CN111250033A - Metal oxide porous micro-nano hierarchical structure modified honeycomb stone and preparation method and application thereof - Google Patents
Metal oxide porous micro-nano hierarchical structure modified honeycomb stone and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a metal oxide porous micro-nano hierarchical structure modified honeycomb stone and a preparation method and application thereof, belonging to the technical field of nano materials. The preparation method of the metal oxide porous micro-nano hierarchical structure modified honeycomb stone provided by the invention comprises the following steps: mixing water-soluble metal salt, hydroxyl slow-release agent, water and honeycomb stone to obtain a raw material mixed solution; carrying out hydrothermal reaction on the raw material mixed solution under a closed condition, then carrying out solid-liquid separation on a reaction solution obtained by the hydrothermal reaction, and drying a solid obtained by the solid-liquid separation to obtain a precursor; and annealing the precursor to obtain the metal oxide porous micro-nano hierarchical structure modified honeycomb stone. The preparation method provided by the invention can form the metal oxide with the micro-nano hierarchical structure on the honeycomb stone, is simple, is easy to implement and is suitable for industrial large-scale production.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a metal oxide porous micro-nano hierarchical structure modified honeycomb stone and a preparation method and application thereof.
Background
Water is an indispensable resource for human survival, so that the removal of pollutants in water is an important issue of common concern at home and abroad. Conventional water treatment methods include biochemical methods, chemical oxidation methods, precipitation-flocculation methods, reverse osmosis methods, distillation methods and adsorption methods. Among them, adsorption technology is one of the most effective methods and is also one of the best choices. Therefore, it is a very significant task to develop an adsorbent material with high adsorption capacity for removing heavy metal ions and organic pollutants from water.
The metal oxide is a common adsorbent and has the advantages of low solubility, easily obtained material, high adsorption rate and the like. However, the traditional metal oxide adsorbing material has the defects of small adsorption capacity, poor dispersibility, easy saturation and the like, which seriously limits the application in practice. The adsorption of metal ions often occurs on the surface of the adsorbent, so that the adsorption performance can be greatly increased by increasing the specific surface area of the adsorbent. The nano metal oxide can provide larger specific surface area and more active sites for adsorption, so that the adsorption performance of the material can be greatly improved. However, due to the small size of the nano material, after the nano material is adsorbed in the solution, the nano material is often separated from the solution by using a centrifugal method, and in practical application, a recycling process needs to be added, so that the recycling difficulty is increased. In recent years, many researchers try to modify a suitable adsorption carrier with a nano metal oxide, and the nano metal oxide is uniformly distributed or assembled and grown on the carrier material in a modification mode to form a micro-nano hierarchical structure-adsorption carrier combined material, so that the specific surface area and active sites of the material are improved, and meanwhile, the nano material is fixed on the carrier, and the excellent properties of the combined material are highlighted in application.
The honeycomb stone, named pumice, is a eruption rock in igneous rock materials, mainly comprises volcanic glass and minerals, has a unique air pore structure and good adsorption capacity, and is a good adsorption material and a carrier of the adsorption material. However, due to the surface of the honeycomb stone is crystalline, it is difficult to load the metal oxide on the honeycomb stone by using the conventional method (i.e., impregnation or precipitation method), so that the application of the honeycomb stone to the metal oxide micro-nano hierarchical structure-adsorption carrier is limited.
Disclosure of Invention
The invention aims to provide a honeycomb stone modified by a metal oxide porous micro-nano hierarchical structure and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a metal oxide porous micro-nano hierarchical structure modified honeycomb stone, which comprises the following steps:
mixing water-soluble metal salt, hydroxyl slow-release agent, water and honeycomb stone to obtain a raw material mixed solution; the hydroxide slow release agent is a compound capable of releasing hydroxide ions in the hydrothermal reaction process;
carrying out hydrothermal reaction on the raw material mixed solution under a closed condition, then carrying out solid-liquid separation on a reaction solution obtained by the hydrothermal reaction, and drying a solid obtained by the solid-liquid separation to obtain a precursor;
and annealing the precursor to obtain the metal oxide porous micro-nano hierarchical structure modified honeycomb stone.
Preferably, the hydroxide slow release agent is urea and/or hexamethyleneimine.
Preferably, the temperature of the hydrothermal reaction is 70-200 ℃ and the time is 2-24 h.
Preferably, the temperature of the drying is less than or equal to 60 ℃.
Preferably, the temperature of the annealing treatment is 250-500 ℃, and the time is 1-6 h.
Preferably, the water-soluble metal salt is a water-soluble salt of at least one of Zn, Mg, Fe, Ni and Cu.
Preferably, the concentration of the water-soluble metal salt in the raw material mixed solution is 0.01-2.0 mol/L, the concentration of the hydroxyl slow-release agent is 0.01-2.0 mol/L, and the concentration of the honeycomb stone is 1-200 g/L.
The invention also provides the metal oxide porous micro-nano hierarchical structure modified honeycomb stone obtained by the preparation method in the technical scheme, which comprises the honeycomb stone and the metal oxide loaded on the surface of the honeycomb stone, wherein the metal oxide is in a micron-sized flower-shaped microsphere assembled by porous nano sheets.
Preferably, the aperture of the nano-pores on the porous nano-sheet is 2-200 nm, the length of the porous nano-sheet is 0.1-10 μm, and the thickness of the porous nano-sheet is 5-20 nm; the particle size of the micron flower-shaped microspheres is 1-200 mu m.
The invention also provides application of the metal oxide porous micro-nano hierarchical structure modified honeycomb stone as a heavy metal adsorption material.
The preparation method of the metal oxide porous micro-nano hierarchical structure modified honeycomb stone provided by the invention comprises the following steps: mixing water-soluble metal salt, hydroxyl slow-release agent, water and honeycomb stone to obtain a raw material mixed solution; the hydroxide slow release agent is a compound capable of releasing hydroxide ions in the hydrothermal reaction process; carrying out hydrothermal reaction on the raw material mixed solution under a closed condition, then carrying out solid-liquid separation on a reaction solution obtained by the hydrothermal reaction, and drying a solid obtained by the solid-liquid separation to obtain a precursor; and annealing the precursor to obtain the metal oxide porous micro-nano hierarchical structure modified honeycomb stone. The method comprises the steps of firstly preparing a raw material mixed solution, uniformly distributing water-soluble metal salt and a hydroxyl slow-release agent into a pore structure of the honeycomb stone, in the hydrothermal reaction process, releasing hydroxyl ions from the hydroxyl slow-release agent, reacting with metal ions and carbonate ions (derived from a hydroxyl corrosion inhibitor or air) to generate nano-sheet basic carbonate on the surface of the honeycomb stone, gathering and assembling to form a flower-shaped microsphere structure, drying to obtain a precursor, annealing the precursor, decomposing the basic carbonate to generate metal oxide, water and carbon dioxide, and releasing the water and the carbon dioxide from a solid to form a porous structure on the nano-sheet. The preparation method provided by the invention can form the metal oxide with the micro-nano hierarchical structure on the honeycomb stone, is simple, is easy to implement and is suitable for industrial large-scale production. In addition, the metal oxide porous micro-nano hierarchical structure modified honeycomb stone obtained by the preparation method provided by the invention has good adsorption performance on heavy metals, can be used for water pollution treatment, and is easy to recover.
Drawings
FIG. 1 is SEM images of the magnesium oxide porous micro-nano hierarchical structure modified honeycombed stone obtained in example 1 at different magnifications;
FIG. 2 is a graph showing isothermal adsorption of cadmium ions by the magnesium oxide porous micro-nano hierarchical structure-modified pumice obtained in example 2, a Langmuir model fitting graph, and a Freundlich model fitting graph;
FIG. 3 is a comparison graph of isothermal adsorption curves of the brucite modified by the magnesium oxide porous micro-nano hierarchical structure obtained in example 2 and the brucite for cadmium ions.
Detailed Description
The invention provides a preparation method of a metal oxide porous micro-nano hierarchical structure modified honeycomb stone, which comprises the following steps:
mixing water-soluble metal salt, hydroxyl slow-release agent, water and honeycomb stone to obtain a raw material mixed solution; the hydroxide slow release agent is a compound capable of releasing hydroxide ions in the hydrothermal reaction process;
carrying out hydrothermal reaction on the raw material mixed solution under a closed condition, then carrying out solid-liquid separation on a reaction solution obtained by the hydrothermal reaction, and drying a solid obtained by the solid-liquid separation to obtain a precursor;
and annealing the precursor to obtain the metal oxide porous micro-nano hierarchical structure modified honeycomb stone.
According to the invention, water-soluble metal salt, hydroxyl slow-release agent, water and honeycomb stone are mixed to obtain a raw material mixed solution.
In the invention, the hydroxide slow-release agent is a compound capable of releasing hydroxide ions in the hydrothermal reaction process, and is preferably urea and/or hexamethyleneimine; the concentration of the hydroxyl slow-release agent in the raw material mixed solution is preferably 0.01-2.0 mol/L, more preferably 0.6-2 mol/L, further preferably 0.6-1.8 mol/L, most preferably 0.6-1.0 mol/L, and particularly preferably 0.01, 0.6, 0.8, 1.0, 1.2, 1.5, 1.8 or 2.0 mol/L. In the invention, the urea can be decomposed to release hydroxide ions and carbonate ions in the hydrothermal reaction process and react with metal cations to generate basic carbonate, while the hexamethyleneimine can release hydroxide ions in the hydrothermal reaction process, and carbon dioxide is usually dissolved due to the contact of water and air so as to contain carbonate, so that the metal ions react with the carbonate ions and the hydroxide ions to generate the basic carbonate.
In the invention, the molar ratio of the water-soluble metal salt to the hydroxyl slow-release agent is preferably 1: 0.5-3, and more preferably 1:1, 1:0.5 or 1: 3.
The water-soluble metal salt is not particularly limited, and may be any water-soluble metal salt commonly used in the art, and in the embodiment of the present invention, the water-soluble metal salt is preferably a water-soluble salt of at least one of Zn, Mg, Fe, Ni, and Cu, the water-soluble salt is preferably a hydrochloride, a nitrate, a phosphate, or an acetate, the water-soluble metal salt is more preferably magnesium sulfate, magnesium nitrate, zinc acetate, zinc sulfate, nickel chloride, copper sulfate, or copper chloride, the water-soluble metal salt is further preferably magnesium sulfate, magnesium nitrate, zinc acetate, zinc sulfate, iron chloride, or iron sulfate, the water-soluble metal salt is further preferably magnesium sulfate, magnesium nitrate, zinc acetate, or zinc sulfate, and the water-soluble metal salt is most preferably magnesium sulfate or magnesium nitrate.
In the present invention, the concentration of the water-soluble metal salt in the raw material mixture is preferably 0.01 to 2.0mol/L, more preferably 0.6 to 2mol/L, even more preferably 0.6 to 1.8mol/L, most preferably 0.6 to 1.0mol/L, and particularly preferably 0.01, 0.6, 0.8, 1.0, 1.2, 1.5, 1.8, or 2.0 mol/L.
In the invention, the concentration of the honeycomb stone in the raw material mixed solution is preferably 1-200 g/L, more preferably 10-200 g/L, further preferably 50-200 g/L, most preferably 100-125 g/L, and particularly preferably 10, 50, 60, 80, 100, 125, 140 or 200 g/L; the average particle size of the honeycomb stone is preferably 0.1-1.0 mm, and specifically, the average particle size of the honeycomb stone can be preferably 0.1mm, 0.3mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm or 1.0 mm. In the present invention, the smaller the particle size of the pumice, the larger the contact area between the pumice and the solution, and the more the surface modification amount.
The mixing sequence of the water-soluble metal salt, the hydroxyl slow-release agent, the water and the honeycomb stone is not specially limited, and the raw material mixed solution can be obtained after uniform mixing. In the embodiment of the present invention, the water-soluble metal salt, the hydroxyl slow-release agent, the water and the honeycomb stone are preferably mixed in this order by dissolving the water-soluble metal salt and the hydroxyl slow-release agent in water and then adding the honeycomb stone. The mixing mode is not specially limited, and the dissolution of the water-soluble metal salt and the hydroxyl slow-release agent and the uniform dispersion of the honeycomb stones can be ensured.
After the raw material mixed solution is obtained, the raw material mixed solution is subjected to hydrothermal reaction under a closed condition, then the reaction liquid obtained by the hydrothermal reaction is subjected to solid-liquid separation, and the solid obtained by the solid-liquid separation is dried to obtain the precursor.
In the invention, the temperature of the hydrothermal reaction is preferably 70-200 ℃, more preferably 100-130 ℃, most preferably 100-120 ℃, and particularly preferably 70, 100, 110, 120, 130, 160 or 200 ℃; the time of the hydrothermal reaction is preferably 2-24 h, more preferably 8-24 h, further preferably 8-20 h, most preferably 10-12 h, and particularly preferably 1, 2, 3, 4 or 6 h; the hydrothermal reaction is preferably carried out for a time period from the time of increasing the temperature to the temperature of the hydrothermal reaction. In the present invention, the rate of heating up to the hydrothermal reaction is not particularly limited, and may be any rate. In the invention, in the hydrothermal reaction process, metal ions react with hydroxide ions and carbonate ions to generate basic carbonate, nano-flakes are formed on the surface of the honeycomb stone, and the honeycomb stone is assembled into a flower-shaped microsphere structure.
The solid-liquid separation mode is not particularly limited, and the solid can be separated, such as filtration and centrifugal separation.
In the present invention, after the solid-liquid separation, the solid obtained by the solid-liquid separation is preferably washed with water and then subjected to the subsequent step (i.e., drying). In the present invention, the water washing can remove the unreacted raw material remaining on the solid surface, and the manner of the water washing is not particularly limited in the present invention, and the raw material remaining on the solid surface may be removed, such as washing, soaking and washing.
In the invention, the drying temperature is preferably less than or equal to 60 ℃, and more preferably 55-60 ℃. In the present invention, the drying atmosphere is not particularly limited, and may be an air atmosphere or a vacuum atmosphere. In the present invention, the drying time is not particularly limited, and a constant weight product can be obtained, and in the present invention, the precursor crystallization can be further reduced at the above-mentioned preferable drying temperature.
After the precursor is obtained, the precursor is annealed to obtain the metal oxide porous micro-nano hierarchical structure modified honeycomb stone. In the present invention, the basic carbonate is decomposed into metal oxide, water and carbon dioxide during the annealing treatment, and the water and carbon dioxide are released from the solid to form a porous structure on the nano-sheet.
In the invention, the annealing treatment temperature is preferably 250-500 ℃, more preferably 300-500 ℃, most preferably 300-400 ℃, and the time is preferably 1-6 h, more preferably 2-6 h, further preferably 3-6 h, and most preferably 4-6 h; the time of the annealing treatment is preferably from the time of raising the temperature to the temperature of the annealing treatment. The temperature rise rate of the annealing treatment temperature is not particularly limited, and can be any temperature rise rate; the annealing temperature is proper, so that the metal oxide precursor (namely the basic carbonate) can be completely decomposed to generate a proper amount of pore structure, and the phenomenon that the adsorption performance of the material is influenced by the damage of the pore structure caused by overhigh temperature can be avoided.
The invention also provides the metal oxide porous micro-nano hierarchical structure modified honeycomb stone obtained by the preparation method in the technical scheme, which comprises the honeycomb stone and the metal oxide loaded on the surface of the honeycomb stone, wherein the metal oxide is in a micron-sized flower-shaped microsphere assembled by porous nano sheets.
In the invention, the pore diameter of the nano-pores on the porous nano-sheets is preferably 2-200 nm, more preferably 32-200 nm, even more preferably 32-45 nm, and most preferably 40-45 nm; the length of the porous nanosheet is preferably 0.1-10 μm, more preferably 5-10 μm, the thickness is preferably 5-20 nm, more preferably 10-20 nm, further preferably 16-20 nm, and most preferably 20 nm; the particle size of the micron-sized flower-like microspheres is preferably 1-200 μm, more preferably 70-200 μm, even more preferably 70-100 μm, and most preferably 75-90 μm.
The invention also provides application of the honeycomb stone modified by the metal oxide porous micro-nano hierarchical structure in the technical scheme as a heavy metal adsorption material; the heavy metal adsorbing material is preferably an adsorbing material for adsorbing cadmium ions and lead ions.
The following provides a detailed description of a metal oxide porous micro-nano hierarchical structure modified honeycomb stone, a preparation method and applications thereof with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing magnesium sulfate, urea and water, stirring for 10min, dissolving the magnesium sulfate and the urea, then adding honeycomb stones with the average particle size of 0.9mm, and uniformly stirring to obtain a raw material mixed solution, wherein the concentrations of the magnesium sulfate and the urea are both 0.6mol/L, and the concentration of the honeycomb stones is 125 g/L;
placing the raw material mixed solution in a container, sealing, then placing in an oven, heating to 100 ℃, preserving heat for 10 hours, completing a hydrothermal reaction, carrying out solid-liquid separation on the obtained reaction solution, washing the solid obtained by the solid-liquid separation, and drying in the oven at 60 ℃ to constant weight to obtain a magnesium oxide porous micro-nano hierarchical structure modified honeycombed rock precursor;
and (3) placing the magnesium oxide porous micro-nano hierarchical structure modified pumice precursor in a muffle furnace, heating to 300 ℃, and annealing for 4 hours to obtain the magnesium oxide porous micro-nano hierarchical structure modified pumice.
Fig. 1 is SEM images of the magnesium oxide porous micro-nano hierarchical structure modified honeycombed stone obtained in the present example at different magnifications, wherein a, b, c and d are SEM images with scales of 200, 100, 10 and 1 μm in sequence. The MgO microspheres can be seen from a and b to grow on the surface of the honeycomb stone to present a flower-shaped microsphere structure, the diameter of the flower-shaped microsphere structure is 50-100 mu m, the surface of the honeycomb stone is uniformly modified, and the flower-shaped MgO microspheres are uniform in size; c, clearly showing that the single flower-shaped MgO microsphere is assembled by MgO porous nano sheets in a layered mode and is superposed layer by layer, and finally forming a flower-shaped microsphere structure with a porous micro-nano hierarchical structure; from d, the length of the nano-sheet is about 5 μm, and a plurality of pore structures are distributed on the surface of the nano-sheet.
The structure of the magnesium oxide on the honeycomb stone modified by the porous micro-nano hierarchical structure of the magnesium oxide obtained in the embodiment is tested by adopting a scanning electron microscope observation method, and specifically, the magnesium oxide is loaded on the honeycomb stone in a flower-like microsphere structure formed by gathering and assembling nano-sheet structures, the average particle size of the flower-like microsphere structure is 75 micrometers, the length of the nano-sheet is 5 micrometers, the thickness of the nano-sheet is 20nm, and the average pore size of the pore structure on the nano-sheet is 40 nm.
Example 2
Mixing magnesium nitrate, urea and water, stirring for 30min, dissolving the magnesium nitrate and the urea, then adding honeycomb stones with the average particle size of 0.5mm, and uniformly stirring to obtain a raw material mixed solution, wherein the concentrations of the magnesium nitrate and the urea are both 1.0mol/L, and the concentration of the honeycomb stones is 100 g/L;
placing the raw material mixed solution in a container, sealing, then placing in an oven, heating to 120 ℃, preserving heat for 12 hours, completing a hydrothermal reaction, carrying out solid-liquid separation on the obtained reaction solution, washing the solid obtained by the solid-liquid separation, and drying in the oven at 60 ℃ to constant weight to obtain a magnesium oxide porous micro-nano hierarchical structure modified honeycombed rock precursor;
and (3) placing the magnesium oxide porous micro-nano hierarchical structure modified pumice precursor in a muffle furnace, heating to 400 ℃, and annealing for 6h to obtain the magnesium oxide porous micro-nano hierarchical structure modified pumice.
The structure of the magnesium oxide on the honeycomb stone modified by the porous micro-nano hierarchical structure of the magnesium oxide obtained in the embodiment is tested by adopting a scanning electron microscope observation method, and specifically, the magnesium oxide is loaded on the honeycomb stone in a flower-like microsphere structure formed by gathering and assembling nano-sheet structures, the average particle size of the flower-like microsphere structure is 90 microns, the length of the nano-sheet is 10 microns, the thickness of the nano-sheet is 20nm, and the average pore size of the pore structure on the nano-sheet is 45 nm.
Testing Cd of pH value of 7 of the magnesium oxide porous micro-nano hierarchical structure modified honeycomb stone obtained in the embodiment at 25 DEG C2+Isothermal adsorption curves in aqueous solution, as shown in a in FIG. 2, where the abscissa is Cd of the solution at adsorption equilibrium2+The concentration and the ordinate are the adsorption capacity of the honeycomb stone modified by the magnesium oxide porous micro-nano hierarchical structure, and the concentration and the ordinate are respectively known from a2+The concentration is continuously increased, the adsorption of the magnesium oxide porous micro-nano hierarchical structure modified honeycomb stone shows a steady increase trend, the adsorption performance is excellent, and the method is used for Cd2+The maximum adsorption capacity of the adsorbent exceeds 68.83 mg/g; adsorption isotherms in a were fitted linearly using the Langmuir model,the obtained fitting curve is shown as b in fig. 2, a Freundlich model is used for linearly fitting the adsorption isotherm in a, the obtained fitting curve is shown as c in fig. 2, a, b and c show that the adsorption process of the magnesium oxide porous micro-nano hierarchical structure modified pumice on cadmium ions conforms to a Langmuir model, the correlation coefficient is 0.989, and the condition that the adsorption of the magnesium oxide porous micro-nano hierarchical structure modified pumice on cadmium ions is monolayer adsorption is shown.
The result of testing the isothermal adsorption curve of the pumice under the same conditions is shown in fig. 3, and for comparison, the isothermal adsorption curve of example 2 is shown in fig. 3, and it can be seen from fig. 3 that the adsorption capacity of the pumice modified by the magnesium oxide porous micro-nano hierarchical structure provided by the present invention for cadmium ions is significantly improved compared to the pumice before modification.
Example 3
Mixing zinc acetate, urea and water, stirring for 30min, dissolving the zinc acetate and the urea, then adding honeycomb stones with the average particle size of 0.8mm, and uniformly stirring to obtain a raw material mixed solution, wherein the concentrations of the zinc acetate and the urea are respectively 3mol/L and 1.5mol/L, and the concentration of the honeycomb stones is 50 g/L;
placing the raw material mixed solution in a container, sealing, then placing in an oven, heating to 100 ℃, preserving heat for 8 hours, completing a hydrothermal reaction, carrying out solid-liquid separation on the obtained reaction solution, washing the solid obtained by the solid-liquid separation, and drying in the oven at 60 ℃ to constant weight to obtain a zinc oxide porous micro-nano hierarchical structure modified honeycombed rock precursor;
and (3) placing the honeycombed rock precursor modified by the zinc oxide porous micro-nano hierarchical structure in a muffle furnace, heating to 500 ℃, and annealing for 3 hours to obtain the honeycombed rock modified by the zinc oxide porous micro-nano hierarchical structure.
The structure of zinc oxide on the honeycomb stone modified by the zinc oxide porous micro-nano hierarchical structure obtained in the embodiment is tested by adopting a scanning electron microscope observation method, and specifically, the zinc oxide is loaded on the honeycomb stone in a flower-like microsphere structure formed by gathering and assembling nano-sheet structures, the average particle size of the flower-like microsphere structure is 70 micrometers, the length of the nano-sheet is 7 micrometers, the thickness of the nano-sheet is 18nm, and the average pore size of the pore structure on the nano-sheet is 32 nm.
Example 4
Mixing zinc sulfate, hexamethyleneimine and water, stirring for 60min to dissolve the zinc sulfate and the hexamethyleneimine, then adding honeycomb stone with the average particle size of 0.3mm, and uniformly stirring to obtain a raw material mixed solution, wherein the concentrations of the zinc sulfate and the hexamethyleneimine are both 1.8mol/L, and the concentration of the honeycomb stone is 200 g/L;
placing the raw material mixed solution in a container, sealing, then placing in an oven, heating to 110 ℃, preserving heat for 20 hours, completing a hydrothermal reaction, carrying out solid-liquid separation on the obtained reaction solution, washing the solid obtained by the solid-liquid separation, and drying in the oven at 60 ℃ to constant weight to obtain a zinc oxide porous micro-nano hierarchical structure modified honeycombed rock precursor;
and (3) placing the honeycombed rock precursor modified by the zinc oxide porous micro-nano hierarchical structure in a muffle furnace, heating to 320 ℃, and annealing for 4 hours to obtain the honeycombed rock modified by the zinc oxide porous micro-nano hierarchical structure.
The structure of zinc oxide on the honeycomb stone modified by the zinc oxide porous micro-nano hierarchical structure obtained in the embodiment is tested by adopting a scanning electron microscope observation method, and specifically, the zinc oxide is loaded on the honeycomb stone in a flower-like microsphere structure formed by gathering and assembling nano-sheet structures, the average particle size of the flower-like microsphere structure is 100 micrometers, the length of the nano-sheet is 9 micrometers, the thickness of the nano-sheet is 16nm, and the average pore size of the pore structure on the nano-sheet is 40 nm.
Example 5
Mixing ferric chloride, hexamethyleneimine and water, stirring for 300min, dissolving the ferric chloride and the hexamethyleneimine, then adding honeycomb stones with the average particle size of 0.1mm, and uniformly stirring to obtain a raw material mixed solution, wherein the concentrations of the ferric chloride and the hexamethyleneimine are both 2.0mol/L, and the concentration of the honeycomb stones is 100 g/L;
placing the raw material mixed solution in a container, sealing, then placing in an oven, heating to 130 ℃, preserving heat for 24 hours, completing a hydrothermal reaction, carrying out solid-liquid separation on the obtained reaction solution, washing the solid obtained by the solid-liquid separation, and drying in the oven at 60 ℃ to constant weight to obtain a castolite precursor modified by the iron oxide porous micro-nano hierarchical structure;
and (3) placing the honeycomb stone precursor modified by the porous micro-nano hierarchical structure of the iron oxide in a muffle furnace, heating to 250 ℃, and annealing for 6 hours to obtain the honeycomb stone modified by the porous micro-nano hierarchical structure of the iron oxide.
The structure of the iron oxide on the honeycomb stone modified by the iron oxide porous micro-nano hierarchical structure obtained in the embodiment is tested by adopting a scanning electron microscope observation method, and specifically, the iron oxide is loaded on the honeycomb stone in a flower-like microsphere structure formed by gathering and assembling nano-sheet structures, the average particle size of the flower-like microsphere structure is 200 μm, the length of the nano-sheet is 10 μm, the thickness of the nano-sheet is 20nm, and the average pore size of the pore structure on the nano-sheet is 180 nm.
Example 6
Mixing ferric sulfate, hexamethyleneimine and water, stirring for 300min, dissolving the ferric sulfate and the hexamethyleneimine, then adding honeycomb stone with the average particle size of 0.6mm, and uniformly stirring to obtain a raw material mixed solution, wherein the concentrations of the ferric sulfate and the hexamethyleneimine are both 0.8mol/L, and the concentration of the honeycomb stone is 50 g/L;
placing the raw material mixed solution in a container, sealing, then placing in an oven, heating to 100 ℃, preserving heat for 10 hours, completing a hydrothermal reaction, carrying out solid-liquid separation on the obtained reaction solution, washing the solid obtained by the solid-liquid separation, and drying in the oven at 55 ℃ to constant weight to obtain a castolite precursor modified by the iron oxide porous micro-nano hierarchical structure;
and (3) placing the honeycomb stone precursor modified by the porous micro-nano hierarchical structure of the iron oxide in a muffle furnace, heating to 300 ℃, and annealing for 2h to obtain the honeycomb stone modified by the porous micro-nano hierarchical structure of the iron oxide.
The structure of the iron oxide on the honeycomb stone modified by the iron oxide porous micro-nano hierarchical structure obtained in the embodiment is tested by adopting a scanning electron microscope observation method, and specifically, the iron oxide is loaded on the honeycomb stone in a flower-like microsphere structure formed by gathering and assembling nano-sheet structures, the average particle size of the flower-like microsphere structure is 85 micrometers, the length of the nano-sheet is 5 micrometers, the thickness of the nano-sheet is 10nm, and the average pore size of the pore structure on the nano-sheet is 200 nm.
Example 7
Mixing nickel sulfate, hexamethyleneimine and water, stirring for 20min, dissolving the nickel sulfate and the hexamethyleneimine, then adding honeycomb stones with the average particle size of 0.5mm, and uniformly stirring to obtain a raw material mixed solution, wherein the concentrations of the nickel sulfate and the hexamethyleneimine are 0.01mol/L and 0.03mol/L respectively, and the concentration of the honeycomb stones is 10 g/L;
placing the raw material mixed solution in a container, sealing, then placing in an oven, heating to 70 ℃, preserving heat for 20 hours, completing a hydrothermal reaction, carrying out solid-liquid separation on the obtained reaction solution, washing the solid obtained by the solid-liquid separation, and drying in the oven at 60 ℃ to constant weight to obtain a nickel oxide porous micro-nano hierarchical structure modified honeycombed rock precursor;
and (3) placing the honeycombed rock precursor modified by the nickel oxide porous micro-nano hierarchical structure in a muffle furnace, heating to 400 ℃, and annealing for 1h to obtain the honeycombed rock modified by the nickel oxide porous micro-nano hierarchical structure.
The structure of nickel oxide on the honeycomb stone modified by the nickel oxide porous micro-nano hierarchical structure obtained in the embodiment is tested by adopting a scanning electron microscope observation method, specifically, the nickel oxide is loaded on the honeycomb stone in a flower-like microsphere structure formed by gathering and assembling nano-sheet structures, the average particle size of the flower-like microsphere structure is 20 micrometers, the length of the nano-sheet is 2 micrometers, the thickness of the nano-sheet is 5nm, and the average pore size of the pore structure on the nano-sheet is 2 nm.
Example 8
Mixing nickel chloride, urea and water, stirring for 30min, dissolving the nickel chloride and the urea, then adding honeycomb stones with the average particle size of 0.7mm, and uniformly stirring to obtain a raw material mixed solution, wherein the concentrations of the nickel chloride and the urea are both 1.2mol/L, and the concentration of the honeycomb stones is 80 g/L;
placing the raw material mixed solution in a container, sealing, then placing in an oven, heating to 200 ℃, preserving heat for 12 hours, completing a hydrothermal reaction, carrying out solid-liquid separation on the obtained reaction solution, washing the solid obtained by the solid-liquid separation, and drying in the oven at 60 ℃ to constant weight to obtain a nickel oxide porous micro-nano hierarchical structure modified honeycombed rock precursor;
and (3) placing the honeycombed rock precursor modified by the nickel oxide porous micro-nano hierarchical structure in a muffle furnace, heating to 300 ℃, and annealing for 4 hours to obtain the honeycombed rock modified by the nickel oxide porous micro-nano hierarchical structure.
The structure of nickel oxide on the honeycomb stone modified by the nickel oxide porous micro-nano hierarchical structure obtained in the embodiment is tested by adopting a scanning electron microscope observation method, specifically, the nickel oxide is loaded on the honeycomb stone in a flower-like microsphere structure formed by gathering and assembling nano-sheet structures, the average particle size of the flower-like microsphere structure is 25 micrometers, the length of the nano-sheet is 3 micrometers, the thickness of the nano-sheet is 7nm, and the average pore size of the pore structure on the nano-sheet is 10 nm.
Example 9
Mixing copper sulfate, urea and water, stirring for 15min to dissolve the copper sulfate and the urea, then adding honeycomb stones with the average particle size of 0.9mm, and uniformly stirring to obtain a raw material mixed solution, wherein the concentrations of the copper sulfate and the urea are both 1.5mol/L, and the concentration of the honeycomb stones is 140 g/L;
placing the raw material mixed solution in a container, sealing, then placing in an oven, heating to 160 ℃, preserving heat for 10 hours, completing a hydrothermal reaction, carrying out solid-liquid separation on the obtained reaction solution, washing the solid obtained by the solid-liquid separation, and drying in the oven at 60 ℃ to constant weight to obtain a copper oxide porous micro-nano hierarchical structure modified honeycombed rock precursor;
and (3) placing the copper oxide porous micro-nano hierarchical structure modified pumice precursor in a muffle furnace, heating to 350 ℃, and annealing for 6h to obtain the copper oxide porous micro-nano hierarchical structure modified pumice.
The structure of copper oxide on the honeycomb stone modified by the copper oxide porous micro-nano hierarchical structure obtained in the embodiment is tested by adopting a scanning electron microscope observation method, and specifically, the copper oxide is loaded on the honeycomb stone in a flower-like microsphere structure formed by gathering and assembling nano-sheet structures, the average particle size of the flower-like microsphere structure is 1 μm, the length of the nano-sheet is 0.1 μm, the thickness of the nano-sheet is 12nm, and the average pore size of the pore structure on the nano-sheet is 2 nm.
Example 10
Mixing copper chloride, hexamethyleneimine and water, stirring for 30min, dissolving the copper chloride and the hexamethyleneimine, then adding honeycomb stones with the average particle size of 1.0mm, and uniformly stirring to obtain a raw material mixed solution, wherein the concentrations of the copper chloride and the hexamethyleneimine are both 1.8mol/L, and the concentration of the honeycomb stones is 60 g/L;
placing the raw material mixed solution in a container, sealing, then placing in an oven, heating to 100 ℃, preserving heat for 24 hours, completing a hydrothermal reaction, carrying out solid-liquid separation on the obtained reaction solution, washing the solid obtained by the solid-liquid separation, and drying in the oven at 60 ℃ to constant weight to obtain a copper oxide porous micro-nano hierarchical structure modified honeycombed rock precursor;
and (3) placing the copper oxide porous micro-nano hierarchical structure modified pumice precursor in a muffle furnace, heating to 250 ℃, and annealing for 4 hours to obtain the copper oxide porous micro-nano hierarchical structure modified pumice.
The structure of copper oxide on the honeycomb stone modified by the copper oxide porous micro-nano hierarchical structure obtained in the embodiment is tested by adopting a scanning electron microscope observation method, and specifically, the copper oxide is loaded on the honeycomb stone in a flower-like microsphere structure formed by gathering and assembling nano-sheet structures, the average particle size of the flower-like microsphere structure is 7 microns, the length of the nano-sheet is 0.4 microns, the thickness of the nano-sheet is 15nm, and the average pore size of the pore structure on the nano-sheet is 10 nm.
Testing the saturated adsorption capacity of the honeycomb stone modified by the metal oxide porous micro-nano hierarchical structure obtained in the embodiment 1-10 on cadmium ions and lead ions, wherein the specific test method comprises the following steps:
preparing cadmium ion and lead ion solutions with different concentration gradients (50, 100, 200, 400, 600, 800 and 1000mg/L), weighing 50mg of honeycomb stone modified by a metal oxide porous micro-nano hierarchical structure, placing the honeycomb stone in 10mL of cadmium ion and lead ion solutions with different concentrations, carrying out oscillation reaction for 12h at 25 ℃ under the condition that the pH value of the solution is 7, taking supernatant, filtering the supernatant through a 0.45 mu m filter membrane, and measuring the adsorption capacity of the cadmium ion and the lead ion in the solution through an inductive coupling plasma spectrometer; and performing isothermal line fitting on the obtained data to obtain saturated adsorption capacity, namely the adsorption capacity of the material to lead ions and cadmium ions.
As shown in table 1, it can be seen from table 1 that the honeycombed stone modified by the metal oxide porous micro-nano hierarchical structure prepared by the method provided by the present invention has good adsorption for cadmium ions and lead ions, and especially the honeycombed stone modified by the magnesium oxide porous micro-nano hierarchical structure has the best adsorption performance.
Table 1 test results of saturation adsorption capacity of metal oxide porous micro-nano hierarchical structure-modified pumice for cadmium ions and lead ions obtained in examples 1 to 10
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Cadmium ion (mg/g) | 66.91 | 68.83 | 36.18 | 39.84 | 20.35 |
| Lead ion (mg/g) | 71.38 | 75.97 | 40.66 | 42.71 | 26.93 |
| Item | Example 6 | Example 7 | Example 8 | Example 9 | Example 10 |
| Cadmium ion (mg/g) | 18.79 | 7.89 | 11.57 | 10.32 | 12.48 |
| Lead ion (mg/g) | 23.62 | 9.16 | 12.28 | 12.65 | 15.13 |
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a metal oxide porous micro-nano hierarchical structure modified honeycomb stone is characterized by comprising the following steps:
mixing water-soluble metal salt, hydroxyl slow-release agent, water and honeycomb stone to obtain a raw material mixed solution; the hydroxide slow release agent is a compound capable of releasing hydroxide ions in the hydrothermal reaction process;
carrying out hydrothermal reaction on the raw material mixed solution under a closed condition, then carrying out solid-liquid separation on a reaction solution obtained by the hydrothermal reaction, and drying a solid obtained by the solid-liquid separation to obtain a precursor;
and annealing the precursor to obtain the metal oxide porous micro-nano hierarchical structure modified honeycomb stone.
2. The method of claim 1, wherein the hydroxide-releasing agent is urea and/or hexamethyleneimine.
3. The preparation method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 70 to 200 ℃ for 2 to 24 hours.
4. The method of claim 1, wherein the drying temperature is 60 ℃ or less.
5. The method according to claim 1, wherein the annealing is performed at a temperature of 250 to 500 ℃ for 1 to 6 hours.
6. The production method according to claim 1, wherein the water-soluble metal salt is a water-soluble salt of at least one of Zn, Mg, Fe, Ni, and Cu.
7. The method according to any one of claims 1 to 6, wherein the concentration of the water-soluble metal salt in the raw material mixture is 0.01 to 2.0mol/L, the concentration of the hydroxyl slow-release agent is 0.01 to 2.0mol/L, and the concentration of the pumice is 1 to 200 g/L.
8. The metal oxide porous micro-nano hierarchical structure modified honeycomb stone obtained by the preparation method of any one of claims 1 to 7 is characterized by comprising honeycomb stone and metal oxide loaded on the surface of the honeycomb stone, wherein the metal oxide is in the form of micron-sized flower-like microspheres assembled by porous nanosheets.
9. The metal oxide porous micro-nano hierarchical structure modified honeycomb stone according to claim 8, wherein the pore diameter of the nano pores on the porous nano sheets is 2-200 nm, the length of the porous nano sheets is 0.1-10 μm, and the thickness of the porous nano sheets is 5-20 nm; the particle size of the micron flower-shaped microspheres is 1-200 mu m.
10. The application of the metal oxide porous micro-nano hierarchical structure modified honeycomb stone as a heavy metal adsorption material according to claim 8 or 9.
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