment.
Background technology
In recent years, use the industry of chromium compound such as plating, chemical industry, leather industry etc., remarkable in economical benefits, thus promoted the large-scale production of chromium salt factory greatly.Chromium residue that produces in the chromium salt production process and the high concentration chromium ion in the waste water, to all toxic effect of human body, crops, livestock, the chromium of sexavalence forms chromium oxide after entering blood of human body, cause hemoglobin to become ferrihemoglobin, red blood cell carries the function generation obstacle of oxygen, cause cell to suffocate, thereby be detrimental to health.And the occurring in nature Cr VI mainly exists with the acid group form, thereby explores and synthetic a kind of novel positively charged function adsorbent has very big Research Significance.
The method of removing heavy metal ion at present mainly contain the precipitation method (Journal of Hazardous Materials, 2008,159,435-439), ion-exchange and absorption (hydrometallurgy [J], 1994,49,16-20; Techniques and Equipment for Environmental Pollution Control [J], 2000,46-51), liquid-liquid extraction (Colloids and Surfaces A:Physicochem.Eng.Aspects, 2003,223,239-249.) and solid phase extraction (Journal of Hazardous Materials, 2005,121,79-87.) etc.The efficient of the precipitation method is low, and will introduce other impurity in precipitate metal ion; The poor selectivity and the exchange capacity of ion-exchange are low; Liquid-liquid extraction method will use different solvents, will produce secondary pollution to environment, but also relate to the solvent recovery problem; Solid phase extraction is the main method of separation/enriched in metals ion of growing up in recent years, and the research and development of sorbing material are key technologies, though the sorbing material kind of exploitation is various at present, but deficiency is separately arranged all, summarize and to get up mainly to have following defective: 1) adsorption capacity is low, 2) sorbing material is on the high side.
Summary of the invention
An object of the present invention is to provide a kind of nanometer SiO
2Sorbing material can overcome above defective, is a kind of cheap, the significant new material of adsorption effect.
Another object of the present invention provides a kind of nanometer SiO
2The preparation method of sorbing material.
Another object of the present invention provides a kind of nanometer SiO
2The purposes of sorbing material can be used for environment trace Cr to the sorbing material that makes
2O
7 2-Separation/enrichment.
Technical scheme of the present invention is as follows:
A kind of nanometer SiO
2Sorbing material comprises nanometer SiO
2, the aminopropyl silylation and-CO-C
6H
4-CH
2P
+(C
6H
5)
3Br
-Base.The aminopropyl silylation respectively with nanometer SiO
2With-CO-C
6H
4-CH
2P
+(C
6H
5)
3Br
-The base covalent bond.Nanometer SiO
2, the aminopropyl silylation and-CO-C
6H
4-CH
2P
+(C
6H
5)
3Br
-The mol ratio of base is 1: 2.5: 2.5.
A kind of nanometer SiO
2Sorbing material, its structure is as follows:
Wherein,
Expression nanometer SiO
2, Ph is phenyl C
6H
5
Nanometer SiO
2With the reaction of crosslinking agent aminopropyl triethoxysilane, pass through SiO
2On hydroxyl and aminopropyl silylation covalent bond, as follows:
Afterwards, add ClCO-C
6H
4-CH
2P (C
6H
5)
3The Br reaction promptly.The gained reactant dissolves with distilled water, suction filtration, drying
Another kind of nanometer SiO
2The preparation method of sorbing material, step is as follows:
1) nano silicon is earlier through 110 ℃ of hot preliminary treatment 4 hours.
2) pretreated nano silicon is dissolved in the toluene solvant, adds aminopropyl triethoxysilane behind the ultrasonic degas, once more ultrasonic degas.
3) logical N
2Under the condition, 75 ℃ of-80 ℃ of stirring reactions are more than 7 hours, preferred 9 hours.
4) afterwards, add ClOC-C
6H
4-CH
2P (C
6H
5)
3Br, 1,2-dichloroethanes and anhydrous pyridine, 80 ℃ the reaction more than 6 hours promptly.
ClOC-C
6H
4-CH
2P (C
6H
5)
3The preparation method of Br is as follows: bromo methyl acid, triphenylphosphine and oxolane after 80 ℃ of reactions, are cooled to room temperature, add ether, separate out post precipitation and filter.Product is heated, when temperature rises to 80 ℃, begins thionyl chloride, dropwise follow-up continuation of insurance temperature more than 1 hour, till no longer including gas and overflowing, again after distillation and drying promptly.A kind of preparation ClOC-C
6H
4-CH
2P (C
6H
5)
3The embodiment of Br is: to bromo methyl acid (1.70g, 7.9mmol), triphenylphosphine (2.10g, 8.0mmol) and oxolane (30mL) in 80 ℃ the reaction 8 hours, be cooled to room temperature, add ether 10mL, separate out post precipitation and filter, heating, when temperature rises to 80 ℃, begin thionyl chloride (7mL), drip off after 20 minutes, continue insulation 3 hours, till no longer including gas and overflowing, again after distillation and drying promptly.
Nanometer SiO of the present invention
2The preparation method of sorbing material, nanometer SiO
2, the aminopropyl silylation and-CO-C
6H
4-CH
2P
+(C
6H
5)
3Br
-The mol ratio of base is 1: 2.5: 2.5.
Nanometer SiO of the present invention
2Sorbing material can be used for environment trace Cr
2O
7 2-Separation/enrichment.In pH value of solution=1 o'clock to Cr
2O
7 2-Ionic adsorption efficient reaches maximum, Cr
2O
7 2-Adsorption effect the best when ion concentration is 50mg/L.
The beneficial effect that technical solution of the present invention realizes:
The invention provides a kind of nanometer SiO
2Sorbing material is by nanometer SiO
2, the aminopropyl silylation and-CO-C
6H
4-CH
2P
+(C
6H
5)
3Br
-The mol ratio of base is 1: 2.5: 2.5 covalently bound forming, and the preparation method is simple, mild condition, can be used for environment trace Cr
2O
7 2-Separation/enrichment.
Description of drawings
Fig. 1 raw material nano silica infrared spectrogram;
Fig. 2 nanometer titanium dioxide silicon materials of the present invention infrared spectrogram;
Fig. 3 pH is to the influence of adsorption efficiency;
Fig. 4 shakes the influence of time to adsorption efficiency;
Fig. 5 Cr
2O
7 2-Concentration to the influence of adsorption efficiency.
The specific embodiment
Below describe technical scheme of the present invention in detail.
Synthesizing of embodiment 1 nanometer titanium dioxide silicon materials
Accurately take by weighing 4 hours nano silicon of 110 ℃ of hot preliminary treatment of 1.00g (0.017mol) in the 150mL three-neck flask, add 50mL toluene, ultrasonic degas 30 minutes adds 0.0425 aminopropyl triethoxysilane (KH-550), ultrasonic degas 10 minutes.At logical N
2Under the condition, reaction temperature is controlled at 80 ℃, and stirring reaction 9 hours gets nano silicon aminopropyl silane.
To bromo methyl acid (1.70g, 7.9mmol), triphenylphosphine (2.10g, 8.0mmol) and oxolane (30mL) in 80 ℃ of reactions 8 hours, be cooled to room temperature, add ether 10mL, separating out post precipitation filters, heating begins thionyl chloride (7mL) when temperature rises to 80 ℃, drip off after 20 minutes, continue insulation 3 hours, till no longer including the gas effusion, distillation obtains rufous solid ClOC-C after the drying
6H
5-CH
2P (Ph)
3Br.
At last, add nano silicon aminopropyl silane 2.00g (0.0103mol) and 1 in the 150mL there-necked flask, 2-dichloroethanes (10mL) adds several anhydrous pyridines and ClOC-C
6H
5-CH
2P (Ph)
3Br (4.50g, 9.7mmol) the control temperature is 80 ℃, reacts 8 hours, and reactant dissolves with distilled water, suction filtration and drying.
Synthetic nano silicon bonding organic functions reagent adsorbent and raw material nano silica have been carried out structural characterization-infrared spectrogram.
Raw material Nano-SiO
2There is a large amount of hydroxyls on the surface, so at 3435.68cm
-1Near bigger absworption peak is arranged.1625.95cm
-1The place absworption peak then from adsorbed water, 1107.03cm
-1The strong absorption at place comes from the asymmetric stretching vibration of Si-O-Si key, 789.19cm
-1And 464.86cm
-1Place's absworption peak is from the flexural vibrations of Si-O-Si key.1684.32cm in Fig. 2
-1A strong absworption peak at place is from the stretching vibration of carbonyl, 3435.68cm
-1The stretching vibration that strong absworption peak comes self-association amino at place, 3052.97cm
-1The absworption peak at place is then from the stretching vibration of C-H in the phenyl ring, 1113.51cm
-1The strong absorption at place comes from the asymmetric stretching vibration of Si-O-Si key, 776.22cm
-1And 471.35cm
-1Place's absworption peak is from the flexural vibrations of Si-O-Si key, 1638.92cm
-1Place's absworption peak then comes from the stretching vibration of C=C in the phenyl ring, 1515.68cm
-1Place's absworption peak then comes from amino deformation vibration.
Comparison diagram 1 and Fig. 2, associate amino stretching vibration and vibration are arranged in Fig. 2, also have the stretching vibration of carbonyl that the flexural vibrations of Si-O-Si key and the asymmetric stretching vibration of Si-O-Si key are arranged again, this illustrates that all synthetic material has the various functional groups of target molecule.
Determining of embodiment 3 pH value of solution values
Nanometer titanium dioxide silicon materials (Si| (the CH that the 0.1g that packs in 5 100mL ground conical flasks has made
2)
3-NH-CO-Ph-CH
2-P-(C
6H
5)
3-Br), add the Cr of 2.00mL concentration 50 μ g/mL
2O
7 2-Solution is regulated pH, shakes 30 minutes, leaves standstill 1h, pipettes supernatant liquor centrifugal 10 minutes, and concentration dilution detects residual Cr to the optimum linear scope with flame atomic absorption spectrometry
2O
7 2-The ion residual volume calculates its adsorption rate A%, is relatively its adsorption effect, compares experiment with the nano silicon of equivalent.Experimental result as shown in Figure 3, He Cheng adsorbent adsorption efficiency when pH=1 also reaches and is 97.79% to the maximum as we can see from the figure.Along with the increase of pH, adsorption efficiency constantly reduces.And nano silicon when pH=1 to Cr
2O
7 2-It is 75.75% that ionic adsorption efficient reaches maximum, and along with the increase of pH, adsorption efficiency also obviously reduces.Relatively two curves can be seen, synthetic adsorbent is to Cr
2O
7 2The adsorption efficiency of ion will be apparently higher than Nano-SiO
2To Cr
2O
7 2-The adsorption efficiency of ion.
Regulate pH=1, Cr
2O
7 2-Initial ion concentration is 50mg/L, adds 0.02g, 0.05g, 0.1g, 0.2g and 0.3g Si| (CH under 25 ℃ of conditions respectively
2)
3-NH-CO-Ph-CH
2-P (C
6H
5)
3Br, concussion 30min leaves standstill 1h, and concentration dilution is surveyed Cr to the optimum linear scope with flame atomic absorption spectrometry
2O
7 2-The equilibrium concentration of ion is investigated the adsorbent consumption to Cr
2O
7 2-The influence of adsorption rate.The result shows: Si| (CH
2)
3-NH-CO-Ph-CH
2-P (C
6H
5)
3Br is to Cr
2O
7 2-Adsorption rate improve along with the increase of adsorbent addition, when the adsorbent consumption reached 0.1g, adsorption rate can reach more than 95%, took all factors into consideration this experimental selection Si| (CH
2)
3-NH-CO-Ph-CH
2-P (C
6H
5)
3The absorption consumption of Br is 0.1g.Fixedly the consumption of new adsorbent is 0.1g simultaneously, investigated the concussion time during pH=1 to be respectively 10,20, and 30,60,90,120,150 minutes influence, the result is as shown in Figure 4.Curve can be found from figure, and adsorption effect was best when the concussion time was 30 minutes.
Regulate pH=1, Cr
2O
7 2-Initial ion concentration is respectively 10,20,50,100,150mg/L, adds the 0.1g new adsorbent respectively under 25 ℃ of conditions, and concussion 30min leaves standstill 1h, and centrifugal, concentration dilution is surveyed Cr to the optimum linear scope with flame atomic absorption spectrometry
2O
7 2-The equilibrium concentration of ion is investigated Cr
2O
7 2-Initial ion concentration is to Cr
2O
7 2-The influence of adsorption rate.Adsorption effect was best when as can be seen from Figure 5, initial concentration was 50mg/L.
Prepare a series of Cr
6+Standard liquid (c=0.1 μ g/mL, 0.5 μ g/mL, 1.0 μ g/mL, 2.0 μ g/mL, 3.0 μ g/mL, 4.0 μ g/mL, 5.0 μ g/mL), measure its absorbance, the result shows: Cd (II) content is the better linearity relation at 0.5 μ g/mL～4.0 μ g/mL, linear equation is: A=0.003175C+0.010819, the dependent linearity coefficient is 0.9995, detecting of this method is limited to 0.084 μ g/mL, measures the Cr of 2.0 μ g/mL
2O
7 2-10 times, RSD is 1.09%
Embodiment 7
For verifying the accuracy of this analytical method, respectively to Cr in sanitary sewage, pond water and three kinds of water samples of industrial wastewater
2O
7 2-Content measure.With the mark-on method to Cr in three kinds of water samples
2O
7 2-The content and the rate of recovery measure, the results are shown in table 1.
Cr in table 1 environmental water sample
2O
7 2-Mensuration and mark-on reclaim experiment (n=5)
" ± " is relative standard deviation
Claims (8)
1. nanometer SiO
2Sorbing material is characterized in that comprising nanometer SiO
2, the aminopropyl silylation and-CO-C
6H
4-CH
2P
+(C
6H
5)
3Br
-Base, described aminopropyl silylation respectively with described nanometer SiO
2With described-CO-C
6H
4-CH
2P
+(C
6H
5)
3Br
-The base covalent bond.
2. nanometer SiO according to claim 1
2Sorbing material is characterized in that described nanometer SiO
2, described aminopropyl silylation and described-CO-C
6H
4-CH
2P
+(C
6H
5)
3Br
-The mol ratio of base is 1: 2.5: 2.5.
3. nanometer SiO according to claim 1
2Sorbing material is characterized in that described nanometer SiO
2The sorbing material structure is as follows:
Wherein,
Expression nanometer SiO
2, Ph is phenyl C
6H
5
4. nanometer SiO according to claim 1
2The preparation method of sorbing material, step is as follows:
1) nano silicon is earlier through 110 ℃ of hot preliminary treatment 4 hours;
2) pretreated nano silicon is dissolved in the toluene solvant, adds aminopropyl triethoxysilane behind the ultrasonic degas, once more ultrasonic degas;
3) logical N
2Under the condition, 75 ℃ of-80 ℃ of stirring reactions are more than 7 hours;
4) afterwards, add ClOC-C
6H
4-CH
2P (C
6H
5)
3Br, 1,2-dichloroethanes and anhydrous pyridine, 80 ℃ the reaction more than 6 hours promptly.
5. nanometer SiO according to claim 4
2The preparation method of sorbing material is characterized in that described ClOC-C
6H
4-CH
2P (C
6H
5)
3The preparation method of Br is as follows: bromo methyl acid, triphenylphosphine and oxolane after 80 ℃ of reactions, are cooled to room temperature, add ether, separate out post precipitation and filter; Product is heated, when temperature rises to 80 ℃, begins thionyl chloride, dropwise follow-up continuation of insurance temperature more than 1 hour, till no longer including gas and overflowing, again after distillation and drying promptly.
6. nanometer SiO according to claim 1
2Sorbing material is used for environment trace Cr
2O
7 2-Separate or enrichment.
7. nanometer SiO according to claim 6
2The purposes of sorbing material is characterized in that containing described Cr
2O
7 2-PH value of solution be 1.
8. nanometer SiO according to claim 6
2The purposes of sorbing material is characterized in that containing described Cr
2O
7 2-Concentration be 50mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010242232XA CN101890338B (en) | 2010-07-30 | 2010-07-30 | Nano-SiO2 adsorption material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010242232XA CN101890338B (en) | 2010-07-30 | 2010-07-30 | Nano-SiO2 adsorption material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101890338A true CN101890338A (en) | 2010-11-24 |
| CN101890338B CN101890338B (en) | 2012-07-11 |
Family
ID=43099777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010242232XA Expired - Fee Related CN101890338B (en) | 2010-07-30 | 2010-07-30 | Nano-SiO2 adsorption material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101890338B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013168035A1 (en) * | 2012-05-11 | 2013-11-14 | Impala Platinum Holdings Limited | A molecular recognition resin and method of manufacturing same |
| CN103406092A (en) * | 2013-08-28 | 2013-11-27 | 武汉理工大学 | Preparation method of amino-functionalization mesoporous gamma-Al2O3 absorbent |
| CN103913565A (en) * | 2014-04-26 | 2014-07-09 | 济南大学 | Preparation method and application of immunosensor constructed by difunctional marker |
| CN109675523A (en) * | 2018-12-19 | 2019-04-26 | 昆明理工大学 | A kind of yellow phosphorus furnace slag prepares the method and application of chromium adsorbent |
| CN111790438A (en) * | 2020-07-06 | 2020-10-20 | 中国科学院山西煤炭化学研究所 | Catalyst for cycloaddition reaction of ethylene oxide and carbon dioxide and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070014260A (en) * | 2005-07-28 | 2007-02-01 | 주식회사 다산솔루션 | The precipitation of heavy metal adsorbant derived from natural materials and the product thereof |
| CN101249415A (en) * | 2008-02-15 | 2008-08-27 | 郜洪文 | Barium based adsorption material and method of preparing the same |
-
2010
- 2010-07-30 CN CN201010242232XA patent/CN101890338B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070014260A (en) * | 2005-07-28 | 2007-02-01 | 주식회사 다산솔루션 | The precipitation of heavy metal adsorbant derived from natural materials and the product thereof |
| CN101249415A (en) * | 2008-02-15 | 2008-08-27 | 郜洪文 | Barium based adsorption material and method of preparing the same |
Non-Patent Citations (1)
| Title |
|---|
| 《应用化学》 20100331 高学超等 接枝型偕胺肟树脂/SiO2功能复合微粒的制备 1-3 第27卷, 第3期 2 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013168035A1 (en) * | 2012-05-11 | 2013-11-14 | Impala Platinum Holdings Limited | A molecular recognition resin and method of manufacturing same |
| CN103406092A (en) * | 2013-08-28 | 2013-11-27 | 武汉理工大学 | Preparation method of amino-functionalization mesoporous gamma-Al2O3 absorbent |
| CN103913565A (en) * | 2014-04-26 | 2014-07-09 | 济南大学 | Preparation method and application of immunosensor constructed by difunctional marker |
| CN103913565B (en) * | 2014-04-26 | 2015-05-06 | 济南大学 | Preparation method and application of immunosensor constructed by difunctional marker |
| CN109675523A (en) * | 2018-12-19 | 2019-04-26 | 昆明理工大学 | A kind of yellow phosphorus furnace slag prepares the method and application of chromium adsorbent |
| CN111790438A (en) * | 2020-07-06 | 2020-10-20 | 中国科学院山西煤炭化学研究所 | Catalyst for cycloaddition reaction of ethylene oxide and carbon dioxide and preparation method and application thereof |
| CN111790438B (en) * | 2020-07-06 | 2021-12-03 | 中国科学院山西煤炭化学研究所 | Catalyst for cycloaddition reaction of ethylene oxide and carbon dioxide and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101890338B (en) | 2012-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101890338B (en) | Nano-SiO2 adsorption material and preparation method and application thereof | |
| CA1283090C (en) | Bonded phase of silica for solid phase extraction | |
| CN104923163B (en) | A kind of silica gel absorber of Adsorption of Heavy Metal Ions and preparation method thereof | |
| CN102513064A (en) | Preparation method and application of ionic liquid bonded silica adsorbent | |
| CN106076279A (en) | A kind of adsorbent for heavy metal and its preparation method and application | |
| JPS61257237A (en) | Coupling phase of silica and carboalkoxy alkylsilanes for extracting solid phase | |
| CN105974001A (en) | Method for pretreating soil or sediment sample and method for determining dioxin | |
| CN108394950B (en) | Method for adsorbing noble metal gold ions | |
| Gao et al. | Study on recognition and separation of rare earth ions at picometre scale by using efficient ion-surface imprinted polymer materials | |
| CN110618224B (en) | [ H ]2Nmim][NTf2]@ UiO-66-Br nano composite material and application thereof | |
| CN103949228A (en) | Preparation method of molecularly-imprinted magnetic silica microsphere with hydrophilic external surface | |
| CN103980524B (en) | The preparation method of metal ion intermediary diosgenin imprinted polymer and application | |
| Ma et al. | Functionally modified cross-linked molecularly imprinted resins: separation and purification of camptothecin and its theoretical study | |
| CN111019147A (en) | Metal organic framework adsorbent, one-step preparation method and application thereof | |
| CN110479206A (en) | A kind of preparation method of the mercapto-modified magnetic Nano material for Adsorption of Mercury | |
| CN108114705A (en) | A kind of silica matrix basic amino acid bonded stationary phase and its preparation and application | |
| CN105561954B (en) | A kind of design preparation of chelating resin and its research application for cadmium ion in rice | |
| CN113176369B (en) | Method for determining organic tin in marine shellfish product | |
| Zhai et al. | Thallium (I) salts: New partners for calix [4] pyrroles | |
| CN108201881B (en) | Modified resin material and preparation method and application thereof | |
| CN106946926A (en) | One kind have multiple tooth ammonia carboxylic class dimer chelating agent and preparation method thereof, using and separating medium | |
| CN106984065B (en) | Method for separating chromium form on site | |
| Pu et al. | Synthesis of the p-tert-butyl calix [4] arene symmetrical sulfide derivatives and its extraction properties towards U (VI) from aqueous solution | |
| CN103897180B (en) | Preparation method of heavy metal ion complete antigen | |
| CN109433157A (en) | Catechol modified mesoporous silicon adsorbent, its preparation method and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120711 Termination date: 20130730 |