CN114950353A - High-activity-site molybdenum disulfide/carbon nanofiber aerogel adsorbent and preparation method thereof - Google Patents
High-activity-site molybdenum disulfide/carbon nanofiber aerogel adsorbent and preparation method thereof Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 89
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 85
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 63
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000003463 adsorbent Substances 0.000 title claims abstract description 50
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 34
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- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims abstract description 17
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 6
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- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 2
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- 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
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0218—Compounds of Cr, Mo, W
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- 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
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
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- 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
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- B01J20/28047—Gels
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- 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
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- C02F2101/20—Heavy metals or heavy metal compounds
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention belongs to the technical field of sewage treatment agents, and provides a molybdenum disulfide/carbon nanofiber aerogel adsorbent with high active sites and a preparation method thereof, wherein the method comprises the following steps: soaking and washing the cellulose acetate in deionized water, and then placing the cellulose acetate in a tubular furnace in a nitrogen protective atmosphere to heat to 400-700 ℃ for heat preservation to obtain black carbon nanofiber aerogel; weighing ammonium molybdate tetrahydrate and thiourea, adding deionized water, performing ultrasonic treatment until the ammonium molybdate tetrahydrate and the thiourea are completely dissolved, and uniformly stirring to obtain a mixed solution A; adding the mixed solution A and the carbon nanofiber aerogel into a polytetrafluoroethylene reaction kettle; reacting under a hydrothermal condition, and performing solid-liquid separation on the obtained product to obtain a crude sample B; and washing the crude sample B with deionized water, and putting the crude sample B into a freeze vacuum drier for drying to obtain a sample which is the aerogel adsorbent. The product obtained by the method has stronger chelation with metal ions and more adsorption sites, and has excellent treatment effect on the sewage containing mercury ions.
Description
Technical Field
The invention relates to the technical field of sewage treatment agents, in particular to a molybdenum disulfide/carbon nanofiber aerogel adsorbent with high active sites and a preparation method thereof.
Background
Mercury is one of the highly toxic heavy metal contaminants that can cause birth defects, brain damage and disease in humans and other species, and has long been a threat to public health and the environment. Mercury is not biodegradable and therefore can accumulate in organisms, threatening human health through the food chain. Therefore, research on designing and preparing the high-efficiency mercury adsorbent is concerned by researchers at home and abroad.
Currently, many conventional methods for removing heavy metal ions from wastewater have been developed, such as ion exchange, membrane separation, electrochemical treatment, chemical precipitation, and adsorption methods. Among them, the adsorption method has become a generally accepted choice due to its advantages of high removal efficiency, simple operation, wide applicability, high cost performance, etc. At present, common adsorbents such as activated carbon, zeolite, clay and the like are used for adsorbing heavy metal ions, however, due to low adsorption efficiency, difficulty in separation, difficulty in reuse and the like, the feasibility of practical application of the adsorbents is reduced. Therefore, it is necessary to prepare a mercury adsorbent with low cost, simple process and high efficiency.
To date, various sulfur-containing materials have been paired with Hg due to the strong soft-soft interaction between sulfur and mercury 2+ The ions have strong binding affinity and become a unique mercury ion adsorbent. Recently, thiol-functionalized metal organic frameworks, organic polymers, carbon nanotubes, etc. have been reported as Hg 2+ Ion adsorbents (J.colloid.Interf.Sci.2015,456: 22-31; ACS Sustainable chem.Eng.2018,6, 6175-. However, due to the low sulfur content of these materials orLow sulfur utilization, and still exhibit relatively low Hg 2+ Ion adsorption capacity, and many materials are subject to complex synthetic procedures and high synthetic costs, limiting the possibilities of these materials for large scale synthesis and application. Molybdenum disulfide (MoS) 2 ) As one of typical representatives of transition metal sulfides, the transition metal sulfides have the advantages of abundant sulfur atoms, unique layered structure, controllable interlayer spacing, large specific surface area and the like, and have great potential for removing heavy metals. However, currently MoS 2 There are still limitations in the application process, such as MoS 2 The polymer has poor dispersibility in water and is easy to aggregate, so that a large number of adsorption sites cannot be effectively utilized, and the adsorption capacity of the polymer is reduced. In addition, the separation and recovery difficulty of the powdery molybdenum disulfide is high when the powdery molybdenum disulfide is dispersed in water, and secondary pollution is easily caused. By mixing MoS 2 The nanosheet is assembled with other carriers with a net structure to form a three-dimensional composite material, so that the limitations can be effectively overcome, and the separating and recycling capacity of the adsorbent is improved.
Carbon-based aerogels consisting of interconnected three-dimensional (3D) networks have attracted considerable attention due to their low cost, low density, high conductivity, porosity and specific surface area. The CNF aerogel produced by pyrolyzing BC belongs to one of biochar and can be converted into different three-dimensional functional nano materials. Biochar is known as Pb because of its higher carbon and hydrogen content, more oxygen-containing functional groups (e.g., O-H and C ═ O) 2+ 、Zn 2+ 、Hg 2+ And (3) a modifier for the water body and soil polluted by heavy metals. However, biochar has poor selectivity for heavy metal ions, so it needs to be modified to enhance the heavy metal adsorption capacity of the material by enhancing specific surface and chemical properties. Therefore, the CNF aerogel modified can effectively enhance the adsorption sites of the material, and is meaningful for researching and removing the sewage containing mercury ions.
Disclosure of Invention
The invention aims to: aiming at the problems, the invention provides a molybdenum disulfide/carbon nanofiber aerogel adsorbent with high active sites and a preparation method thereof, and the invention obtains the adsorbent with unique active sites by an improved methodW-MoS of specific molecular Structure 2 CNF, not only increasing MoS 2 The interlayer spacing of (2) also avoids MoS 2 The possibility of secondary pollution of the adsorbent is reduced; compared with other chelating agents, the water treatment agent has stronger chelation with metal ions and more adsorption sites, and has excellent treatment effect on the sewage containing mercury ions.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the high-activity-site molybdenum disulfide/carbon nanofiber aerogel adsorbent comprises the following steps:
(1) soaking and washing the cellulose acetate with deionized water, and then placing the cellulose acetate in a tubular furnace in a nitrogen protective atmosphere to heat to 400-plus-700 ℃, and preserving the heat for 150min at the temperature of 100-plus-150 min to obtain black carbon nanofiber aerogel;
(2) weighing soluble ammonium molybdate tetrahydrate and soluble thiourea according to the molar ratio of 1:10-1:50, adding deionized water with the solid-liquid ratio of 1g:8-15ml, carrying out ultrasonic treatment until the ammonium molybdate tetrahydrate and the soluble thiourea are completely dissolved, and stirring uniformly to obtain a mixed solution A;
(3) adding the mixed solution A and the carbon nanofiber aerogel into a polytetrafluoroethylene reaction kettle; the solid-to-liquid ratio of the carbon nanofiber aerogel to the deionized water added in the step (2) is 1g:700-1750 ml; reacting under hydrothermal conditions, wherein the reaction temperature is 175-190 ℃, the hydrothermal time is 10-24 hours, and performing solid-liquid separation on the obtained product to obtain a crude sample B;
(4) washing the crude sample B with deionized water, and drying in a freeze vacuum dryer to obtain the sample W-MoS of the high-activity-site molybdenum disulfide/carbon nanofiber 2 CNF aerogel adsorbent.
In the present invention, it is preferable that the temperature rise in the step (1) is performed at a rate of 5 ℃/min.
In the present invention, preferably, the temperature of the heat preservation in the step (1) is 500 ℃, and the heat preservation time is 120 min.
In the present invention, preferably, the molar ratio of ammonium molybdate tetrahydrate and soluble thiourea in step (2) is 1: 30.
in the present invention, it is preferable that the reaction temperature in the step (3) is 180 ℃.
In the present invention, preferably, the freeze vacuum drying machine in step (4) is used for drying, the freezing temperature is-45 ℃, the time is 48 hours, and the vacuum degree is less than 20 Pa.
The invention protects the molybdenum disulfide/carbon nanofiber aerogel adsorbent with high active sites prepared by the preparation method.
The invention also protects the application of the molybdenum disulfide/carbon nanofiber aerogel adsorbent with high active sites, which is prepared by the preparation method, in sewage treatment or the application of the molybdenum disulfide/carbon nanofiber aerogel adsorbent as a sewage treatment agent.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the invention takes carbon nanofiber aerogel as a carrier, and has W-MoS with a unique molecular structure through simple one-step hydrothermal reaction 2 CNF aerogel nano-adsorbent. The carbon nanofiber aerogel obtained by carbonizing the cellulose acetate is in a nanometer level, and has a larger specific surface area and a rich microporous structure compared with micron-sized natural fibers selected in previous work. The cellulose (coconut) of the bacillus aceticus has wide source and low cost. The carbon nanofiber aerogel is used as one of biochar, so that the cost can be effectively reduced, and the environment cannot be polluted. On this basis, through inlaying molybdenum disulfide nanosheet on porous graphitization charcoal surface, on the one hand use carbon nanofiber aerogel can realize that molybdenum disulfide nanosheet distributes more evenly as the carrier, avoids molybdenum disulfide nanosheet to the at utmost to appear piling up the phenomenon of reuniting, can improve the load factor to molybdenum disulfide to a certain extent greatly. On the other hand, the molybdenum disulfide nanosheets with widened interlayer spacing and increased defects can expose more sulfur-containing sites, mercury ions can be fully combined with the adsorbent, the effect of treating the sewage containing the mercury ions is very excellent, and the W-MoS prepared by the method disclosed by the invention 2 The adsorption capacity of the CNF aerogel on mercury ions in sewage reaches 1562mg/g, the removal rate is about 99 percent, and the CNF aerogel has higher adsorption capacity, better removal efficiency and excellent separation on mercury metal ions in sewageSub-selectivity, can be applied to the field of sewage treatment.
2. Under the best condition, the selective removal of mercury ions in the aqueous solution by other metal ions has no obvious influence, and the removal efficiency of the adsorbent on the mercury ions can still reach 99%. After the water body is purified according to the method provided by the invention, the adsorbent can be clamped out by using tweezers, and the separation of pollutants from the water body can be realized. And the adsorbent material can be recycled by soaking it in a 1M hydrochloric acid solution. In addition, the 2 times of purification-recovery-purification circulation does not disturb the order of the structure, the adsorption performance of the adsorption material per se has no sign of attenuation, and the adsorption material can be repeatedly used for further separating mercury ions in water.
3. The preparation method of the invention is convenient to operate, the raw materials are cheap and easy to obtain, and the industrial production and popularization and use are easy. The method has good application prospect in water environment pollution events, and particularly has extremely high efficiency in removing mercury ions.
Drawings
FIG. 1 shows the W-MoS high active site prepared in example 2 2 Powder diffraction (XRD) pattern of CNF aerogel.
FIG. 2 is the MoS prepared in example 4 2 Powder diffraction (XRD) pattern of CNF aerogel.
FIG. 3 is the MoS prepared in example 5 2 Powder diffraction (XRD) pattern of CNF aerogel.
FIG. 4 shows the W-MoS high active site prepared in example 2 2 Scanning Electron Microscope (SEM) image of CNF aerogel.
FIG. 5 shows the W-MoS high active site prepared in example 2 2 Transmission Electron Microscopy (TEM) image of/CNF aerogel.
FIG. 6 is the MoS prepared in example 4 2 Transmission Electron Microscopy (TEM) image of/CNF aerogel.
FIG. 7 is the MoS prepared in example 5 2 Transmission Electron Microscopy (TEM) image of/CNF aerogel.
FIG. 8 shows the W-MoS high active sites prepared in examples 1 to 3 2 CNF aerogel to Hg 2+ Adsorption kinetics curve of (1).
FIG. 9 shows the W-MoS high active sites prepared in examples 1 to 3 2 CNF aerogel to Hg 2+ Adsorption isotherm of (2).
FIG. 10 shows the W-MoS high active sites prepared in examples 1 to 3 2 /CNF aerogel can be used for treating Hg in interfering ion environment 2+ Ion selectivity of (1).
FIG. 11 shows the high active site W-MoS prepared in examples 1-3 2 The removal rate of CNF aerogel after twice recycling.
Detailed Description
In order to express the present invention more clearly, the present invention will be further illustrated by the following specific examples and comparative examples.
First, preparation example:
example 1
The preparation method of the high-activity-site molybdenum disulfide/carbon nanofiber aerogel adsorbent comprises the following steps:
(1) soaking and washing the cellulose acetate with deionized water for 3 times, and then placing the cellulose acetate in a tubular furnace in a nitrogen protective atmosphere to heat to 400 ℃ at a speed of 4 ℃/min, and preserving the heat for 150min to obtain black carbon nanofiber aerogel;
(2) weighing 1.24g of soluble ammonium molybdate tetrahydrate and 0.76g of soluble thiourea according to the molar ratio of 1:10, adding 16ml of deionized water, performing ultrasonic treatment until the ammonium molybdate tetrahydrate and the soluble thiourea are completely dissolved, and uniformly stirring to obtain a mixed solution A;
(3) adding the mixed solution A and the carbon nanofiber aerogel into a polytetrafluoroethylene reaction kettle; the solid-to-liquid ratio of the carbon nanofiber aerogel to the deionized water added in the step (2) is 1g to 700 ml; reacting under a hydrothermal condition, wherein the reaction temperature is 175 ℃, the hydrothermal time is 24 hours, and performing solid-liquid separation on the obtained product to obtain a crude sample B;
(4) washing the crude sample B with deionized water, and drying in a freeze vacuum drier at-45 deg.C for 48 hr with vacuum degree less than 20Pa to obtain the sample W-MoS of the high-activity-site molybdenum disulfide/carbon nanofiber 2 CNF aerogel adsorbent.
Example 2
The preparation method of the high-activity-site molybdenum disulfide/carbon nanofiber aerogel adsorbent comprises the following steps:
(1) soaking and washing the cellulose acetate with deionized water for several times, and then placing the cellulose acetate in a tubular furnace in a nitrogen protective atmosphere, heating to 500 ℃ at a speed of 5 ℃/min, and preserving heat for 120min to obtain black carbon nanofiber aerogel;
(2) weighing 1.24g of soluble ammonium molybdate tetrahydrate and 2.28g of soluble thiourea according to the molar ratio of 1:30, adding 35ml of deionized water, performing ultrasonic treatment until the ammonium molybdate tetrahydrate and the soluble thiourea are completely dissolved, and uniformly stirring to obtain a mixed solution A;
(3) adding the mixed solution A and the carbon nanofiber aerogel into a polytetrafluoroethylene reaction kettle; the solid-to-liquid ratio of the carbon nanofiber aerogel to the deionized water added in the step (2) is 1g to 875 ml; reacting under a hydrothermal condition, wherein the reaction temperature is 180 ℃, the hydrothermal time is 24 hours, and performing solid-liquid separation on the obtained product to obtain a crude sample B;
(4) washing the crude sample B with deionized water, and drying in a freeze vacuum drier at-45 deg.C for 48 hr with vacuum degree less than 20Pa to obtain the sample W-MoS of the high-activity-site molybdenum disulfide/carbon nanofiber 2 CNF aerogel adsorbent.
Example 3
The preparation method of the high-activity-site molybdenum disulfide/carbon nanofiber aerogel adsorbent comprises the following steps:
(1) soaking and washing the cellulose acetate with deionized water for several times, and then placing the cellulose acetate in a tubular furnace in a nitrogen protective atmosphere, heating to 700 ℃ at the speed of 6 ℃/min, and preserving heat for 100min to obtain black carbon nanofiber aerogel;
(2) weighing 1.24g of soluble ammonium molybdate tetrahydrate and 2.8g of soluble thiourea according to the molar ratio of 1:50, adding 60.6ml of deionized water, performing ultrasonic treatment until the solution is completely dissolved, and uniformly stirring to obtain a mixed solution A;
(3) adding the mixed solution A and the carbon nanofiber aerogel into a polytetrafluoroethylene reaction kettle; the solid-to-liquid ratio of the carbon nanofiber aerogel to the deionized water added in the step (2) is 1g to 1750 ml; reacting under a hydrothermal condition, wherein the reaction temperature is 190 ℃, the hydrothermal time is 10 hours, and performing solid-liquid separation on the obtained product to obtain a crude sample B;
(4) washing the crude sample B with deionized water, and drying in a freeze vacuum drier at-45 deg.C for 48 hr with vacuum degree less than 20Pa to obtain the sample W-MoS of the high-activity-site molybdenum disulfide/carbon nanofiber 2 CNF aerogel adsorbent.
Example 4
The preparation method of the molybdenum disulfide/carbon nanofiber aerogel adsorbent comprises the following steps:
(1) soaking and washing the cellulose acetate with deionized water for several times, and then placing the cellulose acetate in a tubular furnace in a nitrogen protective atmosphere, heating to 500 ℃ at a speed of 5 ℃/min, and preserving heat for 120min to obtain black carbon nanofiber aerogel;
(2) weighing 1.24g of soluble ammonium molybdate tetrahydrate and 2.28g of soluble thiourea according to the molar ratio of 1:30, adding 35ml of deionized water, performing ultrasonic treatment until the ammonium molybdate tetrahydrate and the soluble thiourea are completely dissolved, and uniformly stirring to obtain a mixed solution A;
(3) adding the mixed solution A and the carbon nanofiber aerogel into a polytetrafluoroethylene reaction kettle; the solid-to-liquid ratio of the carbon nanofiber aerogel to the deionized water added in the step (2) is 1g to 875 ml; reacting under a hydrothermal condition, wherein the reaction temperature is 170 ℃, the hydrothermal time is 24 hours, and performing solid-liquid separation on the obtained product to obtain a crude sample B;
(4) washing the crude sample B with deionized water, and drying in a freeze vacuum drier at-45 deg.C for 48 hr with vacuum degree less than 20Pa to obtain the sample MoS 2 CNF aerogel adsorbent.
Example 5
The preparation method of the molybdenum disulfide/carbon nanofiber aerogel adsorbent comprises the following steps:
(1) soaking and washing the cellulose acetate with deionized water for several times, and then placing the cellulose acetate in a tubular furnace in a nitrogen protective atmosphere, heating to 500 ℃ at a speed of 5 ℃/min, and preserving heat for 120min to obtain black carbon nanofiber aerogel;
(2) weighing 1.24g of soluble ammonium molybdate tetrahydrate and 2.28g of soluble thiourea according to the molar ratio of 1:30, adding 35ml of deionized water, performing ultrasonic treatment until the ammonium molybdate tetrahydrate and the soluble thiourea are completely dissolved, and uniformly stirring to obtain a mixed solution A;
(3) adding the mixed solution A and the carbon nanofiber aerogel into a polytetrafluoroethylene reaction kettle; the solid-to-liquid ratio of the carbon nanofiber aerogel to the deionized water added in the step (2) is 1g to 875 ml; reacting under a hydrothermal condition, wherein the reaction temperature is 195 ℃, the hydrothermal time is 24 hours, and performing solid-liquid separation on the obtained product to obtain a crude sample B;
(4) washing the crude sample B with deionized water, and drying in a freeze vacuum drier at-45 deg.C for 48 hr with vacuum degree less than 20Pa to obtain the sample MoS 2 CNF aerogel adsorbent.
Second, product confirmation
1. The W-MoS prepared in examples 1-3 was used 2 The CNF aerogel is subjected to X-ray powder diffraction analysis, and the W-MoS can be seen from the X-ray powder diffraction structure characterization of the material 2 the/CNF aerogel has obvious characteristic diffraction peaks in a low-angle area less than 10 degrees, corresponds to (002) diffraction peaks on a standard card (PDF #37-1492) of molybdenum disulfide, and obtains MoS in the composite material through calculation 2 Has a layer spacing of
The layer spacing of the raw molybdenum disulfide material without broadening is
Illustrating the broadening of the interlayer spacing of molybdenum disulfide in the composite, wherein the W-MoS obtained in example 2 2 The powder diffraction (XRD) pattern of the/CNF aerogel is shown in figure 1.
For the W-MoS obtained in examples 4 and 5 2 The CNF aerogel is subjected to X-ray powder diffraction analysis, and the W-MoS can be seen from the X-ray powder diffraction structure characterization of the material 2 CNF aerogels at low angles of less than 10 DEGThe degree zone has obvious characteristic diffraction peak corresponding to (002) diffraction peak on standard card (PDF #37-1492) of molybdenum disulfide, and MoS in the composite material is obtained by calculation 2 Has a layer spacing of
And
indicating that the interlayer spacing of molybdenum disulfide in the composite did not expand to a sufficiently wide distance, where the MoS obtained in examples 4 and 5 2 The powder diffraction (XRD) patterns of the/CNF aerogel are shown in figures 2 and 3.
2. For the W-MoS prepared in examples 1-3 2 SEM scanning electron microscope analysis of/CNF aerogel shows that the composite material maintains the net-shaped three-dimensional structure of the carbon nanofiber aerogel and the surface of the fiber is coated with MoS 2 The molybdenum disulfide has a nano-scale sheet structure and has a certain degree of curling, which is the subsequent Hg 2+ Provides a larger specific surface area and more adsorption sites. Wherein, the W-MoS obtained in example 2 2 The Scanning Electron Microscope (SEM) image of the/CNF aerogel is shown in FIG. 4.
3. For the W-MoS prepared in examples 1-3 2 TEM transmission electron microscope analysis of the/CNF aerogel shows that the spacing between adjacent lattice fringes is about
Corresponding to MoS 2 The spacing of (002) crystal planes of (A) is consistent with XRD data, and W-MoS is further confirmed 2 MoS in CNF aerogel 2 The inter-layer spacing is widened. HRTEM image display MoS 2 The presence of a large number of crystal defects in the nanosheets revealed MoS 2 Defect-rich features and relatively disordered arrangement of atoms along the substrate plane due to large numbers of dislocations and twists. Selected Area Electron Diffraction (SAED) maps further confirm this feature. These defects may lead to the formation of cracks and cavities on the basal plane, which may act as Hg 2+ Additional diffusion channels. Wherein, the W-MoS obtained in example 2 2 A Transmission Electron Microscope (TEM) image of the/CNF aerogel is shown in FIG. 5.
MoS obtained in examples 4 and 5 2 TEM transmission electron microscope analysis of the/CNF aerogel shows that the spacing between adjacent lattice fringes is about
And
corresponding to MoS 2 The spacing of (002) crystal planes is consistent with XRD data, and MoS is further confirmed 2 MoS in CNF aerogel 2 Interlayer spacing versus commercial MoS 2 Widening but slightly smaller interlayer spacing compared to example 2. In which the MoS obtained in examples 4 and 5 2 Transmission Electron Microscopy (TEM) images of the/CNF aerogels are shown in FIGS. 6 and 7.
Examples 4 and 5 differ from example 2 in the temperature of the hydrothermal reaction, which shows that the control of the temperature in the present invention has a large influence on the morphology of the product and ultimately on the activity of the material, and examples 4 and 5 fail to obtain W-MoS having a greatly improved morphology 2 /CNF aerogel.
Thirdly, performance test:
1. 50mg of the adsorbents prepared in the above examples 1 to 3 were weighed, added to 100mL of a mercury ion-containing solution with a concentration of 10ppm, shaken at a constant temperature of 25 ℃, sampled at different times within 0 to 24 hours, and the obtained samples were subjected to ICP-MS measurement of the concentration of mercury ions. Drawing W-MoS 2 The adsorption kinetics curve of the/CNF aerogel is shown in FIG. 8, and when the adsorption equilibrium is reached, the mercury ion removal rate of the prepared adsorbent is 99%.
2. 50mg of the adsorbent prepared in the above examples 1 to 3 was weighed and placed in 100mL of a mercury ion-containing solution with a concentration of 1 to 500ppm, and the solution was shaken at a constant temperature of 25 ℃ for 24 hours, and the concentration of mercury ions in the solution after reaction equilibrium was measured by ICP-MS. Drawing W-MoS 2 The adsorption isotherm of the/CNF aerogel is shown in FIG. 9, and after the reaction is balanced, the maximum adsorption capacity of the adsorbent reaches 1562 mg/g. Higher than the literature (j. colloid. inter. sci.2019,551,251-260.) reported Fe 3 O 4 @MoS 2 The maximum adsorption capacity for adsorbing mercury ions is 526 mg/g. Proves that the W-MoS of the invention 2 The CNF aerogel has better mercury ion adsorption effect.
3. The anti-interference ion capacity of the adsorption material synthesized by the invention is measured. 50mg of the adsorbent prepared in examples 1-3 above was loaded in 100mL of a solution of zinc (Zn) 2+ ) Manganese (Mn) 2+ ) Nickel (Ni) 2+ ) Cadmium (Cd) 2+ ) Cobalt (Co) 2+ ) Chromium (Cr) 3+ ) Copper (Cu) 2+ ) Lead (Pb) 2+ ) The removal rate and K of the adsorbent were measured under the interference of various ions (the above ion concentrations were all 10ppm) d The value is obtained. For the W-MoS synthesized in the invention 2 The anti-interference ion capacity of the CNF aerogel is measured. As a result, as shown in FIG. 10, the distribution coefficient of the material to mercury ions can still reach 10 5 mLg -1 And the removal rate reaches 99 percent.
4. Respectively weighing 50mg of the adsorbent prepared in the above examples 1-3, adding the adsorbent into 100mL of mercury ion-containing solution with the concentration of 10ppm, shaking at a constant temperature of 25 ℃, and measuring the concentration of mercury ions by using ICP-MS after 20 min; the adsorbent was taken out and immersed in a 1M hydrochloric acid solution to be recycled. Taking back the recycled adsorbing material, cleaning, adding into 100mL of mercury ion-containing solution with the concentration of 10ppm, shaking at constant temperature of 25 ℃, and measuring the concentration of mercury ions by using ICP-MS after 20 min; the mercury ion removal rate is calculated each time, as shown in fig. 11, it can be seen that the mercury ion removal rate of the recycled adsorbent is still 99%, and the recycled adsorbent has better recyclability.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.
Claims (8)
1. The preparation method of the high-activity-site molybdenum disulfide/carbon nanofiber aerogel adsorbent is characterized by comprising the following steps of:
(1) soaking and washing the cellulose acetate with deionized water, and then placing the cellulose acetate in a tubular furnace in a nitrogen protective atmosphere to heat to 400-plus-700 ℃, and preserving the heat for 150min at the temperature of 100-plus-150 min to obtain black carbon nanofiber aerogel;
(2) weighing soluble ammonium molybdate tetrahydrate and soluble thiourea according to the molar ratio of 1:10-1:50, adding deionized water with the solid-liquid ratio of 1g:8-15ml, carrying out ultrasonic treatment until the ammonium molybdate tetrahydrate and the soluble thiourea are completely dissolved, and stirring uniformly to obtain a mixed solution A;
(3) adding the mixed solution A and the carbon nanofiber aerogel into a polytetrafluoroethylene reaction kettle; the solid-to-liquid ratio of the carbon nanofiber aerogel to the deionized water added in the step (2) is 1g: 700-; reacting under hydrothermal conditions, wherein the reaction temperature is 175-190 ℃, the hydrothermal time is 10-24 hours, and performing solid-liquid separation on the obtained product to obtain a crude sample B;
(4) washing the crude sample B with deionized water, and drying in a freeze vacuum drier to obtain the sample W-MoS of the high-activity-site molybdenum disulfide/carbon nanofiber 2 CNF aerogel adsorbent.
2. The method of claim 1, wherein: the temperature rise in the step (1) is carried out at a speed of 5 ℃/min.
3. The method of claim 1, wherein: the temperature for heat preservation in the step (1) is 500 ℃, and the heat preservation time is 120 min.
4. The method of claim 1, wherein: the mol ratio of the ammonium molybdate tetrahydrate to the soluble thiourea in the step (2) is 1: 30.
5. the method of claim 1, wherein: the reaction temperature in the step (3) is 180 ℃.
6. The method of claim 1, wherein: and (4) drying by using the freezing vacuum dryer in the step (4), wherein the freezing temperature is-45 ℃, the time is 48 hours, and the vacuum degree is less than 20 Pa.
7. The high-activity-site molybdenum disulfide/carbon nanofiber aerogel adsorbent prepared according to the preparation method of any one of claims 1 to 6.
8. The application of the high-activity-site molybdenum disulfide/carbon nanofiber aerogel adsorbent prepared by the preparation method according to any one of claims 1 to 6 in sewage treatment or as a sewage treatment agent.
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