CN114832802A - Preparation method and application of polythiophene-pyrrole modified MCM-41 - Google Patents
Preparation method and application of polythiophene-pyrrole modified MCM-41 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 108
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 17
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000020477 pH reduction Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 85
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 43
- 239000007864 aqueous solution Substances 0.000 claims description 38
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 36
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 35
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229930192474 thiophene Natural products 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 36
- 239000000463 material Substances 0.000 abstract description 20
- 239000011148 porous material Substances 0.000 abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 description 21
- 229910001385 heavy metal Inorganic materials 0.000 description 17
- 238000003795 desorption Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- -1 LDH Substances 0.000 description 6
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 6
- 239000013335 mesoporous material Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920000128 polypyrrole Polymers 0.000 description 4
- 229920000123 polythiophene Polymers 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 229960002089 ferrous chloride Drugs 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- RABBMOYULJIAFU-UHFFFAOYSA-N 1h-pyrrole;thiophene Chemical compound C=1C=CNC=1.C=1C=CSC=1 RABBMOYULJIAFU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JJWSNOOGIUMOEE-UHFFFAOYSA-N Monomethylmercury Chemical compound [Hg]C JJWSNOOGIUMOEE-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000132521 Erigeron Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 101710138657 Neurotoxin Proteins 0.000 description 1
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- 208000001647 Renal Insufficiency Diseases 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 208000029028 brain injury Diseases 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 201000006370 kidney failure Diseases 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 239000002581 neurotoxin Substances 0.000 description 1
- 231100000618 neurotoxin Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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Abstract
The invention belongs to the technical field of mesoporous adsorption materials, and particularly relates to a preparation method and application of polythiophene-pyrrole modified MCM-41. The preparation method comprises the steps of diatomite acidification; preparing a solution; MCM-41 preparation and polythiophene-pyrrole modified MCM-41 preparation. The application is that the prepared composite material is used for adsorbing bivalent mercury in water. The technical scheme provided by the invention is that MCM-41 is prepared from natural diatomite by a hydrothermal method, compared with the prior art, the synthetic method is short in time, low in energy consumption and high in practical application value, and the prepared MCM-41 has high specific surface area and high pore volume.
Description
Technical Field
The invention belongs to the technical field of mesoporous adsorption materials, and particularly relates to a preparation method and application of polythiophene-pyrrole modified MCM-41.
Background
Mercury, a heavy metal, is extremely dangerous because of its durability, high bioaccumulation and difficult degradability. In addition, bivalent mercury in water is easily converted into more lethal methylmercury under the action of certain bacteria, and the methylmercury is a high-efficiency neurotoxin and can cause a series of diseases such as serious brain injury, renal failure, endocrine dyscrasia and the like.
With the continuous development of adsorbents, some conventional adsorption materials such as clay, LDH, carbon nanotubes, Layered Double Hydroxide (LDH), zeolite, etc. have been reported to remove divalent mercury in water.
According to the definition of International Union of applied chemistry (IUPAC), the pore size of the mesoporous material is 2-50nm, and the pore size is between that of the microporous material and the macroporous material. However, compared with the problems of too small or too large pore diameter and specific surface area of microporous materials and macroporous materials, mesoporous materials are receiving more and more attention due to their controllable size, pore morphology and easy functionalization.
In a mesoporous material family, MCM-41 has a two-dimensional straight pore channel structure, is a hexagonal crystal form, is the most important one in an M41S series, has a huge specific surface area and a highly ordered pore channel structure, and has the potential of an ideal adsorbent. At present, the hydrothermal synthesis method for preparing the MCM-41 mesoporous molecular sieve has been studied to a certain extent, but most of the hydrothermal synthesis methods have the defects of long preparation time and the like. Such as: sunpi et al use waste diatomite as a silicon source, CTAB as a template agent, and adopt a hydrothermal method to synthesize the mesoporous molecular sieve MCM-41, wherein the whole preparation process takes 109 hours and the preparation time is too long. For another example: the Jingjing fleaban and the like adopt a hydrothermal crystallization method to synthesize an ordered mesoporous molecular sieve MCM-41 with the specific surface area up to 512.3m and taking bentonite as a silicon source and CTAB as a template agent 2 The preparation time is as long as 37.5h per gram, and the preparation time is relatively long.
On the other hand, MCM-41 synthesized by pure silica bone has the defects of poor hydrothermal stability, low reaction catalysis efficiency, poor ion exchange capacity and the like, so that the application requirements of the MCM-41 in the aspects of adsorption, catalysis, biomedicine and the like cannot be met. In order to improve the related performance of MCM-41, the structure and the surface of the MCM-41 need to be subjected to functional modification.
In the synthesis method of the composite mesoporous material, modification of the mesoporous material is mostly complex, relatively high temperature is required, energy is consumed, and some organic solvents with high risk are even adopted. On the other hand, the prepared MCM-41 composite material has limited adsorption capacity to heavy metals, and the selective adsorption of the divalent mercury is less researched.
Chinese patent CN101972632A provides a preparation method for removing mercury ions in wastewater. Dissolving a silane coupling agent KH-550 in ethanol, adding a certain amount of baked mesoporous molecular sieve MCM-41, refluxing in a water bath at the temperature of 60-80 ℃ for 6-12 h, washing and drying a product after centrifugal separation to obtain aminopropyl functionalized MCM-41, wherein the adsorption capacity of the product to bivalent mercury in the solution is 23.92mg/g, and the prepared material not only consumes long time but also has relatively low adsorption capacity to mercury ions.
Disclosure of Invention
The invention provides a preparation method and application of polythiophene-pyrrole modified MCM-41, and aims to solve the problems that the selective adsorption and adsorption rate of the currently prepared mesoporous material MCM-41 to bivalent mercury are not ideal.
In order to solve the technical problems, the technical scheme of the invention is as follows: the preparation method of the polythiophene-pyrrole modified MCM-41 comprises the following steps:
1) and (3) diatomite acidification: mixing and heating natural diatomite and a hydrochloric acid aqueous solution, then filtering, washing and drying a filter cake to obtain acidified diatomite;
2) preparing a solution: the solution A is a sodium hydroxide aqueous solution, the solution B is a template agent aqueous solution, the solution C is a ferric trichloride aqueous solution, and the template agent is CTAB (cetyl trimethyl ammonium bromide);
3) preparation of MCM-41: dispersing the acidified diatomite prepared in the step 1) in the solution A, heating to 120-160 ℃ for reaction for 2-6 hours, then adding the solution B, finally adjusting the pH value to 9-10 by using a sulfuric acid aqueous solution, heating to 90-110 ℃ for reaction for 10-16 hours, and performing post-treatment calcination to remove a surfactant to obtain MCM-41;
4) preparation of polythiophene-pyrrole modified MCM-41: dispersing the MCM-41 prepared in the step 3) in a hydrochloric acid aqueous solution, adding sodium dodecyl sulfate, mixing, introducing nitrogen, adding pyrrole and thiophene, stirring, finally dropwise adding the solution C and hydrogen peroxide, keeping the mass ratio of ferric trichloride to hydrogen peroxide in a reaction system to be 1: 8-1: 10, filtering, washing and drying a filter cake after the reaction is finished, and obtaining the polythiophene-pyrrole modified MCM-41.
Optionally, in the step 1), the concentration of the hydrochloric acid solution is 5mol/L, and the solute mass ratio of the natural diatomite to the hydrochloric acid aqueous solution is 1: 5-1: 10.
Optionally, in step 1), the heating temperature is 105 ℃ and the heating time is 3-6 hours.
Optionally, in step 1), washing with deionized water for multiple times after filtering, wherein the drying temperature is 50-70 ℃ and the drying time is 3-6 hours.
Optionally, in the step 2), the mass concentration of sodium hydroxide in the solution A is 2.8-4.2%, the mass concentration of the template in the solution B is 6-6.5%, and the mass concentration of ferric trichloride in the solution C is 8-10%.
Optionally, in the step 3), the mass ratio of the sodium hydroxide in the solution a to the acidified diatomite is 1: 2-1: 4, and the solution a and the acidified diatomite are uniformly mixed by ultrasonic waves (the ultrasonic time is 10min, and the ultrasonic power is more than 150W).
Optionally, in the step 3), the mass ratio of CTAB in the acidified diatomite and the solution B is 1: 0.85-1: 2.25, and the concentration of the sulfuric acid aqueous solution is 2 mol/L.
Optionally, in step 3), the mass ratio of CTAB to solution B after acidification is 1: 2.25.
Optionally, in step 3), washing with deionized water for multiple times after filtering, wherein the drying temperature is 50-70 ℃ and the drying time is 3-6 hours.
Optionally, in the step 4), the concentration of the hydrochloric acid aqueous solution is 0.05mol/L, and the addition amount of the sodium dodecyl sulfate is 1/30-1/20 of the MCM-41 obtained in the step 3).
Optionally, in step 4), adding sodium dodecyl sulfate, and ultrasonically stirring the mixture (the ultrasonic time is 15min, and the ultrasonic power is more than 200W).
Optionally, in the step 4), after nitrogen is introduced, the reaction system is magnetically stirred for 30min, and the rotating speed is controlled to be 250-400 r/min.
Optionally, in the step 4), the added pyrrole and thiophene and MCM-41 in the system are proportioned as follows in parts by mass:
MCM-411 parts
0.8 to 1.2 portions of pyrrole
1-1.5 parts of thiophene.
Optionally, in the step 4), after adding pyrrole and thiophene, magnetically stirring for 1 hour at a stirring speed of 200- & lt 300 & gt r/min.
Optionally, in the step 4), the solution C and hydrogen peroxide are added and then reacted for 2 hours.
Optionally, in step 4), washing with deionized water for multiple times after filtering, wherein the drying temperature is 50-70 ℃ and the drying time is 3-6 hours.
The invention also provides application of the modified diatomite-based MCM-41 composite material in adsorption of bivalent mercury in water.
Compared with the prior art, the technical scheme provided by the invention has the following advantages:
1) compared with the prior art, the synthesis method has the advantages of short time, low energy consumption and practical application value, and the prepared MCM-41 has high specific surface area and high pore volume.
2) MCM-41 is modified by polythiophene-pyrrole, so that the polymer can realize overload in a substrate material with large specific surface area, the problem that heavy metal ions are difficult to reach active sites on the surface of a modified material in a pore channel is solved, and the adsorption performance of the material on the heavy metal ions is improved;
3) the prepared composite material can well adsorb heavy metal ions in water, has large adsorption capacity, has high selective adsorption on heavy metal mercury ions in electroplating wastewater, and is far higher than other heavy metal ions such as Cu 2+ 、Ni 2+ 、Cd 2+ And the like.
Drawings
FIG. 1 is an SEM image of a polythiophene-pyrrole modified MCM-41 composite prepared in example 1;
FIG. 2 is a TEM image of a polythiophene-pyrrole modified MCM-41 composite prepared in example 1;
FIG. 3 is an infrared FTIR profile of a polythiophene-pyrrole modified MCM-41 composite prepared according to example 1;
FIG. 4 shows the effect of the polypyrrole modified MCM-41, polythiophene modified MCM-41 and polythiophene-pyrrole modified MCM-41 composite material prepared in example 6 on heavy metal Hg in water 2+ The removal effect map of (1);
FIG. 5 shows the coupling of the polythiophene-pyrrole modified MCM-41 composite material prepared in example 7 to Hg in electroplating wastewater 2+ The selective adsorption pattern of (1).
Detailed Description
For the purpose of facilitating understanding, the modified diatomaceous earth-based MCM-41 composite, its method of preparation and use are described below in connection with examples, which are to be understood as merely illustrative of the present invention and not as limiting the scope of the present invention.
The conditions used in the examples may be further adjusted according to the specific conditions of the manufacturer, and the conditions not specified are generally the conditions in routine experiments.
Example 1 preparation of Polythiophene-pyrrole modified MCM-41 composite Material
(1) Acidifying: weighing a certain amount of natural diatomite in a three-neck flask, adding 5mol/L hydrochloric acid aqueous solution, wherein the mass ratio of the natural diatomite to the hydrochloric acid aqueous solution is 1:10, performing oil bath on the mixed solution at 105 ℃ for 4 hours, filtering by using a vacuum suction filter, washing for 3 times by using deionized water, and drying for 4 hours at 50 ℃ to obtain the acidified diatomite.
(2) Preparing a solution: 2.1, the solution A is an aqueous solution of sodium hydroxide, wherein the mass concentration of the sodium hydroxide is 2.8 percent; 2.2, the solution B is a template agent aqueous solution, the template agent is CTAB, and the mass concentration is 6%; and 2.3, the solution C is an iron trichloride aqueous solution, wherein the mass concentration of the iron trichloride is 8%.
(3) Preparation of MCM-41:
3.1 weighing 0.45g of acidified diatomite, dispersing in 8mL of solution A (namely the mass ratio of the acidified diatomite to the solid sodium hydroxide is 2:1), carrying out ultrasonic treatment on the mixture at room temperature for 10 minutes, wherein the ultrasonic power is not less than 150W, and transferring the mixture to a reaction kettle to react for 4 hours at about 140 ℃;
3.2 adding 17ml of solution B, namely adding a template CTAB in a mass ratio of the added amount of the template CTAB to the acidified diatomite of 1:2.25, then dropwise adding 2mol/L sulfuric acid aqueous solution into the system until the pH value of the solution is 9, heating the solution in a reaction kettle, and reacting the solution at about 90 ℃ for 12 hours;
3.3 washing the reaction with pure water 3 times and filtering with vacuum filtration device, drying at 50 deg.C for 4h, transferring to mortar to muffle furnace and calcining at 450 deg.C for 4h to remove surfactant to obtain MCM-41.
Through N 2 The specific surface area of the prepared MCM-41 can reach 775.5m measured by an adsorption and desorption isotherm curve test 2 Per g, pore volume of 0.71cm 3 /g。
(4) Preparation of polythiophene-pyrrole modified MCM-41:
4.1, weighing 0.6g of MCM-41, dispersing the MCM-41 in 60mL of 0.05mol/L hydrochloric acid aqueous solution, adding 30.0mg of lauryl sodium sulfate, namely the mass ratio of the MCM-41 to the lauryl sodium sulfate is 20:1, and ultrasonically stirring the mixture at room temperature for 15min, wherein the ultrasonic power is not less than 200W;
4.2 introducing nitrogen into the mixed solution after the ultrasonic treatment, magnetically stirring for 30min, controlling the rotating speed to be 250r/min, and dropwise adding pyrrole and thiophene monomer solution into the solution, wherein the adding amount is as follows:
MCM-410.6 g 1 part
0.5ml of pyrrole 0.8 parts
Thiophene 0.57ml 1 part;
after the addition, the magnetic stirring speed is controlled to be 200r/min, and the stirring is continued for 1 h;
4.3 dropwise adding the solution C into the mixed solution, then slowly dropwise adding hydrogen peroxide, controlling the mass ratio of the ferrous chloride to the hydrogen peroxide in the solution C to be 1:10, and continuing to react for 2 hours after the addition is finished; 4.4 repeating the process for 4.3, filtering the reacted mixed solution by using a vacuum filter, washing the filtered mixed solution for 3 times by using deionized water, drying the washed mixed solution for 4 hours at 50 ℃, and grinding the dried mixed solution into powder to obtain the polythiophene-pyrrole modified MCM-41.
Through N 2 The specific surface area of the prepared polythiophene-pyrrole modified MCM-41 is 525.7m measured by an adsorption and desorption isothermal curve test 2 Per g, pore volume of 0.452cm 3 /g。
Compared with MCM-41 before modification, the specific surface area and the pore volume of the polythiophene-pyrrole modified MCM-41 material are respectively reduced by 32.2% and 36.3%, and the mass is increased by 0.37g compared with that of the MCM-41 material (0.6g), which shows that the polythiophene-pyrrole copolymer generates a multilayer structure on the MCM-41 surface (as shown in figure 2) due to self-polymerization, thereby realizing overload.
On the other hand, MCM-41 is added into 60mg/L mercury stock solution under the condition of pH 7 for Hg 2+ The adsorption capacity is only 40.91mg/g, and after the polythiophene-pyrrole is modified, the adsorption capacity can reach 544.37mg/g, which shows that the polythiophene-pyrrole modified MCM-41 material leads Hg in the solution to be in a multilayer dense flocculent structure on the surface 2+ Can quickly enter a material pore passage to realize Hg 2+ Rapid removal of (3).
In FIG. 1, after pyrrole and thiophene polymerization modification, a layer of dense flocculent particles covers the surface of MCM-41, and it can be found from FIG. 2 that the surface of MCM-41 subjected to ultrasonic stripping is wrapped by a layer of pyrrole thiophene polymer, which fully proves that a large amount of modified material polythiophene-pyrrole is loaded on the surface of mesoporous molecular sieve MCM-41. In FIG. 3, after pyrrole and thiophene polymerization modification, the polythiophene-pyrrole modified MCM-41 material is 1701cm -1 And 1180cm -1 The nearby peaks are due to stretching vibration of C ═ O bonds and C — O bonds, demonstrating the presence of carbonyl and hydroxyl groups on the polymer. In addition, at 1564cm -1 、1469cm -1 、968cm -1 And 936cm -1 The characteristic peaks appeared here can be attributed to C-S and C-N flexural vibrations in the pyrrole thiophene polymer, demonstrating that pyrrole and thiophene copolymers were successfully introduced to the surface of MCM-41.
Example 2 preparation of Polythiophene-pyrrole modified MCM-41 composite Material
(1) Acidifying: weighing a certain amount of natural diatomite in a three-neck flask, adding 5mol/L hydrochloric acid aqueous solution, wherein the mass ratio of the natural diatomite to the hydrochloric acid aqueous solution is 1:8, performing oil bath on the mixed solution at 105 ℃ for 4 hours, filtering by using a vacuum suction filter, washing for 3 times by using deionized water, and drying for 4 hours at 60 ℃ to obtain the acidified diatomite.
(2) Preparing a solution:
2.1, the solution A is a sodium hydroxide aqueous solution, wherein the mass concentration of sodium hydroxide is 3.6 percent;
2.2, the solution B is a template aqueous solution, the template is CTAB, and the mass concentration is 6.3%;
and 2.3, the solution C is an iron trichloride aqueous solution, wherein the mass concentration of the iron trichloride is 9%.
(3) Preparation of MCM-41:
3.1 weighing 0.86g of acidified diatomite, dispersing in 8mL of solution A (namely the mass ratio of the acidified diatomite to the solid sodium hydroxide is 3:1), carrying out ultrasonic treatment on the mixture at room temperature for 10 minutes, wherein the ultrasonic power is not less than 150W, and transferring the mixture to a reaction kettle to react for 6 hours at about 120 ℃;
3.2 adding 17ml of solution B, namely adding a template CTAB in a mass ratio of the added amount of the template CTAB to the acidified diatomite of 1:1.25, then dropwise adding 2mol/L sulfuric acid aqueous solution into the system until the pH value of the solution is 9.5, heating the solution in a reaction kettle, and reacting for 12 hours at about 100 ℃;
3.3 washing the reaction with pure water 3 times and filtering with vacuum filtration device, drying at 60 deg.C for 4h, transferring to mortar to muffle furnace, calcining at 450 deg.C for 4h to remove surfactant to obtain MCM-41.
Through N 2 The specific surface area of the prepared MCM-41 can reach 779.6m measured by an adsorption and desorption isothermal curve test 2 Per g, pore volume of 0.68cm 3 /g。
(4) Preparation of polythiophene-pyrrole modified MCM-41:
4.1, weighing 0.75g of MCM-41, dispersing the MCM-41 in 60mL of 0.05mol/L hydrochloric acid aqueous solution, adding 30.0mg of lauryl sodium sulfate, namely the mass ratio of the MCM-41 to the lauryl sodium sulfate is 25:1, and ultrasonically stirring the mixture at room temperature for 15min, wherein the ultrasonic power is not less than 200W;
4.2 introducing nitrogen into the mixed solution after the ultrasonic treatment, magnetically stirring for 30min, controlling the rotating speed to be 300r/min, and dropwise adding pyrrole and thiophene monomer solution into the solution, wherein the adding amount is as follows:
MCM-410.75 g 1 part
Pyrrole 0.78ml 1 part
Thiophene 0.71ml 1.2 parts;
after the addition, the magnetic stirring speed is controlled to be 250r/min, and the stirring is continued for 1 h;
4.3 dropwise adding the solution C into the mixed solution, then slowly dropwise adding hydrogen peroxide, controlling the mass ratio of the ferrous chloride to the hydrogen peroxide in the solution C to be 1:9, and continuing to react for 2 hours after the addition is finished;
4.4 repeating the process of 4.3, filtering the reacted mixed solution by using a vacuum filter, washing the filtered mixed solution for 3 times by using deionized water, drying the washed mixed solution for 4 hours at the temperature of 60 ℃, and grinding the washed mixed solution into powder to obtain the polythiophene-pyrrole modified MCM-41.
Through N 2 The specific surface area of the prepared polythiophene-pyrrole modified MCM-41 is 530.1m measured by an adsorption and desorption isothermal curve test 2 Per g, pore volume of 0.457cm 3 /g。
Example 3 preparation of Polythiophene-pyrrole modified MCM-41 composite Material
(1) Acidifying: weighing a certain amount of natural diatomite into a three-neck flask, adding 5mol/L hydrochloric acid aqueous solution, wherein the mass ratio of the natural diatomite to the hydrochloric acid aqueous solution is 1:5, performing oil bath on the mixed solution at 105 ℃ for 4 hours, filtering by using a vacuum suction filter, washing by using deionized water for 3 times, and drying at 60 ℃ for 4 hours to obtain the acidified diatomite.
(2) Preparing a solution:
2.1, the solution A is an aqueous solution of sodium hydroxide, wherein the mass concentration of the sodium hydroxide is 4.2 percent;
2.2, the solution B is a template aqueous solution, the template is CTAB, and the mass concentration is 6.5%;
and 2.3, the solution C is an iron trichloride aqueous solution, wherein the mass concentration of the iron trichloride is 10%.
(3) Preparation of MCM-41:
3.1 weighing 1.34g of acidified diatomite, dispersing in 8mL of solution A (namely the mass ratio of the acidified diatomite to the solid sodium hydroxide is 4:1), carrying out ultrasonic treatment on the mixture at room temperature for 10 minutes, wherein the ultrasonic power is not less than 150W, and transferring the mixture to a reaction kettle to react for 2 hours at about 160 ℃;
3.2 adding 17ml of solution B, namely adding a template CTAB in a mass ratio of 1:0.85 to the acidified diatomite, then dropwise adding 2mol/L sulfuric acid aqueous solution into the system until the pH value of the solution is 10, heating the solution in a reaction kettle, and reacting for 10 hours at about 110 ℃;
3.3 washing the reaction with pure water 3 times and filtering with vacuum filtration device, drying at 70 deg.C for 3h, transferring to mortar to muffle furnace, calcining at 450 deg.C for 4h to remove surfactant to obtain MCM-41.
Through N 2 The specific surface area of the prepared MCM-41 can reach 783.4m measured by an adsorption and desorption isothermal curve test 2 Per g, pore volume of 0.69cm 3 /g。
(4) Preparation of polythiophene-pyrrole modified MCM-41:
4.1, weighing 0.9g of MCM-41, dispersing the MCM-41 in 60mL of 0.05mol/L hydrochloric acid aqueous solution, adding 30.0mg of lauryl sodium sulfate, namely the mass ratio of the MCM-41 to the lauryl sodium sulfate is 30:1, and ultrasonically stirring the mixture at room temperature for 15min, wherein the ultrasonic power is not less than 200W;
4.2 introducing nitrogen into the mixed solution after the ultrasonic treatment, magnetically stirring for 30min, controlling the rotating speed to be 400r/min, and dropwise adding pyrrole and thiophene monomer solution into the solution, wherein the adding amount is as follows:
MCM-410.9 g 1 part
1.12ml of pyrrole 1.2 parts
1.28ml of thiophene and 1.5 parts of thiophene;
after the addition, the magnetic stirring speed is controlled to be 300r/min, and the stirring is continued for 1 h;
4.3 dropwise adding the solution C into the mixed solution, then slowly dropwise adding hydrogen peroxide, controlling the mass ratio of the ferrous chloride to the hydrogen peroxide in the solution C to be 1:10, and continuing to react for 2 hours after the addition is finished;
4.4 repeating the process of 4.3, filtering the reacted mixed solution by using a vacuum filter, washing the filtered mixed solution for 3 times by using deionized water, drying the washed mixed solution for 3 hours at 70 ℃, and grinding the dried mixed solution into powder to obtain the polythiophene-pyrrole modified MCM-41.
Through N 2 The specific surface area of the prepared polythiophene-pyrrole modified MCM-41 is 520.8m measured by an adsorption and desorption isothermal curve test 2 Per g, pore volume 0.462cm 3 /g。
Example 4 Polythiophene-pyrrole modified MCM-41 composite for heavy metal Hg in water 2+ Removal of
100mL of heavy metal Hg with 60mg/L is taken 2+ Putting the ionic solution into a 250mL conical flask, adjusting the pH to 7 by using hydrochloric acid or sodium hydroxide and the like, adding 0.01g of the polythiophene-pyrrole modified MCM-41 composite material prepared in the example 1, oscillating for 9 hours at normal temperature, performing solid-liquid separation, obtaining the supernatant of the conical flask, and adopting a cold atom mercury absorption mercury detector to absorb the residual heavy metal Hg in the solution 2+ Detecting the ion concentration, the detection result and Hg in the solution before adsorption 2+ After the initial concentrations of the ions are compared, the polythiophene-pyrrole modified MCM-41 composite material is obtained by calculation for heavy metal Hg 2+ Has an adsorption capacity of 544.37mg/g, at which point the heavy metal Hg is 2+ The removal efficiency of (2) is as high as 90.72%.
Example 5 adsorption of Hg by Polythiophene-pyrrole modified MCM-41 composite Material 2+ Post desorption reuse
(1) Desorption process
100mL of a 1M HCl solution containing 5% thiourea was taken in a 250mL Erlenmeyer flask, and 20mg of example 4 adsorbed Hg was added 2+ And (3) oscillating the recycled material in a normal-temperature water bath in a shaking table for 1h, washing the material with pure water after the acid washing desorption is finished, and drying the material for later use.
(2) Adsorption process after desorption
Taking 5mg of the adsorbent after the analysis is finished, carrying out the adsorption experiment again, and taking 100mL of the adsorbent containing 60mg/L of heavy metal Hg 2+ The ionic solution is placed in a 250mL conical flask, the pH value is adjusted to 7 by hydrochloric acid, sodium hydroxide and the like, and the ionic solution is shaken in a water bath at normal temperature for 9 hours to carry out an adsorption experiment. The adsorption capacity of the material can still reach 87 percent of the initial adsorption capacity after 5 times of desorption-adsorption, and the regeneration utilization rate of the material is high.
Example 6 polypyrrole modified MCM-41, polythiophene modified MCM-41, and polythiophene-pyrrole modified MCM-41 composite materials on heavy metal Hg in water 2+ Comparative test for removal of
Polypyrrole-modified MCM-41 and polythiophene-modified MCM-41 were prepared by the method of reference example 1.
Adding 100mL of mercury stock solution with initial concentration of 60mg/L into 3 conical flasks of 250mL respectively, adjusting the pH of the solution to 7 completely, adding 0.01g of polypyrrole modified MCM-41, 0.01g of polythiophene modified MCM-41 and 0.01g of the polythiophene-pyrrole modified MCM-41 composite material prepared in the example 1 into the 3 conical flasks respectively, and oscillating the composite material in water bath for 9 hours at normal temperature;
taking supernatant respectively to carry out residual Hg 2+ And (3) detecting the concentration, and calculating to obtain:
polypyrrole modified MCM-41 to Hg 2+ The removal rate of (a) is 24.84%,
polythiophene modified MCM-41 to Hg 2+ The removal rate of (a) is only 17.55%,
polythiophene-pyrrole modified MCM-41 to Hg 2+ The removal rate of the catalyst is as high as 90.72 percent;
as shown in FIG. 4, the adsorption capacity of MCM-41 modified by pyrrole and thiophene copolymer to divalent mercury is much higher than that of monomer modified MCM-41, because Hg between pyrrole and thiophene copolymer and in solution 2+ Strong chelation was formed.
Example 7 polythiophene-pyrrole modified MCM-41 composite material to Hg in electroplating wastewater 2+ Selective adsorption of
Taking out and containing Cu 2+ 、Cd 2+ 、Cr 6+ 、Ni 2+ 、Zn 2+ 、Hg 2+ Putting 100mL of actual electroplating wastewater into a 250mL conical flask, firstly adjusting the pH of the solution to 7, adding 5mg of polythiophene-pyrrole modified MCM-41 prepared in example 1, oscillating for 9 hours at normal temperature, then carrying out solid-liquid separation, taking supernate and utilizing an ICP-OES instrument to determine the concentration of residual heavy metal ions in the solution.
As shown in FIG. 5, the removal rate of Hg2+ in the solution by the polythiophene-pyrrole modified MCM-41 is close to 90%, and the adsorption affinity with most other heavy metal ions is relatively highPoor result shows that the prepared mesoporous composite material is opposite to Hg 2+ Has excellent selective adsorption.
Finally, it should be noted that: the above examples are only for illustrating the technical solutions of the present invention, and are not limited thereto. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: it is to be understood that modifications may be made to the technical solutions described in the foregoing embodiments, or some or all of the technical features may be equivalently replaced, and such modifications or replacements may not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A preparation method of polythiophene-pyrrole modified MCM-41 is characterized by comprising the following steps:
1) and (3) diatomite acidification: mixing and heating natural diatomite and a hydrochloric acid aqueous solution, then filtering, washing and drying a filter cake to obtain acidified diatomite;
2) preparing a solution: the solution A is a sodium hydroxide aqueous solution, the solution B is a template agent aqueous solution, the solution C is a ferric trichloride aqueous solution, and the template agent is CTAB;
3) preparation of MCM-41: dispersing the acidified diatomite prepared in the step 1) in the solution A, heating to 120-160 ℃ for reaction for 2-6 hours, then adding the solution B, finally adjusting the pH value to 9-10 by using a sulfuric acid aqueous solution, heating to 90-110 ℃ for reaction for 10-16 hours, and performing post-treatment calcination to remove a surfactant to obtain MCM-41;
4) preparation of polythiophene-pyrrole modified MCM-41: dispersing the MCM-41 prepared in the step 3) in a hydrochloric acid aqueous solution, adding sodium dodecyl sulfate, mixing, introducing nitrogen, adding pyrrole and thiophene, stirring, finally dropwise adding the solution C and hydrogen peroxide, keeping the mass ratio of ferric trichloride to hydrogen peroxide in a reaction system to be 1: 8-1: 10, filtering, washing and drying a filter cake after the reaction is finished, and obtaining the polythiophene-pyrrole modified MCM-41.
2. The method for preparing polythiophene-pyrrole modified MCM-41 according to claim 1, wherein in step 1), the concentration of the hydrochloric acid solution is 5mol/L, and the solute mass ratio of the natural diatomite to the hydrochloric acid aqueous solution is 1: 5-1: 10.
3. The method for preparing polythiophene-pyrrole modified MCM-41 according to claim 1, wherein the mass concentration of sodium hydroxide in solution A is 2.8-4.2%, the mass concentration of template agent in solution B is 6-6.5%, and the mass concentration of ferric trichloride in solution C is 8-10%.
4. The method for preparing polythiophene-pyrrole modified MCM-41 according to claim 1, wherein in step 3), the mass ratio of sodium hydroxide in solution A to the acidified diatomite is 1: 2-1: 4, and the solution A and the acidified diatomite are uniformly mixed through ultrasonic.
5. The method for preparing polythiophene-pyrrole modified MCM-41 of claim 1, wherein in step 3), the mass ratio of CTAB in acidified diatomite and solution B is 1: 0.85-1: 2.25.
6. The method for preparing polythiophene-pyrrole modified MCM-41 according to claim 5, wherein in step 3), the mass ratio of CTAB to solution B after acidification is 1: 2.25.
7. The method for preparing polythiophene-pyrrole modified MCM-41 according to claim 1, wherein in step 4), the concentration of the hydrochloric acid aqueous solution is 0.05mol/L, and the addition amount of the sodium dodecyl sulfate is 1/30-1/20 of MCM-41 obtained in step 3).
8. The method for preparing polythiophene-pyrrole modified MCM-41 according to claim 1, wherein in step 4), the mass parts of added pyrrole and thiophene and MCM-41 in the system are as follows:
MCM-411 parts
0.8 to 1.2 portions of pyrrole
1-1.5 parts of thiophene.
9. Use of the modified diatomaceous earth-based MCM-41 composite prepared by the preparation method of any of claims 1-8 for adsorbing divalent mercury in water.
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