CN109732098B - Method for green modification of nano-iron-tin bimetallic particles by using pine bark - Google Patents
Method for green modification of nano-iron-tin bimetallic particles by using pine bark Download PDFInfo
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Abstract
A method for green modification of nano-iron-tin bimetallic particles by pine bark belongs to the technical field of nano-materials and wastewater treatment. Pulverizing dried cortex Pini, soaking in anhydrous methanol, ultrasonic treating, and filtering to obtain cortex Pini extractive solution; mixing the pine bark extract with a ferrous sulfate solution to obtain a ferric salt-pine bark extract mixed solution, and then adding a potassium borohydride solution to obtain a pine bark modified nano-iron particle suspension; and then adding stannous chloride solution to generate the pine bark modified nano-iron-tin bimetallic particles, and washing with deionized water and acetone. The removal rate of the reactive brilliant blue KN-R in the wastewater reaches more than 99 percent.
Description
Technical Field
The invention belongs to the field of nano materials and wastewater treatment, and relates to a method for synthesizing modified nano iron-based metal by using natural plant bark and application thereof, in particular to a method for synthesizing green modified iron-tin bimetallic particles by using natural pine bark and application thereof in removing dye in wastewater.
Background
The demand and consumption of the dye in China are huge, the annual dye production capacity accounts for more than 60% of the total world production capacity, and the dye is the first in the world. In various dyeing processes, approximately 12% of the dye is lost and is discharged to the environment in the form of printing waste water. Generally, the printing and dyeing wastewater has complex components, poor biodegradability, higher chromaticity and certain photolysis and oxidation resistance, which is extremely unfavorable for the treatment of the printing and dyeing wastewater. Moreover, the printing and dyeing wastewater is directly discharged into a natural water body without being treated, the light transmittance of the water body is influenced, the photosynthesis of algae and the like in the water body is inhibited, and certain dye components have ecological toxicity to aquatic organisms and seriously influence the aquatic ecological environment, so that the high-efficiency treatment of the printing and dyeing wastewater arouses the attention of people. Anthraquinone dyes are one of the most widely used dyes, and are more difficult to decolorize based on their conjugated structure.
The nano iron and the bimetal have excellent removal effect on most pollutants, the nano iron palladium, the nano iron nickel, the nano iron copper and other bimetals are known environment repairing materials capable of effectively degrading pollutants, but the research on the nano iron tin bimetal is less at present. Due to its own magnetism and van der waals force, and high reactivity, nano-iron-based metal particles are very easy to agglomerate and be oxidized to lose reactivity. The nano iron metal is modified, so that the dispersibility of the particles is improved, and the reaction activity is maintained. Polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone and the like are commonly used modifiers, but chemical agents cause environmental pollution if being improperly used, and are high in cost, so that the use of modified nano iron-based particles is limited. Biodegradable green materials are of interest to many researchers due to their resource reusability and environmental friendliness.
Pine trees are one of the most widely distributed tree species in China, and the pine trees spread all over the country, and the pine bark of the pine trees falls off during growth, felling and processing, so that the pine trees become waste and leave the pine trees unused. Researches have proved that the pine bark is rich in procyanidine, is a natural polyphenol compound and has strong effects of resisting oxidation and scavenging free radicals. The reactive brilliant blue KN-R is a common anthraquinone dye, an extracting solution is prepared by utilizing waste pine bark, nano iron-tin bimetallic particles are subjected to green modification, the nano iron-tin bimetallic particles modified by the pine bark are synthesized, and the waste water containing the reactive brilliant blue KN-R is treated.
Disclosure of Invention
The invention aims to provide a preparation method of modified nano-iron-tin bimetallic particles, which has low cost, mild operating conditions and environmental protection. The invention also provides an application method of the modified nano-iron bimetallic particles for removing the reactive brilliant blue KN-R in the wastewater.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of pine bark green modified nano-iron-tin bimetallic particles comprises the following steps:
(1) the pine bark is washed clean and dried, preferably at 100 ℃ for 24 h.
(2) Pulverizing dried cortex Pini, preferably sieving to below 300 μm to obtain cortex Pini powder;
(3) preferably, soaking the pine bark powder in anhydrous methanol according to the proportion of 20-60 g/L for ultrasonic treatment, preferably for 0.5-1.5 h;
(4) filtering methanol solution of pine bark to obtain a filtrate, namely a pine bark extract;
(5) mixing the pine bark extract with a ferrous sulfate solution at room temperature to obtain a ferric salt-pine bark extract mixed solution; mixing, preferably oscillating for 5min in a constant-temperature water bath shaking table, wherein the rotating speed is 210-250 rpm, and the temperature is 25 ℃;
(6) slowly adding the potassium borohydride solution into the ferric salt-pine bark extract liquid mixed solution obtained in the step (5) to obtain a pine bark modified nano-iron particle suspension; and preferably, oscillating while adding, immediately bubbling the solution to generate a black solid in the system, and standing the potassium borohydride solution after adding until the system does not bubble any more.
(7) Mixing the stannous chloride solution with the pine bark modified nano-iron suspension obtained in the step (6) to generate pine bark modified nano-iron-tin bimetallic particles; preferably shaking in a constant temperature water bath shaker at 25 deg.C for 20-50 min.
(8) And (4) separating the pine bark modified nano iron-tin bimetallic particles in the step (7) by a magnetic separation method, washing with deionized water and acetone, and storing the particles in acetone.
The ultrasonic power in the step (3) of the invention is 60-100W, and the temperature is 20-40 ℃.
The mass ratio of the dry pine bark powder to the ferrous sulfate in the step (5) is 0-5.3955 and is not 0; the mass ratio of the potassium borohydride to the ferrous sulfate is 0.3880-0.7761; the mass ratio of the dry pine bark powder to the stannous chloride is 0-938.9072, and is not 0.
The pine bark modified nano iron-tin bimetallic particle provided by the invention can be used for removing reactive brilliant blue KN-R dye in wastewater. And (2) removing acetone at room temperature, washing the pine bark modified nano iron-tin bimetallic particles twice by using deionized water, adding wastewater containing reactive brilliant blue KN-R dye, shaking or stirring until the dye is not decolored, filtering and separating, adjusting the filtrate to be neutral, and discharging to finish the removal of the pine bark modified nano iron-tin bimetallic particles on the reactive brilliant blue KN-R. The initial pH value of the system is 2.0-10.0, the adding concentration of the bimetallic particles is 0.224-2.016 g/L, and the initial concentration of the reactive brilliant blue KN-R dye in the wastewater is 300-1500 mg/L.
The invention has the advantages and beneficial effects that:
(1) the waste pine bark is easy to obtain and low in cost, and the pine bark extract prepared by using the waste pine bark as the raw material is used for replacing a chemical agent with higher price and modifying unmodified nano iron-tin bimetal particles, so that the synthesis cost of modified nano iron-series bimetal is reduced;
(2) the traditional chemical agent is used as the modifier of the unmodified nano iron-tin bimetallic particles, which can cause secondary environmental pollution. The pine bark is biodegradable plant waste, and the pine bark extract is an environment-friendly modifier and has little influence on the environment.
(3) Unfortunately, the waste pine bark is discarded, and the unmodified nano iron-tin bimetallic particles are modified by the pine bark extracting solution, so that the waste pine bark is effectively utilized, the resource utilization of waste is realized, and the development concept of green chemistry is met. And the modifier of the unmodified nano-iron-tin bimetallic particles comes from waste, and the pine bark modified nano-iron-tin bimetallic particles are used for removing the wastewater containing the reactive brilliant blue KN-R, so that a new way for treating the wastewater by using the waste is developed.
(4) The introduction of the pine bark extract obviously improves the removal effect of the unmodified nano iron-tin bimetallic particles on the reactive brilliant blue KN-R. The removal rate of the pine bark modified nano iron-tin bimetallic particles synthesized according to the conditions that the volume ratio of the pine bark extract to the ferrous sulfate solution is 2.5:1, the pH value (4.4) during the synthesis reaction is not regulated, and the tin load is 2.0% is up to more than 99.63% within 10min, and is higher than 94.84% of that of the unmodified nano iron-tin bimetallic particles.
Drawings
FIG. 1 shows the effect of different pine bark extract dosages on the removal of reactive brilliant blue KN-R from wastewater by pine bark modified nano-Fe-Sn bimetallic particles.
FIG. 2 shows the effect of pH value of the pine bark modified nano-Fe-Sn bimetal particles on the removal of reactive brilliant blue KN-R from wastewater during different synthetic reactions.
FIG. 3 shows the effect of different tin loadings on the removal of reactive brilliant blue KN-R from wastewater by pine bark modified nano-Fe-Sn bimetallic particles.
FIG. 4 is a scanning electron microscope image of the unmodified nano-Fe-Sn bimetal particle (a) of the present invention and the pine bark modified nano-Fe-Sn bimetal particle before (b) and after (c) reacting with the reactive brilliant blue KN-R.
FIG. 5 is a Fourier transform infrared spectrum of the unmodified nano-Fe-Sn bimetal particle of the present invention and the pine bark modified nano-Fe-Sn bimetal particle before and after the reaction with the reactive brilliant blue KN-R.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the present invention is not limited to these examples.
Example 1
After washing the pine bark by deionized water, drying the pine bark at 100 ℃ for 24 h. Crushing dried cortex Pini, sieving, selecting cortex Pini powder with particle diameter below 300 μm, soaking in anhydrous methanol at a ratio of 20g/L, and performing ultrasonic treatment (60W, 20 deg.C) for 1 h. Vacuum filtering the pine bark powder methanol solution with 0.45 μm organic filter membrane, and collecting filtrate to obtain pine bark extract. Mixing the pine bark extract with 20mL of 11.1204g/L ferrous sulfate solution at a volume ratio of 0:1, 0.5:1, 1.0:1, 1.5:1, 2.0:1, 2.5:1 and 3.0:1 (the pine bark extract is 0, 10, 20, 30, 40, 50 and 60mL) to obtain iron salt-pine bark extract mixed solution, and shaking in a constant temperature water bath shaking table for 5min (210rpm, 25 deg.C). Then, 20mL of 4.3152g/L potassium borohydride solution was added dropwise to the mixture, and the mixture was shaken while adding. Black solid is generated in the system and continuously bubbles, and the black solid is the pine bark modified nano iron particles. After the system does not bubble any more, adding 20mL of 0.0852/L stannous chloride solution into the system, starting slow bubbling of the system, placing the system in a constant-temperature water bath shaking table, and oscillating for 20min (210rpm, 25 ℃) to obtain the pine bark modified nano iron-tin bimetallic particles. The particles were washed twice with deionized water and acetone in sequence and then stored in acetone.
At room temperature, 0.0448g of the pine bark modified nano-Fe-Sn bimetallic particles prepared in the example 1 is added with 200mL of wastewater with the initial pH value of 2.0 and the initial concentration of 300mg/L of active brilliant blue KN-R. Theoretically, the mass ratio of the loaded tin to the iron, namely, the tin loading amount is 2%, and the adding amount of the particles is 0.224 g/L. Stirring at room temperature until the reactive brilliant blue KN-R does not fade any more, filtering and separating, adjusting the filtrate to be neutral, and discharging to remove the wastewater containing the reactive brilliant blue KN-R by the pine bark modified nano-iron-tin bimetallic particles.
The effect of different pine bark extract dosages on the removal of reactive brilliant blue KN-R is shown in FIG. 1. After the extracting solution is introduced, the final removal rate (10min) of the pine bark modified nano iron-tin bimetallic particles to the reactive brilliant blue KN-R is obviously improved, the highest removal rate of the reactive brilliant blue KN-R is 99.63% when the volume ratio of the pine bark extracting solution to the ferrous sulfate solution reaches 2.5:1 and is higher than 94.84% when the extracting solution is not introduced, and the removal rate of the unmodified nano iron-tin bimetallic particles to the reactive brilliant blue KN-R is the lowest when the volume ratio of the pine bark extracting solution to the ferrous sulfate solution is 0:1 (unmodified nano iron-tin bimetallic particles). In order to realize higher removal rate of the reactive brilliant blue KN-R and save cost and avoid excessive use of the pine bark extract, the volume ratio of the pine bark extract to the ferrous sulfate solution is selected to be 2.5:1 for carrying out subsequent examples.
Example 2
After washing the pine bark by deionized water, drying the pine bark at 100 ℃ for 24 h. Crushing dried cortex Pini, sieving, selecting cortex Pini powder with particle diameter below 300 μm, soaking in anhydrous methanol at a ratio of 30g/L, and performing ultrasonic treatment (70W, 25 deg.C) for 1 h. Vacuum filtering the pine bark powder methanol solution with 0.45 μm organic filter membrane, and collecting filtrate to obtain pine bark extract. Mixing cortex Pini extract with 20mL of 33.3612g/L ferrous sulfate solution at volume ratio of 2.5:1 (the usage amount of cortex Pini extract is 50mL) to obtain mixed solution of iron salt and cortex Pini extract, and shaking in constant temperature water bath shaking table for 5min (220rpm, 25 deg.C). After the pH of the mixture was adjusted to 3.0, 4.4 (without adjusting the pH), 5.0, 7.0, 9.0 and 11.0, 20ml of 16.1820g/L potassium borohydride solution was added dropwise to the mixture, and the mixture was shaken while adding. And (3) generating black solid in the system when the pH value of the synthesis reaction is 3.0, 4.4 (without adjusting the pH value) and 5.0, and continuously bubbling, wherein the black solid is the pine bark modified nano iron particles. The system does not generate black solid when the pH value of the synthesis reaction is 7.0, 9.0 and 11.0. After the system does not bubble any more under the conditions that the pH value of the synthesis reaction is 3.0, 4.4 (pH value is not adjusted) and 5.0, adding 20mL of 0.2556g/L stannous chloride solution into the system, slowly bubbling the system again, placing the system in a constant-temperature water bath shaking table, and oscillating for 20min (220rpm, 25 ℃) to obtain the pine bark modified nano-iron-tin bimetallic particles. The particles were washed twice with deionized water and acetone in sequence and then stored in acetone.
At room temperature, 0.1344g of the pine bark modified nano-iron-tin bimetallic particles prepared in the example 2 is added with 200mL of wastewater with the initial pH value of 4.0 and the initial concentration of 600mg/L of active brilliant blue KN-R. The tin loading was 2% and the amount of pellets added was 0.672 g/L. Stirring at room temperature until the reactive brilliant blue KN-R does not fade any more, filtering and separating, adjusting the filtrate to be neutral, and discharging to remove the wastewater containing the reactive brilliant blue KN-R by the pine bark modified nano-iron-tin bimetallic particles.
The influence of the pH value on the effect of the pine bark modified nano-iron-tin bimetal particles in removing the reactive brilliant blue KN-R during different synthesis reactions is shown in figure 2. When the synthesis reaction is 7.0, 9.0 and 11.0, the pine bark modified nano-iron-tin bimetallic particles cannot be synthesized, and when the synthesis reaction is respectively 3.0, 4.4 (without adjusting the pH value) and 5.0, the removal rates of the synthesized pine bark modified nano-iron-tin bimetallic particles to the active brilliant blue KN-R are respectively 98.77%, 99.63% and 99.66%. Under the weak acidic condition, the pine bark modified nano iron-tin bimetallic particles with stronger activity can be synthesized. When the pH value of the synthetic reaction is not adjusted, the synthesized pine bark modified nano iron-tin bimetallic particles have good removal effect on the reactive brilliant blue KN-R, and when the pH value of the synthetic reaction is not adjusted, the time and the economic cost are saved, so that the subsequent examples are carried out when the pH value of the synthetic reaction is 4.4 (the pH value is not adjusted).
Example 3
After washing the pine bark by deionized water, drying the pine bark at 100 ℃ for 24 h. Crushing dried cortex Pini, sieving, selecting cortex Pini powder with particle diameter below 300 μm, soaking in anhydrous methanol at a ratio of 40g/L, and performing ultrasonic treatment (80W, 30 deg.C) for 1 h. Vacuum filtering the pine bark powder methanol solution with 0.45 μm organic filter membrane, and collecting filtrate to obtain pine bark extract. Mixing the pine bark extract with 20mL of 55.6020g/L ferrous sulfate solution at a volume ratio of 2.5:1 (the pine bark extract is 50mL) to obtain iron salt-pine bark extract mixed solution, and shaking in a constant temperature water bath shaking table for 5min (230rpm, 25 deg.C). And (3) dropwise adding 20mL of 32.3640g/L potassium borohydride solution into the mixed solution with the initial pH value of 4.4 (without adjusting the pH value), oscillating while adding, generating black solid in the system, and continuously bubbling, wherein the black solid is the pine bark modified nano iron-tin bimetallic particles. After the system does not bubble any more, respectively adding 20mL of stannous chloride solutions with the concentration of 0, 0.1065, 0.2130, 0.4260, 1.0650, 2.1301 and 4.2603g/L, starting to bubble slowly, placing the system in a constant-temperature water bath shaking table to oscillate for 20min (230rpm, 25 ℃) to obtain the pine bark modified nano iron-tin bimetallic particles with the tin loading amounts of 0, 0.5%, 1.0%, 2.0%, 5.0%, 10.0% and 20.0%. The particles were washed twice with deionized water and acetone in sequence and then stored in acetone.
At room temperature, 0.224g of the pine bark modified nano iron-tin bimetallic particles with tin loading of 0, 0.5%, 1.0%, 2.0%, 5.0%, 10.0% and 20.0% prepared in example 3 are taken, 200mL of wastewater with initial pH value of 6.0 and initial concentration of 900mg/L containing reactive brilliant blue KN-R is added, and the adding amount of the particles is 1.12 g/L. Stirring at room temperature until the reactive brilliant blue KN-R does not fade any more, filtering and separating, adjusting the filtrate to be neutral, and discharging to remove the wastewater containing the reactive brilliant blue KN-R by the pine bark modified nano-iron-tin bimetallic particles.
The effect of different tin loading on the removal effect of reactive brilliant blue KN-R by the pine bark modified nano iron-tin bimetallic particles is shown in figure 3. As the tin loading increased from 0 (pine bark modified nano-iron particles) to 20.0%, the removal rate of the pine bark modified nano-iron-tin bimetallic particles with 6 gradient tin loadings to the reactive brilliant blue KN-R differed a little and was more than 99%. When the tin loading is 2.0%, the rate of removing the reactive brilliant blue KN-R by the pine bark modified nano iron-tin bimetallic particles is the highest, the tin consumption is less, the synthetic cost of removing the pine bark modified nano iron-tin bimetallic particles is saved, and the tin loading is 2.0% for carrying out subsequent examples.
Example 4
After washing the pine bark by deionized water, drying the pine bark at 100 ℃ for 24 h. Crushing dried cortex Pini, sieving, selecting cortex Pini powder with particle diameter below 300 μm, soaking in anhydrous methanol at a ratio of 50g/L, and performing ultrasonic treatment (90W, 35 deg.C) for 1 h. Vacuum filtering the pine bark powder methanol solution with 0.45 μm organic filter membrane, and collecting filtrate to obtain pine bark extract. Mixing the pine bark extract with 20mL of 77.8428g/L ferrous sulfate solution at volume ratios of 0:1 and 2.5:1 (the pine bark extract is 0 and 50mL) to obtain mixed solution of iron salt and pine bark extract, and shaking in constant temperature water bath shaking table for 5min (240rpm, 25 deg.C). And (3) dropwise adding 20mL of 52.8612g/L potassium borohydride solution into the mixed solution with the initial pH value of 4.4 (without adjusting the pH value), oscillating while adding, generating black solid in the system, continuously bubbling, wherein the black solid is the pine bark modified nano-iron particles, and when the pine bark extracting solution is not added, the obtained black solid is the unmodified nano-iron particles. After the system does not bubble any more, adding 20mL of 0.5964g/L stannous chloride solution into the system, starting slow bubbling of the system, placing the system in a constant temperature water bath shaking table for 20min (240rpm, 25 ℃), and oscillating to obtain pine bark modified nano iron-tin bimetallic particles and unmodified nano iron-tin bimetallic particles which do not react with the active brilliant blue KN-R. The particles were washed twice with deionized water and acetone in sequence and then stored in acetone.
At room temperature, 0.3136g of the pine bark modified nano-iron-tin bimetallic particles prepared in example 4 were added into 200mL of wastewater with initial pH of 7.8 (without pH adjustment) and initial concentration of 1200mg/L of reactive brilliant blue KN-R, the tin loading capacity was 2.0%, and the addition amount of the particles was 1.568 g/L. Stirring at room temperature until the reactive brilliant blue KN-R does not fade any more, filtering and separating, adjusting the filtrate to be neutral, discharging, removing the wastewater containing the reactive brilliant blue KN-R by the pine bark modified nano iron-tin bimetallic particles, and retaining the pine bark modified nano iron-tin bimetallic particles after reaction.
Scanning electron microscope analysis was performed on the unmodified nano-fe-sn bimetallic particles, the pine bark modified nano-fe-sn bimetallic particles before reaction with the reactive brilliant blue KN-R, and the pine bark modified nano-fe-sn bimetallic particles after reaction with the reactive brilliant blue KN-R, as shown in fig. 4. FIGS. 4a, 4b, and 4c are the images of the morphology of the unmodified nano-Fe-Sn bi-metallic particle, the pine bark modified nano-Fe-Sn bi-metallic particle before reaction with the reactive brilliant blue KN-R, and the pine bark modified nano-Fe-Sn bi-metallic particle after reaction with the reactive brilliant blue KN-R, respectively. The unmodified nano-iron-tin bimetallic particles are spherical and aggregated into a chain, the particles are seriously aggregated, the pine bark modified nano-iron-tin bimetallic particles before the reaction with the reactive brilliant blue KN-R are also spherical and have smaller particle size, the aggregation phenomenon is improved, and the surfaces of the particles are obviously coated by biological components, which shows that the biological components in pine bark leaves protect the particles from being passivated and improve the dispersibility of the particles. After the pine bark modified nano-iron-tin bimetallic particles react with the reactive brilliant blue KN-R, the particles become rough obviously, the shapes of the particles are changed from spherical to linear and flaky, and the agglomeration phenomenon of the particles occurs, which indicates that iron is consumed in the reaction process.
Example 5
After washing the pine bark by deionized water, drying the pine bark at 100 ℃ for 24 h. Crushing dried cortex Pini, sieving, selecting cortex Pini powder with particle diameter below 300 μm, soaking in anhydrous methanol at a ratio of 60g/L, and performing ultrasonic treatment (100W, 40 deg.C) for 1 h. Vacuum filtering the pine bark powder methanol solution with 0.45 μm organic filter membrane, and collecting filtrate to obtain pine bark extract. Mixing the pine bark extract with 20mL of 100.0836g/L ferrous sulfate solution at volume ratios of 0:1 and 2.5:1 (the pine bark extract is 0 and 50mL) to obtain mixed solution of iron salt and pine bark extract, and shaking in constant temperature water bath shaking table for 5min (250rpm, 25 deg.C). And (3) dropwise adding 20mL of 77.6736g/L potassium borohydride solution into the mixed solution with the initial pH value of 4.4 (without adjusting the pH value), oscillating while adding, generating black solid in the system, continuously bubbling, wherein the black solid is the pine bark modified nano-iron particles, and when the pine bark extracting solution is not added, the obtained black solid is the unmodified nano-iron particles. After the system does not bubble any more, adding 20mL of 0.7668g/L stannous chloride solution into the system, starting slow bubbling of the system, placing the system in a constant temperature water bath shaking table, and oscillating for 20min (250rpm, 25 ℃) to obtain pine bark modified iron-cobalt bimetallic particles and unmodified iron-cobalt bimetallic particles which do not react with the active brilliant blue KN-R. The particles were washed twice with deionized water and acetone in sequence and then stored in acetone.
0.4032g of pine bark modified iron-cobalt bimetallic particles prepared in example 5 were added to 200mL of wastewater with an initial pH of 10.0 and an initial concentration of 1500mg/L containing reactive brilliant blue KN-R at room temperature, wherein the cobalt loading was 1.0% and the particle addition was 2.016 g/L. Stirring at room temperature until the reactive brilliant blue KN-R does not fade any more, filtering and separating, adjusting the filtrate to be neutral, discharging, removing the wastewater containing the reactive brilliant blue KN-R by the pine bark modified iron-cobalt bimetal, and retaining the pine bark modified iron-cobalt bimetal particles after reaction.
Fourier transform infrared spectroscopy analysis was performed on the unmodified nano-Fe-Sn bimetallic particles prepared in this example, the pine bark modified nano-Fe-Sn bimetallic particles before reaction with the reactive brilliant blue KN-R, and the pine bark modified nano-Fe-Sn bimetallic particles after reaction with the reactive brilliant blue KN-R, as shown in FIG. 5. Three kinds of particles are in 3430cm-1The wide band of the vibration band corresponds to the stretching vibration of-OH at 2922 and 2852cm-1Two fine peaks at the position respectively correspond to-CH2In the range of 1620cm-1And 1260cm-1The peak of the position corresponds to the stretching vibration and the deformation vibration of C ═ O and is 1083cm-1The peak corresponds to C-OH stretching vibration, and after pine bark extract is added, -OH, -CH2The pine bark modified nano-iron-tin bimetallic particles before the reaction of the signals C ═ O and C-OH with the reactive brilliant blue KN-R are more obvious than those on the unmodified nano-iron-tin bimetallic particles, which indicates that the pine bark modified nano-iron-tin bimetallic particles are covered by biological components of the pine bark, such as polyphenol molecules such as procyanidine and the like. At 564cm-1And 478cm-1The peak of each corresponds to Fe3O4And Fe2O3The stretching vibration of the Fe-O shows that the iron of the three particles is partially oxidized, and after the iron is reacted with the reactive brilliant blue KN-R, the pine bark modified nano iron-tin bimetallic particle is 1526cm-1The peak of the vibration is corresponding to the variable angle vibration of N-H at 1561cm-1And 1392cm-1The peak of (A) corresponds to the stretching vibration of the aromatic ring C ═ C, at 1175cm-1Corresponding to C-N stretching vibration at 1010cm-1The peak of the reactive dye corresponds to the stretching vibration of C-O-C, and in addition, signals of-OH, C ═ O and C-OH are more obvious on modified nano iron-tin bimetallic particles after reaction with the reactive brilliant blue KN-R than on pine bark modified nano iron-tin bimetallic particles which do not react with the reactive brilliant blue KN-R, which shows that after the reaction with the reactive brilliant blue KN-R, functional groups such as benzene ring carbon-carbon double bonds, hydroxyl groups, carbonyl groups, amine groups, ether bonds and the like in the molecular structure of the reactive brilliant blue KN-R cover the surface of the pine bark modified nano iron-tin bimetallic particles after the reaction with the reactive brilliant blue KN-R.
Claims (6)
1. A preparation method of pine bark green modified nano-iron-tin bimetallic particles is characterized by comprising the following steps:
(1) cleaning pine bark, and drying;
(2) pulverizing dried cortex Pini, and sieving to below 300 μm to obtain dry cortex Pini powder;
(3) soaking pine bark powder in anhydrous methanol, and performing ultrasonic treatment;
(4) filtering methanol solution of pine bark to obtain a filtrate, namely a pine bark extract;
(5) mixing the pine bark extract with a ferrous sulfate solution at room temperature to obtain a ferric salt-pine bark extract mixed solution;
(6) slowly adding the potassium borohydride solution into the ferric salt-pine bark extract liquid mixed solution obtained in the step (5) to obtain a pine bark modified nano-iron particle suspension;
(7) mixing the stannous chloride solution with the pine bark modified nano-iron suspension obtained in the step (6) to generate pine bark modified nano-iron-tin bimetallic particles;
(8) separating the pine bark modified nano-iron-tin bimetallic particles in the step (7) by a magnetic separation method, and washing with deionized water and acetone;
the mass ratio of the dry pine bark powder to the ferrous sulfate in the step (5) is 0-5.3955 and is not 0;
the mass ratio of the potassium borohydride to the ferrous sulfate is 0.3880-0.7761;
the mass ratio of the dry pine bark powder to the stannous chloride is 0-938.9072, and is not 0.
2. The preparation method of the pine bark green-modified nano iron-tin bimetallic particle as claimed in claim 1, wherein in the step (3), the pine bark powder is soaked in anhydrous methanol at a ratio of 20-60 g/L and subjected to ultrasonic treatment for 0.5-1.5 h; oscillating for 5min in a constant-temperature water bath shaking table during mixing in the step (5), wherein the rotating speed is 210-250 rpm, and the temperature is 25 ℃; oscillating while adding potassium borohydride solution dropwise; placing the reaction product in the step (7) in a constant-temperature water bath shaking table to oscillate for 20-50min at the temperature of 25 ℃.
3. The preparation method of the pine bark green-modified nano-sized Fe-Sn bimetal particle as claimed in claim 1, wherein the ultrasonic power in the step (3) is 60-100W, and the temperature is 20-40 ℃.
4. The method for preparing pine bark green-modified nano-sized fe-sn bi-metal particles according to claim 1, wherein the pine bark modified nano-sized fe-sn bi-metal particles are covered with pine bark polyphenol molecules.
5. The method for preparing pine bark green modified nano Fe-Sn bi-metal particles as claimed in claim 1, which is used for removing reactive brilliant blue KN-R dye in wastewater.
6. The method for preparing pine bark green modified nano Fe-Sn bimetallic particle as claimed in claim 1, wherein the initial pH value of the system for removing the reactive brilliant blue KN-R dye in the wastewater is 2.0-10.0, the adding concentration of the bimetallic particle is 0.224-2.016 g/L, and the initial concentration of the reactive brilliant blue KN-R dye in the wastewater is 300-1500 mg/L.
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