CN109331807B - Self-supporting perovskite type oxide nanofiber catalytic purification material and preparation method thereof - Google Patents

Self-supporting perovskite type oxide nanofiber catalytic purification material and preparation method thereof Download PDF

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CN109331807B
CN109331807B CN201811156894.8A CN201811156894A CN109331807B CN 109331807 B CN109331807 B CN 109331807B CN 201811156894 A CN201811156894 A CN 201811156894A CN 109331807 B CN109331807 B CN 109331807B
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毛雪
吴红
刘呈坤
阳智
孙润军
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Xian Polytechnic University
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Abstract

The invention discloses a self-supporting perovskite type oxide nanofiber catalytic purification material, which consists of an A element metal salt, a B element metal salt and an inorganic polymeric flocculant, wherein the A element metal salt and the B element metal salt jointly form the metal salt, and the molar ratio of the total metal salt to the inorganic polymeric flocculant is 1: 0.001-0.05. The invention also discloses a preparation method of the self-supporting perovskite type oxide nanofiber catalytic purification material, which comprises the following steps: 1) hydrolyzing the element A metal salt and the element B metal salt together to form perovskite type oxide nano colloidal particles, adding an inorganic polymeric flocculant, and uniformly stirring to obtain a precursor solution; 2) preparing precursor nano-fibers from the precursor solution by adopting an electrostatic spinning process; 3) and calcining the precursor nanofiber in an air atmosphere to obtain the self-supporting perovskite type oxide nanofiber catalytic purification material. The invention has low manufacturing cost and good filtering effect.

Description

Self-supporting perovskite type oxide nanofiber catalytic purification material and preparation method thereof
Technical Field
The invention belongs to the technical field of new material preparation, relates to a self-supporting perovskite type oxide nanofiber catalytic purification material, and further relates to a preparation method of the self-supporting perovskite type oxide nanofiber catalytic purification material.
Background
In recent years, with rapid development of economy and advanced development of industry, the problem of environmental pollution is becoming more serious, and air pollutants mainly come from harmful gases such as nitric oxide, carbon monoxide and hydrogen sulfide discharged from factories, automobiles and power plants, and have an important influence on the quality of life and the health level of people, so that the development of a multi-effect catalyst which is efficient and can simultaneously remove the harmful gases is receiving more and more attention from people. At present, the commonly used multiple-effect catalysts basically adopt precious metals as active components, and although the catalytic performance is better, the precious metals are expensive and difficult to be widely applied, so that the development of perovskite type oxide catalysts which are low in price and can be widely popularized becomes a research hotspot at present.
The general formula of the perovskite type oxide molecule is ABO3Wherein, the A site is a rare earth metal element or an alkaline earth metal element with larger ionic radius, can coordinate with 12 oxygens and is positioned at the center of the cube; the B site is generally a transition metal element with a small ionic radius, can coordinate with 6 oxygens and is positioned at the top corner of the cube. The perovskite type oxide has a unique crystal structure, and the structure can control oxygen holes and the content thereof and the activity of oxygen in crystal lattices, and greatly improve the redox and thermal stability of the catalyst, so that the perovskite can be used for replacing active components of noble metals in many fields, has obvious price advantage and can be widely applied.
Chinese patent CN101745405A discloses a catalyst of perovskite type oxide for purifying exhaust gas of internal combustion engine, which is prepared by gel technology, and the catalyst is in powder structure, difficult to recycle and difficult to recover. Chinese patent CN107876066A discloses a preparation method and application of a palladium-iridium bimetallic alloy perovskite automobile exhaust catalyst, the catalyst improves the catalytic performance of the catalyst by adjusting the synergistic effect of bimetal, but noble metal is required to be added in the preparation process, the preparation process is complex, the production cost is high, and the catalyst is difficult to be widely applied. Paper on the grant of the right of the book "research on perovskite catalysts for purifying diesel engine exhaust gas" (Chongqing environmental science, 1993 (6): 10-15]The preparation of different types of perovskite catalysts by impregnation is disclosed, using gamma-Al2O3And gamma-Al2O3Ceramic of bluestone structureHoneycomb as carrier according to ABO3The perovskite catalyst is prepared by a multiple impregnation method, the catalyst prepared by the method has good low-temperature activity, however, the process is complex, and the active component can be migrated in the drying process, so that the fiber catalysis efficiency is reduced.
Disclosure of Invention
The invention aims to provide a self-supporting perovskite type oxide nanofiber catalytic purification material, and solves the problems of high production cost, complex process and relatively low fiber catalytic efficiency in the prior art.
The invention also aims to provide a preparation method of the self-supporting perovskite type oxide nanofiber catalytic purification material.
The invention adopts the technical scheme that the self-supporting perovskite type oxide nanofiber catalytic purification material consists of an A element metal salt, a B element metal salt and an inorganic polymeric flocculant, wherein the A element metal salt and the B element metal salt jointly form the metal salt, and the molar ratio of the total metal salt to the inorganic polymeric flocculant is 1: 0.001-0.05.
The invention adopts another technical scheme that the preparation method of the self-supporting perovskite type oxide nanofiber catalytic purification material is implemented according to the following steps:
step 1: hydrolyzing the element A metal salt and the element B metal salt together to form perovskite type oxide nano colloidal particles, and then adding an inorganic polymeric flocculant and uniformly stirring to obtain a uniform and stable precursor solution; wherein the molar ratio of the total of the A element metal salt and the B element metal salt to the inorganic polymeric flocculant is 1: 0.001-0.05;
the hydrolysis of the element A metal salt and the element B metal salt means that strong base and weak acid salt is stirred for 30-180min for hydrolysis under the condition that the pH value is 3-5, or strong acid and weak base salt is stirred for 30-180min for hydrolysis under the condition that the pH value is 10-12, so that perovskite type oxide nano colloidal particles are formed; stirring for 10-120min after adding inorganic polymeric flocculant;
step 2: preparing the precursor solution into precursor nano-fibers by adopting an electrostatic spinning process;
and step 3: and calcining the precursor nanofiber in an air atmosphere to obtain the self-supporting perovskite type oxide nanofiber catalytic purification material.
The invention has the beneficial effects that firstly, the A element metal salt and the B element metal salt are hydrolyzed to form perovskite type oxide nano colloidal particles, then the inorganic polymeric flocculant is added to be uniformly stirred, and a uniform and stable precursor solution is formed between the perovskite type oxide nano colloidal particles and the inorganic polymeric flocculant through the hydrogen bond effect, wherein the precursor solution has a molecular chain with a stable three-dimensional interlocking net structure; organic high molecular polymers are not required to be added into the precursor solution, the yield of the perovskite type oxide fiber is obviously improved, and the finally prepared perovskite type oxide nanofiber catalytic purification material shows better flexibility and tensile strength. The self-supporting perovskite type oxide nanofiber catalytic purification material can effectively filter particulate pollutants while catalytically decomposing harmful gases, the removal rate of the harmful gases is over 95 percent, the filtration efficiency of the particulate matters with the particle size of 0.02-10 mu m is over 99.99 percent, and the resistance pressure drop is less than 200 Pa.
Drawings
FIG. 1 is a view showing a self-supporting perovskite-type La prepared in example 1 of the present invention0.4Ce0.6CoO3Micrographs of nanofiber catalytic purification material.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The self-supporting perovskite type oxide nanofiber catalytic purification material consists of an element A metal salt, an element B metal salt and an inorganic polymeric flocculant, wherein the element A metal salt and the element B metal salt jointly form the metal salt, and the molar ratio of the total metal salt to the inorganic polymeric flocculant is 1: 0.001-0.05.
The preparation method of the self-supporting perovskite type oxide nanofiber catalytic purification material is implemented according to the following steps:
step 1: hydrolyzing the element A metal salt and the element B metal salt together to form perovskite type oxide nano colloidal particles, and then adding an inorganic polymeric flocculant and uniformly stirring to obtain a uniform and stable precursor solution, wherein the dynamic viscosity of the precursor solution is 0.05 Pa.s-5 Pa.s;
wherein the molar ratio of the total of the A element metal salt and the B element metal salt to the inorganic polymeric flocculant is 1: 0.001-0.05; the hydrolysis of the element A metal salt and the element B metal salt means that strong base and weak acid salt is stirred for 30-180min for hydrolysis under the condition that the pH value is 3-5, or strong acid and weak base salt is stirred for 30-180min for hydrolysis under the condition that the pH value is 10-12, so that perovskite type oxide nano colloidal particles are formed, and the size of the colloidal particles is 1-60 nm; stirring for 10-120min after adding inorganic polymeric flocculant;
the general chemical formula of the perovskite type oxide is ABO3Wherein, the A site is one or more of rare earth elements or alkaline earth elements such as La, Ce, Pr, Nd, Sm, Y, Sc, Be, Ca, Sr, Ba and the like; the A element metal salt is selected from one or more of nitrate, sulfate and nitrate, chlorate, high chlorate and acetate corresponding to rare earth elements and alkaline earth elements; b site is one or more of transition metal elements such as Mn, Ti, Fe, Co, Ni, Cr and the like; the B element metal salt is selected from one or more of manganese salt, copper salt, iron salt, titanium salt, zirconium salt, cobalt salt, nickel salt, aluminum salt, chromium salt, tin salt and zinc salt;
manganese salt is selected from manganese acetylacetonate, manganese acetate, manganese chloride, manganese sulfate tetrahydrate or manganese nitrate;
the copper salt is selected from copper sulfate pentahydrate, copper nitrate, copper tartrate, basic copper carbonate, copper chloride or copper citrate;
the ferric salt is selected from ferrocene, ferric acetylacetonate, ammonium ferrous sulfate hexahydrate, ferric trichloride or ferric ammonium citrate;
the titanium salt is selected from titanium tetrachloride, isopropyl titanate, tetrabutyl titanate or titanyl sulfate;
the zirconium salt is selected from zirconium acetate, zirconium chloride, zirconium acetylacetonate, aluminum zirconium oxide octahydrate, zirconyl nitrate or zirconium n-propoxide;
cobalt salt is selected from cobalt acetylacetonate, cobalt nitrate octahydrate, cobalt chloride hexahydrate, cobalt acetate or cobalt oxalate;
the nickel salt is selected from nickel nitrate, nickel oxalate, nickel sulfate hexahydrate, nickel chloride or nickel acetylacetonate;
the aluminum salt is selected from aluminum chloride hexahydrate, aluminum isopropoxide, aluminum acetylacetonate or aluminum nitrate nonahydrate;
the chromium salt is selected from chromium acetate, chromium sulfate, chromium chloride hexahydrate or chromium nitrate nonahydrate;
the tin salt is selected from stannic chloride, stannous sulfate or tributyltin chloride;
the zinc salt is selected from zinc acetylacetonate, zinc chloride, zinc sulfate heptahydrate, zinc dimethacrylate, zinc acetate dihydrate or zinc phosphate hexahydrate.
The inorganic polymeric flocculant is one of polyaluminium chloride, polyaluminium sulfate, polyferric chloride, polyferric sulfate, polyaluminium silicate, polyaluminum phosphonitrichloride, polyaluminum silicate chloride, polyaluminum sulfate chloride, polyaluminum silicate sulfate, polyaluminum silicate chloride, polyal.
Step 2: preparing the precursor solution into precursor nano-fibers by adopting an electrostatic spinning process,
when the charge repulsion force of the liquid drop at the tip of the spinning nozzle exceeds the surface tension force of the spinning nozzle, the jet flow sprayed out of the surface of the liquid drop is subjected to high-speed stretching of the electric field force, solvent volatilization and final solidification and deposition on a receiving device to obtain precursor nanofiber, wherein the precursor nanofiber is uniform in diameter and good in continuity;
the electrostatic spinning process parameters are that the precursor solution is spun at the perfusion speed of 0.1-6 mL/h under the conditions of the temperature of 10-30 ℃ and the relative humidity of 20-75%, the distance between a receiving device and a spinning nozzle is 15-30 cm, and the voltage applied by the spinning nozzle is 10-30 kV.
And step 3: calcining the precursor nanofiber in an air atmosphere, gradually increasing the calcining temperature from room temperature to 800-1200 ℃, increasing the temperature at a speed of 1-5 ℃/min, and keeping the temperature at the highest calcining temperature for 30-120min to obtain the self-supporting perovskite oxide nanofiber catalytic purification material. The average fiber diameter of the self-supporting perovskite type oxide nanofiber catalytic purification material is 10nm-900nm, the specific surface area of the fiber membrane is 30m2/g-200m2(ii)/g; the tensile strength of the self-supporting perovskite type oxide nanofiber catalytic purification material is 5MPa-500 MPa.
The inorganic polymeric flocculant is mainly used in the field of industrial water treatment at present, and the purpose of purifying water quality is finally achieved by the adhesion, bridging and crosslinking actions of hydroxyl on the surface of the inorganic polymeric flocculant and larger-sized impurity particles (including colloidal particles, dyes, larger blocky particles and the like) in water. However, in the preparation method of the invention, only hydrogen bond action is generated between the inorganic polymeric flocculant and the perovskite type oxide nano colloidal particles to form a stable three-dimensional interlocking reticular structure molecular chain, because the size of the perovskite type oxide nano colloidal particles in the precursor solution of the invention is in the order of magnitude of nanometer, and is less than 100nm, and simultaneously, the quantity of the nano colloidal particles is huge and reaches hundreds of millions, after a very small quantity of the inorganic polymeric flocculant is added, hydrogen bond adsorption action is generated between the perovskite type oxide nano colloidal particles and hydroxyl on the surface of the inorganic polymeric flocculant, the nano colloidal particles can completely wrap the inorganic polymeric flocculant to form the inorganic polymeric flocculant, other hydroxyl on the surface of the nano colloidal particles can adsorb other inorganic polymeric flocculant molecules to finally form the stable three-dimensional interlocking reticular structure molecular chain, and in the process, because the large quantity of the nano colloidal particles can not generate coagulation sedimentation action between the inorganic polymeric, therefore, the uniform spinnable precursor solution with certain viscosity is obtained, and the precursor nanofiber is uniform and has better continuity.
Example 1
Preparation of self-supporting perovskite La0.4Ce0.6CoO3The nano-fiber catalytic purification material.
Step 1: lanthanum nitrate, cerium nitrate and cobalt chloride hexahydrate are stirred for 60min under the condition that the pH value is 11 to complete hydrolysis, and composite hydroxide nano colloidal particles are formed, wherein the average diameter of the colloidal particles is 30 nm; then adding inorganic polymeric flocculant polymeric ferric sulfate, and continuously stirring for 50 min;
wherein the molar ratio of lanthanum nitrate, cerium nitrate and cobalt chloride hexahydrate is 20: 30: 50, the molar ratio of the total metal salt to the polymeric ferric sulfate serving as the inorganic polymeric flocculant is 1: 0.05; uniformly mixing to prepare a uniform and stable precursor solution with the dynamic viscosity of 0.05 Pa.s. The molecular chain in the precursor solution has a stable three-dimensional interlocking network structure formed by lanthanum hydroxide, cerium hydroxide, cobalt hydroxide nano colloidal particles and an inorganic polymeric flocculant polymeric ferric sulfate long chain, and the structural formula is as follows:
Figure BDA0001819086470000071
stable three-dimensional interlocking network structure of example 1
Step 2: preparing the precursor solution into precursor nano-fibers by adopting an electrostatic spinning process;
the electrostatic spinning process parameters are as follows: the spinning temperature is 10 ℃, the relative humidity is 50%, the perfusion speed is 3.5mL/h, the receiving distance is 26cm, and the spinning voltage is 23 kV;
and step 3: calcining the precursor nanofiber in an air atmosphere, gradually increasing the calcining temperature from room temperature to 1100 ℃, increasing the temperature at a speed of 4 ℃/min, and keeping the temperature for 100min at the highest calcining temperature to obtain the self-supporting La0.4Ce0.6CoO3The nano-fiber catalytic purification material.
Referring to FIG. 1, the self-supporting perovskite La prepared in example 1 of the present invention0.4Ce0.6CoO3Micrographs of nanofiber catalytic purification material. The self-supporting La0.4Ce0.6CoO3The average fiber diameter of the nano-fiber catalytic purification material is 600nm, and the specific surface area is 180m2And the tensile strength of the nanofiber catalytic purification material is 500 MPa.
The self-supporting La0.4Ce0.6CoO3The nanofiber catalytic purification material is used for catalytically decomposing harmful gases and simultaneously effectively filtering particulate pollutants, the removal rate of 0.3 wt% of hydrogen sulfide gas is 95.8%, the filtering efficiency of particles with the particle size of 0.03-8 mu m is 99.996%, and the resistance pressure drop is 108 Pa.
Example 2
Preparation of self-supporting perovskite type LaFe0.8Al0.2O3The nano-fiber catalytic purification material.
Step 1: lanthanum sulfate, ammonium ferrous sulfate hexahydrate and aluminum nitrate nonahydrate are stirred together for 180min under the condition that the pH value is 12, so that hydrolysis is completed, and composite hydroxide nano colloidal particles are formed, wherein the average diameter of the colloidal particles is 1 nm; adding inorganic polymeric flocculant polyaluminium sulfate, and continuously stirring for 85 min;
wherein the molar ratio of lanthanum sulfate, ammonium ferrous sulfate hexahydrate and aluminum nitrate nonahydrate is 50: 40: 10, the molar ratio of the metal salt to the polyaluminium sulfate is 1: 0.012; uniformly mixing to prepare a uniform and stable precursor solution with the dynamic viscosity of 0.8 Pa.s. The molecular chain in the precursor solution has a stable three-dimensional interlocking mesh structure formed by lanthanum hydroxide, ferric hydroxide, aluminum hydroxide nano colloidal particles and polyaluminium sulfate long chains, and the structural formula is as follows:
Figure BDA0001819086470000081
example 2 Stable three-dimensional interlocking mesh Structure
Step 2: preparing the precursor solution into precursor nano-fibers by adopting an electrostatic spinning process;
the electrostatic spinning process parameters are as follows: the spinning temperature is 25 ℃, the relative humidity is 58%, the perfusion speed is 0.8mL/h, the receiving distance is 15cm, and the spinning voltage is 30 kV;
and step 3: calcining the precursor nanofiber in an air atmosphere, gradually increasing the calcining temperature from room temperature to 900 ℃, increasing the temperature at the speed of 3 ℃/min, and keeping the temperature for 55min at the highest calcining temperature to obtain the self-supporting LaFe0.8Al0.2O3The nano-fiber catalytic purification material.
The self-supporting LaFe0.8Al0.2O3The average fiber diameter of the nano-fiber catalytic purification material is 10nm, and the specific surface area is 170m2The tensile strength of the nano-fiber catalytic purification material is 260 MPa.
The self-supporting LaFe0.8Al0.2O3The nanofiber catalytic purification material is used for catalytically decomposing harmful gases and simultaneously effectively filtering particulate pollutants, the removal rate of 1 wt% of sulfur dioxide gas is 98.3%, the filtration efficiency of particulate matters with the particle size of 0.05-6 mu m is 99.995%, and the resistance pressure drop is 174 Pa.
Example 3
Preparation of self-supporting perovskite type Ce0.9Y0.1Mn0.7Cu0.3O3The nano-fiber catalytic purification material.
Step 1: stirring cerium nitrate and yttrium nitrate together under the condition that the pH value is 10 for 30min to complete hydrolysis, and forming cerium hydroxide and yttrium hydroxide nano colloidal particles; meanwhile, stirring manganese acetate and copper nitrate for 50min under the condition that the pH value is 3 to complete hydrolysis, forming manganese hydroxide and copper hydroxide nano colloidal particles, and mixing the manganese hydroxide and copper hydroxide nano colloidal particles together to form composite hydroxide nano colloidal particles, wherein the average diameter of the colloidal particles is 60 nm; then adding an inorganic polymeric flocculant polyaluminum silicate chloride, and continuously stirring for 45 min; wherein the molar ratio of cerium nitrate to yttrium nitrate to manganese acetate to copper nitrate is 90: 10: 70: 30, the molar ratio of the total metal salts to the poly-aluminum chloride is 1: 0.021; uniformly mixing to prepare a uniform and stable precursor solution with the dynamic viscosity of 5 Pa.s, wherein the molecular chains in the precursor solution have a stable three-dimensional interlocking mesh structure similar to that in the embodiment 1;
step 2: preparing the precursor solution into precursor nano-fibers by adopting an electrostatic spinning process;
the electrostatic spinning process parameters are as follows: the spinning temperature is 20 ℃, the relative humidity is 42%, the perfusion speed is 0.1mL/h, the receiving distance is 20cm, and the spinning voltage is 25 kV;
and step 3: calcining the precursor nanofiber in air atmosphere, gradually increasing the calcining temperature from room temperature to 1000 ℃, increasing the temperature at the speed of 2 ℃/min, and keeping the temperature for 80min at the highest calcining temperature to obtain the self-supporting Ce0.9Y0.1Mn0.7Cu0.3O3The nano-fiber catalytic purification material.
The self-supporting Ce0.9Y0.1Mn0.7Cu0.3O3Of catalytic purifying material of nano-fiberThe average diameter of the fiber is 850nm, and the specific surface area is 135m2And the tensile strength of the nanofiber catalytic purification material is 345 MPa.
The self-supporting Ce0.9Y0.1Mn0.7Cu0.3O3The nanofiber catalytic purification material is used for catalytically decomposing harmful gases and simultaneously effectively filtering particulate pollutants, the removal rate of 0.5 wt% of nitric oxide gas is 96%, the filtration efficiency of particles with the particle size of 0.03-7 mu m is 99.994%, and the resistance pressure drop is 135 Pa.
Example 4
Preparation of self-supporting perovskite Y0.6Sr0.4TiO3The nano-fiber catalytic purification material.
Step 1: stirring yttrium nitrate and strontium nitrate together under the condition that the pH value is 11 for 85min to complete hydrolysis, and forming yttrium hydroxide and strontium hydroxide nano colloidal particles; simultaneously, stirring isopropyl titanate for 80min under the condition that the pH value is 4 to complete hydrolysis, and then mixing the isopropyl titanate and the isopropyl titanate together to form composite hydroxide nano colloidal particles, wherein the average diameter of the colloidal particles is 25 nm; then adding an inorganic polymeric flocculant polyaluminium chloride, and continuously stirring for 100 min; wherein the molar ratio of yttrium nitrate to strontium nitrate to isopropyl titanate is 30: 20: 50, the molar ratio of the metal salt to the polyaluminium chloride is 1: 0.001; uniformly mixing to prepare a uniform and stable precursor solution with the dynamic viscosity of 0.36 Pa.s, wherein the molecular chains in the precursor solution have a stable three-dimensional interlocking mesh structure similar to that in the embodiment 2;
step 2: preparing the precursor solution into precursor nano-fibers by adopting an electrostatic spinning process;
the electrostatic spinning process parameters are as follows: the spinning temperature is 26 ℃, the relative humidity is 75%, the perfusion speed is 2.4mL/h, the receiving distance is 28cm, and the spinning voltage is 20 kV;
and step 3: calcining the precursor nanofiber in air atmosphere, gradually increasing the calcining temperature from room temperature to 800 ℃, increasing the temperature at the speed of 1 ℃/min, and keeping the temperature for 90min at the highest calcining temperature to obtain the self-supporting Y0.6Sr0.4TiO3The nano-fiber catalytic purification material.
The self-supporting Y0.6Sr0.4TiO3The average fiber diameter of the nano-fiber catalytic purification material is 540nm, and the specific surface area is 80m2And the tensile strength of the nanofiber catalytic purification material is 5 MPa.
The self-supporting Y0.6Sr0.4TiO3The nano-fiber catalytic purification material is used for catalytically decomposing harmful gases and simultaneously effectively filtering particulate pollutants, the removal rate of 0.8 wt% of carbon monoxide gas is 97.3%, the filtering efficiency of particles with the particle size of 0.02-5 mu m is more than 99.999%, and the resistance pressure drop is 45 Pa.
Example 5
Preparation of self-supporting perovskite type BaCr0.2Zn0.8O3The nano-fiber catalytic purification material.
Step 1: stirring barium acetate, chromium acetate and zinc acetylacetonate for 120min under the condition of pH being 5 to complete hydrolysis, and forming composite hydroxide nano colloidal particles, wherein the average diameter of the colloidal particles is 50 nm; then adding inorganic polymeric flocculant polymeric ferric chloride, and continuously stirring for 60 min; wherein the molar ratio of the chromium acetate to the zinc acetylacetonate to the barium acetate is 10: 40: 50, the molar ratio of the metal salt to the polymeric ferric chloride is 1: 0.006; uniformly mixing to prepare a uniform and stable precursor solution with the dynamic viscosity of 0.43 Pa.s, wherein the molecular chains in the precursor solution have a stable three-dimensional interlocking mesh structure similar to that in the embodiment 1;
step 2: preparing the precursor solution into precursor nano-fibers by adopting an electrostatic spinning process;
the electrostatic spinning process parameters are as follows: the spinning temperature is 18 ℃, the relative humidity is 46%, the perfusion speed is 6mL/h, the receiving distance is 30cm, and the spinning voltage is 22 kV;
and step 3: calcining the precursor nanofiber in an air atmosphere, gradually increasing the calcining temperature from room temperature to 1000 ℃, increasing the temperature at the speed of 3 ℃/min, and keeping the temperature for 120min at the highest calcining temperature to obtain the self-supporting BaCr0.2Zn0.8O3The nano-fiber catalytic purification material.
The self-supporting BaCr0.2Zn0.8O3Nano fiber catalytic purifying material fiberThe average diameter is 900nm and the specific surface area is 160m2The tensile strength of the nanofiber catalytic purification material is 205 MPa.
The self-supporting BaCr0.2Zn0.8O3The nanofiber catalytic purification material is used for catalytically decomposing harmful gases and simultaneously effectively filtering particulate pollutants, the removal rate of 1 wt% of sulfur dioxide gas is 96.8%, the filtering efficiency of particulate matters with the particle size of 0.03-10 mu m is 99.991%, and the resistance pressure drop is 89 Pa.
Example 6
Preparation of self-supporting perovskite La0.7Ca0.3Sn0.9Zr0.1O3The nano-fiber catalytic purification material.
Step 1: lanthanum nitrate, calcium nitrate, stannic chloride and titanium tetrachloride are stirred together for 145min under the condition that the pH value is 10 to complete hydrolysis, and composite hydroxide nano colloidal particles are formed, wherein the average diameter of the colloidal particles is 45 nm; then adding inorganic polymeric flocculant poly-phosphorus aluminum chloride, and continuously stirring for 5 min; wherein the molar ratio of lanthanum nitrate, calcium nitrate, stannic chloride and titanium tetrachloride is 70: 30: 90: 10, the molar ratio of the metal salt to the poly-phosphorus aluminum chloride is 1: 0.017; uniformly mixing to prepare a uniform and stable precursor solution with the dynamic viscosity of 0.25 Pa.s, wherein the molecular chains in the precursor solution have a stable three-dimensional interlocking mesh structure similar to that in the embodiment 2;
step 2: preparing the precursor solution into precursor nano-fibers by adopting an electrostatic spinning process;
the electrostatic spinning process parameters are as follows: the spinning temperature is 30 ℃, the relative humidity is 20%, the perfusion speed is 1.4mL/h, the receiving distance is 18cm, and the spinning voltage is 10 kV;
and step 3: calcining the precursor nanofiber in an air atmosphere, gradually increasing the calcining temperature from room temperature to 1200 ℃, increasing the temperature at a speed of 5 ℃/min, and keeping the temperature for 30min at the highest calcining temperature to obtain the self-supporting La0.7Ca0.3Sn0.9Zr0.1O3The nano-fiber catalytic purification material.
The self-supporting La0.7Ca0.3Sn0.9Zr0.1O3The average fiber diameter of the nano-fiber catalytic purification material is 485nm, and the specific surface area is 200m2The tensile strength of the nanofiber catalytic purification material is 385 MPa.
The self-supporting La0.7Ca0.3Sn0.9Zr0.1O3The nanofiber catalytic purification material is used for catalytically decomposing harmful gases and simultaneously effectively filtering particulate pollutants, the removal rate of 0.6 wt% of nitric oxide gas is 99%, the filtering efficiency of particles with the particle size of 0.03-9 mu m is 99.996%, and the resistance pressure drop is 75 Pa.

Claims (3)

1. A preparation method of a self-supporting perovskite type oxide nanofiber catalytic purification material is characterized by comprising the following steps:
step 1: the A element metal salt is selected from one or more of nitrate, sulfate and nitrate, chlorate, high chlorate and acetate corresponding to rare earth elements and alkaline earth elements; the B element metal salt is selected from one or more of manganese salt, copper salt, iron salt, titanium salt, zirconium salt, cobalt salt, nickel salt, aluminum salt, chromium salt, tin salt and zinc salt; the inorganic polymeric flocculant is one of polyaluminium chloride, polyaluminium sulfate, polyferric chloride, polyferric sulfate, polyaluminium silicate, polyaluminum phosphonitrichloride, polyaluminum silicate chloride, polyaluminum sulfate chloride, polyaluminum silicate sulfate, polyaluminum silicate chloride or polyaluminum silicate zinc;
hydrolyzing the element A metal salt and the element B metal salt together to form perovskite type oxide nano colloidal particles, and then adding an inorganic polymeric flocculant and uniformly stirring to obtain a uniform and stable precursor solution; wherein the molar ratio of the total of the A element metal salt and the B element metal salt to the inorganic polymeric flocculant is 1: 0.001-0.05;
the hydrolysis of the element A metal salt and the element B metal salt means that strong base and weak acid salt is stirred for 30-180min for hydrolysis under the condition that the pH value is 3-5, or strong acid and weak base salt is stirred for 30-180min for hydrolysis under the condition that the pH value is 10-12, so that perovskite type oxide nano colloidal particles are formed; stirring for 10-120min after adding inorganic polymeric flocculant;
step 2: preparing the precursor solution into precursor nano-fibers by adopting an electrostatic spinning process;
and step 3: and calcining the precursor nanofiber in an air atmosphere to obtain the self-supporting perovskite type oxide nanofiber catalytic purification material.
2. The method for preparing self-supporting perovskite type oxide nanofiber catalytic purification material according to claim 1, characterized in that: in the step 2, the electrostatic spinning process parameters are that the precursor solution is spun at a filling speed of 0.1-6 mL/h at the temperature of 10-30 ℃ and the relative humidity of 20-75%, the distance between a receiving device and a spinning nozzle is 15-30 cm, and the voltage applied by the spinning nozzle is 10-30 kV.
3. The method for preparing self-supporting perovskite type oxide nanofiber catalytic purification material according to claim 1, characterized in that: in the step 3, the calcining temperature is gradually increased to 800-1200 ℃ from the room temperature, the temperature rising speed is 1-5 ℃/min, and the calcining temperature is kept for 30-120min at the highest calcining temperature.
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