CN114471709B - Iron-doped cellulose-based microsphere with high catalytic performance as well as preparation method and application thereof - Google Patents
Iron-doped cellulose-based microsphere with high catalytic performance as well as preparation method and application thereof Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 53
- 239000001913 cellulose Substances 0.000 title claims abstract description 53
- 239000004005 microsphere Substances 0.000 title claims abstract description 49
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 125000005385 peroxodisulfate group Chemical group 0.000 claims abstract description 7
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims description 21
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims description 21
- 230000015556 catabolic process Effects 0.000 claims description 15
- 238000006731 degradation reaction Methods 0.000 claims description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 229920002301 cellulose acetate Polymers 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 230000005526 G1 to G0 transition Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 229920000875 Dissolving pulp Polymers 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000002386 leaching Methods 0.000 abstract description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004098 Tetracycline Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229960002180 tetracycline Drugs 0.000 description 2
- 229930101283 tetracycline Natural products 0.000 description 2
- 235000019364 tetracycline Nutrition 0.000 description 2
- 150000003522 tetracyclines Chemical class 0.000 description 2
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000004484 Briquette Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000013319 spin trapping Methods 0.000 description 1
- -1 sulfate radicals Chemical class 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention discloses a high-catalytic-performance iron-doped cellulose-based microsphere, a preparation method and application thereof. The method for preparing the high-catalytic-performance iron-doped cellulose-based microspheres is simple, low in cost, good in catalytic effect, free of external conditions after adding the peroxodisulfate in the catalytic oxidation process, small in influence on the pH value of water before and after the reaction, and high in practical applicability, iron is attached to the microspheres, the leaching rate of the iron is reduced, the iron is easy to recycle, and the method is reusable.
Description
Technical Field
The invention belongs to the technical field of material synthesis and water treatment, and particularly relates to a high-catalytic-performance iron-doped cellulose-based microsphere, and a preparation method and application thereof.
Background
Tetracycline hydrochloride is widely used as an antibiotic drug in people's life. In recent years, various water environment media in China such as drinking water sources, surface water, underground water, effluent of sewage treatment plants and the like all detect tetracycline hydrochloride with different concentrations, which indicates that many water bodies in China are subjected to micro-pollution with different degrees. The common methods for treating the tetracycline hydrochloride in the water mainly comprise an adsorption method, a photocatalytic degradation method, an electrochemical method and the like, but have the defects of high treatment cost, limitation of reaction conditions and the like.
Most researches show that Advanced Oxidation Processes (AOPs) based on highly oxidative free radicals have advantages of high efficiency, universality, thoroughness and the like in terms of organic matter removal, and persulfate systems are more advantageous than hydrogen peroxide and ozone in advanced oxidation processes because of low cost and higher chemical stability in transportation and storage. Iron as crust of earthThe second abundant transition element of (2) is environmentally friendly, inexpensive and readily available, and is used for the activation of persulfates to generate sulfate radicals (SO) in homogeneous or heterogeneous oxidation by utilizing the change in valence state 4 - However, the use of iron-activated persulfates alone to degrade contaminants during the reaction may result in an increase in the iron content of the water. Cellulose is a bio-based material, can be obtained from various materials (plants and bacteria), has low toxicity, is degradable, structurally has the characteristics of layering and high cohesiveness, and is a good material carrier. Chinese patent CN 100522343C discloses an iron-loaded spherical cellulose adsorbent, its preparation and application, which uses high adsorption activity iron hydroxide as active center, spherical cellulose as carrier, and removes arsenic, fluorine and other heavy metals in drinking water source with high efficiency and high selectivity, but its adsorption performance is affected by iron element content, multiple times of iron loading is needed to achieve the required purpose, and the removal of organic matters is not involved.
The liquid drop micro-fluidic technology is a new technology for manipulating micro-volume liquid developed on a micro-fluidic chip, and forms liquid drops at a micro-channel interface by using complementary compatible two-phase fluid under the action of shearing force and interfacial tension, and is characterized by small consumption of samples and reagents, high mixing speed, strong anti-interference capability, good repeatability and easy precise control, and is mainly applied to aspects of enzyme reaction dynamics analysis, single cell analysis, protein crystallization, influence of crystal nucleus formation on crystallization, molecular synthesis, simulation of complex processes, nanoparticle synthesis and microparticle synthesis at present. However, no report on preparing the iron-containing cellulose catalyst by utilizing a droplet microfluidic technology is known at present.
Disclosure of Invention
Aiming at the problem of poor catalytic degradation effect of tetracycline hydrochloride in the prior art, the invention provides the iron-doped cellulose-based microsphere with high catalytic performance, and the preparation method and application thereof.
The invention is realized by the following technical scheme:
an iron-doped cellulose-based microsphere with high catalytic performance is prepared by the following method:
(1) Dissolving cellulose in an organic solvent, adding an iron source, then adding a pore-forming agent, and stirring until the cellulose is completely dissolved to form a continuous phase;
(2) And (3) taking deionized water as a stationary phase, taking the solution in the step (1) as a continuous phase, reacting in a liquid drop microfluidic system, filtering, washing, and drying at 60-80 ℃ to obtain the iron-doped cellulose-based microsphere with high catalytic performance.
Further, the cellulose in the step (1) is cellulose acetate; the organic solvent is dimethyl sulfoxide or N, N-dimethylformamide; the iron source is ferrous sulfate or ferrous chloride.
Further, the flow rate of the continuous phase in the step (2) is 10-14.5 mL/h.
Further, the mass ratio of the iron source to the cellulose in the step (1) is 1:3-10.
Further, the pore-forming agent in the step (1) is sodium bicarbonate and sodium sulfate, the addition amount of the sodium bicarbonate is 5-15% of the mass of the cellulose, and the addition amount of the sodium sulfate is 20-40% of the mass of the cellulose.
In the invention, the preparation method of the high-catalytic-performance iron-doped cellulose-based microsphere comprises the following steps:
(1) Dissolving cellulose in an organic solvent, adding an iron source, then adding a pore-forming agent, and stirring until the cellulose is completely dissolved to form a continuous phase;
(2) Taking water as a stationary phase, taking the solution in the step (1) as a continuous phase, reacting in a liquid drop microfluidic system, and then filtering, washing and drying to obtain the iron-doped cellulose-based microsphere with high catalytic performance.
The invention discloses an application of the high-catalytic-performance iron-doped cellulose-based microsphere in catalytic degradation of tetracycline hydrochloride.
Further, the iron-doped cellulose-based microsphere with high catalytic performance is used as a catalyst for catalyzing peroxodisulfate to degrade tetracycline hydrochloride.
Furthermore, the high-catalytic-performance iron-doped cellulose-based microspheres can be reused after being washed and dried.
The method has the advantages of low cost and easy obtainment of raw materials, environmental friendliness, low cost, simple operation, simple preparation method, little pH change of the solution before and after the wastewater reaction, easy recovery of the catalyst and repeated utilization, and is used for synthesizing the iron-doped cellulose-based microspheres by utilizing a microfluidic technology. The iron-doped cellulose-based microspheres are used as catalysts for treating tetracycline hydrochloride wastewater, the catalytic degradation effect is remarkable, the degradation rate can reach about 85% in 90min, no external conditions are needed after the peroxodisulfate is added in the catalytic oxidation process, the energy consumption can be reduced, and the practical applicability is high.
Advantageous effects
The method for preparing the high-catalytic-performance iron-doped cellulose-based microspheres has the advantages of simple process, low cost, good catalytic effect, no need of external conditions after adding the peroxodisulfate in the catalytic oxidation process, small influence on the pH value of water before and after reaction, capability of enabling iron to be attached to the microspheres, reduction of the leaching rate of iron, easy recovery, reusability, strong practicability, and high catalytic treatment of tetracycline hydrochloride wastewater for 90min, and the degradation rate of tetracycline hydrochloride reaches about 85%, and is beneficial to further application in the field of environmental protection water treatment.
Drawings
FIG. 1 is an SEM surface view and a cross-sectional view of the iron-doped cellulose-based microspheres produced;
FIG. 2 is an XPS diagram of the iron-doped cellulose-based microspheres produced;
FIG. 3 is N of the iron-doped cellulose-based microspheres produced 2 Adsorption-desorption drawing;
FIG. 4 is a FTIR graph of the resulting iron-doped cellulose-based microspheres;
FIG. 5 is an EPR diagram of the iron-doped cellulose-based microspheres produced;
FIG. 6 is a graph showing the concentration change of the prepared iron-doped cellulose-based microspheres in different time periods for catalytic degradation of tetracycline hydrochloride solution.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Example 1
(1) Adding 0.5g of cellulose acetate into a beaker containing 5mL of dimethyl sulfoxide, stirring for 6 hours by a magnetic stirrer to completely dissolve the cellulose acetate, adding 0.1g of ferrous sulfate, stirring for 1 hour, then adding 0.05g of sodium bicarbonate and 0.2g of anhydrous sodium sulfate, and magnetically stirring until the cellulose acetate is completely dissolved to form a continuous phase;
(2) Taking water as a stationary phase, taking the solution in the step (1) as a continuous phase, reacting in a liquid drop microfluidic system, controlling the speed of the continuous phase to be 14.4mL/h, filtering after the reaction, washing the solid with deionized water for 5 times, and drying in an oven at 80 ℃ to obtain the iron-doped cellulose-based microsphere CA-Fe with high catalytic performance.
Example 2
(1) Adding 0.5g of cellulose acetate into a beaker containing 5mLN and N-dimethylformamide, stirring for 6 hours by a magnetic stirrer to completely dissolve the cellulose acetate, adding 0.2g of ferrous chloride, stirring for 1 hour, then adding 0.075g of sodium bicarbonate and 0.1g of anhydrous sodium sulfate, and magnetically stirring to completely dissolve the cellulose acetate to obtain a continuous phase;
(2) Taking water as a stationary phase, taking the solution in the step (1) as a continuous phase, carrying out reaction in a liquid drop microfluidic system, wherein the speed of the continuous phase is 12.4mL/h, filtering after the reaction is finished, washing the solid with deionized water for 5 times, and drying in a 70 ℃ oven to obtain the iron-doped cellulose-based microsphere CA-Fe with high catalytic performance.
Example 3
(1) Adding 0.5g of cellulose acetate into a beaker containing 5mL of dimethyl sulfoxide, stirring for 6 hours by a magnetic stirrer to completely dissolve the cellulose acetate, adding 0.1g of ferrous sulfate, stirring for 1 hour, then adding 0.05g of sodium bicarbonate and 0.2g of anhydrous sodium sulfate, and magnetically stirring until the cellulose acetate is completely dissolved to form a continuous phase;
(2) Taking water as a stationary phase, taking the solution in the step (1) as a continuous phase, carrying out reaction in a liquid drop microfluidic system, wherein the speed of the continuous phase is 10.0mL/h, filtering after the reaction is finished, washing the solid with deionized water for 3 times, and drying in an oven at 80 ℃ to obtain the iron-doped cellulose-based microsphere CA-Fe with high catalytic performance.
Performance detection
The SEM surface and cross-section of the high catalytic performance iron-doped cellulose-based microspheres prepared in example 1 are shown in fig. 1, the surfaces of the microspheres are smooth, and the interiors of the microspheres are in a honeycomb briquette shape;
as can be seen from FIG. 2, the XPS chart of the high catalytic performance iron-doped cellulose-based microspheres prepared in example 1 shows that the detected chemical binding energies are 284.1eV, 536.4eV and 712.5eV, respectively corresponding to C1s、 O 1s、 Fe 2pThe track, the material contains these three elements, which indicates that the element iron is successfully doped into the microsphere;
n of high catalytic Performance iron-doped cellulose-based microspheres prepared in example 1 2 The adsorption-desorption diagram is shown in FIG. 3, and it can be seen from FIG. 3 that the adsorption-desorption ratio is 0.8-1.0P/P 0 There is a distinct hysteresis loop, proving that the microsphere has a porous structure. The result shows that the transition metal element Fe is doped in the synthesis process of the microsphere, so that the specific surface area of the microsphere is increased, the structure of the microsphere is changed, the number of active sites is increased, and the catalytic performance of the catalyst is enhanced;
the FTIR chart of the high catalytic performance iron-doped cellulose-based microspheres prepared in example 1 is shown in FIG. 4, and from FIG. 4, 1750cm -1 For telescopic vibration of-c=o, 3490cm -1 Is a characteristic peak of hydroxyl (-OH), 2835 cm -1 And 2935cm -1 Is methylene (-CH) 2 - ) With methyl (-CH) 3 ) 1240 cm of the stretching vibration peak of (c) -1 Characteristic absorption peak at-C-O, 1375 cm -1 And 1437cm -1 The absorption peak at the site is-CH 3 Is a symmetric and asymmetric deformation vibration of 1640 cm -1 The bending vibration peak of H-O-H combined with water molecule is shown;
EPR experiments were carried out using 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) as spin-trapping agent, the EPR diagram of the high catalytic performance iron-doped cellulose-based microsphere prepared in example 1 is shown in FIG. 5,as is clear from FIG. 5, when Persulfate (PS) was not added for 0min, the presence of HO. And SO in the solution was not detected 4 - DMPO-HO (intensity ratio 1:2:2:1) and DMPO-SO occurred 15 min after PS addition 4 - Characteristic peak signal of adduct (intensity ratio 1:1:1:1), and characteristic peak signal of free radical was stronger when CA-Fe microspheres were added than when PS alone was added, indicating more HO and SO 4 - Generation.
Application example
(1) The high catalytic performance iron-doped cellulose-based microsphere prepared in the example 1 is used as a catalyst to catalyze the peroxodisulfate to degrade the tetracycline hydrochloride, and the specific operation is as follows:
under the condition of room temperature (25 ℃), 25mL of 20mg/L tetracycline hydrochloride solution is put into two 50mL conical flasks, 0.1gCA-Fe microspheres are added into a second conical flask, the two conical flasks are vibrated by an oscillator, the two conical flasks are taken every few minutes (starting from the time of adding the catalyst, the two conical flasks are firstly saturated by adsorption and then PS.), the absorbance of the two conical flasks is measured in an ultraviolet spectrophotometer with the wavelength of 253nm and recorded, the first 70 minutes is absorbed, and after the adsorption saturation is reached, 2mM persulfate is added, and the absorbance is continuously recorded by sampling every few minutes until the absorbance is stable. Degradation efficiency of tetracycline hydrochloride:
R=(1-C/C 0 )·100%
wherein R represents the degradation rate of tetracycline,%; absorbance of tetracycline hydrochloride at time C-t, mg/L; c (C) 0 Initial absorbance of tetracycline, mg/L.
The catalyst after use is recovered, fully dried, subjected to the next catalytic experiment, and the degradation conditions are kept consistent with the degradation conditions before, and circulated for 3 times.
The concentration change diagrams of the iron-doped cellulose-based microsphere catalytic degradation tetracycline hydrochloride solution in different time periods are shown in fig. 6, and after persulfate is added, the tetracycline hydrochloride in the solution is rapidly degraded, and the degradation efficiency can reach more than 80% within 90 minutes.
(2) The high catalytic performance iron-doped cellulose-based microsphere prepared in examples 1-3 is used for detecting the performance of catalyzing the peroxodisulfate to degrade tetracycline hydrochloride, the detection method is the same as that in (1), absorbance is calculated by an ultraviolet spectrophotometer after persulfate is added for 40 minutes, and then the degradation rate of tetracycline hydrochloride is calculated, and the result is shown in the following table 1:
TABLE 1 analysis of high catalytic Performance iron-doped cellulose-based microspheres for the degradation rate of Tetracycline hydrochloride
。
Claims (5)
1. The preparation method of the high-catalytic-performance iron-doped cellulose-based microsphere for catalytic degradation of tetracycline hydrochloride is characterized by comprising the following steps of:
(1) Dissolving cellulose in an organic solvent, adding an iron source, then adding a pore-forming agent, and stirring until the cellulose is completely dissolved to form a continuous phase;
(2) Taking deionized water as a stationary phase, taking the solution in the step (1) as a continuous phase, reacting in a liquid drop microfluidic system, filtering, washing, and drying at 60-80 ℃ to obtain the iron-doped cellulose-based microsphere with high catalytic performance;
the cellulose in the step (1) is cellulose acetate; the organic solvent is dimethyl sulfoxide or N, N-dimethylformamide; the iron source is ferrous sulfate or ferrous chloride;
the mass ratio of the iron source to the cellulose in the step (1) is 1 (3-10);
the pore-forming agent in the step (1) is sodium bicarbonate and sodium sulfate.
2. The method according to claim 1, wherein the flow rate of the continuous phase in the step (2) is 10 to 14.5ml/h.
3. The preparation method of claim 1, wherein the sodium bicarbonate in the step (1) is added in an amount of 5-15% by mass of cellulose, and the sodium sulfate is added in an amount of 20-40% by mass of cellulose.
4. An application of the high-catalytic-performance iron-doped cellulose-based microsphere prepared by the preparation method of any one of claims 1-3 in catalyzing peroxodisulfate to degrade tetracycline hydrochloride.
5. The use according to claim 4, wherein the iron-doped cellulose-based microspheres with high catalytic performance can be reused after washing and drying.
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| CN202210003809.4A CN114471709B (en) | 2022-01-04 | 2022-01-04 | Iron-doped cellulose-based microsphere with high catalytic performance as well as preparation method and application thereof |
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| CN202210003809.4A CN114471709B (en) | 2022-01-04 | 2022-01-04 | Iron-doped cellulose-based microsphere with high catalytic performance as well as preparation method and application thereof |
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| CN103724635A (en) * | 2013-12-06 | 2014-04-16 | 中国烟草总公司郑州烟草研究院 | Preparation method for cellulose acetate porous microspheres and product applying preparation method |
| CN103816843A (en) * | 2014-02-25 | 2014-05-28 | 武汉大学 | Preparation method of uniformly-sized regenerated cellulose microspheres |
| CN113663737A (en) * | 2021-08-19 | 2021-11-19 | 南京医科大学康达学院 | CMC-Fe-based microsphere and preparation method and application thereof |
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| CN103724635A (en) * | 2013-12-06 | 2014-04-16 | 中国烟草总公司郑州烟草研究院 | Preparation method for cellulose acetate porous microspheres and product applying preparation method |
| CN103816843A (en) * | 2014-02-25 | 2014-05-28 | 武汉大学 | Preparation method of uniformly-sized regenerated cellulose microspheres |
| CN113663737A (en) * | 2021-08-19 | 2021-11-19 | 南京医科大学康达学院 | CMC-Fe-based microsphere and preparation method and application thereof |
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| Mengjie Zhang, et al.Fabrication of porous cellulose microspheres with controllable structures by microfluidic and flash freezing method.Materials Letters.2019,第262卷文章摘要，第127193(1)页第2节. * |
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