CN110723801A - Preparation method and application of high-dispersion supported palladium-copper modified nano-iron - Google Patents
Preparation method and application of high-dispersion supported palladium-copper modified nano-iron Download PDFInfo
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Abstract
The invention discloses a preparation method of high-dispersion supported palladium-copper modified nano iron, which comprises the following steps: step a, adding deionized water into ferric salt, dissolving, and adding porous silicon dioxide carrier powder; b, adding a borohydride solution into the solution obtained in the step a; and c, sequentially adding palladium salt and copper salt solution into the solution obtained in the step b, and stirring to obtain the high-dispersion supported palladium-copper modified nano iron. The high-dispersion supported palladium-copper modified nano iron prepared by the invention can increase the long-acting stability and the number of surface active sites of nano zero-valent iron particles and improve the removal efficiency of micromolecules/saturated chlorohydrocarbons such as dichloroethane and the like in underground water.
Description
Technical Field
The invention relates to the technical field of polluted groundwater remediation and treatment, in particular to a preparation method of high-dispersion supported palladium-copper modified nano-iron, and further relates to application of the high-dispersion supported palladium-copper modified nano-iron in removing chlorinated hydrocarbons in groundwater.
Background
Chlorinated hydrocarbons are a common class of volatile, non-degradable organic contaminants that are frequently detected in soil and groundwater due to accidental leakage and improper disposal. Most of the chlorinated hydrocarbons have persistent environmental pollution in natural aquifers and have carcinogenic, teratogenic and mutagenic effects on human bodies. Some typical chlorinated hydrocarbons have been listed as priority pollutants in the united states, the european union, and china. In 2008 to 2009, Bi et al collected 130 shallow groundwater samples in east China, and the results show that 36 volatile organic pollutants are detected together, wherein chlorinated hydrocarbon pollution has a large proportion: chloroform (16.9%), 1, 2-dichloroethane (16.2%), 1, 2-dichloropropane (13.1%). In 2012, high-quality prosperity and the like have developed pollution detection and characteristic research on underground water volatile halogenated hydrocarbons in 69 cities in China, and underground water samples 791 groups are collected, wherein various chlorinated hydrocarbons such as chloroform, tetrachloroethylene, 1, 2-dichloroethane, 1, 2-dichloropropane, carbon tetrachloride, trichloroethylene, dichloromethane, 1, 2-trichloroethane and the like have high detection rates.
Pioneering studies of Gillham and O' Hannesin show that the degradation rate of zero-valent iron to halogenated organic matters is far greater than that of a non-biodegradation process under natural conditions, so that the zero-valent iron material has great application potential in the aspect of removing pollutants. Wherein, the nanoscale zero-valent iron (nZVI) has larger specific surface area, thereby having excellent surface adsorption capacity and higher chemical reaction activity. In recent years, the application of nZVI in environmental pollution treatment is gradually developed into a new pollution control technology, and the material can be relatively safely injected into a heavily polluted area of an aquifer to form a high-efficiency in-situ reaction zone so as to quickly repair a pollutant plume in a source area. However, due to the small particle size and high activity, the particles are easy to agglomerate and deactivate, and the application of the particles in practical engineering is limited. Various approaches have been reported to effectively prolong its stability: modifying an organic polymer; adjusting the pH of the system to be alkaline; the surface is coated with iron oxide/silicon dioxide/emulsion film and the like.
However, Liu et al examined the relationship between the C-Cl bond dissociation energy and the degradation rate of chlorinated aliphatic hydrocarbon by the electrolytic reduction method, and the research result shows that the logarithm ln (1/Kc) of the reaction rate constant is in a linear relationship with the C-Cl bond strength. The C-Cl bond dissociation energy of micromolecule chlorohydrocarbon or saturated chlorohydrocarbon is large, the activation energy required by dechlorination is high, the electron migration capability of a single nZVI system or the transfer capability of active hydrogen atoms is still not enough to quickly overcome the higher C-Cl bond energy of partial chlorohydrocarbon, and the quick and thorough degradation of the chlorohydrocarbon is realized. Aiming at the pollution sites, various nZVI modified repair technologies are developed at home and abroad in recent years, and the latest research results at the present stage mainly comprise: sulfurizing nZVI, modifying palladium (Pd), and carrying and immobilizing. Based on the current research, various novel modified nZVI repair materials show higher reaction activity on unsaturated chlorohydrocarbons such as trichloroethylene and tetrachloroethylene, but still have lower reaction activity on micromolecule/saturated chlorohydrocarbons such as dichloroethane. Therefore, it is necessary to develop a highly dispersed modified nano-iron to improve the removal rate of small molecules/saturated chlorohydrocarbons such as dichloroethane in groundwater.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of high-dispersion supported palladium-copper modified nano iron, and the modified nano iron prepared by the method can increase the long-acting stability and the number of surface active sites of nano zero-valent iron particles and improve the removal efficiency of micromolecules/saturated chlorohydrocarbons such as dichloroethane and the like in underground water.
In order to solve the technical problems, the invention provides a preparation method of high-dispersion supported palladium-copper modified nano iron, which comprises the following steps:
step a, adding deionized water into ferric salt, dissolving, and adding porous silicon dioxide carrier powder;
b, adding a borohydride solution into the solution obtained in the step a;
and c, sequentially adding palladium salt and copper salt solution into the solution obtained in the step b, and stirring to obtain the high-dispersion supported palladium-copper modified nano iron.
In the step a, the ferric salt is ferrous sulfate or ferrous chloride, and the mass ratio of Fe in the ferric salt to the porous silica carrier is 0.05-0.2.
In the preparation method of the high-dispersion supported palladium-copper modified nano-iron, in the step b, the borohydride is potassium borohydride or sodium borohydride, wherein BH is4 -/Fen+Is 2 to 4.
In the step c, the palladium salt is palladium chloride, palladium sulfate or palladium nitrate, and the copper salt is copper sulfate or copper chloride.
In the preparation method of the high-dispersion supported palladium-copper modified nano iron, in the step c, the mass ratio of Pd to Fe in the added palladium salt is 0.001-0.008; the mass ratio of Cu to Fe in the added copper salt is 0.001-0.008.
In the preparation method of the high-dispersion supported palladium-copper modified nano iron, in the step c, the mass ratio of Pd in the added palladium salt to Cu in the added copper salt is 0.5-3, and preferably 1: 1.
The preparation method of the high-dispersion supported palladium-copper modified nano iron comprises the following steps: fully mixing and dissolving the structure directing agent in deionized water, adjusting the pH value to 9-11, then dripping a silicon source solution, hydrolyzing for 1-2h at the constant temperature of 15-30 ℃, transferring to a crystallization tank, carrying out hydrothermal reaction for 15-30h at the temperature of 80-120 ℃, washing with deionized water and ethanol until the product is neutral, drying at the temperature of 90-130 ℃, and calcining at the temperature of 500-600 ℃ for 2-6h to obtain the porous silicon dioxide carrier. Wherein the structure directing agent is selected from at least one of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, octane and ethyl acetate; the silicon source is at least one of tetraethoxysilane, sodium silicate and white carbon black.
The invention also provides a high-dispersion supported palladium-copper modified nano iron prepared by the preparation method.
The invention also provides application of the high-dispersion supported palladium-copper modified nano iron in degrading chlorinated hydrocarbons in underground water.
The preparation method of the high-dispersion supported palladium-copper modified nano-iron has the following beneficial effects:
1. according to the preparation method of the high-dispersion supported palladium-copper modified nano iron, the porous silicon dioxide with high specific surface area is selected as the loading substrate, and two transition metals with strong stability and high reducibility are introduced to carry out surface modification on zero-valent iron, so that the multi-scale pore structure of the carrier has excellent diffusion adsorbability and strong dispersion and fixation effects on nano particles, the active sites of the material are favorably and fully contacted with pollutants for a long time, and the problems of easy agglomeration, easy inactivation and the like of the nano zero-valent iron in the reaction are further improved.
2. According to the preparation method of the high-dispersion supported palladium-copper modified nano iron, two transition metals Pd and Cu with strong stability and high reducibility are introduced to modify the surface of the zero-valent iron, so that a high-dispersion supported multi-element active metal system is constructed, the long-acting stability and the number of surface active sites of nano zero-valent iron particles are increased, and the stability of the high-dispersion supported palladium-copper modified nano iron and the removal efficiency of chlorinated hydrocarbon in underground water are improved.
Drawings
FIG. 1 is a scanning electron microscope image of the high-dispersion supported palladium-copper modified nano-iron prepared in example 2;
fig. 2 is an X-ray diffraction pattern of the high dispersion supported palladium-copper modified nano-iron prepared in example 2.
Detailed Description
The present invention is described in detail below with reference to the drawings and examples.
Preparation method of high-dispersion supported palladium-copper modified nano iron
Example 1
1. Preparation of porous silica support
Fully dissolving 1.3g of Cetyl Trimethyl Ammonium Bromide (CTAB) in deionized water at the constant temperature of 25-30 ℃, then adding 10mL of n-octane, fully stirring at the speed of 350 revolutions per minute for 30min, adjusting the pH value of a system to be 11 by using 1mol/L of ammonia water, then dropwise adding 7.2mL of Tetraethoxysilane (TEOS), uniformly hydrolyzing at the stirring speed of 400 revolutions per minute for 1.5h, and carrying out the process under the constant temperature condition of a water bath at the temperature of 25-30 ℃. And finally, transferring the porous silicon dioxide carrier to a crystallization tank with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 30h at 80 ℃, washing the cooled product to be neutral by deionized water and ethanol, drying at 130 ℃, and calcining at 600 ℃ for 5h to obtain the porous silicon dioxide carrier.
2. Preparation of high-dispersion supported palladium-copper modified nano-iron
Taking 70ml deionized water in a three-neck flask, introducing nitrogen for more than 30min, and weighing 0.25g of FeSO4·7H2Directly adding O into a three-necked flask, stirring, adding 1g of porous silicon dioxide carrier after completely dissolving, and stirring at high speed for 30min to obtain Fe/SiO2The mass ratio was 0.05. Followed by the following procedure in accordance with BH4 -/Fe2+Under the condition of the molar ratio of 2, 30ml of KBH was prepared4The aqueous solution was purged with nitrogen for 30min, and then transferred to a constant pressure funnel and dropped into a three-necked flask at a rate of 1 drop per second. After the dropwise addition is completed, high-speed stirring is continuously carried out for 30min, and a palladium chloride solution and a copper sulfate solution are sequentially added, wherein the mass of Pd in the added palladium chloride and the mass of Cu in the added copper sulfate are respectively Fe0And the mass is 0.8 percent, namely the mass ratio of the added Pd to the added Cu is 1, and finally, strong stirring is continuously kept for more than 30min to obtain the high-dispersion supported palladium-copper modified nano iron.
Example 2:
1. preparation of porous silica support
Fully dissolving 1.3g of Cetyl Trimethyl Ammonium Bromide (CTAB) in deionized water at the constant temperature of 25-30 ℃, then adding 10mL of n-octane, fully stirring at the speed of 350 revolutions per minute for 30min, adjusting the pH value of a system to 10 by using 1mol/L of ammonia water, then dropwise adding 7.2mL of Tetraethoxysilane (TEOS), uniformly hydrolyzing at the stirring speed of 400 revolutions per minute for 1h, and carrying out the process under the constant temperature condition of a water bath at the temperature of 25-30 ℃. And finally, transferring the porous silicon dioxide carrier to a crystallization tank with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 24h at 100 ℃, washing the cooled product to be neutral by using deionized water and ethanol, drying at 100 ℃, and calcining at 550 ℃ for 6h to obtain the porous silicon dioxide carrier.
2. Preparation of high-dispersion supported palladium-copper modified nano-iron
Taking 70ml deionized water in a three-neck flask, introducing nitrogen for more than 30min, and weighing 0.5g of FeSO4·7H2Directly adding O into a three-necked flask, stirring, adding 1g of porous silicon dioxide carrier after completely dissolving, and stirring at high speed for 30min to obtain Fe/SiO2The mass ratio was 0.1. Followed by the following procedure in accordance with BH4 -/Fe2+Under the condition that the molar ratio of (3) is 3, 30ml of KBH is prepared4The aqueous solution was purged with nitrogen for 30min, and then transferred to a constant pressure funnel and dropped into a three-necked flask at a rate of 1 drop per second. After the dropwise addition is completed, high-speed stirring is continuously carried out for 30min, and a palladium chloride solution and a copper sulfate solution are sequentially added, wherein the mass of Pd in the added palladium chloride and the mass of Cu in the added copper sulfate are respectively Fe0And the mass is 0.5 percent, namely the mass ratio of the added Pd to the added Cu is 1, and finally, strong stirring is continuously kept for more than 30min to obtain the high-dispersion supported palladium-copper modified nano iron.
The scanning electron microscope image and the X-ray diffraction image of the high-dispersion supported palladium-copper modified nano-iron prepared in the example 2 are shown in the figure 1 and the figure 2 respectively. As can be seen from fig. 1, the high-dispersion supported palladium-copper modified nano iron prepared in the present example has the nano zero-valent iron uniformly dispersed on the surface of the carrier, and the particles are uniform spheres, and as can be seen from fig. 2, except the characteristic diffraction peak of the porous silica carrier between 20 ° and 30 °, a significant diffraction peak appears only at about 44.6 °, corresponding to Fe0(110) And crystal faces show that the zero-valent iron particles are successfully loaded on the carrier and correspond to the electron microscope picture. The content of palladium and copper introduced in the invention is very low, which is only 0.5 percent of the mass of zero-valent iron and is lower than the peak range of XRD, so that no corresponding characteristic peak appears in the figure.
Example 3:
1. preparation of porous silica support
Fully dissolving 1.3g of Cetyl Trimethyl Ammonium Bromide (CTAB) in deionized water at the constant temperature of 25-30 ℃, then adding 10mL of n-octane, fully stirring for 30min at the speed of 350 revolutions per minute, adjusting the pH value of a system to be 9 by using 1mol/L of ammonia water, then dropwise adding 7.2mL of Tetraethoxysilane (TEOS), uniformly hydrolyzing for 1h at the stirring speed of 400 revolutions per minute, and carrying out the process under the constant temperature condition of a water bath at the temperature of 25-30 ℃. And finally, transferring the porous silicon dioxide carrier to a crystallization tank with a polytetrafluoroethylene lining, carrying out hydrothermal reaction for 15h at 120 ℃, washing the cooled product to be neutral by using deionized water and ethanol, drying at 90 ℃ and calcining at 500 ℃ for 6h to obtain the porous silicon dioxide carrier.
2. Preparation of high-dispersion supported palladium-copper modified nano-iron
Introducing nitrogen into 70ml of deionized water in a three-neck flask for more than 30min, and weighing 1g of FeSO4·7H2Directly adding O into a three-necked flask, stirring, adding 1g of porous silicon dioxide carrier after completely dissolving, and stirring at high speed for 30min to obtain Fe/SiO2The mass ratio was 0.2. Followed by the following procedure in accordance with BH4 -/Fe2+Under the condition of a molar ratio of 4, 30ml of KBH was prepared4The aqueous solution was purged with nitrogen for 30min, and then transferred to a constant pressure funnel and dropped into a three-necked flask at a rate of 1 drop per second. After the dropwise addition is completed, high-speed stirring is continuously carried out for 30min, and a palladium chloride solution and a copper sulfate solution are sequentially added, wherein the mass of Pd in the added palladium chloride and the mass of Cu in the added copper sulfate are respectively Fe0And the mass is 0.1 percent, namely the mass ratio of the added Pd to the added Cu is 1, and finally, strong stirring is continuously kept for more than 30min to obtain the high-dispersion supported palladium-copper modified nano iron.
Example 4
The same preparation method as that of example 2, except that the addition amounts of the palladium chloride solution and the copper sulfate solution were different, and the mass of Pd in the added palladium chloride was Fe00.33% of the mass, and the mass of Cu in the added copper sulfate is Fe00.66% by mass, that is, the mass ratio of Pd to Cu added was 0.5.
Example 5
The same preparation method as that of example 2, except that the addition amounts of the palladium chloride solution and the copper sulfate solution were different, and the mass of Pd in the added palladium chloride was Fe00.75% of the weight of the copper sulfate, and the weight of Cu in the added copper sulfate is Fe00.25% by mass, i.e., the mass ratio of Pd to Cu added, was 3.
Comparative example 1:
the same procedure as in example 2 was repeated, except that no addition ofCopper sulfate solution, only adding palladium chloride solution, wherein the mass of Pd in the added palladium chloride is Fe01% by mass.
Comparative example 2:
the same preparation method as that of example 2 was followed, except that no palladium chloride solution was added, only a copper sulfate solution was added, and the mass of Cu in the added copper sulfate was Fe01% by mass.
Application of high-dispersion supported palladium-copper modified nano-iron in degradation of underground water chlorinated hydrocarbon
Under the protection of nitrogen, chlorohydrocarbon underground water and the high-dispersion supported palladium-copper modified nano iron prepared in the examples 1-5 and the comparative examples 1-2 are respectively mixed and added into a serum bottle without leaving a headspace, and the mixture is compressed and sealed by an aluminum cover with a Teflon gasket and reacts at room temperature. Wherein the concentration of 1, 2-dichloroethane in the chlorohydrocarbon underground water is 10mg/L, and the addition amount of the high-dispersion supported palladium-copper modified nano-iron is 2 g/L. Samples were taken at regular intervals and tested for chlorinated hydrocarbon concentration using a purge trap-gas chromatograph-mass spectrometer. The chromatographic column parameters used in the determination were: DB-624column (Agilent, 60 m.times.250 μm.times.1.4 μm, 20 ℃ C. -260 ℃ C.), the detection method is: the temperature of the column box is 40 ℃, the temperature of the detector is 260 ℃, the retention time is 19min, and the split ratio is 20: 1. The removal rate of 1, 2-dichloroethane as a contaminant with respect to the reaction time is shown in table 1, and the removal rate is (1-measured concentration C/initial concentration C)0)×100％。
TABLE 1
Note: 1. fe is SiO2The mass ratio of Fe in iron salt to the porous silica carrier is referred to;
2. fe is the mass ratio of Pd to Fe in the added palladium salt;
3. fe refers to the mass ratio of Cu to Fe in the added copper salt;
4. the mass ratio of Pd in the added palladium salt to Cu in the added copper salt is Pd: Cu;
5. 1 day, 3 days, 6 days refer to the reaction time.
From the results in table 1, it can be seen that when the addition amount of Fe is the same, compared with comparative examples 1 and 2, the high-dispersion supported palladium-copper modified nano iron prepared in example 2 has a significantly better effect of removing chlorinated hydrocarbons than nano iron obtained by modifying Pd or Cu alone, and the removal rates of 1, 2-dichloroethane are respectively increased by 17.2% and 19.9% after 6 days, which indicates that the co-introduction of metal palladium and copper has a significant synergistic effect on the removal of chlorinated hydrocarbons.
In example 1, the addition amount of Fe is 0.05, in comparative examples 1 and 2, the addition amount of Fe is 0.1, and in the case that the addition amount of Fe is halved, the effect of removing the target chlorinated hydrocarbon by the high-dispersion supported palladium-copper modified nano iron prepared in example 1 is better than that of comparative examples 1 and 2.
In examples 1 to 3, the removal rate of the target chlorinated hydrocarbon is improved with the increase of the addition amount of Fe, but the improvement of the repair efficiency of example 3 is a slow trend, and the contents of Pd and Cu are increased by times while the addition amount of Fe is increased, so that the excessive concentration of the chemical agent is accompanied by the excessive introduction of the metal in the practical application process, thereby causing secondary pollution.
Comparing example 2 with examples 4 and 5, the addition ratio of Pd and Cu in example 2 is 1:1, Pd: Cu in example 4 is 0.5, Pd: Cu in example 5 is 3, and the removal rate of the chlorinated hydrocarbon by the nano-iron prepared in example 2 is obviously higher than that of examples 4 and 5, so that the addition ratio of Pd and Cu has a larger influence on the removal rate of the chlorinated hydrocarbon, and the addition ratio of Pd and Cu is preferably 1:1 in the invention.
According to the invention, the porous carrier with high specific surface area is combined with the modification of the multi-element active metal, so that the reaction activity of the nano zero-valent iron is effectively prolonged, the removal efficiency of the nano zero-valent iron on chlorinated hydrocarbon in a water phase is improved, and the method has a wide application prospect in the field of groundwater remediation.
Claims (10)
1. A preparation method of high-dispersion supported palladium-copper modified nano-iron comprises the following steps:
step a, adding deionized water into ferric salt, dissolving, and adding porous silicon dioxide carrier powder;
b, adding a borohydride solution into the solution obtained in the step a;
and c, sequentially adding palladium salt and copper salt solution into the solution obtained in the step b, and stirring to obtain the high-dispersion supported palladium-copper modified nano iron.
2. The preparation method of the high-dispersion supported palladium-copper modified nano-iron as claimed in claim 1, wherein in the step a, the iron salt is ferrous sulfate or ferrous chloride, and the mass ratio of Fe in the iron salt to the porous silica carrier is 0.05-0.2.
3. The preparation method of the high-dispersion supported palladium-copper modified nano-iron as claimed in claim 1, wherein in the step b, the borohydride is potassium borohydride or sodium borohydride, wherein BH is4 -/Fen+Is 2 to 4.
4. The preparation method of the high-dispersion supported palladium-copper modified nano-iron as claimed in claim 1, wherein in the step c, the palladium salt is palladium chloride, palladium sulfate or palladium nitrate, and the copper salt is copper sulfate or copper chloride.
5. The method for preparing high dispersion supported palladium-copper modified nano-iron as claimed in claim 1, wherein in step c, the mass ratio of Pd to Fe in the added palladium salt is 0.001-0.008; the mass ratio of Cu to Fe in the added copper salt is 0.001-0.008.
6. The method for preparing high dispersion supported palladium-copper modified nano-iron as claimed in claim 1, wherein in step c, the mass ratio of Pd in the added palladium salt to Cu in the added copper salt is 0.5-3.
7. The preparation method of the high-dispersion supported palladium-copper modified nano-iron as claimed in claim 6, wherein in the step c, the mass ratio of Pd in the added palladium salt to Cu in the added copper salt is 1: 1.
8. The preparation method of the high-dispersion supported palladium-copper modified nano-iron as claimed in claim 1, wherein the preparation method of the porous silica carrier in the step a comprises the following steps: fully mixing and dissolving a structure directing agent in deionized water, adjusting the pH value to 9-11, then dripping a silicon source solution, hydrolyzing for 1-2h at the constant temperature of 15-30 ℃, transferring to a crystallization tank, carrying out hydrothermal reaction for 15-30h at the temperature of 80-120 ℃, washing the product to be neutral by the deionized water and ethanol, drying at the temperature of 90-130 ℃, and calcining for 2-6h at the temperature of 500-600 ℃ to obtain the porous silicon dioxide carrier, wherein the structure directing agent is at least one selected from hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, octane and ethyl acetate, and the silicon source is at least one selected from ethyl orthosilicate, sodium silicate and white carbon black.
9. A high-dispersion supported palladium-copper modified nano-iron prepared by the preparation method of any one of claims 1 to 9.
10. The use of the high dispersion supported palladium-copper modified nano-iron of claim 9 in the degradation of underground water chlorinated hydrocarbons.
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| CN112320918B (en) * | 2020-10-19 | 2021-10-22 | 武汉大学 | Method for doping Fe (OH) by metal ions2Method for removing halogenated organic pollutants in water |
| CN113493237A (en) * | 2021-07-15 | 2021-10-12 | 南京工业大学 | Preparation of modified nano-iron and method for treating high-concentration nitrate wastewater by using modified nano-iron |
| CN113493237B (en) * | 2021-07-15 | 2023-01-03 | 南京工业大学 | Preparation of modified nano-iron and method for treating high-concentration nitrate wastewater by using modified nano-iron |
| CN114314564A (en) * | 2021-12-22 | 2022-04-12 | 长沙晟天新材料有限公司 | Carbon nanotube conductive network coated SiO @ C composite material and preparation method and application thereof |
| CN114314564B (en) * | 2021-12-22 | 2023-11-28 | 湖南京舟股份有限公司 | Carbon nanotube conductive network coated SiO@C composite material and preparation method and application thereof |
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