CN111804930A - Nano zero-valent ferro-manganese bimetal and preparation method and application thereof - Google Patents
Nano zero-valent ferro-manganese bimetal and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nanometer zero-valent ferro-manganese bimetal and a preparation method and application thereof. The method has the advantages of simple process, easily obtained raw materials, lower requirement on equipment, simple process and strong controllability of reaction conditions, the addition of Mn can effectively improve the dispersibility of the nano zero-valent iron, prevent the nano zero-valent iron from agglomerating and simultaneously slow down the passivation effect of the nano zero-valent iron and manganese, and the prepared nano zero-valent iron and manganese bimetal has excellent reaction activity. The nanometer zero-valent iron-manganese bimetal prepared by the method has strong catalytic oxidation-reduction capability, has a good removal effect on organic pollutants, has good migration distribution characteristics and good degradation capability in simulated groundwater environment, and can be applied to degradation removal of organic pollutants in surface water or groundwater.
Description
Technical Field
The invention belongs to the field of nano material environmental remediation, and particularly relates to a nano zero-valent ferro-manganese bimetal and a preparation method and application thereof.
Background
In recent years, the nano zero-valent iron has excellent performance in solving the problem of organic pollution in surface water or underground water, is one of the most extensive and perfect technologies for in-situ chemical oxidation-reduction development of underground water pollution, and is listed as a standard technology for repairing underground water pollution by the U.S. environmental protection agency. The nanometer zero-valent iron has strong reduction activity and wide source, and is not easy to cause secondary pollution, but the problems of easy agglomeration, easy oxidation and passivation, poor electron selectivity and the like exist in the application process of the zero-valent iron. Extensive research has been carried out on the modification of zero-valent iron, and the modification is very successful, wherein the doping of bimetal can increase the reactivity of the nano-particles and provide good passivation protection. However, some of the metal elements such as noble metals used in the research process are partially toxic and not environmentally friendly, and noble metals do not show any improvement in economic value.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the nanometer zero-valent iron-manganese bimetal and the preparation method and the application thereof, and the addition of the zero-valent manganese can ensure that the nanometer zero-valent iron has better dispersibility and improve the agglomeration effect of nanometer particles; the oxidation capability in the system can be enhanced by adding the nano zero-valent manganese, so that the bimetal has two catalytic capabilities of oxidation and reduction, and organic pollutants can be degraded more favorably and efficiently; the invention utilizes the valence change property brought by transition metal elements of iron and manganese, can recycle the iron and manganese elements in the system, and improves the utilization efficiency of the bimetal in the using process. The nano zero-valent Fe/Mn bimetal composite material is applied to simulated groundwater environment, so that the bimetal in a medium has good migration distribution characteristics, has a good removal effect on pollutants in simulated groundwater, and can be applied to degradation removal of organic pollutants in surface water or groundwater.
The specific technical scheme is as follows:
the invention provides a preparation method of a nanometer zero-valent ferro-manganese bimetal, which mainly comprises the following steps:
a method for preparing a nanometer zero-valent ferro-manganese bimetal comprises the steps of taking ferrous salt as an iron source and taking manganous salt as a manganese source, and preparing the nanometer zero-valent ferro-manganese bimetal through two-step liquid phase reduction.
The preparation method specifically comprises the following preparation steps:
dissolving bivalent iron salt in alcohol-water system, and then adding NaBH4Dissolving in deoxygenated water, dropwise adding into a reaction container by using a dropper, and reacting for 30min to ensure that iron ions are reduced into zero-valent iron;
then adding a divalent manganese salt to ensure that the mass ratio of Fe to Mn is 5-20: 1, continuously stirring for 30 minutes after adding the divalent manganese salt to ensure that the solution is completely mixed, and then dissolving NaBH in deoxygenated water4Dropwise adding into a reaction vessel, and continuously stirring for 30min after the dropwise adding is finished;
the reaction process is mechanically stirred and N is introduced2Carrying out reaction protection;
carrying out solid-liquid separation on the prepared nano zero-valent iron-manganese bimetal by adopting a magnet, and alternately cleaning the bimetal by using absolute ethyl alcohol and deoxidized deionized water for a plurality of times;
placing the cleaned nano zero-valent ferro-manganese bimetal in a vacuum drying oven at 60 ℃ for drying for 4 hours; and (3) placing the dried nano zero-valent ferro-manganese bimetal powder into a mortar for grinding and sieving by a 200-mesh sieve to obtain the nano zero-valent ferro-manganese bimetal. Transferring the collected nano zero-valent iron to a brown reagent bottle for sealing, vacuum drying and storing.
Further, the ferrous salt and the ferrous manganese salt are nitrate, sulfate or chloride.
The nanometer zero-valent ferro-manganese bimetal prepared by the preparation method is used for degrading organic pollutants in surface water or underground water.
Compared with single nanometer zero-valent iron and nanometer zero-valent manganese, the nanometer ferro-manganese bimetal provided by the invention has more excellent catalytic performance. According to the invention, the divalent manganese salt is added in the preparation process of the nano zero-valent iron as a source of zero-valent manganese, and due to the doping of the zero-valent manganese, the dispersity of the nano zero-valent iron is successfully increased and the agglomeration effect of nano metal is improved as can be seen from a bimetallic TEM image.
The oxidation capability in the system can be enhanced by adding the nano zero-valent manganese, and the bimetal has two catalytic capabilities of oxidation and reduction, so that pollutants can be degraded more favorably and efficiently. By comparing the removal capacities of the single metal and the double metal to the pollutants, the removal capacity and the removal efficiency of the double metal to the pollutants are higher than those of the nano zero-valent iron and the nano zero-valent manganese.
By utilizing the valence change property brought by transition metal elements of iron and manganese, the iron and manganese elements in the system can be circulated, and the utilization efficiency of the bimetal in the using process is improved. Through test analysis of the bimetallic material before and after removing the pollutants, the valence states of the two elements in the system are changed mutually and have a circulating effect.
The invention provides a preparation method of a nanometer zero-valent ferro-manganese bimetal, which simplifies and greens the preparation of the bimetal. The preparation method of the nanometer zero-valent ferro-manganese bimetal selects a common liquid phase reduction method, is simple, convenient and quick to operate, and is safe and environment-friendly.
Compared with the prior art, the invention has the following characteristics and advantages:
1) the raw materials used in the invention are common chemical reagents, and have wide sources, low price and easy obtainment;
2) the preparation method has the advantages of simple preparation process, low requirement on equipment, simple process and strong controllability of reaction conditions;
3) the nano zero-valent iron-manganese bimetal is prepared by a conventional liquid phase reduction method, and the nano zero-valent manganese is doped into the nano zero-valent iron to obtain the nano zero-valent iron-manganese bimetal, so that the agglomeration effect of the nano zero-valent iron is improved, and the pollutant degradation capability of the nano zero-valent iron is also improved.
Drawings
FIG. 1 is a schematic flow chart of a nano-Fe-Mn bimetallic sample prepared in example 1;
FIG. 2a is an SEM of a nano-Fe-Mn bi-metal sample prepared in example 1;
FIG. 2b is a mapping diagram of the nano-FeMn bimetal sample prepared in example 1;
FIG. 2c is an EDS diagram of a nano-sized bimetal Fe-Mn sample prepared in example 1;
FIG. 3a is a 200nmTEM graph of the nano-FeMn bimetal sample prepared in example 1;
FIG. 3b is the 50nmTEM graph of the nano-FeMn bimetal sample prepared in example 1;
FIG. 3c is the 5nmTEM graph of the nano-FeMn bimetal sample prepared in example 1;
FIG. 3d is the SEAD diffraction pattern of the nano-Fe-Mn bi-metal sample prepared in example 1;
FIG. 4 is Zeta potential diagram of the nano-FeMn bimetal sample prepared in example 1;
FIG. 5a is a comparison graph of XPS full spectrum of the nano-Fe-Mn bimetallic sample prepared in example 1 before degrading tetracycline;
FIG. 5b is a comparison graph of XPS survey spectra of the nano-Fe-Mn bi-metal sample prepared in example 1 after tetracycline degradation;
FIG. 6 is a graph of the degradation efficiency of the 15mg nano-sized bi-metal and mono-metal samples prepared in example 1 for degrading 50ml of tetracycline at a concentration of 100 mg/L;
FIG. 7a is a graph of the effect of different anions of the system of example 2 on the degradation efficiency of nano-sized ferro-manganese bi-metal on tetracycline in a simulated groundwater environment;
FIG. 7b is a graph of the effect of different cations of the system of example 2 on the degradation efficiency of nano-sized ferro-manganese bi-metal on tetracycline in a simulated groundwater environment;
FIG. 8a is a graph of the penetration of nano-sized ferro-manganese bi-metal in the column under different media of different particle sizes in example 3;
FIG. 8b is the concentration profile of the nano-sized ferro-manganese bi-metal retained by the sand column after penetration of the bi-metal in the column in example 3 under different media particle sizes;
FIG. 8c is a graph of the penetration of nano-sized ferro-manganese bi-metal in the column at different bi-metal concentrations in example 3;
FIG. 8d is a graph showing the bimetal concentration retained by the sand column after the penetration of nano-ferro-manganese bimetal in the column at different bimetal concentrations in example 3;
FIG. 8e is the graph of the penetration of the nano-Fe-Mn bi-metal in the column at different injection rates in example 3;
FIG. 8f is the concentration profile of the nano-sized ferro-manganese bi-metal retained by the sand column after penetration of the bi-metal in the column at different injection rates in example 3;
FIG. 8g is a graph of the degradation efficiency of trapped nano-sized ferro-manganese bi-metal to tetracycline under three composite factors of injection rate, bi-metal concentration and medium particle size.
Detailed Description
In order to enhance the understanding of the present invention, the present invention will be further described in detail and fully hereinafter with reference to examples.
Example 1
Preparing nanometer zero-valent ferro-manganese bimetal: weighing 2.782g of FeSO4·7H2Dissolving O in alcohol-water system, 1.5134g NaBH4Dissolving in 100mL of deionized water, dropwise adding into a three-neck flask by using a dropper, and reacting for 30min to ensure that iron ions are reduced into zero-valent iron; then adding MnSO with different qualities4·H2O, the mass ratio of Fe to Mn is 5:1, 10:1, 15:1 and 20:1 respectively, and MnSO is added4·H2After O stirring was continued for 20 minutes to ensure complete mixing of the solution, 1.5134g of NaBH were added4Dissolved in 100mL of deionized water and added dropwise into the three-neck flask by using a dropper, and stirring is continued for 30min after the dropwise addition is finished. The reaction is mechanically stirred in a three-neck flask, and N is introduced during the reaction process2And carrying out reaction protection. And (2) carrying out solid-liquid separation on the prepared nano zero-valent iron-manganese bimetal by adopting a magnet, alternately cleaning the bimetal by using absolute ethyl alcohol and deoxidized deionized water for several times so as to ensure that sodium borohydride and other impurities in the reaction process are washed away, and drying the cleaned nano zero-valent iron in a vacuum drying oven at the temperature of 60 ℃ for 4 hours. Placing the dried nano zero-valent iron powderGrinding in a mortar, sieving with a 200-mesh sieve, transferring the collected nanoscale zero-valent iron to a brown reagent bottle, sealing, drying in vacuum and storing. The preparation process is schematically shown in figure 1.
FIGS. 2a, 2b, and 2C are SEM and surface scanning EDS mapping graphs of nano zero-valent ferro-manganese bi-metal prepared in example 1, and it can be seen that ferro-manganese in the nano-particles is completely mixed and deposited together, the particle size is too fine to make it agglomerate, because of the addition of manganese element, so that the zero-valent iron particles are dispersed a lot, the bi-metal composite material is mainly composed of four elements of Fe (49.78%), Mn (3.51%), O (43.66%) and C (3.05%), wherein Fe and Mn are core elements of the composite material, i.e. the elements capable of degrading pollutants, and O and C are the elements incorporated by air exposure in the preparation process and the test process. From the view of the element distribution diagram, the Fe and Mn elements are uniformly distributed in the composite material and can be well combined together.
Fig. 3a to 3d are TEM images and SEAD diffraction images of the nano-fe-mn bimetallic sample prepared in example 1, which can more clearly show the combination and distribution of the two elements, and the darker part has more fe than mn, so the color is darker; on the contrary, when the manganese element is more than the iron element, the TEM image is displayed with lighter color at some parts, but both of them are seen to have more uniform structural composition in the composite material. Multiple clear electron diffraction rings appeared in the SAED image, indicating that the sample was polycrystalline and the lattice fringes were evident.
FIG. 4 is a Zeta potential diagram of the nano-Fe-Mn bimetallic sample prepared in example 1, and it can be seen that the change of the values of the individual zero-valent iron in pure water under different pH conditions gradually decreases from 35.3mV to-33.4 mV when the pH is increased from 3 to 9, but the absolute values are all above 30, which indicates that the nano-zero-valent iron is stable in the system, and the dispersion and dissolution of the solution can resist the aggregation effect. It can be seen from the figure that under the same conditions, when the pH value of the nano Fe/Mn bimetal is increased from 3 to 9, the Zeta potential of the nano Fe/Mn bimetal is gradually reduced from 27.2mV to-25.6 mV, probably caused by shielding part of the surface charge of the nano zero-valent iron by adding manganese, but the absolute value of the nano Fe/Mn bimetal is close to the Zeta potential of the nano zero-valent iron, which indicates that the instability of the composite material in a system is not greatly reduced by the zero-valent iron after the manganese is added. The nano material can also be applied to a wider pH range, which is proved when pH is examined in a preliminary experiment for degrading tetracycline by nano Fe/Mn bimetal.
FIGS. 5a and 5b are XPS full spectrum comparison graphs before and after the nano-Fe-Mn bimetallic sample prepared in example 1 degrades tetracycline, and it can be seen that characteristic peaks including C1s, O1s, Mn2p, Fe2p and the like are respectively corresponding to the positions of the bands, namely 284.8ev, 531.67ev, 641.67ev and 710.9 ev. Through comparison, the elements in the composite material and the energy band positions where the characteristic peaks appear are almost consistent and do not change, and the tracks where the elements are located can also be in one-to-one correspondence, which shows that the composite material has better stability in the whole reaction process. The only difference is that the peak intensity of each element characteristic peak is changed before and after the reaction, because in the process of the reaction, the iron manganese element is converted between different valence states, and one valence state is reduced and then one valence state is increased.
FIG. 6 is a graph showing the degradation efficiency of the 15mg nano-sized bimetal and monometal sample prepared in example 1 in degrading 50ml of tetracycline at a concentration of 100 mg/L. From the figure, the degradation efficiency and the degradation rate of the nano ferro-manganese bimetal on tetracycline are far higher than those of nano zero-valent iron and nano zero-valent manganese monometal.
Example 2
The degradation experiment of the nano zero-valent iron-manganese bimetal on tetracycline under the action of various underground water common ions is as follows:
the experimental water is prepared by self to simulate the concentration of eight major anions and cations contained in underground water. Wherein Na+The concentration is 20mg/L, K+Concentration of 30mg/L, Ca+The concentration is 25Mg/L, Mg+Concentration 5mg/L, Cl-The concentration of the active carbon is 10mg/L,
the concentration of the active carbon is 20mg/L,
at a concentration of88mg/L，
The concentration was 5mg/L and the pH was 6.78. When five anions are present
Cl-，
And
at the concentration of 5.0mg/L, the degradation efficiency of Fe/Mn bimetal on tetracycline is reduced from 99.05 percent to 71.57 percent, 66.79 percent, 76.63 percent, 83.64 percent and 98.54 percent in sequence, and in the whole reaction process, the influence of anions on the system is as follows:
it can be seen that in the course of the reaction, Cl-The influence on the degradation of the Fe/Mn bimetal on the tetracycline is the largest probably because the chloride ions can more strongly occupy the active sites of the Fe/Mn bimetal during the reaction process, thereby inhibiting the degradation of the tetracycline. Four cations (K)+、Na+、Ca2+、Mg2+) After the addition of the Fe/Mn bimetal, the degradation efficiency of the Fe/Mn bimetal on the tetracycline is reduced to 85.57%, 91.63%, 86.79% and 83.64% in sequence. The inhibition of the cation on the reaction system is as follows: mg (magnesium)2+＞K+＞Na+＞Ca2+The experimental results are shown in fig. 7a and 7 b.
Example 3
The migration capability of the nano zero-valent iron-manganese bimetal prepared by the invention in a water-soil medium can influence the contact condition of the repair material and pollutants, and a reaction zone is formed within a certain range. The nano repairing material has stronger migration capability in water and soil media, can better repair underground water pollution, and finally achieves better repairing effect on the underground water polluted by tetracycline. The experiments were as follows:
the material that the post experiment adopted is organic glass, and length 50cm, internal diameter are 3.0cm, and the top and the bottom of organic glass post all adopt screw thread mouth lock, and the punishment of 5cm do not sets up a sample connection apart from intaking and going out water, and the centre sets up a sample connection respectively every 10cm, 5 in total. The liquid flow rate was controlled using a peristaltic pump. Simulating a real groundwater environment. Sieving purchased quartz sand according to fine sand, medium sand and coarse sand, soaking the quartz sand for 30min by using 3M HCl under an ultrasonic condition, washing the quartz sand for multiple times by using ultrapure water until the solution in the sand is neutral, and drying the quartz sand for 12h at 60 ℃ in a forced air drying oven for later use. Two ends of the simulation column are respectively paved with a layer of 200-mesh gauze to prevent the quartz sand from losing. Firstly, 0.5-1mm quartz sand with the height of 0.5cm is filled at the bottom of the column, so that the water flow is ensured to be uniformly distributed, and the prepotency flow can not be formed along the wall of the organic glass column. Then filling quartz sand with different medium particle sizes, wherein the filling height of the sand column is 49cm, and the top of the sand column is also filled with 0.5-1mm of quartz sand with the height of 0.5cm, so as to ensure the uniform concentration of effluent liquid. In the filling process, tamping and water injection are needed when 10cm is filled, and tamping is carried out while filling, so that the condition of cracks or faults caused by filling in the running process of the sand column is avoided. And (3) saturating the simulation column with simulated underground water for a certain time from bottom to top, pumping the prepared tetracycline solution and the nano Fe/Mn bimetal slurry into the reactor from bottom to top through a peristaltic pump, and sampling at regular intervals for testing.
For nano Fe/Mn bimetal, the research takes iron as a main test object, adopts flame atomic absorption spectrometry to measure the total iron concentration, and draws a corresponding penetration curve. When the effluent is equilibrated for a period of time after breakthrough, the simulated underground water solution is continuously pumped for flushing and sampling until the effluent concentration reaches equilibrium.
When the migration of the nanometer Fe/Mn bimetal is researched, sampling is carried out on each sampling hole, the nanometer material existing in each section of the sand column is tested, and a retention distribution condition graph is drawn. The degradation of the trapped bimetal on tetracycline under the condition of compounding the three factors is shown. As can be seen from the figure, after 20pv 100mg/L of tetracycline is continuously injected, and the concentration of the tetracycline in the effluent is also detected, it is found that after the injection amount is 15pv, tetracycline is detected in the effluent successively, but the concentration is only 1% -3% of the initial concentration, which indicates that the nano Fe/Mn bimetal has better degradation capability on the tetracycline in the environment, and can provide a certain basis for the application of the nano Fe/Mn bimetal in the actual environment, and the results are shown in fig. 8a to fig. 8 g.
The above description is only a preferred example of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like of the present invention shall be included in the protection scope of the present invention.
Claims (5)
1. A preparation method of nanometer zero-valent ferro-manganese bimetal is characterized by comprising the following steps: the nanometer zero-valent ferro-manganese bimetal is prepared by two-step liquid phase reduction by taking ferrous salt as an iron source and taking divalent manganese salt as a manganese source.
2. The method for preparing the nano zero-valent ferro-manganese bimetal according to claim 1, which is characterized by comprising the following preparation steps:
dissolving bivalent iron salt in alcohol-water system, and then adding NaBH4Dissolving in deoxygenated water, dropwise adding into a reaction container by using a dropper, and reacting for 30min to ensure that iron ions are reduced into zero-valent iron;
then adding a divalent manganese salt to ensure that the mass ratio of Fe to Mn is 5-20: 1, continuously stirring for 30 minutes after adding the divalent manganese salt to ensure that the solution is completely mixed, and then dissolving NaBH in deoxygenated water4Dropwise adding into a reaction vessel, and continuously stirring for 30min after the dropwise adding is finished;
the reaction process is mechanically stirred and N is introduced2Carrying out reaction protection;
carrying out solid-liquid separation on the prepared nano zero-valent iron-manganese bimetal by adopting a magnet, and alternately cleaning the bimetal by using absolute ethyl alcohol and deoxidized deionized water for a plurality of times;
placing the cleaned nano zero-valent ferro-manganese bimetal in a vacuum drying oven at 60 ℃ for drying for 4 hours; and (3) placing the dried nano zero-valent ferro-manganese bimetal powder into a mortar for grinding and sieving by a 200-mesh sieve to obtain the nano zero-valent ferro-manganese bimetal.
3. The method for preparing the nanometer zero-valent ferro-manganese bimetal according to claim 1 or 2, characterized in that: the ferrous salt and the ferrous manganese salt are nitrate, sulfate or chloride.
4. A nano zero-valent ferro-manganese bimetal, characterized in that the bimetal is prepared by the preparation method of any one of claims 1 to 3.
5. The use of the nano zero-valent ferro-manganese bimetal of claim 4, wherein: the method is used for degrading organic pollutants in surface water or underground water.
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