CN101890338B - 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
- CN101890338B CN101890338B CN201010242232XA CN201010242232A CN101890338B CN 101890338 B CN101890338 B CN 101890338B CN 201010242232X A CN201010242232X A CN 201010242232XA CN 201010242232 A CN201010242232 A CN 201010242232A CN 101890338 B CN101890338 B CN 101890338B
- Authority
- CN
- China
- Prior art keywords
- nano
- preparation
- nano sio
- hours
- sio2
- 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.)
- Expired - Fee Related
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 32
- 229910052681 coesite Inorganic materials 0.000 title claims abstract description 28
- 229910052906 cristobalite Inorganic materials 0.000 title claims abstract description 28
- 229910052682 stishovite Inorganic materials 0.000 title claims abstract description 28
- 229910052905 tridymite Inorganic materials 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 title abstract description 28
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- -1 2Aminopropylsilyl Chemical group 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 6
- 239000005543 nano-size silicon particle Substances 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- CQQSQBRPAJSTFB-UHFFFAOYSA-N 4-(bromomethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CBr)C=C1 CQQSQBRPAJSTFB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000009997 thermal pre-treatment Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000012141 concentrate Substances 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 24
- 239000003463 adsorbent Substances 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 229910002808 Si–O–Si Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZPZDIFSPRVHGIF-UHFFFAOYSA-N 3-aminopropylsilicon Chemical compound NCCC[Si] ZPZDIFSPRVHGIF-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010061951 Methemoglobin Proteins 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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 invention relates to a modified material, in particular to nano SiO modified by an organic functional reagent2Adsorbing material and preparation method thereof, and prepared adsorbing material can be used for trace Cr in environment2O7 2-Separation/enrichment.
Background
In recent years, the industries applying chromium compounds, such as electroplating, chemical industry, leather industry and the like, have remarkable economic benefits, thereby greatly promoting the mass production of chromium salt factories. Chromium-containing waste residues and high-concentration hexavalent chromium ions in wastewater generated in the production process of chromium salt have toxic action on human bodies, crops and livestock, and hexavalent chromium enters human blood to form chromium oxide, so that hemoglobin is changed into methemoglobin, and the function of oxygen carried by red blood cells is obstructed, so that cells are suffocated, and the human health is harmed. And hexavalent chromium exists mainly in the form of acid radical in nature, so that the exploration and synthesis of a novel functional adsorbent with positive charge have great research significance.
The current methods for removing heavy metal ions mainly include precipitation (Journal of Hazardous Materials, 2008, 159, 435-. The precipitation method has low efficiency, and other impurities are introduced while metal ions are precipitated; the ion exchange process has poor selectivity and low exchange capacity; the liquid-liquid extraction method uses different solvents, causes secondary pollution to the environment and also relates to the problem of solvent recovery; the solid phase extraction method is a main method for separating/enriching metal ions developed in recent years, research and development of adsorbing materials are key technologies, and the currently developed adsorbing materials have various types but have respective defects, and the following defects mainly exist in summary: 1) low adsorption capacity, 2) high price of the adsorption material.
Disclosure of Invention
An object of the present invention is to provide a nano SiO2The adsorbing material can overcome the defects and is a novel material with low price and remarkable adsorbing effect.
Another object of the present invention is to provide a nano SiO2A preparation method of the adsorbing material.
Another object of the present invention is to provide a nano SiO2Use of the adsorbent material, and use of the adsorbent materialTrace amount of Cr in the environment2O7 2-Separation/enrichment.
The technical scheme of the invention is as follows:
nano SiO2Adsorption material comprising nano SiO2Aminopropylsilyl and-CO-C6H4-CH2P+(C6H5)3Br-And (4) a base. Aminopropyl silane radical is respectively reacted with nano SiO2and-CO-C6H4-CH2P+(C6H5)3Br-The radicals are covalently bonded. Nano SiO2Aminopropylsilyl and-CO-C6H4-CH2P+(C6H5)3Br-The molar ratio of the radicals is 1: 2.5.
Nano SiO2An adsorbent having the following structure:
wherein,
represents nano SiO2Ph is phenyl C6H5。
Nano SiO2Reacting with a crosslinking agent aminopropyltriethoxysilane through SiO2The hydroxyl groups on (a) are covalently bound to the aminopropylsilyl groups as shown below:
then adding ClCO-C6H4-CH2P(C6H5)3And reacting Br to obtain the catalyst. The reaction obtained is carried out with distilled waterDissolving, filtering, and drying
Another kind of nano SiO2The preparation method of the adsorbing material comprises the following steps:
1) the nano silicon dioxide is firstly subjected to thermal pretreatment for 4 hours at 110 ℃.
2) Dissolving the pretreated nano silicon dioxide in a toluene solvent, adding aminopropyl triethoxysilane after ultrasonic degassing, and performing ultrasonic degassing again.
3) General formula (N)2The reaction is stirred for more than 7 hours, preferably 9 hours at the temperature of 75-80 ℃.
4) Then adding ClOC-C6H4-CH2P(C6H5)3Br, 1, 2-dichloroethane and anhydrous pyridine, reacting for more than 6 hours at 80 ℃ to obtain the catalyst.
ClOC-C6H4-CH2P(C6H5)3The preparation method of Br is as follows: reacting p-bromomethylbenzoic acid, triphenylphosphine and tetrahydrofuran at 80 ℃, cooling to room temperature, adding diethyl ether, precipitating, and filtering. Heating the product, starting to dropwise add thionyl chloride when the temperature rises to 80 ℃, keeping the temperature for more than 1 hour after the dropwise addition is finished until no gas escapes, and distilling and drying the product to obtain the product. Preparation of ClOC-C6H4-CH2P(C6H5)3Embodiments of Br are: p-bromomethylbenzoic acid (1.70g, 7.9mmol), triphenylphosphine (2.10g, 8.0mmol) and tetrahydrofuran (30mL) react at 80 ℃ for 8 hours, the reaction product is cooled to room temperature, 10mL of diethyl ether is added, precipitate is separated out, filtered and heated, thionyl chloride (7mL) is added dropwise when the temperature rises to 80 ℃, the dripping is finished after 20 minutes, the temperature is kept for 3 hours until no gas escapes, and the catalyst is obtained after distillation and drying.
The invention relates to nano SiO2Preparation method of adsorbing material and nano SiO2Aminopropylsilyl and-CO-C6H4-CH2P+(C6H5)3Br-The molar ratio of the radicals is 1: 2.5.
The invention relates to nano SiO2The adsorbing material can be used for adsorbing trace Cr in the environment2O7 2-Separation/enrichment. For Cr at solution pH 12O7 2-The ion adsorption efficiency reaches the maximum value, Cr2O7 2-The best adsorption effect is achieved when the ion concentration is 50 mg/L.
The technical scheme of the invention has the following beneficial effects:
the invention provides a nano SiO2Adsorption material of nano SiO2Aminopropylsilyl and-CO-C6H4-CH2P+(C6H5)3Br-The molar ratio of the base groups is 1: 2.5, the preparation method is simple, the condition is mild, and the method can be used for trace Cr in the environment2O7 2-Separation/enrichment.
Drawings
FIG. 1 is an infrared spectrum of a raw material of nano-silica;
FIG. 2 is an infrared spectrum of a nanosilica material of the present invention;
FIG. 3 influence of pH on adsorption efficiency;
FIG. 4 influence of oscillation time on adsorption efficiency;
FIG. 5Cr2O7 2-The effect of concentration of (a) on the adsorption efficiency.
Detailed Description
The technical solution of the present invention is described in detail below.
Example 1 Synthesis of nanosilica materials
1.00g (0.017mol) of nanosilica which had been thermally pretreated at 110 ℃ for 4 hours were accurately weighed into a 150mL three-necked flask, 50mL of toluene was added, ultrasonic degassing was performed for 30 minutes, and 0.0425 aminopropyltriethoxysilane (KH-550) was added, and ultrasonic degassing was performed for 10 minutes. In general N2Under the condition, the reaction temperature is controlled at 80 ℃, and the nano silicon dioxide aminopropyl silane is obtained after stirring reaction for 9 hours.
P-bromomethylbenzoic acid (1.70g, 7.9mmol), triphenylphosphine (2.10g, 8.0mmol) and tetrahydrofuran (30mL) react at 80 ℃ for 8 hours, the reaction product is cooled to room temperature, 10mL of diethyl ether is added, precipitate is separated out and filtered, heating is carried out, thionyl chloride (7mL) is added dropwise when the temperature rises to 80 ℃, the dripping is finished after 20 minutes, the heat preservation is continued for 3 hours until no gas escapes, distillation is carried out, and a reddish brown solid ClOC-C is obtained after drying6H5-CH2P(Ph)3Br。
Finally, 2.00g (0.0103mol) of nanosilica aminopropylsilane and 1, 2-dichloroethane (10mL) were added to a 150mL three-necked flask, and a few drops of anhydrous pyridine and ClOC-C were added6H5-CH2P(Ph)3Br (4.50g, 9.7mmol) was controlled at 80 ℃ and reacted for 8 hours, and the reaction was dissolved in distilled water, filtered and dried.
Example 2
And carrying out structural characterization-infrared spectrogram on the synthesized nano-silica bonded organic functional reagent adsorbent and the raw material nano-silica.
Raw material Nano-SiO2The surface has a large number of hydroxyl groups, so that the thickness of the film is 3435.68cm-1And a larger absorption peak is nearby. 1625.95cm-1The absorption peak is from the adsorbed water, 1107.03cm-1Strong absorption of (A) from asymmetric stretching vibration of Si-O-Si bond, 789.19cm-1And 464.86cm-1The absorption peak comes from the bending vibration of the Si-O-Si bond. 1684.32cm in FIG. 2-1A strong absorption peak at (B) comes from stretching vibration of carbonyl group, 3435.68cm-1A strong absorption peak comes from the stretching vibration of the associated aminoDynamic 3052.97cm-1The absorption peak is from C-H stretching vibration in benzene ring, 1113.51cm-1Strong absorption of (A) from asymmetric stretching vibration of Si-O-Si bond, 776.22cm-1And 471.35cm-1The absorption peak comes from the bending vibration of the Si-O-Si bond, 1638.92cm-1The absorption peak is derived from the stretching vibration of C ═ C in the benzene ring, 1515.68cm-1The absorption peak is from the deformation vibration of the amino group.
Comparing FIGS. 1 and 2, in FIG. 2, there are stretching vibration and vibration of the associated amino group, and also stretching vibration of the carbonyl group, bending vibration of the Si-O-Si bond, and asymmetric stretching vibration of the Si-O-Si bond, which all indicate that the synthesized substance has various functional groups of the target molecule.
EXAMPLE 3 determination of the pH of the solution
The prepared nanosilica material (Si | (CH) was charged in 5 100mL ground Erlenmeyer flasks (0.1 g)2)3-NH-CO-Ph-CH2-P-(C6H5)3Br) was added thereto 2.00mL of Cr at a concentration of 50. mu.g/mL2O7 2-Adjusting the pH of the solution, shaking for 30 minutes, standing for 1 hour, transferring supernatant, centrifuging for 10 minutes, diluting the concentration to the optimal linear range, and detecting residual Cr by flame atomic absorption spectrometry2O7 2-The residual ion content was calculated, and the adsorption rate A% was calculated, and for comparison of the adsorption effect, a comparative experiment was conducted using the same amount of nano-silica. As shown in fig. 3, it can be seen that the adsorption efficiency of the synthesized adsorbent reached a maximum of 97.79% at pH 1. The adsorption efficiency decreases continuously with increasing pH. And nano silicon dioxide to Cr when pH is 12O7 2-The ion adsorption efficiency reaches a maximum of 75.75%, and the adsorption efficiency is obviously reduced along with the increase of pH. Comparing the two curves, it can be seen that the synthesized adsorbent is on Cr2O7 2The adsorption efficiency of ions is obviously higher than that of Nano-SiO2For Cr2O7 2-The efficiency of the adsorption of ions.
Example 4
Adjusting pH to 1, Cr2O7 2-The initial ion concentration is 50mg/L, and 0.02g, 0.05g, 0.1g, 0.2g and 0.3g Si (CH) are added at 25 deg.C2)3-NH-CO-Ph-CH2-P(C6H5)3Br, shaking for 30min, standing for 1h, diluting the concentration to the optimal linear range, and measuring Cr by flame atomic absorption spectrometry2O7 2-Ion equilibrium concentration, investigating adsorbent dosage versus Cr2O7 2-Influence of adsorption rate. The results show that: si | (CH)2)3-NH-CO-Ph-CH2-P(C6H5)3Br to Cr2O7 2-The adsorption rate of the adsorbent is improved along with the increase of the addition amount of the adsorbent, when the dosage of the adsorbent reaches 0.1g, the adsorption rate can reach more than 95 percent, and Si (CH) is selected comprehensively in consideration of the experiment2)3-NH-CO-Ph-CH2-P(C6H5)3The amount of Br adsorbed was 0.1 g. Meanwhile, the effect of shaking time of 10, 20, 30, 60, 90, 120, 150 minutes was examined when the amount of the novel fixed adsorbent was 0.1g and pH was 1, and the result is shown in fig. 4. From the graph, it can be seen that the adsorption effect is best when the shaking time is 30 minutes.
Example 5
Adjusting pH to 1, Cr2O7 2-Initial ion concentrations of 10, 20, 50, 100 and 150mg/L, respectively adding 0.1g of novel adsorbent at 25 deg.C, shaking for 30min, standing for 1 hr, centrifuging, diluting to the optimum linear range, and measuring Cr by flame atomic absorption spectrometry2O7 2-Ion equilibrium concentration, investigation of Cr2O7 2-Initial ion concentration vs. Cr2O7 2-Influence of adsorption rate. As can be seen from FIG. 5, the adsorption effect was the best at an initial concentration of 50 mg/L.
Example 6
Preparing a series of Cr6+0.1. mu.g/mL (c: 05. mu.g/mL, 1.0. mu.g/mL, 2.0. mu.g/mL, 3.0. mu.g/mL, 4.0. mu.g/mL, 5.0. mu.g/mL) and the absorbance thereof was measured, and the results showed that: the content of Cd (II) is in a better linear relation between 0.5 mu g/mL and 4.0 mu g/mL, and the linear equation is as follows: a is 0.003175C +0.010819, the correlation linearity coefficient is 0.9995, the detection limit of the method is 0.084 mu g/mL, and 2.0 mu g/mL of Cr is measured2O7 2-10 times, the RSD is 1.09%
Example 7
In order to verify the accuracy of the analysis method, Cr in three water samples, namely domestic sewage, pond water and industrial wastewater are respectively analyzed2O7 2-The content of (b) is measured. Method for adding standard to Cr in three water samples2O7 2-The contents and the recovery rates of (A) were measured, and the results are shown in Table 1.
TABLE 1 Cr in environmental water samples2O7 2-Measurement and recovery test (n ═ 5)
"+/-" is the relative standard deviation
Claims (1)
1. Nano SiO2A method for preparing an adsorbing material, which comprises the steps of,
the nano SiO2The adsorbing material comprises nano SiO2Aminopropylsilyl and-CO-C6H4-CH2P+(C6H5)3Br-The aminopropylsilyl groups are respectively connected with the nano SiO2And said-CO-C6H4-CH2P+(C6H5)3Br-Covalently bonding the groups;
the preparation steps are as follows:
1) the nano silicon dioxide is firstly subjected to thermal pretreatment for 4 hours at 110 ℃;
2) dissolving the pretreated nano silicon dioxide in a toluene solvent, adding aminopropyl triethoxysilane after ultrasonic degassing, and performing ultrasonic degassing again;
3) general formula (N)2Under the condition, stirring and reacting for more than 7 hours at the temperature of 75-80 ℃;
4) then adding ClOC-C6H4-CH2P(C6H5)3Br, 1, 2-dichloroethane and anhydrous pyridine, react for more than 6 hours at 80 ℃ to obtain the catalyst; the ClOC-C6H4-CH2P(C6H5)3The preparation method of Br is as follows: reacting p-bromomethylbenzoic acid, triphenylphosphine and tetrahydrofuran at 80 ℃, cooling to room temperature, adding diethyl ether, precipitating, and filtering; heating the product, starting to dropwise add thionyl chloride when the temperature rises to 80 ℃, keeping the temperature for more than 1 hour after the dropwise addition is finished until no gas escapes, and distilling and drying the product to obtain the product.
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 CN101890338A (en) | 2010-11-24 |
| CN101890338B true 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) |
Families Citing this family (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 |
| CN103406092B (en) * | 2013-08-28 | 2015-12-09 | 武汉理工大学 | The mesoporous γ of a kind of functional amido-Al 2o 3the preparation method of adsorbent |
| 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 |
| 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 |
Family Cites Families (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
Also Published As
| Publication number | Publication date |
|---|---|
| CN101890338A (en) | 2010-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101890338B (en) | Nano-SiO2 adsorption material and preparation method and application thereof | |
| Krishnapriya et al. | A new chitosan biopolymer derivative as metal-complexing agent: synthesis, characterization, and metal (II) ion adsorption studies | |
| Tighadouini et al. | Removal efficiency of Pb (II), Zn (II), Cd (II) and Cu (II) from aqueous solution and natural water by ketoenol–pyrazole receptor functionalized silica hybrid adsorbent | |
| Zhu et al. | Selective solid-phase extraction of lead (II) from biological and natural water samples using surface-grafted lead (II)-imprinted polymers | |
| He et al. | Synthesis and applications of surface-grafted Th (IV)-imprinted polymers for selective solid-phase extraction of thorium (IV) | |
| Radi et al. | Organically modified silica with pyrazole-3-carbaldehyde as a new sorbent for solid-liquid extraction of heavy metals | |
| CN108976430B (en) | Acylhydrazone-linked covalent organic framework material and preparation method and application thereof | |
| Krawczyk et al. | Application of dendrimer modified halloysite nanotubes as a new sorbent for ultrasound-assisted dispersive micro-solid phase extraction and sequential determination of cadmium and lead in water samples | |
| Sayin et al. | Synthesis of calix [4] arene bearing pyridinium units supported silica gel for sorption of arsenate and dichromate anions | |
| Yang et al. | Preparation of stoichiometric molecularly imprinted polymer coatings on magnetic particles for the selective extraction of auramine O from water | |
| Gübbük et al. | Synthesis, characterization, and sorption properties of silica gel-immobilized Schiff base derivative | |
| Budnyak et al. | Adsorption of V (V), Mo (VI) and Cr (VI) oxoanions by chitosan–silica composite synthesized by Mannich reaction | |
| Li et al. | Solid-phase extraction of chromium (III) with an ion-imprinted functionalized attapulgite sorbent prepared by a surface imprinting technique | |
| Tighadouini et al. | Synthesis of 1-(Furan-2-yl) imine functionalized silica as a chelating sorbent and its preliminary use in metal Ion adsorption | |
| Liu et al. | Tailor‐made ion‐imprinted polymer based on functionalized graphene oxide for the preconcentration and determination of trace copper in food samples | |
| CN113278157B (en) | Cadmium coordination polymer and preparation method and application thereof | |
| Liu et al. | Synthesis, characterization and properties of 3, 3′-diethyl-1, 1′-oxydiethylenedicarbonyl bis (thiourea) | |
| Depecker et al. | Synthesis and applications of XAD-4-DAN chelate resin for the separation and determination of Se (IV) | |
| Dadfarnia et al. | Synthesis and application of a nanoporous ion‐imprinted polymer for the separation and preconcentration of trace amounts of vanadium from food samples before determination by electrothermal atomic absorption spectrometry | |
| Gierczyk et al. | New gel-like polymers as selective weak-base anion exchangers | |
| Wang et al. | An imprinted organic–inorganic hybrid sorbent for selective separation of copper ion from aqueous solution | |
| Rykowska et al. | Extraction of copper ions using silica gel with chemically modified surface | |
| CN111077196A (en) | Processing method of nano material composite and application of nano material composite in bisphenol A detection | |
| CN106946926A (en) | One kind have multiple tooth ammonia carboxylic class dimer chelating agent and preparation method thereof, using and separating medium | |
| Sharma et al. | Diacetylmonoxime functionalized silica gel: an efficient and recyclable organic inorganic hybrid material for selective removal of copper from fly ash ameliorated soil samples |
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 |