CN115920854A - Preparation method of corn bract adsorption material modified by zinc sulfide - Google Patents
Preparation method of corn bract adsorption material modified by zinc sulfide Download PDFInfo
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Abstract
The invention provides a preparation method of a corn bract adsorbing material modified by zinc sulfide, which comprises the following steps: dissolving corn bract and dopamine hydrochloride in water to obtain a first mixed solution; adding a Tris-HCl buffer solution into the first mixed solution for reaction, and washing and drying after the reaction to obtain a corn bract/dopamine product; dissolving the corn bract/dopamine product and zinc chloride in ethylene glycol to obtain a second mixed solution; dissolving thiourea in a mixed solution of n-butylamine and ethylene glycol to obtain a third mixed solution; and mixing the second mixed solution and the third mixed solution for reaction, washing and drying after the reaction to obtain the corn bract/dopamine @ zinc sulfide composite material. The preparation method of the corn bract adsorbing material modified by zinc sulfide provided by the invention has the advantages of rich raw material sources, simple preparation process, low preparation cost and good mercury adsorption effect.
Description
Technical Field
The invention relates to the technical field of adsorbing materials, and particularly relates to a preparation method of a corn bract adsorbing material modified by zinc sulfide.
Background
In recent years, with the rapid development of social economy, the problem of environmental pollution is becoming more serious, and one of the most serious problems is the pollution of heavy metals to the environment. Mercury, as the first group of five toxins (mercury, lead, chromium, cadmium and arsenic), belongs to one of the most toxic heavy metal elements. However, mercury has been widely used in various fields due to its specific physicochemical properties, for example: mining industry, metallurgy industry, electroplating, battery manufacturing, metal finish machining, pesticides, fertilizers, chemical manufacturing, leather making and other fields. According to the data of the environmental planning agency of the united nations, the mercury content in the ocean waters of the world is doubled in the last century when the depth is 100 meters or more, and increased by 25% in the waters with the depth of less than 100 meters. Industrial production is a major cause of mercury increase, mainly due to mining, which is a by-product of the mining of ores such as coal, iron and other metals. The largest source of mercury release in the environment is gold mine exploitation, and 650-1000 tons of mercury are generated each year. The chlor-alkali industry is the third industry to cause mercury pollution, and mercury-containing batteries, mercury-containing fluorescent lamps and dental mercury-containing alloys also produce small amounts of mercury.
The characteristics of biological accumulation and biological amplification enable mercury to be enriched into the human body from phytoplankton to small carnivorous fish, and mercury salt with high solubility is easy to be absorbed by the human body, so that mercury is finally accumulated in the human body in a large amount. When mercury accumulates in human body organs, the body organs including pituitary, hypothalamus, gonads, and adipose tissue are destroyed. In particular, unborn babies and infants are extremely susceptible to mercury, and the nervous system, reproductive system, vision, hearing, speech ability, etc. of infants are easily damaged. In addition, many diseases are caused by mercury poisoning, including acral pain (pink) disease, water ensure disease, hunter-rocin syndrome, and the like. Therefore, the mercury ions in the water have great harm to aquatic organisms and human health, and the removal of the mercury ions from the industrial wastewater has important practical significance.
At present, the adsorption method is proved to be an economic and environment-friendly method in the aspect of treating mercury-containing wastewater. The adsorption method has the advantages of high utilization rate, simple operation, strong economic benefit, capability of efficiently reducing the concentration of heavy metal ions to trace, trace and the like. The adsorption method includes a physical adsorption method and a chemical adsorption method. The physical adsorption mainly utilizes the porous structure of the adsorption material or other existing special functional groups for adsorption. Chemisorption is the coordination of an adsorbent having active sites present in itself or a modified active site adsorbent to metal ions to form a stable complex. The adsorption method has the characteristic of environmental protection, and shows great superiority in the current adsorption field. At present, many kinds of adsorbent materials are generated in research on removing mercury ions in water, and the adsorption mechanism of the adsorbent materials to the mercury ions in water is different due to the difference of the adsorbent materials. The selection of the adsorbent material includes, in addition to the key factor of adsorption capacity, the source of the material, the formation of the process, and the problems of stability and recyclability. Therefore, how to select a proper adsorbent material is still the focus of research on removing heavy metal ions in water in the future.
Corn Bract (CB) is a common agricultural byproduct in China and is usually used as a feed for livestock or discarded and burnt, so that resource waste and environmental pollution problems are caused. The longitudinal natural crimp of the corn bract is similar to cotton fiber, and the cross section of the corn bract also has an irregular hollow structure. The corn bract leaves have a large amount of cellulose with unique structure composition, large specific surface area and good ductility. The corn bract is rich in-OH group and-NH 2 The groups have good adsorption effect on mercury ions, but the adsorption process is physical adsorption. Therefore, the organic silicon-carbon composite material is applied to the field of adsorption and is converted into valuable materials, so that the environment can be effectively improved, and the organic silicon-carbon composite material has the possibility of large-scale application due to the characteristics of low price and easy availability.
Polydopamine (PDA) has applications in almost all fields of material science and engineering as a biologically inspired novel material. The PDA surface is simple in functionalization and strong in adaptability, and the surface of the material can be subjected to functional modification under a mild condition. The most widely used method for producing PDA is the solution oxidation method, which is simple to operate, and by putting monomeric dopamine into an alkaline buffer solution with pH =8.5, the dopamine undergoes aerobic autopolymerization to form a PDA layer with a controllable thickness. PDA can be formed on the surface of all materials and used as a general platform for secondary reaction to realize the preparation of the coating. One of its most important properties is that the PDA surface has firm adhesion. Meanwhile, PDA and thiol group or amino group have higher chemical reaction activity and have chelation with multiple polyvalent metal ions. The method is commonly used for functionally modifying an adsorbent material in the field of pollutant adsorption to improve the adsorption capacity of the adsorbent.
The zinc sulfide (ZnS) has stable chemical property and large specific surface area, so that the ZnS has wide application prospect in the aspects of luminescent materials, sensors, photodegradation, solar cells and the like. In recent years, adsorption studies for removing heavy metal ions by using zinc sulfide have also been receiving attention. A series of researches on the adsorption and removal effects of nano ZnS materials on elemental mercury show that the nano ZnS materials have stronger adsorption effect compared with commercial activated carbon.
If agricultural waste corn bracts are selected as raw materials, and polydopamine and zinc sulfide are used for modification on the surfaces of the agricultural waste corn bracts to obtain the corn bracts/dopamine @ zinc sulfide (CB/PDA @ ZnS) composite material with high affinity for mercury ions, the secondary utilization of the agricultural waste corn bracts can be realized, and the composite material can also be used for adsorbing heavy metal ions, so that the effect of treating wastes with processes of wastes against one another can be achieved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a zinc sulfide modified corn bract adsorbing material, which has the advantages of rich raw material sources, simple preparation process and low preparation cost.
In order to solve the technical problems, the invention provides a preparation method of a corn bract adsorbing material modified by zinc sulfide, which comprises the following steps:
dissolving corn bracts and dopamine hydrochloride in water to obtain a first mixed solution;
adding a Tris-HCl buffer solution into the first mixed solution for reaction, and washing and drying after the reaction to obtain a corn bract/dopamine product;
dissolving the corn bract/dopamine product and zinc chloride in ethylene glycol to obtain a second mixed solution;
dissolving thiourea in a mixed solution of n-butylamine and ethylene glycol to obtain a third mixed solution;
and mixing the second mixed solution and the third mixed solution for reaction, washing and drying after the reaction to obtain the corn bract/dopamine @ zinc sulfide composite material.
Further, the corn bract and dopamine hydrochloride are dissolved in water to obtain a first mixed solution, and the first mixed solution is obtained by mixing the corn bract and dopamine hydrochloride, adding the mixture into deionized water, and performing ultrasonic dispersion for 10-50 min.
Further, the mass ratio of the corn bracts to the polydopamine is 5:1-10.
Further, the mass ratio of the corn bracts to the polydopamine is 8:1.
Further, adding the Tris-HCl buffer solution into the first mixed solution for reaction, namely dropwise adding 20-50mmol/L Tris-HCl buffer solution into the first mixed solution, adjusting the pH value of the reaction mixed solution to 8.5, and stirring and reacting at room temperature for 10-15h.
Further, the mass ratio of the corn bract/polydopamine product to zinc chloride is 3.5.
Further, the thiourea is dissolved in a mixed solution of 25-50mL of n-butylamine and 50-100mL of ethylene glycol per 15mmol to obtain a third mixed solution.
Further, the mixed reaction of the second mixed solution and the third mixed solution is carried out for 10 to 15 hours at the temperature of between 100 and 150 ℃.
Further, the second mixed solution and the third mixed solution are mixed and reacted for 12 hours at the temperature of 120 ℃.
Further, the washing and drying are carried out for multiple times by using deionized water and absolute ethyl alcohol, and then the drying is carried out for 12-24h at the temperature of 60-80 ℃.
The invention provides a preparation method of a corn bract adsorption material modified by zinc sulfide, which comprises the steps of taking corn bracts as raw materials, using polydopamine as a binder to load zinc sulfide products with different proportions on the surfaces of the corn bracts, reacting for a certain time at a certain temperature, carrying out suction filtration, washing and drying to remove redundant zinc ions, and finally obtaining the corn bract/polydopamine @ zinc sulfide composite material with good adsorption capacity. The corn bracts are used as basic materials to prepare the adsorbing material, so that the secondary utilization of agricultural wastes of the corn bracts can be realized, and the composite material prepared by the invention has good adsorption effect on adsorbing heavy metal ions such as mercury ions and the like, thereby achieving the effect of treating wastes with processes of wastes against one another.
According to the preparation method of the corn bract adsorbing material modified by zinc sulfide, provided by the invention, the corn bract is modified by dopamine (PDA) with excellent adhesion property, so that the mercury adsorption capacity of the material can be improved, and the loading capacity and stability of zinc sulfide can be improved. In addition, the composite material prepared by the invention contains rich-OH and-NH 2 And S ion functional groups can well perform complexation reaction or electrostatic adsorption with Hg (II) and the like, and sulfur ions, mercury ions and mercury simple substances on the composite material have strong chelating capacity, so that the introduction of zinc sulfide can improve the sulfur content in the composite material, and can also improve the adsorption efficiency and the maximum adsorption capacity of the composite material on the mercury ions.
In addition, the composite material prepared by the preparation method of the corn bract adsorbing material modified by zinc sulfide provided by the invention has a stable structure, has strong acid and alkali resistance and the like, can be recycled for many times, and does not generate secondary pollution. The composite material is convenient to use, high in adsorption speed, strong in adsorption capacity and high in removal rate, has good adsorption performance on mercury in water, and is very suitable for adsorption treatment of mercury in industrial wastewater. Through regeneration experiments of the composite material prepared by the method, the removal rate of the corn bract/polydopamine @ zinc sulfide composite material after five times of adsorption-desorption can still reach 93.33%, a high adsorption effect is still maintained, and the composite material has excellent recycling performance.
Meanwhile, the preparation method of the corn bract adsorbing material modified by zinc sulfide provided by the invention has the advantages of simple and feasible preparation process, rich sources of required raw materials, cheap and easily-obtained raw materials, no need of expensive equipment and harsh production conditions, and low preparation cost. Meanwhile, the prepared material is non-toxic, odorless, pollution-free and reusable, can further greatly reduce the production cost, has higher economic benefit, is worthy of popularization and application, and has better application prospect.
Drawings
FIG. 1 is a flow chart of a method for preparing a corn bract adsorbing material modified by zinc sulfide according to an embodiment of the invention;
FIG. 2 is a FT-IR spectrum of CB and CB/PDA @ ZnS materials provided by the embodiment of the invention;
FIG. 3 is an XRD spectrum of CB and CB/PDA @ ZnS materials provided by the embodiment of the invention;
FIG. 4 is an SEM spectrogram of CB/PDA and CB/PDA @ ZnS materials provided by the embodiment of the invention;
FIG. 5 is an XPS full spectrogram of the CB/PDA @ ZnS @ Hg composite material and the CB/PDA @ ZnS @ Hg thereof after adsorbing mercury provided by the embodiment of the invention;
FIG. 6 is a Hg4f high resolution plot of XPS spectrogram of CB/PDA @ ZnS composite material provided by the embodiment of the present invention;
FIG. 7 is a C1s resolution graph of the CB/PDA @ ZnS composite material provided by the embodiment of the invention before (i) and after (ii) adsorption;
FIG. 8 is a resolution graph of O1s before (i) and after (ii) adsorption of the CB/PDA @ ZnS composite material provided by the embodiment of the present invention;
FIG. 9 is a resolution chart of N1s before (i) and after (ii) adsorption of the CB/PDA @ ZnS composite material provided by the embodiment of the present invention;
FIG. 10 is a resolution graph of S2p before (i) and after (ii) adsorption of the CB/PDA @ ZnS composite material provided by the embodiment of the present invention.
Detailed Description
Referring to fig. 1, the preparation method of the corn bract adsorbing material modified by zinc sulfide provided by the embodiment of the invention comprises the following steps:
step 1) dissolving corn bracts and dopamine hydrochloride in deionized water, and performing ultrasonic dispersion for 10-50min to obtain a first mixed solution.
Wherein the mass ratio of the corn bract to the polydopamine is 5:1-10.
In a preferred embodiment of the present invention, the mass ratio of corn bract to polydopamine is 8:1.
Step 2) adding a Tris-HCl buffer solution of 20-50mmol/L slowly dropwise into the first mixed solution obtained in the step 1), and adjusting the pH of the solution to 8.5. Stirring and reacting for 10-15h at room temperature, after the reaction is finished, washing the obtained product for multiple times by using deionized water and absolute ethyl alcohol to remove unreacted dopamine hydrochloride, and then drying at the temperature of 60-80 ℃ for 12-24h to obtain a corn bract/dopamine (CB/PDA) product. The prepared corn bract/dopamine (CB/PDA) product is characterized by surface morphology by a scanning electron microscope, and an SEM spectrogram of the corn bract/dopamine (CB/PDA) product is shown in FIG. 4.
In a preferred embodiment of the present invention, the first mixture and the Tris-HCl buffer solution are stirred at room temperature at pH 8.5 for a period of 12 hours.
As a best embodiment of the invention, the optimal drying temperature of the process is 80 ℃, and the optimal drying time is 24h.
And 3) dissolving the corn bract/dopamine (CB/PDA) product and zinc chloride in ethylene glycol to obtain a second mixed solution. Wherein the mass ratio of the corn bract/polydopamine (CB/PDA) product to the zinc chloride is 3.5.
And 4) dissolving thiourea in the mixed solution of n-butylamine and glycol to obtain a third mixed solution. Wherein, thiourea is dissolved in the mixed solution of 25-50mL n-butylamine and 50-100mL glycol per 15mmol to obtain a third mixed solution.
And step 5) mixing the second mixed solution obtained in the step 3) and the third mixed solution obtained in the step 4) to react for 10-15h at the temperature of 100-150 ℃, washing the obtained product for multiple times by using deionized water and ethanol after the reaction, and then drying the product for 12-24h at the temperature of 60-80 ℃ to obtain the corn bract/dopamine @ zinc sulfide composite material (CB/PDA @ ZnS).
In a preferred embodiment of the present invention, the optimal reaction temperature for the mixing reaction of the second mixed solution obtained in step 3) and the third mixed solution obtained in step 4) is 120 ℃, and the optimal reaction time is 12 hours.
As a best embodiment of the invention, the optimal drying temperature in the process is 80 ℃, and the optimal drying time is 24h.
The FT-IR spectrogram of the corn bract/dopamine @ zinc sulfide (CB/PDA @ ZnS) material prepared by the embodiment of the invention is shown in figure 2. In the figure 2, CB is an infrared spectrogram (FT-IR spectrogram) of the corn bract, and CB/PDA @ ZnS is an infrared spectrogram (FT-IR spectrogram) of the corn bract/dopamine @ zinc sulfide composite material. As can be seen from FIG. 2, in the CB infrared spectrum, 3419cm -1 The characteristic peak of the position corresponds to the stretching vibration of a CB/PDA @ ZnS composite material-OH group, and the modification of PDA causes the stretching vibration peak of-OH to be shifted compared with CB. At 2929cm -1 、1620cm -1 And 1032cm -1 Respectively correspond to-NH 2 The stretching vibration peak of the C-H, C-O group is weakened corresponding to the peak intensity in the CB, indirectly shows that the PDA is stably formed on the CB and is 617cm at the same time -1 The position is the stretching vibration peak of C-S, which can further show that the invention successfully prepares the CB/PDA @ ZnS composite material.
The XRD spectrogram of the corn bract/dopamine @ zinc sulfide (CB/PDA @ ZnS) material prepared by the embodiment of the invention is shown in figure 3. Wherein, CB is an X-ray diffraction (XRD) spectrogram of 5-90 degrees of the corn bract within the range of 2 theta, and CB/PDA @ ZnS is an X-ray diffraction (XRD) spectrogram of 5-90 degrees of the corn bract/dopamine @ zinc sulfide composite material within the range of 2 theta. As can be seen from fig. 3, the prominent diffraction peaks at 2 θ =28.57 °, 48.27 ° and 56.26 ° correspond to the (111), (220) and (311) crystal planes of ZnS, respectively, indicating that the present invention successfully produces the corn husk/dopamine @ zinc sulfide (CB/pda @ ZnS) composite.
The SEM spectrogram of the CB/PDA @ ZnS material prepared by the embodiment of the invention is shown in FIG. 4. Wherein, FIG. 4 (d-f) is a representation of the surface morphology of the corn bract/dopamine @ zinc sulfide (CB/PDA @ ZnS) composite material by using a scanning electron microscope. As can be seen from the SEM spectrogram of the corn bract/dopamine (CB/PDA) material in fig. 4 (a-c), the modification of the corn bract by dopamine causes the surface of the CB to become smoother and denser, and as can be seen from the SEM spectrogram of the corn bract/dopamine @ zinc sulfide (CB/PDA @ ZnS) composite material in fig. 4 (d-f), znSs are all spherical particles and are uniformly distributed on the surface of the CB/PDA, thereby further proving the success of preparing the CB/PDA @ ZnS composite material of the invention.
In order to verify the mercury adsorption effect of the corn bract/dopamine @ zinc sulfide (CB/PDA @ ZnS) composite material prepared in the embodiment of the invention, the XPS technology is adopted to measure the surface component binding energy of the corn bract/dopamine @ zinc sulfide (CB/PDA @ ZnS) composite material prepared in the embodiment of the invention and the CB/PDA @ ZnS @ Hg obtained by adsorbing mercury by the composite material.
An XPS full spectrum of the CB/PDA @ ZnS composite material prepared by the embodiment of the invention and the CB/PDA @ ZnS @ Hg after adsorbing mercury is shown in FIG. 5. As can be seen from FIG. 5, the new binding energy bands of Hg4f, hg4d5 and Hg4d3 appear in the CB/PDA @ ZnS @ Hg spectrum, which shows that the prepared CB/PDA @ ZnS @ Hg has better adsorption effect on Hg (II).
The Hg4f high resolution graph of the XPS spectrogram of the CB/PDA @ ZnS composite material prepared by the embodiment of the invention is shown in FIG. 6. Wherein 104.53eV and 100.52eV are respectively Hg4f 5/2 And Hg4f 7/2 High resolution spectral binding energy of Hg4f 5/2 And Hg4f 7 /2 The binding energy gap of (3) is 4.01eV.
The resolution diagrams of C1s before (i) and after (ii) adsorption of the CB/PDA @ ZnS composite material prepared in the example of the present invention are shown in FIG. 7. Before adsorption, the C1s high-resolution XPS spectrum respectively shows three peaks of C-C (284.65 eV), C-N (285.41 eV) and C-O (285.86 eV), and the binding energy of C-N, C-O has slight position shift after the adsorbent adsorbs Hg (II) ions, which shows that N, O functional groups connected with C adsorb the Hg (II) ions.
The resolution graphs of O1s before (i) and after (ii) adsorption of the CB/PDA @ ZnS composite material prepared in the example of the present invention are shown in FIG. 8. Before adsorption, it is known from an O1s high-resolution XPS spectrum that a characteristic peak appears at 531.45eV of-OH groups, and after Hg (II) ions are adsorbed, the binding energy of the characteristic peak of C-O is also shifted, thus confirming the interaction between the-OH groups and the Hg (II) ions.
The resolution graphs of N1s before (i) and after (ii) adsorption of the CB/PDA @ ZnS composite material prepared in the embodiment of the invention are shown in FIG. 9. Before adsorption, the binding energy 399.56eV is N atom-NH 2 Characteristic peak, post-adsorption-NH 2 The binding energy of the characteristic peak was shifted higher, confirming-NH 2 Interaction with Hg (II) ions.
The resolution plots of S2p before (i) and after (ii) adsorption of the CB/PDA @ ZnS composite material prepared in the example of the present invention are shown in FIG. 10. (ii) S2p high resolution XPS Spectroscopy before adsorption (i) see that S2p 3/2 And S2p 1/2 The characteristic peaks of (a) occur at 161.23eV and 162.48eV, and the S2p characteristic peak was found to shift to a high binding energy by comparison of (II) after adsorption with (i) before adsorption, indicating that the S group is also involved in chelating Hg (II) ions. Therefore, three atoms in the CB/pda @ zns adsorbent (O, N, S) can participate in the adsorption of Hg (II) together.
The following will explain in detail the preparation method of the corn bract adsorbing material modified by zinc sulfide provided by the invention with reference to several specific examples. These examples are only for illustrating the present invention and are not intended to limit the scope of application of the present invention. Various changes or modifications to the invention and the like which are equivalent to the above embodiments are also intended to be included within the scope of the invention as defined in the appended claims.
The instrument and the characterization method adopted by the invention are as follows:
FT-IR was tested using a Spectrum One infrared spectrometer from PE, USA. The solid sample adopts KBr tabletting, the liquid sample is coated on a KBr wafer, and the wave number range of absorption spectrum scanning is 4000-500 cm -1 And 3 times of scanning.
X-ray diffractometer (XRD) adopted Bruker D8 ADVANCE Germany wide-angle X-ray diffractometer, cu target: (
) The scanning range is 0-10 degrees.
Scanning Electron Microscopy (SEM) images of the swept samples were recorded using hitachi SU 8010.
The X-ray photoelectron spectroscopy was tested using a Japanese PHI X-tool fully automatic scanning type micro-region XPS probe.
The invention uses TU-1901 double-beam ultraviolet-visible spectrophotometer of Beijing Pujingyu general-purpose instrument, LLC. The test method refers to the dithizone spectrophotometry to measure the content of mercury ions (GB 7469-87)
In acidic mercury ion solution, hg 2+ And reacting with dithizone to generate an orange chelate, wherein the maximum absorption wavelength of the orange chelate is 485nm, and the molar absorption coefficient is 7.1 multiplied by 104L/(mol.cm). Therefore, the Hg can be measured by spectrophotometry 2+ The absorbance of the solution was varied and Hg was determined from the standard curve 2+ The concentration of the solution. The minimum detection concentration of mercury was 2. Mu.g/L, and the upper limit of the measurement was 40. Mu.g/L.
Hg 2+ The concentration is 2-40 mug/L, the absorbance intensity of the mercury dithizone chelate at the wavelength of 485nm shows a good linear relation, and the linear fit is as follows:
A＝0.0076C-0.0022 R 2 ＝0.9997
a is absorbance and C is Hg 2+ The concentration of (c).
Example 1:
(1) 8g of Corn Bract (CB) and 1g of dopamine hydrochloride (PDA) were mixed and added to 100mL of deionized water, and dispersed with ultrasound for 30min, followed by slowly dropping 30mmol/L of Tris-HCl buffer solution to adjust the pH of the mixed solution to 8.5. Stirring and reacting for 12h at room temperature, after the reaction is finished, washing the obtained product for multiple times by using deionized water and absolute ethyl alcohol to remove dopamine hydrochloride which does not participate in the reaction, and drying for 24h at the temperature of 80 ℃ to obtain a corn bract/dopamine (CB/PDA) product.
(2) Mixing 2.5g of corn bract/dopamine, 1.25mmol of zinc chloride and 250mL of glycol solution, adding the mixture into a 500mL three-neck flask provided with a condenser, dissolving 1g of thiourea (15 mmol) in a mixed solution of 50mL of n-butylamine and 100mL of glycol, adding the mixture into the three-neck flask, reacting at the temperature of 120 ℃ for 12h, washing the obtained product with deionized water and ethanol for multiple times, and drying at the temperature of 60 ℃ for 24h to obtain the corn bract/dopamine @ zinc sulfide composite material (CB/PDA @ ZnS)
(3) When m (corn bract): m (polydopamine) =8 (corn bract/polydopamine): (zinc sulfide) =20, and the adsorption capacity of the prepared composite material to mercury ions is 260.8mg/g, and the removal rate is 77.6%.
Example 2:
(1) The synthesis was the same as in step (1) in example 1.
(2) Mixing 2.5g of corn bract/dopamine, 2.5mmol of zinc chloride and 250mL of glycol solution, adding the mixture into a 500mL three-neck flask provided with a condenser, dissolving 1g of thiourea (15 mmol) in a mixed solution of 50mL of n-butylamine and 100mL of glycol, adding the mixture into the three-neck flask, reacting at the temperature of 120 ℃ for 12h, washing the obtained product with deionized water and ethanol for multiple times, and drying at the temperature of 60 ℃ for 24h to obtain the corn bract/dopamine @ zinc sulfide composite material (CB/PDA @ ZnS)
(3) When m (corn bract): m (polydopamine) =8 (corn bract/polydopamine): (zinc sulfide) =10, and the adsorption amount of the prepared composite material to mercury ions is 283.3mg/g, and the removal rate is 84.3%.
Example 3:
(1) The synthesis was the same as in step (1) in example 1.
(2) Mixing 2.5g of corn bract/dopamine and 5mmol of zinc chloride with 250mL of glycol solution, adding the mixture into a 500mL three-neck flask provided with a condenser, simultaneously dissolving 1g of thiourea (15 mmol) in 50mL of n-butylamine and 100mL of glycol mixed solution, adding the mixture into the three-neck flask, reacting at the temperature of 120 ℃ for 12h, washing the obtained product with deionized water and ethanol for multiple times, and drying at the temperature of 60 ℃ for 24h to obtain the corn bract/dopamine @ zinc sulfide composite material (CB/PDA @ ZnS)
(3) When m (corn bract): m (polydopamine) =8 (corn bract/polydopamine): (zinc sulfide) =5:1, the adsorption capacity of the prepared composite material to mercury ions is 333.03mg/g, and the removal rate is 99.1%.
Example 4:
(1) The synthesis is the same as the step (1) in the example 1;
(2) Mixing 2.5g of corn bract/dopamine and 7.5mmol of zinc chloride with 250mL of glycol solution, adding the mixture into a 500mL three-neck flask provided with a condenser, dissolving 1g of thiourea (15 mmol) in 50mL of n-butylamine and 100mL of glycol mixed solution, adding the mixture into the three-neck flask, reacting at the temperature of 120 ℃ for 12h, washing the obtained product with deionized water and ethanol for multiple times, and drying at the temperature of 60 ℃ for 24h to obtain the corn bract/dopamine @ zinc sulfide composite material (CB/PDA @ ZnS)
(3) When m (corn bract): m (polydopamine) =8 (corn bract/polydopamine): (zinc sulfide) =3.5, and the adsorption capacity of the prepared composite material to mercury ions is 333.83mg/g, and the removal rate is 99.6%.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention is described in detail with reference to examples, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a corn bract adsorption material modified by zinc sulfide is characterized by comprising the following steps:
dissolving corn bracts and dopamine hydrochloride in water to obtain a first mixed solution;
adding a Tris-HCl buffer solution into the first mixed solution for reaction, and washing and drying after the reaction to obtain a corn bract/dopamine product;
dissolving corn bract/dopamine and zinc chloride in ethylene glycol to obtain a second mixed solution;
dissolving thiourea in a mixed solution of n-butylamine and ethylene glycol to obtain a third mixed solution;
and mixing the second mixed solution and the third mixed solution for reaction, washing and drying after the reaction to obtain the corn bract/dopamine @ zinc sulfide composite material.
2. The method for preparing a corn bract adsorbing material modified by zinc sulfide according to claim 1, which is characterized in that: the corn bract and dopamine hydrochloride are dissolved in water to obtain a first mixed solution, and the first mixed solution is obtained by mixing the corn bract and dopamine hydrochloride, adding the mixture into deionized water, and performing ultrasonic dispersion for 10-50 min.
3. The method for preparing a corn bract adsorbing material modified by zinc sulfide according to claim 2, which is characterized in that: the mass ratio of the corn bracts to the polydopamine is 5:1-10.
4. The method for preparing a corn bract adsorbing material modified by zinc sulfide according to claim 3, wherein: the mass ratio of the corn bracts to the polydopamine is 8:1.
5. The method for preparing a corn bract adsorbing material modified by zinc sulfide according to claim 1, which is characterized in that: the step of adding the Tris-HCl buffer solution into the first mixed solution for reaction is to dropwise add 20-50mmol/L of Tris-HCl buffer solution into the first mixed solution, adjust the pH value of the reaction mixed solution to 8.5, and stir for reaction at room temperature for 10-15h.
6. The method for preparing a corn bract adsorbing material modified by zinc sulfide according to claim 1, which is characterized in that: the mass ratio of the corn bract/polydopamine product to the zinc chloride is 3.5.
7. The method for preparing a corn bract adsorbing material modified by zinc sulfide according to claim 1, which is characterized in that: dissolving 15mmol of thiourea in a mixed solution of 25-50mL of n-butylamine and 50-100mL of ethylene glycol to obtain a third mixed solution.
8. The method for preparing a corn bract adsorbing material modified by zinc sulfide according to claim 1, which is characterized in that: the mixed reaction of the second mixed solution and the third mixed solution is carried out for 10 to 15 hours at the temperature of between 100 and 150 ℃.
9. The method for preparing a corn bract adsorbing material modified by zinc sulfide according to claim 8, wherein: the mixed reaction of the second mixed solution and the third mixed solution is carried out for 12 hours at the temperature of 120 ℃.
10. The method for preparing a corn bract adsorbing material modified by zinc sulfide according to claim 1, which is characterized in that: the washing and drying are carried out for a plurality of times by using deionized water and absolute ethyl alcohol, and then the drying is carried out for 12 to 24 hours at the temperature of between 60 and 80 ℃.
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| Title |
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| PENG LI等: "Effective and reusable 3D CuxS nanocluster structured magnetic adsorbent for mercury extraction from wastewater", 《CHEMOSPHERE》, vol. 301, 3 May 2022 (2022-05-03), pages 134818 - 1, XP087084434, DOI: 10.1016/j.chemosphere.2022.134818 * |
| XIAOXU XU等: "Highly effective removal of Hg(II) solution using corn bract@MoS2 as a new biomass adsorbent", 《RSC ADV》, vol. 12, 7 November 2022 (2022-11-07), pages 31792 * |
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