CN111408382A - Process for preparing nano catalyst substrate with efficient catalytic function - Google Patents

Process for preparing nano catalyst substrate with efficient catalytic function Download PDF

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CN111408382A
CN111408382A CN202010285204.XA CN202010285204A CN111408382A CN 111408382 A CN111408382 A CN 111408382A CN 202010285204 A CN202010285204 A CN 202010285204A CN 111408382 A CN111408382 A CN 111408382A
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aqueous solution
base material
catalyst
porous
substrate
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温良成
曹更玉
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Guangdong University of Petrochemical Technology
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Guangdong University of Petrochemical Technology
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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B01J35/60—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a process for preparing a nano catalyst substrate with a high-efficiency catalytic function. The process of the invention separates the aqueous solution of the catalyst particle reagent and the aqueous solution of the precipitant into two systems, the porous substrate is soaked in the aqueous solution of the catalyst particle reagent, and the aqueous solution of the precipitant is placed in the ultrasonic tank. Taking out the soaked porous base material, quickly placing the porous base material into a precipitant aqueous solution, starting ultrasonic waves at the same time, enabling the precipitate to be concentrated in the base material by the porous base material attached with the catalyst particle reagent aqueous solution, assisting the crushing and oscillation of the precipitate particles by the ultrasonic waves to avoid the further agglomeration of the particles, enabling the porous base material to be uniformly attached by the catalyst particles, and finally enabling the nano particles to be uniformly dispersed on any surface inside and outside the base material through proper heat treatment temperature in a reduction environment to achieve the effect of improving the surface chemical reaction area and finish the nano catalyst base material with high catalytic reaction surface area.

Description

Process for preparing nano catalyst substrate with efficient catalytic function
Technical Field
The invention relates to the technical field of catalyst substrate preparation, in particular to a process for preparing a nano catalyst substrate with a high-efficiency catalytic function.
Background
With the increasing number of global population and the increasing population density, the modern society faces various problems of energy and environment. In the aspect of energy, the search for alternative energy sources to effectively utilize sunlight for energy conversion is an important research field at present, and a reaction mechanism for catalytic hydrogen production is one of key technologies; in the environmental field, especially in the public health field, with the global population increasing and the urbanized population density concentrating, the research of using photocatalyst and surface chemistry technology to improve the prevention and treatment of infectious diseases is attracting attention. The surface catalytic reaction is completed through a series of processes of reactant adsorption, diffusion reaction, desorption and the like on the surface of the catalyst, and belongs to an interface phenomenon. The nanometer particle has large surface area, total surface energy and large hole structure, and has unique influence on catalytic activity, selectivity and reactivity as catalyst. The bonding state of the surface of the nanometer particle is different from that of the interior of the particle, and the incomplete coordination of surface atoms leads to the increase of surface active sites, so that the nanometer particle has the advantages of homogeneous and heterogeneous catalysts, and can improve the activity of the catalysts, improve the selectivity and increase the stability of the catalysts. However, the nano-catalyst also has some difficulties in catalytic reaction, such as: the characteristics of the fine structure of the nano material are difficult to master and control; relatively speaking, the cost of the nano catalyst is high; the agglomeration phenomenon of the nano particles is obvious, and the advantages of high surface activity are lost due to poor dispersibility.
The current process technology for nanoparticles is well established, and the basic process methods include physical chemical vapor deposition, mechanical polishing, chemical solution method and atmospheric plasma. In the application field of the catalyst, the nano photocatalyst is usually combined with a stationary phase substrate, and a catalytic object is used as a mobile phase to achieve the purpose of stable use. Generally, the catalyst is uniformly dispersed on the surface of the substrate by various coating techniques, such as doctor blade, screen printing, spin coating, adding adhesive, dispersing agent and heat treatment to stabilize the adhesion, or by using atmospheric plasma spraying.
The above coating techniques are well established for the surface of the substrate, but if the nanoparticles are dispersed in the substrate, the above process techniques are not suitable. Generally, the synthesized nanoparticles are uniformly mixed with the material in the initial state of the base material, and then the composite material is made into the base material. For example, the commercial antibacterial ceramic tile is manufactured by uniformly mixing a nano active metal chemical having a bactericidal effect with ceramic tile powder, then performing mold casting, and performing heat treatment. However, this method easily causes the nano-active particles to be coated with the substrate material and lose the catalytic effect. Or the concentration of the precipitate solution and the precipitant solution is accurately controlled, and the temperature is carefully controlled, so that the precipitation reaction shows rapid nucleation, and the crystal grows slowly to maintain the nano-scale.
The improvement and modification of the process are both to increase the efficiency of the operation. For example, the highest efficiency of converting solar energy into hydrogen in the current photoelectrochemical reaction is 17%, so the conversion efficiency must be further improved by improving the nature of the catalyst material or improving the reaction environment.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a process for preparing a nano catalyst substrate with high catalytic efficiency, wherein the present invention adopts a novel precipitation method in combination with ultrasonic crushing to synthesize nano catalyst particles. The process of the invention separates the aqueous solution of the catalyst particle reagent and the aqueous solution of the precipitant into two systems, the porous substrate is soaked in the aqueous solution of the catalyst particle reagent, and the aqueous solution of the precipitant is placed in the ultrasonic tank. Taking out the soaked porous base material, quickly placing the porous base material into a precipitant aqueous solution, starting ultrasonic waves at the same time, enabling the precipitate to be concentrated in the base material by the porous base material attached with the catalyst particle reagent aqueous solution, assisting the crushing and oscillation of the precipitate particles by the ultrasonic waves to avoid the further agglomeration of the particles, enabling the porous base material to be uniformly attached by the catalyst particles, and finally enabling the nano particles to be uniformly dispersed on any surface inside and outside the base material through proper heat treatment temperature in a reduction environment to achieve the effect of improving the surface chemical reaction area and finish the nano catalyst base material with high catalytic reaction surface area.
The invention adopts the specific technical scheme that:
a process for preparing a nano catalyst substrate with high-efficiency catalytic function comprises the following steps:
(1) immersing the porous substrate in an aqueous solution of a catalyst particle reagent until the aqueous solution is completely permeated;
(2) preparing a precipitant aqueous solution, and placing the precipitant aqueous solution into an ultrasonic tank;
(3) quickly placing the porous base material adhered with the catalyst particle reagent aqueous solution into the precipitant aqueous solution, starting ultrasonic waves at the same time to ensure that the catalyst particles are intensively precipitated in the porous base material, and simultaneously starting a continuous oscillation mode by adopting the ultrasonic waves to continuously break precipitates so as to avoid the catalyst particles from generating an agglomeration phenomenon;
(4) taking out the porous base material to which the precipitated catalyst particles are uniformly attached, and placing the porous base material into an oven for drying;
(5) and (3) carrying out heat treatment on the dried porous base material in a reducing environment, converting the precipitated catalyst particles into nano catalyst particles, and attaching the nano catalyst particles to all surfaces of the porous base material to obtain the nano catalyst base material with the efficient catalytic function.
Further, the preparation method of the aqueous solution of the catalyst particle reagent comprises the following steps: one or more metal compounds are dissolved in deionized water to prepare an aqueous solution of the catalyst particle reagent.
Furthermore, the preparation method of the catalyst particle reagent comprises the following steps: the metal compound is metal carbonate or metal nitrate or a metal ester compound;
furthermore, after the metal compound is dissolved in the deionized water, if the metal compound is not easy to dissolve, a proper amount of concentrated nitric acid can be added to assist the dissolution, and an aqueous solution of the catalyst particle reagent is prepared.
Preferably, the amount of the nitric acid added is 10 to 20% of the total molar number of the metal ions of the metal compound charged into the deionized water.
Preferably, the concentration of the concentrated nitric acid is 16 mol/L.
Further, the concentration of the aqueous solution of the catalyst particle reagent is 0.05-0.5 mol/L;
further, the soaking time of the porous substrate in the step (1) is 0.5-1 h.
Further, the porous substrate is a porous polymer substrate, a porous metal substrate or a porous ceramic substrate.
Further, the concentration of the precipitant aqueous solution is 0.5-1 mol/L
Further, the ultrasonic power in step (3) is 250-300W, and the oscillation frequency is 50-60 kHz.
Further, the drying temperature in the step (4) is 80-150 ℃.
Further, the heat treatment temperature in the step (5) is 300-800 ℃.
The invention has the beneficial effects that:
1. the invention has easy control of process parameters and high reproducibility.
2. The invention can improve the uniformity of blending the nanoparticles into the porous substrate.
3. The invention can lead the nanometer catalyst particles to be intensively precipitated in the base material, so that the nanometer catalyst particles are attached to any surface inside and outside the base material, and the effect of improving the surface chemical reaction area is achieved. Solves the problem that the surface chemical reaction area is too low in the surface coating process.
4. The invention solves the problem of agglomeration after the synthesis of the nano catalyst particles, and can be widely applied to the combination of porous polymer, metal or ceramic base materials and the nano catalyst particles.
5. The invention has wide application range and better market prospect, and can be applied to the field of energy sources, such as catalytic hydrogen production and SOFC fuel cell cathode and anode preparation. Also can be applied to the field of antibacterial disinfection, such as mite-removing, disinfecting and sterilizing filter screens in air cleaners.
Drawings
FIG. 1 shows the effect of heat treatment temperature on the size of the nano-catalyst particles;
FIG. 2 shows the relationship between the concentration of the aqueous solution of the catalyst particle reagent and the specific surface area of the porous catalyst substrate after the preparation.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto, and various substitutions and alterations can be made without departing from the technical idea of the present invention as described above, according to the common technical knowledge and the conventional means in the field.
The following table shows the drugs used in the examples of the present invention:
Figure BDA0002448238510000041
the embodiment of the invention provides a process for preparing a nano catalyst substrate used in a mite-removing, disinfecting and sterilizing filter screen in an air cleaner, which can be applied to the field of antibacterial disinfection, and comprises the following steps:
(1) ZrO (NO)3)2·2H2O(0-0.2g)、Ni(NO3)2·6H2O(0-0.3g)、Cu(NO3)2·3H2O(0.05-0.3g)、AgNO3(0.05-0.3g)、Zn(NO3)2·6H2O(0-0.15g)、Ti(OC4H9)4(0.05-0.3g) is dissolved in 100m L deionized water, 16 mol/L concentrated nitric acid which is 10-20% of the total mole number of metal ions of the metal compounds in the deionized water is added to help dissolve and prepare an aqueous solution of 0.05-0.5 mol/L catalyst particle reagent (optionally, the metal compounds can be mixed and prepared into an aqueous solution of 0.05-0.5 mol/L catalyst particle reagent, similar effects can be obtained, and the using amount of each metal compound is the same as that of the metal compoundsIn the range, when the metal compound is not easy to dissolve, if the metal compound is prepared by 100m L deionized water, the nitric acid is usually added into the solution in a sequence by 5m L nitric acid each time to help the metal compound to completely dissolve, the specific dosage depends on the collocation of the metal compound, and the dosage is in the range of 10-20% of the total molar number of the metal ions), and the porous metal fiber net substrate is immersed into the aqueous solution of the catalyst particle reagent for 0.5-1 h.
(2) Preparing 0.5-1 mol/L NH of precipitant4Putting the OH aqueous solution into an ultrasonic tank.
(3) The porous metal fiber net base material is placed into a precipitator aqueous solution, ultrasonic waves are started simultaneously, so that metal hydroxide is precipitated in the base material, and the metal precipitate concentrated in the porous base material is continuously crushed by adopting a continuous oscillation mode with the ultrasonic wave power of 250-300W and the oscillation frequency of 50-60kHz, so that the agglomeration phenomenon of particles is avoided.
(4) Taking out the porous substrate uniformly attached with the catalyst metal precipitate particles, and drying in an oven at 80-150 ℃.
(5) The porous metal fiber mesh substrate uniformly attached with the metal precipitate particles is subjected to heat treatment in a hydrogen environment at the temperature of 300-1400 ℃, so that the precipitate is converted into nano metal catalyst particles and is attached to all surfaces of the porous substrate. To complete the nano-catalyst porous metal fiber net substrate with high catalytic reaction surface area.
The following examples 1-10 are provided to further illustrate the process of the nano-catalyst substrate.
Example 1
A process for preparing a nano catalyst substrate with high-efficiency catalytic function comprises the following steps:
(1) ZrO (NO)3)2·2H2O(0-0.2g)、Ni(NO3)2·6H2O(0-0.3g)、Cu(NO3)2·3H2O(0.05-0.3g)、AgNO3(0.05-0.3g)、Zn(NO3)2·6H2O(0-0.15g)、Ti(OC4H9)4(0.05-0.3g) is dissolved in 100m L deionized water and added into the deionized water for metallization16 mol/L concentrated nitric acid, 10-20% of the total moles of the compound metal ions, helps to dissolve and formulate an aqueous solution of 0.5 mol/L catalyst particle reagent, and the porous metal fiber web substrate is immersed in the aqueous solution of catalyst particle reagent for 0.5 h.
(2) 0.5 mol/L NH of precipitator is prepared4Putting the OH aqueous solution into an ultrasonic tank.
(3) And (2) putting the porous metal fiber mesh substrate into a precipitator aqueous solution, starting ultrasonic waves at the same time to precipitate metal hydroxide in the substrate, and continuously crushing the metal precipitate concentrated and precipitated in the porous substrate by adopting an ultrasonic wave power of 250W, a vibration frequency of 50kHz and a continuous vibration mode to avoid the agglomeration of particles.
(4) Taking out the porous substrate uniformly attached with the catalyst metal precipitate particles, and placing the porous substrate into an oven to be dried at 150 ℃.
(5) The porous metal fiber mesh substrate to which the metal precipitate particles are uniformly attached is heat-treated in a hydrogen atmosphere at 400 ℃, and the precipitate is converted into nano metal catalyst particles and attached to all surfaces of the porous substrate. To complete the nano-catalyst porous metal fiber net substrate with high catalytic reaction surface area.
Examples 2 to 6
The heat treatment temperature was varied, the process was the same as in example 1, and the specific heat treatment temperature is shown in the following table:
temperature of Heat treatment (. degree.C.)
Example 2 500
Example 3 800
Example 4 1000
Example 5 1200
Example 6 1400
As shown in FIG. 1, it can be seen from FIG. 1 that the heat treatment temperature of 800 ℃ or lower can maintain the appropriate nano-scale, in order to influence the size of the nano-catalyst particles by the heat treatment temperature in examples 1 to 6. And the heat treatment temperature of 300 c or more is set for removing the residual organic matter.
Examples 7 to 10
The process is the same as in example 1 except that the concentration of the aqueous solution of the catalyst particle reagent is different, and the preparation method of the aqueous solution of the catalyst particle reagent is shown in the following table:
Figure BDA0002448238510000071
as shown in FIG. 2, in the relationship between the concentration of the aqueous solution of the catalyst particle reagent and the specific surface area of the porous catalyst substrate prepared, the total surface area of the aqueous solution of the catalyst reagent is in an increasing trend in the concentration of 0.05 to 0.5 mol/L, but the total surface area is gradually increased in the range of 0.3 to 0.5 mol/L as observed by the specific surface analyzer, so the upper limit of the concentration of the aqueous solution of the catalyst reagent is set to 0.5 mol/L.
The embodiment of the invention also provides a process for preparing the nano catalyst substrate which can be applied to the energy field, such as catalytic hydrogen production and SOFC fuel cell cathode and anode preparation, and the process comprises the following steps:
(1) mixing Ni (NO)3)2·6H2O(0.1-0.3g)、Cu(NO3)2·3H2O(0.1-0.3g)、AgNO3(0-0.3g)、Zn(NO3)2·6H2O(0-0.2g)、Ti(OC4H9)4(0-0.15g) is dissolved in 100M L deionized water, 16 mol/L concentrated nitric acid which is 10-20% of the total molar number of metal ions of the metal compounds in the deionized water is added to help dissolve and prepare an aqueous solution of 0.05-0.5M catalyst particle reagent (optionally, the metal compounds can be mixed and prepared into an aqueous solution of 0.05-0.5 mol/L catalyst particle reagent, similar effects can be obtained, the using amount of each metal compound is in the range, when the metal compounds are not easy to dissolve, if the metal compounds are prepared by 100M L deionized water, the metal compounds are usually added into the solution one by the amount of 5M L nitric acid each time to help completely dissolve the metal compounds, the specific using amount depends on the collocation of the metal compounds, and is in the range of 10-20% of the total molar number of the metal ions), porous Al is added2O3The substrate is immersed in the aqueous solution of the catalyst particle reagent for 0.5-1 h.
(2) Preparing 0.5-1 mol/L NH of precipitant4Putting the OH aqueous solution into an ultrasonic tank.
(3) Porous Al2O3The base material is placed into the precipitant aqueous solution, ultrasonic wave is started simultaneously to precipitate the metal hydroxide in the base material, and the metal precipitate concentrated in the porous base material is continuously crushed by adopting the ultrasonic wave power of 250-300W, the oscillation frequency of 50-60kHz and the continuous oscillation mode, so that the agglomeration phenomenon of particles is avoided.
(4) Taking out the porous substrate uniformly attached with the catalyst metal precipitate particles, and drying in an oven at 80-150 ℃.
(5) Porous Al with uniformly adhered metal precipitate particles2O3The substrate is heat treated in a hydrogen atmosphere at 800 ℃ to convert the precipitate into nano metal catalyst particles, and the nano metal catalyst particles are attached to all surfaces of the porous substrate. Nano-catalyst porous Al for completing high catalytic reaction surface area2O3A substrate.
The following examples 11-15 are provided to further illustrate the process of the nano-catalyst substrate.
Example 11
A process for preparing a nano catalyst substrate with high-efficiency catalytic function comprises the following steps:
(1) mixing Ni (NO)3)2·6H2O(0.1-0.3g)、Cu(NO3)2·3H2O(0.1-0.3g)、AgNO3(0-0.3g)、Zn(NO3)2·6H2O(0-0.2g)、Ti(OC4H9)4(0-0.15g) is dissolved in 100M L deionized water, 16 mol/L concentrated nitric acid which is 10-20% of the total mole number of metal ions of the metal compound added into the deionized water is added to help dissolve and prepare an aqueous solution of 0.5M catalyst particle reagent, and porous Al is added2O3The substrate was immersed in an aqueous solution of the catalyst particle reagent for 1 hour.
(2) Preparation of precipitant 1 mol/L NH4Putting the OH aqueous solution into an ultrasonic tank.
(3) Porous Al2O3The base material is placed into a precipitator aqueous solution, ultrasonic waves are started simultaneously, so that the metal hydroxide is precipitated in the base material, and meanwhile, the metal precipitate concentrated and precipitated in the porous base material is continuously crushed by adopting an ultrasonic wave power of 300W, a vibration frequency of 60kHz and a continuous vibration mode, so that the agglomeration phenomenon of particles is avoided.
(4) Taking out the porous substrate uniformly attached with the catalyst metal precipitate particles, and placing the porous substrate into an oven to be dried at 80 ℃.
(5) Porous Al with uniformly adhered metal precipitate particles2O3The substrate is heat treated in a hydrogen atmosphere at 800 ℃ to convert the precipitate into nano metal catalyst particles, and the nano metal catalyst particles are attached to all surfaces of the porous substrate. Nano-catalyst porous Al for completing high catalytic reaction surface area2O3A substrate.
Example 12
A process for preparing a nano catalyst substrate with high-efficiency catalytic function comprises the following steps:
(1) mixing Ni (NO)3)2·6H2O(0.1-0.3g)、Cu(NO3)2·3H2O(0.1-0.3g)、AgNO3(0-0.3g)、Zn(NO3)2·6H2O(0-0.2g)、Ti(OC4H9)4(0-0.15g) dissolved in100M L deionized water, adding 16 mol/L concentrated nitric acid which is 10-20% of the total mole number of metal ions of the metal compound in the deionized water to help dissolve and prepare an aqueous solution of 0.05M catalyst particle reagent, and adding porous Al2O3The substrate was immersed in an aqueous solution of the catalyst particle reagent for 1 hour.
(2) Preparation of precipitant 1 mol/L NH4Putting the OH aqueous solution into an ultrasonic tank.
(3) Porous Al2O3The base material is placed into a precipitator aqueous solution, ultrasonic waves are started simultaneously, so that the metal hydroxide is precipitated in the base material, and meanwhile, the metal precipitate concentrated and precipitated in the porous base material is continuously crushed by adopting an ultrasonic wave power of 300W, a vibration frequency of 60kHz and a continuous vibration mode, so that the agglomeration phenomenon of particles is avoided.
(4) Taking out the porous substrate uniformly attached with the catalyst metal precipitate particles, and placing the porous substrate into an oven to be dried at 80 ℃.
(5) Porous Al with uniformly adhered metal precipitate particles2O3The substrate is heat treated in a hydrogen atmosphere at 800 ℃ to convert the precipitate into nano metal catalyst particles, and the nano metal catalyst particles are attached to all surfaces of the porous substrate. Nano-catalyst porous Al for completing high catalytic reaction surface area2O3A substrate.
Example 13
A process for preparing a nano catalyst substrate with high-efficiency catalytic function comprises the following steps:
(1) mixing Ni (NO)3)2·6H2O(0.1-0.3g)、Cu(NO3)2·3H2O(0.1-0.3g)、AgNO3(0-0.3g)、Zn(NO3)2·6H2O(0-0.2g)、Ti(OC4H9)4(0-0.15g) is dissolved in 100M L deionized water, 16 mol/L concentrated nitric acid which is 10-20% of the total mole number of metal ions of the metal compound added into the deionized water is added to help dissolve and prepare an aqueous solution of 0.1M catalyst particle reagent, and porous Al is added2O3The substrate was immersed in an aqueous solution of the catalyst particle reagent for 1 hour.
(2) Preparation of precipitant 1 mol/L NH4Putting OH aqueous solution into an ultrasonic grooveIn the body.
(3) Porous Al2O3The base material is placed into a precipitator aqueous solution, ultrasonic waves are started simultaneously, so that the metal hydroxide is precipitated in the base material, and meanwhile, the metal precipitate concentrated and precipitated in the porous base material is continuously crushed by adopting an ultrasonic wave power of 300W, a vibration frequency of 60kHz and a continuous vibration mode, so that the agglomeration phenomenon of particles is avoided.
(4) Taking out the porous substrate uniformly attached with the catalyst metal precipitate particles, and placing the porous substrate into an oven to be dried at 80 ℃.
(5) Porous Al with uniformly adhered metal precipitate particles2O3The substrate is heat treated in a hydrogen atmosphere at 800 ℃ to convert the precipitate into nano metal catalyst particles, and the nano metal catalyst particles are attached to all surfaces of the porous substrate. Nano-catalyst porous Al for completing high catalytic reaction surface area2O3A substrate.
Example 14
A process for preparing a nano catalyst substrate with high-efficiency catalytic function comprises the following steps:
(1) mixing Ni (NO)3)2·6H2O(0.1-0.3g)、Cu(NO3)2·3H2O(0.1-0.3g)、AgNO3(0-0.3g)、Zn(NO3)2·6H2O(0-0.2g)、Ti(OC4H9)4(0-0.15g) is dissolved in 100M L deionized water, 16 mol/L concentrated nitric acid which is 10-20% of the total mole number of metal ions of the metal compound added into the deionized water is added to help dissolve and prepare an aqueous solution of 0.2M catalyst particle reagent, and porous Al is added2O3The substrate was immersed in an aqueous solution of the catalyst particle reagent for 1 hour.
(2) Preparation of precipitant 1 mol/L NH4Putting the OH aqueous solution into an ultrasonic tank.
(3) Porous Al2O3The base material is placed into a precipitator aqueous solution, ultrasonic waves are started simultaneously, so that the metal hydroxide is precipitated in the base material, and meanwhile, the metal precipitate concentrated and precipitated in the porous base material is continuously crushed by adopting an ultrasonic wave power of 300W, a vibration frequency of 60kHz and a continuous vibration mode, so that the agglomeration phenomenon of particles is avoided.
(4) Taking out the porous substrate uniformly attached with the catalyst metal precipitate particles, and placing the porous substrate into an oven to be dried at 80 ℃.
(5) Porous Al with uniformly adhered metal precipitate particles2O3The substrate is heat treated in a hydrogen atmosphere at 800 ℃ to convert the precipitate into nano metal catalyst particles, and the nano metal catalyst particles are attached to all surfaces of the porous substrate. Nano-catalyst porous Al for completing high catalytic reaction surface area2O3A substrate.
Example 15
A process for preparing a nano catalyst substrate with high-efficiency catalytic function comprises the following steps:
(1) mixing Ni (NO)3)2·6H2O(0.1-0.3g)、Cu(NO3)2·3H2O(0.1-0.3g)、AgNO3(0-0.3g)、Zn(NO3)2·6H2O(0-0.2g)、Ti(OC4H9)4(0-0.15g) is dissolved in 100M L deionized water, 16 mol/L concentrated nitric acid which is 10-20% of the total mole number of metal ions of the metal compound added into the deionized water is added to help dissolve and prepare an aqueous solution of 0.3M catalyst particle reagent, and porous Al is added2O3The substrate was immersed in an aqueous solution of the catalyst particle reagent for 1 hour.
(2) Preparation of precipitant 1 mol/L NH4Putting the OH aqueous solution into an ultrasonic tank.
(3) Porous Al2O3The base material is placed into a precipitator aqueous solution, ultrasonic waves are started simultaneously, so that the metal hydroxide is precipitated in the base material, and meanwhile, the metal precipitate concentrated and precipitated in the porous base material is continuously crushed by adopting an ultrasonic wave power of 300W, a vibration frequency of 60kHz and a continuous vibration mode, so that the agglomeration phenomenon of particles is avoided.
(4) Taking out the porous substrate uniformly attached with the catalyst metal precipitate particles, and placing the porous substrate into an oven to be dried at 80 ℃.
(5) Porous Al with uniformly adhered metal precipitate particles2O3The substrate is heat-treated in a hydrogen atmosphere at 800 deg.C to convert the precipitate into nano-metal catalyst particles, which are attached to all of the porous substrateA surface. Nano-catalyst porous Al for completing high catalytic reaction surface area2O3A substrate.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the phrases "comprising … …" or "comprising … …" does not exclude the presence of additional elements in a process, method, article, or terminal that comprises the element. Further, herein, "greater than," "less than," "more than," and the like are understood to exclude the present numbers; the terms "above", "below", "within" and the like are to be understood as including the number.
Although the embodiments have been described, once the basic inventive concept is obtained, other variations and modifications of these embodiments can be made by those skilled in the art, so that the above embodiments are only examples of the present invention, and not intended to limit the scope of the present invention, and all equivalent structures or equivalent processes using the contents of the present specification and drawings, or any other related technical fields, which are directly or indirectly applied thereto, are included in the scope of the present invention.

Claims (10)

1. A process for preparing a nano catalyst substrate with high-efficiency catalytic function is characterized by comprising the following steps:
(1) immersing the porous substrate in an aqueous solution of a catalyst particle reagent until the aqueous solution is completely permeated;
(2) preparing a precipitant aqueous solution, and placing the precipitant aqueous solution into an ultrasonic tank;
(3) quickly placing the porous base material adhered with the catalyst particle reagent aqueous solution into the precipitant aqueous solution, starting ultrasonic waves at the same time to ensure that the catalyst particles are intensively precipitated in the porous base material, and simultaneously starting a continuous oscillation mode by adopting the ultrasonic waves to continuously break precipitates so as to avoid the catalyst particles from generating an agglomeration phenomenon;
(4) taking out the porous base material to which the precipitated catalyst particles are uniformly attached, and placing the porous base material into an oven for drying;
(5) and (3) carrying out heat treatment on the dried porous base material in a reducing environment, converting the precipitated catalyst particles into nano catalyst particles, and attaching the nano catalyst particles to all surfaces of the porous base material to obtain the nano catalyst base material with the efficient catalytic function.
2. The process of claim 1, wherein the aqueous solution of the catalyst particle reagent is prepared by: one or more metal compounds are dissolved in deionized water to prepare an aqueous solution of the catalyst particle reagent.
3. The process of claim 2, wherein the catalyst particle reagent is prepared by a method comprising: the metal compound is metal carbonate or metal nitrate or a metal ester compound; and/or
Dissolving metal compound in deionized water, adding proper amount of concentrated nitric acid to dissolve and compounding the water solution of catalyst particle reagent.
4. The process of claim 3, wherein the nitric acid is added in an amount of 10-20% of the total moles of metal ions of the metal compound charged into the deionized water; and/or
The concentration of the concentrated nitric acid is 16 mol/L.
5. The process of any one of claims 1 to 4, wherein the aqueous solution of the catalyst particle reagent has a concentration of 0.05 to 0.5 mol/L, and/or
The soaking time of the porous base material in the step (1) is 0.5-1 h.
6. The process of any one of claims 1-4, wherein the porous substrate is a porous polymer substrate, a porous metal substrate, or a porous ceramic substrate.
7. The process according to any one of claims 1 to 4, wherein the concentration of the aqueous precipitant solution is 0.5 to 1 mol/L.
8. The process according to any one of claims 1-4, wherein the ultrasonic power in step (3) is 250-300W, and the oscillation frequency is 50-60 kHz.
9. The process according to any one of claims 1 to 4, wherein the drying temperature in step (4) is 80 to 150 ℃.
10. The process according to any one of claims 1-4, wherein the heat treatment temperature in step (5) is 300-800 ℃.
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