CN109277074B - Preparation method of metal ion adsorption material - Google Patents

Preparation method of metal ion adsorption material Download PDF

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CN109277074B
CN109277074B CN201811147549.8A CN201811147549A CN109277074B CN 109277074 B CN109277074 B CN 109277074B CN 201811147549 A CN201811147549 A CN 201811147549A CN 109277074 B CN109277074 B CN 109277074B
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nano powder
zinc oxide
oxide nano
metal ion
titanium dioxide
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CN109277074A (en
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金向华
孙猛
栗鹏伟
刘晶
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Jinhong Gas Co ltd
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Suzhou Jinhong Gas Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character

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Abstract

The invention provides a preparation method of a metal ion adsorption material, which comprises the following steps: s1) mixing the titanium oxide nano powder, the zinc oxide nano powder, the alkali metal hydroxide and the silicon-aluminum gel in water, and carrying out hydrothermal reaction to obtain a titanium dioxide nano tube intermediate loaded with zinc oxide; s2) treating the titanium dioxide nanotube intermediate body loaded with zinc oxide with an acid solution, and roasting to obtain the metal ion adsorbing material. Compared with the prior art, the invention uses the zinc oxide nano-particle material to carry out tube surface loading and tube filling on the titanium dioxide nano-tube, and can effectively adsorb metal ions with charges in the n-ethyl silicate; the titanium dioxide nanotube structure has a large specific surface area, so that the contact between the titanium dioxide nanotube structure and the metal ion adsorption material is increased, and the adsorption efficiency of the metal ion adsorption material is improved; furthermore, the metal ion adsorption material takes silicon-aluminum gel as a load material, so that active substances can not fall off to avoid secondary pollution.

Description

Preparation method of metal ion adsorption material
Technical Field
The invention belongs to the technical field of adsorbing materials, and particularly relates to a preparation method of a metal ion adsorbing material.
Background
The semiconductor integrated circuit industry is the high and new technology industry which is developed most rapidly at present, is more and more emphasized by various countries, the development speed is faster than the expectation of people, the annual growth rate of ultrahigh-purity electronic chemicals matched with the semiconductor integrated circuit industry is kept above 8 percent, and the semiconductor integrated circuit industry is the field which is developed most rapidly in the chemical industry.
In recent years, the development of the ultra-pure electronic chemical industry in China is synchronous with the world and is rapid, the annual growth rate of the ultra-pure electronic chemical manufacturing industry in recent years exceeds 20 percent, the ultra-pure electronic chemical industry is a high and new technology industry with high technical content, high investment and high added value, and the ultra-pure electronic chemical industry is one of the most rapid and active industries in the chemical industry. Moreover, the ultra-high purity electronic chemicals are one of the important supporting materials in the semiconductor integrated circuit industry, and the quality of the ultra-high purity electronic chemicals directly affects the quality of semiconductor integrated electronic chips.
Tetraethoxysilane (TEOS) is an important one in ultra-pure electronic chemicals and is mainly used for an LPCVD (low pressure chemical vapor deposition) process in the manufacturing process of semiconductor integrated circuit chips, and specifically, TEOS is evaporated from a liquid state to a gas state at first and then decomposed at 700-750 ℃ and 50Pa pressure to deposit on the surface of a silicon wafer to generate a silicon dioxide film.
Trace metal doping of the silicon dioxide film changes its semiconductor properties and affects the performance of the final chip. Therefore, in the production of semiconductor integrated circuit chips, the metal ions in the raw material TEOS are strictly controlled. However, at present, the domestic and foreign purification process for removing metal ions in TEOS mainly utilizes a rectification mode, and the rectification mode can effectively remove impurity components with large boiling point difference, and has an unsatisfactory effect on removing the metal ions.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a method for preparing a metal ion adsorbing material, which can effectively remove metal ions in tetraethoxysilane.
The invention provides a preparation method of a metal ion adsorption material, which comprises the following steps:
s1) mixing the titanium oxide nano powder, the zinc oxide nano powder, the alkali metal hydroxide and the silicon-aluminum gel in water, and carrying out hydrothermal reaction to obtain a titanium dioxide nano tube intermediate loaded with zinc oxide;
s2) treating the titanium dioxide nanotube intermediate body loaded with zinc oxide with an acid solution, and roasting to obtain the metal ion adsorbing material.
Preferably, the titanium oxide nano powder is titanium oxide nano powder with anatase as a main phase; the zinc oxide nano powder is preferably zinc oxide nano powder mainly containing wurtzite phase.
Preferably, the particle size of the titanium oxide nano powder is 10-50 nm; the particle size of the zinc oxide nano powder is 2-10 nm.
Preferably, the molar ratio of the titanium oxide nano powder to the zinc oxide nano powder is (0.2-0.6): (0.1-0.3).
Preferably, the molar ratio of the titanium oxide nano powder to the alkali metal hydroxide is (0.2-0.6): (0.4-6); the preferable proportion of the titanium oxide nano powder to water is (0.2-0.6) mol: (200-600) ml.
Preferably, the ratio of the titanium oxide nano powder to the silicon-aluminum gel is (0.2-0.6) mol: (30-100) g.
Preferably, the step S1) is specifically: mixing titanium oxide nano powder, zinc oxide nano powder and alkali metal hydroxide with water, then adding silicon-aluminum gel, oscillating and mixing, and carrying out hydrothermal reaction to obtain the titanium dioxide nano tube intermediate loaded with zinc oxide.
Preferably, the shaking and mixing time is 0.5-2 hours; the temperature of the hydrothermal reaction is 120-160 ℃; the time of the hydrothermal reaction is 6-10 h.
Preferably, the pH value of the acid solution is 3-5; the treatment time of the acid solution is 5-10 hours; the roasting temperature is 300-400 ℃; the roasting time is 1-2 h.
The invention also provides a metal ion adsorption device which comprises the metal ion adsorption material.
The invention provides a preparation method of a metal ion adsorption material, which comprises the following steps: s1) mixing the titanium oxide nano powder, the zinc oxide nano powder, the alkali metal hydroxide and the silicon-aluminum gel in water, and carrying out hydrothermal reaction to obtain a titanium dioxide nano tube intermediate loaded with zinc oxide; s2) treating the titanium dioxide nanotube intermediate body loaded with zinc oxide with an acid solution, and roasting to obtain the metal ion adsorbing material. Compared with the prior art, the invention utilizes the zinc oxide nano-particle material to carry out tube surface loading and tube filling on the titanium dioxide nano-tube, and obtains a semiconductor complex through the coupling effect among nano-particles, and because the Fermi energy levels of the two semiconductors are different, a photon-generated carrier is transmitted and analyzed between the semiconductors with different energy gaps, so that the recombination of the photon-generated carrier is inhibited, a large amount of electrons and holes can be generated, and further, metal ions with charges in the ethyl orthosilicate can be effectively adsorbed; the titanium dioxide nanotube structure has a large specific surface area, so that the contact between the tetraethoxysilane gas and the metal ion adsorption material can be increased, and meanwhile, the tetraethoxysilane gas can freely pass through the interior of the metal ion adsorption material, so that the contact between the tetraethoxysilane gas and the metal ion adsorption material is further increased, and the adsorption efficiency of the metal ion adsorption material is improved; moreover, the metal ion adsorption material takes silicon-aluminum gel as a load material, so that active substances can not fall off to avoid secondary pollution, and the metal ion adsorption material can be reused.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a metal ion adsorption material, which comprises the following steps: s1) mixing the titanium oxide nano powder, the zinc oxide nano powder, the alkali metal hydroxide and the silicon-aluminum gel in water, and carrying out hydrothermal reaction to obtain a titanium dioxide nano tube intermediate loaded with zinc oxide; s2) treating the titanium dioxide nanotube intermediate body loaded with zinc oxide with an acid solution, and roasting to obtain the metal ion adsorbing material.
The present invention is not particularly limited in terms of the source of all raw materials, and may be commercially available.
The titanium oxide nanopowder is known to those skilled in the art, and may be one or more of anatase type, rutile type and brookite type titanium oxide nanopowders, without any particular limitation, and in the present invention, the titanium oxide nanopowder mainly containing anatase phase is preferred; the particle size of the titanium oxide nano powder is preferably 10-50 nm.
The zinc oxide nano powder is known to those skilled in the art, and can be one or more of a sphalerite structure, a NaCl structure, a CsCl structure and a wurtzite structure, without any special limitation, and is preferably zinc oxide nano powder mainly composed of a wurtzite phase in the present invention; the particle size of the zinc oxide nano powder is preferably 2-10 nm.
Mixing titanium oxide nano powder, zinc oxide nano powder, alkali metal hydroxide and silicon-aluminum gel in water, preferably mixing the titanium oxide nano powder, the zinc oxide nano powder, the alkali metal hydroxide and the water, and then adding the silicon-aluminum gel; the preferable molar ratio of the titanium oxide nano powder to the zinc oxide nano powder is (0.2-0.6): (0.1 to 0.3); the alkali metal hydroxide is an alkali metal hydroxide known to those skilled in the art, and is not particularly limited, and sodium hydroxide and/or potassium hydroxide are preferable in the present invention; the preferable molar ratio of the titanium oxide nano powder to the alkali metal hydroxide is (0.2-0.6): (0.4-6); the preferable proportion of the titanium oxide nano powder to water is (0.2-0.6) mol: (200-600) ml; in the present invention, it is preferable that an alkali metal hydroxide and water are mixed with titanium oxide nanopowder and zinc oxide nanopowder in the form of an alkali metal hydroxide aqueous solution; the concentration of the alkali metal hydroxide aqueous solution is preferably 5 to 10 mol/L.
After uniformly mixing, adding silicon-aluminum gel, then preferably shaking and mixing, and then carrying out hydrothermal reaction; the preferable proportion of the titanium dioxide nano powder to the silicon-aluminum gel is (0.2-0.6) mol: (30-100) g; the oscillation mixing time is preferably 0.5-2 h; the temperature of the hydrothermal reaction is preferably 120-160 ℃; the time of the hydrothermal reaction is preferably 6-10 h; the hydrothermal reaction is preferably carried out in a closed autoclave, more preferably in a closed hydrothermal kettle; the inner liner of the hydrothermal kettle is preferably made of polytetrafluoroethylene material, the outer wall of the hydrothermal kettle is preferably made of metal material, and after heating, a high-temperature and high-pressure reaction environment can be produced.
After the hydrothermal reaction, preferably washing with water to obtain a titanium dioxide nanotube intermediate loaded with zinc oxide; the number of washing with water is preferably 2 to 10, more preferably 3 to 7, and further preferably 5 to 6.
In the initial stage of the hydrothermal reaction, titanium dioxide nano crystal grains are converted into products with sheet-shaped appearance due to the action of alkali metal hydroxide, and oxidation states after the reaction with the alkali metal hydroxide solution are multi-formed into alkali metal titanate with a layered structure, so that sheet-shaped objects can be generated; with the increase of the hydrothermal treatment time, the sheet-shaped object is gradually curled into short nanotubes, and the spontaneous curling is due to the combined action of multiple factors such as static electricity, surface area, elastic deformation and the like so as to reduce energy; when the hydrothermal reaction time is further prolonged, the nanotubes can be further grown, but when the nanotubes are grown to a certain extent, the nanotubes do not grow with the increase of the hydrothermal reaction time.
Treating the titanium dioxide nanotube intermediate body loaded with zinc oxide with an acid solution; the method for treating the titanium dioxide nanotube by the acid solution is a method well known to those skilled in the art, and is not particularly limited, and in the present invention, the titanium dioxide nanotube intermediate loaded with zinc oxide is preferably soaked in the acid solution; the acid solution is preferably hydrochloric acid solution; the pH value of the acid solution is preferably 3-5; the soaking time, namely the acid solution treatment time, is preferably 5-10 h.
After the acid solution treatment, preferably washing with water, drying, and roasting to obtain a metal ion adsorption material; the water washing is preferably carried out by using deionized water; the drying temperature is preferably 60-100 ℃, more preferably 70-90 ℃, and further preferably 80 ℃; the roasting temperature is preferably 300-400 ℃; the roasting time is preferably 1-2 h.
The invention uses zinc oxide nanometer particle material to load the surface of the titanium dioxide nanometer tube and fill the inside of the tube, and obtains a semiconductor complex through the coupling effect among the nanometer particles, and the essence is the modification of one semiconductor to another semiconductor; because the Fermi energy levels of the two semiconductors are different, the photon-generated carriers are transmitted and analyzed between the semiconductors with different energy gaps, so that the recombination of the photon-generated carriers is inhibited, a large number of electrons and holes can be generated, and further, the metal ions with charges in the ethyl orthosilicate can be effectively adsorbed; the titanium dioxide nanotube structure has a large specific surface area, so that the contact between the tetraethoxysilane gas and the metal ion adsorption material can be increased, and meanwhile, the tetraethoxysilane gas can freely pass through the interior of the metal ion adsorption material, so that the contact between the tetraethoxysilane gas and the metal ion adsorption material is further increased, and the adsorption efficiency of the metal ion adsorption material is improved; moreover, the metal ion adsorption material takes silicon-aluminum gel as a load material, so that active substances can not fall off to avoid secondary pollution, and the metal ion adsorption material can be reused.
The invention also provides a metal ion adsorption device, which comprises the metal ion adsorption material; the metal ion-adsorbing material is preferably packed in a stainless steel container to obtain a metal ion-adsorbing device.
The metal ion adsorption device can be connected to the production line of the preparation process of the ultra-pure ethyl silicate in a spare-use mode.
In order to further illustrate the present invention, the following will describe the preparation method of a metal ion adsorbing material provided by the present invention in detail with reference to the examples.
The reagents used in the following examples are all commercially available.
Example 1
Uniformly mixing 0.2mol of titanium oxide nano powder (with the particle size of 10nm) taking a spherical anatase phase as a main component, 0.1mol of zinc oxide nano powder (with the particle size of 2nm) taking a wurtzite phase as a main component and 200ml of 5mol/L sodium hydroxide solution, then adding 30g of silicon-aluminum gel, and after shaking and mixing for 0.5h, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And placing the mixture in a closed hydrothermal kettle, preserving heat for 6h at 120 ℃, and washing with deionized water for 5 times to obtain the titanium dioxide nanotube intermediate loaded with zinc oxide.
Soaking the titanium dioxide nanotube intermediate loaded with zinc oxide in HCl solution with pH value of 3 for 5h, cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 300 ℃ for 1h to obtain the metal ion adsorbing material.
Example 2
Uniformly mixing 0.2mol of titanium oxide nano powder (with the particle size of 10nm) taking a spherical anatase phase as a main component, 0.2mol of zinc oxide nano powder (with the particle size of 2nm) taking a wurtzite phase as a main component and 200ml of 5mol/L sodium hydroxide solution, then adding 30g of silicon-aluminum gel, and after shaking and mixing for 0.5h, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And placing the mixture in a closed hydrothermal kettle, preserving heat for 6h at 120 ℃, and washing with deionized water for 5 times to obtain the titanium dioxide nanotube intermediate loaded with zinc oxide.
Soaking the titanium dioxide nanotube intermediate loaded with zinc oxide in HCl solution with pH value of 3 for 5h, cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 300 ℃ for 1h to obtain the metal ion adsorbing material.
Example 3
Uniformly mixing 0.2mol of titanium oxide nano powder (with the particle size of 10nm) taking a spherical anatase phase as a main component, 0.3mol of zinc oxide nano powder (with the particle size of 2nm) taking a wurtzite phase as a main component and 200ml of 5mol/L sodium hydroxide solution, then adding 30g of silicon-aluminum gel, and after shaking and mixing for 0.5h, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And placing the mixture in a closed hydrothermal kettle, preserving heat for 6h at 120 ℃, and washing with deionized water for 5 times to obtain the titanium dioxide nanotube intermediate loaded with zinc oxide.
Soaking the titanium dioxide nanotube intermediate loaded with zinc oxide in HCl solution with pH value of 3 for 5h, cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 300 ℃ for 1h to obtain the metal ion adsorbing material.
Example 4
Uniformly mixing 0.4mol of titanium oxide nano powder (with the particle size of 10nm) taking a spherical anatase phase as a main component, 0.1mol of zinc oxide nano powder (with the particle size of 2nm) taking a wurtzite phase as a main component and 200ml of 5mol/L sodium hydroxide solution, then adding 30g of silicon-aluminum gel, and after shaking and mixing for 0.5h, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And placing the mixture in a closed hydrothermal kettle, preserving heat for 6h at 120 ℃, and washing with deionized water for 5 times to obtain the titanium dioxide nanotube intermediate loaded with zinc oxide.
Soaking the titanium dioxide nanotube intermediate loaded with zinc oxide in HCl solution with pH value of 3 for 5h, cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 300 ℃ for 1h to obtain the metal ion adsorbing material.
Example 5
Uniformly mixing 0.6mol of titanium oxide nano powder (with the particle size of 10nm) taking a spherical anatase phase as a main component, 0.1mol of zinc oxide nano powder (with the particle size of 2nm) taking a wurtzite phase as a main component and 200ml of 5mol/L sodium hydroxide solution, then adding 30g of silicon-aluminum gel, and after shaking and mixing for 0.5h, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And placing the mixture in a closed hydrothermal kettle, preserving heat for 6h at 120 ℃, and washing with deionized water for 5 times to obtain the titanium dioxide nanotube intermediate loaded with zinc oxide.
Soaking the titanium dioxide nanotube intermediate loaded with zinc oxide in HCl solution with pH value of 3 for 5h, cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 300 ℃ for 1h to obtain the metal ion adsorbing material.
Example 6
Uniformly mixing 0.2mol of titanium oxide nano powder (with the particle size of 10nm) taking a spherical anatase phase as a main component, 0.1mol of zinc oxide nano powder (with the particle size of 2nm) taking a wurtzite phase as a main component and 600ml of 5mol/L sodium hydroxide solution, then adding 30g of silicon-aluminum gel, and after shaking and mixing for 0.5h, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And placing the mixture in a closed hydrothermal kettle, preserving heat for 6h at 120 ℃, and washing with deionized water for 5 times to obtain the titanium dioxide nanotube intermediate loaded with zinc oxide.
Soaking the titanium dioxide nanotube intermediate loaded with zinc oxide in HCl solution with pH value of 3 for 5h, cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 300 ℃ for 1h to obtain the metal ion adsorbing material.
Example 7
Uniformly mixing 0.2mol of titanium oxide nano powder (with the particle size of 10nm) taking a spherical anatase phase as a main component, 0.1mol of zinc oxide nano powder (with the particle size of 2nm) taking a wurtzite phase as a main component and 200ml of 10mol/L sodium hydroxide solution, then adding 30g of silicon-aluminum gel, and after shaking and mixing for 0.5h, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And placing the mixture in a closed hydrothermal kettle, preserving heat for 6h at 120 ℃, and washing with deionized water for 5 times to obtain the titanium dioxide nanotube intermediate loaded with zinc oxide.
Soaking the titanium dioxide nanotube intermediate loaded with zinc oxide in HCl solution with pH value of 3 for 5h, cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 300 ℃ for 1h to obtain the metal ion adsorbing material.
Example 8
Uniformly mixing 0.2mol of titanium oxide nano powder (with the particle size of 10nm) taking a spherical anatase phase as a main component, 0.1mol of zinc oxide nano powder (with the particle size of 2nm) taking a wurtzite phase as a main component and 200ml of 5mol/L sodium hydroxide solution, then adding 70g of silicon-aluminum gel, and after shaking and mixing for 0.5h, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And placing the mixture in a closed hydrothermal kettle, preserving heat for 6h at 120 ℃, and washing with deionized water for 5 times to obtain the titanium dioxide nanotube intermediate loaded with zinc oxide.
Soaking the titanium dioxide nanotube intermediate loaded with zinc oxide in HCl solution with pH value of 3 for 5h, cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 300 ℃ for 1h to obtain the metal ion adsorbing material.
Example 9
Uniformly mixing 0.2mol of titanium oxide nano powder (with the particle size of 10nm) taking a spherical anatase phase as a main component, 0.1mol of zinc oxide nano powder (with the particle size of 2nm) taking a wurtzite phase as a main component and 200ml of 5mol/L sodium hydroxide solution, then adding 100g of silicon-aluminum gel, and after shaking and mixing for 2 hours, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And placing the mixture in a closed hydrothermal kettle, preserving heat for 6h at 120 ℃, and washing with deionized water for 5 times to obtain the titanium dioxide nanotube intermediate loaded with zinc oxide.
Soaking the titanium dioxide nanotube intermediate loaded with zinc oxide in HCl solution with pH value of 3 for 5h, cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 300 ℃ for 1h to obtain the metal ion adsorbing material.
Example 10
Uniformly mixing 0.2mol of titanium oxide nano powder (with the particle size of 10nm) taking a spherical anatase phase as a main component, 0.1mol of zinc oxide nano powder (with the particle size of 2nm) taking a wurtzite phase as a main component and 200ml of 5mol/L sodium hydroxide solution, then adding 30g of silicon-aluminum gel, and after shaking and mixing for 0.5h, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And placing the mixture in a closed hydrothermal kettle, keeping the temperature at 160 ℃ for 6h, and washing the mixture for 5 times by using deionized water to obtain the titanium dioxide nanotube intermediate loaded with zinc oxide.
Soaking the titanium dioxide nanotube intermediate loaded with zinc oxide in HCl solution with pH value of 3 for 5h, cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 300 ℃ for 1h to obtain the metal ion adsorbing material.
Example 11
Uniformly mixing 0.2mol of titanium oxide nano powder (with the particle size of 10nm) taking a spherical anatase phase as a main component, 0.1mol of zinc oxide nano powder (with the particle size of 2nm) taking a wurtzite phase as a main component and 200ml of 5mol/L sodium hydroxide solution, then adding 30g of silicon-aluminum gel, and after shaking and mixing for 0.5h, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And placing the mixture in a closed hydrothermal kettle, preserving the heat for 10h at 120 ℃, and washing the mixture for 5 times by using deionized water to obtain the titanium dioxide nanotube intermediate loaded with zinc oxide.
Soaking the titanium dioxide nanotube intermediate loaded with zinc oxide in HCl solution with pH value of 3 for 5h, cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 300 ℃ for 1h to obtain the metal ion adsorbing material.
Example 12
Uniformly mixing 0.2mol of titanium oxide nano powder (with the particle size of 10nm) taking a spherical anatase phase as a main component, 0.1mol of zinc oxide nano powder (with the particle size of 2nm) taking a wurtzite phase as a main component and 200ml of 5mol/L sodium hydroxide solution, then adding 30g of silicon-aluminum gel, and after shaking and mixing for 0.5h, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And placing the mixture in a closed hydrothermal kettle, preserving the heat at 160 ℃ for 10h, and washing the mixture for 5 times by using deionized water to obtain the titanium dioxide nanotube intermediate loaded with zinc oxide.
Soaking the titanium dioxide nanotube intermediate loaded with zinc oxide in HCl solution with pH value of 3 for 5h, cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 300 ℃ for 1h to obtain the metal ion adsorbing material.
Example 13
Uniformly mixing 0.2mol of titanium oxide nano powder (with the particle size of 10nm) taking a spherical anatase phase as a main component, 0.1mol of zinc oxide nano powder (with the particle size of 2nm) taking a wurtzite phase as a main component and 200ml of 5mol/L sodium hydroxide solution, then adding 30g of silicon-aluminum gel, and after shaking and mixing for 0.5h, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And placing the mixture in a closed hydrothermal kettle, preserving heat for 6h at 120 ℃, and washing with deionized water for 5 times to obtain the titanium dioxide nanotube intermediate loaded with zinc oxide.
Soaking the titanium dioxide nanotube intermediate loaded with zinc oxide in HCl solution with pH value of 5 for 5h, cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 300 ℃ for 1h to obtain the metal ion adsorbing material.
Example 14
Uniformly mixing 0.2mol of titanium oxide nano powder (with the particle size of 10nm) taking a spherical anatase phase as a main component, 0.1mol of zinc oxide nano powder (with the particle size of 2nm) taking a wurtzite phase as a main component and 200ml of 5mol/L sodium hydroxide solution, then adding 30g of silicon-aluminum gel, and after shaking and mixing for 0.5h, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And placing the mixture in a closed hydrothermal kettle, preserving heat for 6h at 120 ℃, and washing with deionized water for 5 times to obtain the titanium dioxide nanotube intermediate loaded with zinc oxide.
Soaking the titanium dioxide nanotube intermediate loaded with zinc oxide in HCl solution with pH value of 3 for 10h, cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 300 ℃ for 1h to obtain the metal ion adsorbing material.
Example 15
Uniformly mixing 0.2mol of titanium oxide nano powder (with the particle size of 10nm) taking a spherical anatase phase as a main component, 0.1mol of zinc oxide nano powder (with the particle size of 2nm) taking a wurtzite phase as a main component and 200ml of 5mol/L sodium hydroxide solution, then adding 30g of silicon-aluminum gel, and after shaking and mixing for 0.5h, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And placing the mixture in a closed hydrothermal kettle, preserving heat for 6h at 120 ℃, and washing with deionized water for 5 times to obtain the titanium dioxide nanotube intermediate loaded with zinc oxide.
Soaking the titanium dioxide nanotube intermediate loaded with zinc oxide in HCl solution with pH value of 5 for 10h, cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 300 ℃ for 1h to obtain the metal ion adsorbing material.
Example 16
Uniformly mixing 0.2mol of titanium oxide nano powder (with the particle size of 10nm) taking a spherical anatase phase as a main component, 0.1mol of zinc oxide nano powder (with the particle size of 2nm) taking a wurtzite phase as a main component and 200ml of 5mol/L sodium hydroxide solution, then adding 30g of silicon-aluminum gel, and after shaking and mixing for 0.5h, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And placing the mixture in a closed hydrothermal kettle, preserving heat for 6h at 120 ℃, and washing with deionized water for 5 times to obtain the titanium dioxide nanotube intermediate loaded with zinc oxide.
Soaking the titanium dioxide nanotube intermediate loaded with zinc oxide in HCl solution with pH value of 3 for 5h, cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 400 ℃ for 2h to obtain the metal ion adsorbing material.
Comparative example 1
Uniformly mixing 0.2mol of titanium oxide nano powder (with the particle size of 10nm) taking a spherical anatase phase as a main component with 200ml of 5mol/L sodium hydroxide solution, then adding 30g of silicon-aluminum gel, and after shaking and mixing for 0.5h, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And placing the mixture in a closed hydrothermal kettle, preserving heat for 6 hours at 120 ℃, and washing with deionized water for 5 times to obtain a titanium dioxide nanotube intermediate.
Soaking the titanium dioxide nanotube intermediate in HCl solution with the pH value of 3 for 5h, then cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 300 ℃ for 1h to obtain the metal ion adsorbing material.
Comparative example 2
Uniformly mixing 0.1mol of zinc oxide nano powder (with the particle size of 2nm) mainly containing wurtzite phase with 200ml of 5mol/L sodium hydroxide solution, then adding 30g of silicon-aluminum gel, and after shaking and mixing for 0.5h, fully contacting the silicon-aluminum gel with the solution to obtain a mixture.
And (3) placing the mixture in a closed hydrothermal kettle, preserving heat for 6h at 120 ℃, and washing with deionized water for 5 times to obtain an intermediate.
And (3) soaking the intermediate in HCl solution with the pH value of 3 for 5h, cleaning with deionized water, drying in an oven at 80 ℃, and sintering in a sintering furnace at 300 ℃ for 1h to obtain the metal ion adsorbing material.
Respectively putting the metal ion adsorbing materials obtained in the embodiments 1 to 16 and the comparative examples 1 to 2 into a stainless steel container, wherein the lower part of the stainless steel container is provided with a gas inlet, the upper part of the stainless steel container is provided with a gas outlet, heating tetraethoxysilane to 150 ℃ to form tetraethoxysilane gas, introducing the tetraethoxysilane gas through the gas inlet, collecting tetraethoxysilane obtained from the gas outlet, detecting the content of metal ions in the tetraethoxysilane, testing the metal ions by adopting an inductively coupled plasma mass spectrometer (ICP-MS), obtaining results shown in tables 1 to 4, and performing online analysis and detection on the metal ions in the high-purity tetraethoxysilane, wherein the metal ions are not more than 0.02 ppb.
TABLE 1 content of metal ions in raw gas of ethyl orthosilicate
Figure BDA0001817147350000111
Figure BDA0001817147350000121
TABLE 2 content of metal ions after gas treatment of tetraethylorthosilicate
Figure BDA0001817147350000122
TABLE 3 content of metal ions after gas treatment of tetraethylorthosilicate
Figure BDA0001817147350000123
Figure BDA0001817147350000131
TABLE 4 content of metal ions after gas treatment of tetraethylorthosilicate
Figure BDA0001817147350000132

Claims (8)

1. The application of the metal ion adsorption material is characterized in that the metal ion adsorption material is used for removing metal ions in tetraethoxysilane gas, the tetraethoxysilane gas after the metal ions are removed is used for an LPCVD (low pressure chemical vapor deposition) process in the manufacturing process of a semiconductor integrated circuit chip, and the preparation method of the metal ion adsorption material comprises the following steps:
s1) mixing the titanium oxide nano powder, the zinc oxide nano powder, the alkali metal hydroxide and the silicon-aluminum gel in water, and carrying out hydrothermal reaction to obtain a titanium dioxide nano tube intermediate loaded with zinc oxide; the molar ratio of the titanium oxide nano powder to the zinc oxide nano powder is (0.2-0.6): (0.1 to 0.3);
s2) treating the titanium dioxide nanotube intermediate body loaded with zinc oxide with an acid solution, and roasting to obtain a metal ion adsorbing material; the zinc oxide nano powder is mainly a wurtzite phase zinc oxide nano powder.
2. The use according to claim 1, wherein the titanium oxide nanopowder is a titanium oxide nanopowder with an anatase phase as the main component.
3. The application of the titanium oxide nano powder as claimed in claim 1, wherein the particle size of the titanium oxide nano powder is 10-50 nm; the particle size of the zinc oxide nano powder is 2-10 nm.
4. The application of claim 1, wherein the molar ratio of the titanium oxide nanopowder to the alkali metal hydroxide is (0.2-0.6): (0.4-6); the ratio of the titanium oxide nano powder to water is (0.2-0.6) mol: (200-600) ml.
5. The application of the titanium oxide nano powder and the silicon-aluminum gel is characterized in that the ratio of the titanium oxide nano powder to the silicon-aluminum gel is (0.2-0.6) mol: (30-100) g.
6. The application according to claim 1, wherein the step S1) is specifically: mixing titanium oxide nano powder, zinc oxide nano powder and alkali metal hydroxide with water, then adding silicon-aluminum gel, oscillating and mixing, and carrying out hydrothermal reaction to obtain the titanium dioxide nano tube intermediate loaded with zinc oxide.
7. The use according to claim 6, wherein the time of the shaking mixing is 0.5-2 h; the temperature of the hydrothermal reaction is 120-160 ℃; the time of the hydrothermal reaction is 6-10 h.
8. The use according to claim 1, wherein the acid solution has a pH of 3 to 5; the treatment time of the acid solution is 5-10 hours; the roasting temperature is 300-400 ℃; the roasting time is 1-2 h.
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