CN114471709A - 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
- Publication number
- CN114471709A CN114471709A CN202210003809.4A CN202210003809A CN114471709A CN 114471709 A CN114471709 A CN 114471709A CN 202210003809 A CN202210003809 A CN 202210003809A CN 114471709 A CN114471709 A CN 114471709A
- Authority
- CN
- China
- Prior art keywords
- iron
- cellulose
- doped
- catalytic performance
- high catalytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 63
- 239000001913 cellulose Substances 0.000 title claims abstract description 63
- 239000004005 microsphere Substances 0.000 title claims abstract description 57
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 9
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- 230000015556 catabolic process Effects 0.000 claims description 13
- 238000006731 degradation reaction Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 10
- 229920002301 cellulose acetate Polymers 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 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
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000875 Dissolving pulp Polymers 0.000 claims description 4
- 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
- 230000000593 degrading effect Effects 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 8
- 230000008569 process Effects 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 4
- 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
- 238000002835 absorbance Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 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
- 238000004458 analytical method 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
- 238000010586 diagram Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229960002180 tetracycline Drugs 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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-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
- 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
- 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
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 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
- 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
- -1 iron-activated persulfate Chemical class 0.000 description 1
- 238000012933 kinetic analysis Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([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
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 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
- 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
- 239000002352 surface water Substances 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Images
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 and a preparation method and application thereof, which are characterized in that cellulose is dissolved in an organic solvent, an iron source is added, then a pore-forming agent is added, the mixture is stirred until the mixture is completely dissolved and is used as a continuous phase, deionized water is used as a stationary phase, the mixture is reacted in a droplet microfluidic system, and then the high-catalytic-performance iron-doped cellulose-based microsphere is obtained through filtering, washing and drying at the temperature of 60-80 ℃. The method for preparing the iron-doped cellulose-based microspheres with high catalytic performance is simple, low in cost and good in catalytic effect, no additional condition is needed after the peroxydisulfate is added in the catalytic oxidation process, the influence on the pH value of water before and after reaction is small, iron is attached to the microspheres, the leaching rate of the iron is reduced, the iron is easy to recover and can be recycled, and the practical applicability is high.
Description
Technical Field
The invention belongs to the technical field of material synthesis and water treatment, and particularly relates to an iron-doped cellulose-based microsphere with high catalytic performance, and a preparation method and application thereof.
Background
Tetracycline hydrochloride is widely applied to the life of people as an antibiotic drug. In recent years, tetracycline hydrochloride with different concentrations is detected in various water environment media in China, such as drinking water sources, surface water, underground water, effluent of sewage treatment plants and the like, and the fact that a plurality of water bodies in China are slightly polluted to different degrees is shown. The common methods for treating tetracycline hydrochloride in water mainly comprise an adsorption method, a photocatalytic degradation method, an electrochemical method and the like, but all have the defects of high treatment cost, limitation of reaction conditions and the like.
Most studies have shown that Advanced Oxidation Processes (AOPs) based on strongly oxidizing radicals have advantages of high efficiency, universality, and thoroughness in the removal of organic matter, and persulfate systems are more advantageous than hydrogen peroxide and ozone in advanced oxidation processes because of their low cost and high chemical stability in transportation and storage. Iron, as the second most abundant transition element in the earth's crust, is environmentally friendly, inexpensive, and readily available, and is commonly used for persulfate activation to generate sulfate radicals (SO) in homogeneous or heterogeneous oxidation by virtue of its valence state change4 -To remove persistent organic pollutants, but the iron-activated persulfate alone can be used to degrade pollutants during the reaction, possibly resulting in increased iron content in the water. Cellulose is a bio-based material, can be obtained from various materials (plants and bacteria), has the characteristics of low self toxicity, degradability, layering property and high cohesiveness in structure, and is a good material carrier. Chinese patent CN 100522343C discloses an iron-loaded spherical cellulose adsorbent, and a preparation method and an application thereof, wherein a hydroxide of iron with high adsorption activity is used as an active center, spherical cellulose is used as a carrier, arsenic, fluorine and other heavy metals in a drinking water source are efficiently and selectively removed, but the adsorption performance of the adsorbent is influenced by the content of iron elements, the adsorbent can be required only by carrying iron for many times, and the removal of organic matters is not involved.
The liquid drop micro flow control technology is a new technology for operating micro volume liquid developed on a micro flow control chip, uses two phase fluid of complementary phase and intermiscibility to form liquid drops at a micro channel interface under the action of shearing force and interfacial tension, is used as a micro reactor, has the characteristics of less consumption of sample and reagent, high mixing speed, strong anti-interference capability, good repeatability and easy precise control, and is mainly applied to the aspects of enzyme reaction kinetic analysis, single cell analysis, protein crystallization, influence of crystal nucleus formation on crystallization, molecular synthesis, simulation of complex process, nano particle synthesis and micro particle synthesis at present. However, no report on the preparation of the iron-containing cellulose catalyst by using a droplet microfluidic technology is found 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:
the 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 serve as a continuous phase;
(2) and (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 microspheres 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 iron-doped cellulose-based microspheres with high catalytic performance 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 serve as a continuous phase;
(2) and (2) taking water as a stationary phase and 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 microspheres with high catalytic performance.
In the invention, the high-catalytic-performance iron-doped cellulose-based microspheres are applied to catalytic degradation of tetracycline hydrochloride.
Further, the iron-doped cellulose-based microspheres with high catalytic performance are used as catalysts for catalyzing the peroxydisulfate to degrade tetracycline hydrochloride.
Further, the iron-doped cellulose-based microspheres with high catalytic performance can be reused after being washed and dried.
The method has the advantages of cheap and easily-obtained raw materials, environmental friendliness, low cost due to the fact that the iron-doped cellulose-based microspheres are synthesized by the micro-fluidic technology, simplicity and convenience in operation and preparation method, small pH change of the solution before and after wastewater reaction, easiness in recycling of the catalyst and reusability. The iron-doped cellulose-based microspheres are used as a catalyst for treating tetracycline hydrochloride wastewater, the catalytic degradation effect is remarkable, the 90-min degradation rate can reach about 85%, no additional condition is needed after the peroxydisulfate 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 iron-doped cellulose-based microspheres with high catalytic performance has the advantages of simple process, low cost, good catalytic effect, no additional condition after adding the peroxydisulfate in the catalytic oxidation process, small influence on the pH value of water before and after reaction, capability of attaching iron to the microspheres, reduction of the leaching rate of iron, easiness in recycling, reusability and strong practicability, and is beneficial to further application in the field of environment-friendly water treatment, wherein the tetracycline hydrochloride wastewater is subjected to catalytic treatment for 90min, and the degradation rate of tetracycline hydrochloride reaches about 85%.
Drawings
Fig. 1 is a SEM surface view and a cross-sectional view of the prepared iron-doped cellulose-based microspheres;
FIG. 2 is an XPS plot of the iron-doped cellulose-based microspheres prepared;
FIG. 3 shows N of the prepared Fe-doped cellulose-based microspheres2Adsorption-desorption attached figure;
FIG. 4 is a FTIR plot of the resulting iron-doped cellulose-based microspheres;
FIG. 5 is an EPR diagram of the prepared iron-doped cellulose-based microspheres;
FIG. 6 is a graph showing the concentration change of the prepared iron-doped cellulose-based microspheres in different time periods for catalytically degrading tetracycline hydrochloride solution.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope 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 serve as a continuous phase;
(2) and (2) taking water as a stationary phase and 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 is finished, washing the solid for 5 times by using deionized water, 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 filled with 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 stirring by magnetic force until the mixture is completely dissolved to form a continuous phase;
(2) and (2) taking water as a stationary phase and the solution in the step (1) as a continuous phase, reacting 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 for 5 times by deionized water, and drying in a 70 ℃ oven to obtain the high-catalytic-performance iron-doped cellulose-based microsphere CA-Fe.
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 serve as a continuous phase;
(2) and (2) taking water as a stationary phase and the solution in the step (1) as a continuous phase, reacting 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 for 3 times by using deionized water, 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 picture and the cross-sectional view of the iron-doped cellulose-based microspheres with high catalytic performance prepared in example 1 are shown in FIG. 1, the surfaces of the microspheres are smooth, and the interiors of the microspheres are honeycomb-shaped;
XPS (XPS performance graph) of the iron-doped cellulose-based microspheres prepared in example 1 is shown in FIG. 2, and it can be seen from FIG. 2 that 284.1eV, 536.4eV and 712.5eV of the detected chemical binding energy correspond to C1 eV respectivelys、 O 1s、 Fe 2pThe track shows that the material contains the three elements, and the element iron is successfully doped into the microspheres;
n of iron-doped cellulose-based microspheres with high catalytic performance prepared in example 12The attached drawing of adsorption-desorption is shown in figure 3, and can be seen from figure 3, at 0.8-1.0P/P0The existence of a significant hysteresis loop proves 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 microsphere structure is changed, the number of active sites is increased, and the catalytic performance of the catalyst is enhanced;
FTIR (Fourier transform infrared) chart of iron-doped cellulose-based microspheres prepared in example 1 is shown in figure 4, and from figure 4, 1750cm-1Stretching vibration of-C = O, 3490cm-1Is a characteristic peak of hydroxyl (-OH), 2835 cm-1And 2935cm-1Is prepared from methyleneRadical (-CH)2 -) With methyl (-CH)3) Peak of stretching vibration of 1240 cm-1Characteristic absorption peak at-C-O, 1375 cm-1And 1437cm-1Has an absorption peak of-CH3Is vibrated by 1640 cm-1The bending vibration peak is combined by H-O-H and water molecules;
an EPR experiment is carried out by taking 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) as a spin trapping agent, the EPR diagram of the iron-doped cellulose-based microsphere with high catalytic performance prepared in example 1 is shown in figure 5, and as can be seen from figure 5, HO and SO existing in the solution are not detected when Persulfate (PS) is not added at 0min4 -However, after 15 min of PS addition DMPO-HO (strength ratio 1:2:2:1) and DMPO-SO appeared4 -Characteristic peak signals of adducts (intensity ratio 1:1:1:1) and of radicals are stronger with the addition of CA-Fe microspheres than with the addition of PS alone, indicating more HO and SO4 -And (3) generation of (1).
Application example
(1) The iron-doped cellulose-based microspheres with high catalytic performance prepared in example 1 are used as a catalyst to catalyze peroxydisulfate to degrade tetracycline hydrochloride, and the specific operation is as follows:
at room temperature (25 ℃), putting 25mL of 20mg/L tetracycline hydrochloride solution into two 50mL conical flasks, adding 0.1gCA-Fe microspheres into the second conical flask, shaking the second conical flask in an oscillator, taking every few minutes (from the time of adding the catalyst, the adsorption saturation is carried out firstly, then PS is added), putting the sample into an ultraviolet spectrophotometer with the wavelength of 253nm to measure the absorbance, recording the absorbance, adsorbing the sample for the first 70 minutes, adding 2mM persulfate after the adsorption saturation is reached, continuously taking the sample every few minutes to record the absorbance until the absorbance is stable. Degradation efficiency of tetracycline hydrochloride:
R=(1-C/C0)·100%
in the formula, R-tetracycline degradation rate,%; the absorbance of tetracycline hydrochloride at the C-t moment is mg/L; c0- -initial absorbance of tetracycline, mg/L.
And (3) recovering the used catalyst, fully drying, performing the next catalytic experiment, keeping the degradation condition consistent with that of the previous catalyst, and circulating for 3 times.
The graph of the concentration change of the iron-doped cellulose-based microsphere in the solution for catalytically degrading tetracycline hydrochloride in different time periods is shown in fig. 6, 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 performance of the iron-doped cellulose-based microspheres prepared in examples 1-3 and having high catalytic performance for catalyzing the degradation of tetracycline hydrochloride by peroxydisulfate is detected, the detection method is the same as that in (1), the absorbance is calculated by using an ultraviolet spectrophotometer after the persulfate is added for 40 minutes, and then the degradation rate of tetracycline hydrochloride is calculated, and the results are shown in the following table 1:
TABLE 1 analysis of tetracycline hydrochloride degradation rate by Fe-doped cellulose-based microspheres with high catalytic performance
Claims (9)
1. The iron-doped cellulose-based microsphere with high catalytic performance is characterized by being 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 serve as a continuous phase;
(2) and (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 microspheres with high catalytic performance.
2. The iron-doped cellulose-based microsphere with high catalytic performance as claimed in claim 1, wherein the cellulose in step (1) is cellulose acetate; the organic solvent is dimethyl sulfoxide or N, N-dimethylformamide; the iron source is ferrous sulfate or ferrous chloride.
3. The iron-doped cellulose-based microsphere with high catalytic performance as claimed in claim 1, wherein the flow rate of the continuous phase in step (2) is 10-14.5 mL/h.
4. The iron-doped cellulose-based microsphere with high catalytic performance as claimed in claim 1, wherein the mass ratio of the iron source to the cellulose in step (1) is 1: 3-10.
5. The iron-doped cellulose-based microsphere with high catalytic performance as claimed in claim 1, wherein the pore-forming agent in 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.
6. The preparation method of the iron-doped cellulose-based microspheres with high catalytic performance as set forth in any one of claims 1 to 5, characterized by comprising 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 serve as a continuous phase;
(2) and (2) taking water as a stationary phase and 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 microspheres with high catalytic performance.
7. The application of the iron-doped cellulose-based microspheres with high catalytic performance as set forth in any one of claims 1-5 in catalytic degradation of tetracycline hydrochloride.
8. The use of claim 7, wherein the iron-doped cellulose-based microspheres with high catalytic performance are used as a catalyst for degrading tetracycline hydrochloride by peroxydisulfate.
9. The use of claim 8, wherein the iron-doped cellulose-based microspheres with high catalytic performance can be reused after being washed and dried.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114471709A true CN114471709A (en) | 2022-05-13 |
| CN114471709B CN114471709B (en) | 2023-12-19 |
Family
ID=81509534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210003809.4A Active 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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114471709B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100087552A1 (en) * | 2007-01-12 | 2010-04-08 | Yoshiyuki Shiomi | Cellulose fine particles, and liquid or solid dispersion thereof |
| 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 |
-
2022
- 2022-01-04 CN CN202210003809.4A patent/CN114471709B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100087552A1 (en) * | 2007-01-12 | 2010-04-08 | Yoshiyuki Shiomi | Cellulose fine particles, and liquid or solid dispersion thereof |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| MENGJIE ZHANG, ET AL: "Fabrication of porous cellulose microspheres with controllable structures by microfluidic and flash freezing method", MATERIALS LETTERS, vol. 262, pages 127193 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114471709B (en) | 2023-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111013590B (en) | Preparation method of biochar-supported cobaltosic oxide catalytic material | |
| CN110437458B (en) | Reusable Fenton-like catalyst [ NH ]2-MIL-101(Fe)]Preparation and application methods of | |
| CN107519934B (en) | Preparation method of iron-based metal-organic framework material Fenton-like catalyst modified by ferrocene | |
| CN111036285B (en) | Photocatalyst of nitrogen modified perovskite composite molecular sieve and preparation method and application method thereof | |
| CN111790422A (en) | Graphitized radical nitrogen complexed Fe (III) -Fe0Catalyst and synthesis method and application thereof | |
| CN103934034A (en) | Preparation method of loading iron based metal organic skeleton out phase Fenton catalyst and application thereof | |
| Zeng et al. | FeCl3-activated biochar catalyst for heterogeneous Fenton oxidation of antibiotic sulfamethoxazole in water | |
| CN107737594B (en) | Catalyst for degrading formaldehyde wastewater and preparation method and application thereof | |
| CN104743633A (en) | Method for degrading organic waste water by photo-assisted activation of potassium hydrogen persulfate through bismuth ferrite | |
| CN105668759A (en) | Method for recycling Fenton iron mud | |
| CN105413638A (en) | Preparation method of core-shell composite material with SOD zeolite structure | |
| CN105251435A (en) | Preparation method of core-shell type composite material with MTN zeolite configuration | |
| CN104475027A (en) | Novel composite material with SOD zeolite configuration and for enriching and catalytically degrading organics | |
| Shen et al. | Adsorption of 4-chlorophenol by wheat straw biochar and its regeneration with persulfate under microwave irradiation | |
| Zhou et al. | BiOCl0. 875Br0. 125/polydopamine functionalized PVDF membrane for highly efficient visible-light-driven photocatalytic degradation of roxarsone and simultaneous arsenic immobilization | |
| CN105566400A (en) | Heterogeneous cobalt metal-organic skeleton and preparation and application to wastewater treatment field | |
| CN110449162B (en) | Modified manganese slag-iron vitriol slag mixed slag catalyst and preparation method and application thereof | |
| CN104307484A (en) | Novel breathing-effect composite material for enriching and carrying out catalytic degradation on organic matter | |
| Zhang et al. | PAA/TiO2@ C composite hydrogels with hierarchical pore structures as high efficiency adsorbents for heavy metal ions and organic dyes removal | |
| CN111203179A (en) | Preparation method and application of renewable phenol-containing organic wastewater catalytic adsorption material | |
| CN110560064A (en) | Preparation method and application of magnetic carbon sphere loaded cobaltosic oxide catalyst | |
| CN112206779B (en) | Method for catalytic degradation of chloramphenicol in water by MIL-100 (Fe/Co) derived magnetic composite material and application thereof | |
| CN111617759B (en) | Manganese dioxide nano catalytic film for catalyzing ozone to degrade organic wastewater and preparation method thereof | |
| CN114471709B (en) | Iron-doped cellulose-based microsphere with high catalytic performance as well as preparation method and application thereof | |
| CN112973739A (en) | Composite catalyst for catalytic oxidation treatment of antibiotic wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |