Preparation method of nano platinum-loaded porous zeolite particle grafted long carbon chain molecule

Abstract

The invention relates to a preparation method of a nano platinum-loaded porous zeolite particle grafted long carbon chain molecule. The preparation method comprises the following steps: carrying out alkali fusion reaction and hydrolysis reaction on a silicon / aluminum mixture to obtain a hydrolysis solution; adding at least one interface agent and chloroplatinic acid into the hydrolysis solution, carrying out hydrothermal reaction, and drying to obtain nano platinum-loaded porous zeolite (silicon / zinc element) particles; adding the nano-platinum-loaded porous zeolite particles into a grafting molecule solution, and bonding silicon atoms of silyl groups with oxygen atoms of silicon groups on the surfaces of the nano-platinum-loaded porous zeolite particles to form siloxane bonds, so as to obtain the nano-platinum-loaded porous zeolite particles with long carbon chain molecules grafted on the surfaces; therefore, the composite material can be really combined with a polymer colloid and then uniformly coated on a plate, so that the deodorization and antiviral effects can still be effectively achieved after the plate is washed by water for many times.

Description

Technical Field

[0001] The present invention relates to a preparation method of nano-platinum-loaded porous zeolite particles grafted with long carbon chain molecules, and more particularly to a preparation method capable of obtaining nano-platinum-loaded porous zeolite (silicon / zinc element) particles with long carbon chain molecules grafted on the surface, thereby allowing the nano-platinum-loaded porous zeolite particles with long carbon chain molecules grafted on the surface to be effectively combined with a polymer colloid (such as UV glue). Background Art

[0002] Since sulfur functional groups are commonly found in amino acids, many bacteria and viruses contain sulfur in their structures. Sulfur can easily combine with platinum, which makes the sulfur in the structure of bacteria and viruses combine with platinum, thereby making the bacteria and viruses inactive and preventing them from replicating. In addition, nano-platinum also carries an electric charge and can kill bacteria and viruses through the charge. Therefore, nano-platinum has a dual antibacterial mechanism.

[0003] In addition, the human body's sense of smell, whether it is pleasant or unpleasant, has a profound impact on people's emotions and thoughts, especially in certain special environments, such as hospitals, public toilets, storage rooms and garbage collection environments, which face major problems with the sense of smell. However, zeolite is a natural raw material with strong adsorption properties, and can be used in coatings, colloids and solvents, becoming a good material for adsorption and deodorization in indoor and outdoor spaces.

[0004] Therefore, how to develop a method of loading nano-platinum particles on zeolite particles, and then grafting the formed nano-platinum loaded porous zeolite particles, and combining them with a polymer material, which can be applied to various coatings, paints, colloids, etc., and can play a long-term deodorizing and antiviral role in the environment, is the main problem to be solved by the present invention. Summary of the invention

[0005] The object of the present invention is to provide a method for preparing nano-platinum-loaded porous zeolite particles grafted with long carbon chain molecules, the preparation method comprising: S1. Prepare a silicon / aluminum mixture: take a silicon precursor and an aluminum precursor and mix them to obtain the silicon / aluminum mixture.

[0006] S2. Performing an alkali fusion reaction and a hydrolysis reaction in sequence: adding at least one alkaline substance to the silicon / aluminum mixture obtained in the first step and performing an alkali fusion reaction to obtain an alkali fusion reactant, and then adding deionized water to the alkali fusion reactant and performing a hydrolysis reaction to obtain a hydrolysis solution.

[0007] S3, making a nano-platinum-loaded porous zeolite (silicon / zinc element) particle: adding at least one interfacial agent to the hydrolysis solution obtained in step S2, taking chloroplatinic acid and adding it to the hydrolysis solution, and then adding a sulfuric acid solution to adjust the pH value of the hydrolysis solution, and finally subjecting the hydrolysis solution to a hydrothermal reaction. After the hydrothermal reaction is completed, removing the liquid part, and then drying, to obtain a nano-platinum-loaded porous zeolite particle; this step can obtain a powder of the nano-platinum-loaded porous zeolite particle.

[0008] S4, grafting the nano-platinum-loaded porous zeolite particles: the nano-platinum-loaded porous zeolite particles obtained in step S3 are subjected to a rinsing procedure, and then a grafting molecule procedure is performed after the rinsing procedure is completed. The grafting molecule procedure first prepares at least one grafting molecule and dissolves it in an organic solvent to obtain a grafting molecule solution, and the nano-platinum-loaded porous zeolite particle powder is added to the grafting molecule solution. At this time, one end of the grafting molecule is a silane group, so that the silicon atom of the silane group and the oxygen atom of the silicon group on the surface of the nano-platinum-loaded porous zeolite particles are bonded to form a siloxane bond, that is, the nano-platinum-loaded porous zeolite particles with long carbon chain molecules grafted on the surface are obtained.

[0009] Furthermore, in the silicon / aluminum mixture, the molar number of silicon is 1 to 5 times that of aluminum; the silicon precursor is one of sodium silicate, tetramethylsilane, tetraethoxysilane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethoxysilane or vinyltriethoxysilane or vinyltri(2-methoxyethoxy)silane; and the aluminum precursor is one of aluminum sulfate, aluminum chloride, aluminum iodide, aluminum nitrate or aluminum sulfate.

[0010] Furthermore, the alkaline substance is one or a combination of sodium hydroxide or potassium hydroxide, and the weight of the alkaline substance is 1 to 4 times the weight of the silicon / aluminum mixture.

[0011] Furthermore, the concentration of the interfacial agent in the hydrolysis solution is between 0.05 and 0.5 wt %; and the concentration of the chloroplatinic acid in the hydrolysis solution is between 0.005 and 0.03 wt %.

[0012] Furthermore, the interface agent is one or a combination of more than one of sodium dodecylbenzene sulfonate, polydiallyldimethylammonium chloride, polyethylene glycol octylphenyl ether, hexadecyltrimethylammonium bromide, sodium dodecyl sulfate, ethylene glycol stearate, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide or potassium hydrogen phthalate.

[0013] Furthermore, in S3, the sulfuric acid solution is added to adjust the pH value of the hydrolysis solution, and the pH value is between 9 and 11.

[0014] Furthermore, the grafted molecule is dissolved in the organic solvent to prepare a grafted molecule solution with a concentration of 0.1-5 Mm.

[0015] Furthermore, the grafted molecule is one or a combination of thiolpropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, 3-(2,3-epoxypropyloxy)propyltrimethoxysilane or 3-(methacryloyloxy)propyltrimethoxysilane.

[0016] Furthermore, the organic solvent is one of dimethyl sulfoxide, dimethylformamide, acetyl dimethylamide or tetrahydrofuran.

[0017] In addition, the powder of the nano-platinum-loaded porous zeolite particles with long carbon chain molecules grafted on the surface is further added to a polymer colloid to make a coating, paint, glue, etc.

[0018] Thus, by using the above preparation method, nano-platinum-loaded porous zeolite particles with long carbon chain molecules grafted on the surface are obtained; therefore, in further application, the powder of nano-platinum-loaded porous zeolite particles with long carbon chain molecules grafted on the surface can be added to a polymer colloid (such as UV glue). Since the polymer colloids are all hydrocarbons, the nano-platinum-loaded porous zeolite particles with long carbon chain molecules grafted on the surface can be stably combined with the polymer colloid to make a coating, paint, colloid, etc. with long-lasting deodorizing and antibacterial properties. After being coated on a plate or a wall, even if the plate or the wall is washed with water for many times, the deodorizing and antiviral effects can still be effectively achieved, thereby avoiding the existing deodorizing coating which is only a traditional physical bonding embedding preparation method. Once washed with water, the zeolite particles are very easy to physically disappear, resulting in the loss of deodorizing effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.

[0020] Figure 1 : The present invention provides a schematic structural diagram of a nano-platinum-loaded porous zeolite particle.

[0021] Figure 2 The present invention provides a schematic structural diagram of a nano-platinum-loaded porous zeolite particle with a long carbon chain molecule grafted onto its surface.

[0022] Figure 3 : A flow chart of the preparation method of nano-platinum-loaded porous zeolite particles grafted with long carbon chain molecules.

[0023] Description of Reference Numerals 1. Zeolite particles; 2. Nano-platinum particles; 3. Long carbon chain molecules. DETAILED DESCRIPTION

[0024] In order to facilitate and briefly understand the other features and advantages of the present invention and the effects achieved by the present invention, the present invention is now described in detail with reference to the accompanying drawings. The following embodiments further illustrate the viewpoints of the present invention in detail, but are not intended to limit the scope of the present invention in any way.

[0025] See also Figures 1 to 3 As shown, the present invention discloses a method for preparing nano-platinum-loaded porous zeolite particles grafted with long carbon chain molecules, the preparation method comprising: Step 1 (S1): prepare a silicon / aluminum mixture; take a silicon precursor and an aluminum precursor and mix them to obtain a silicon / aluminum mixture. In the first step, the molar ratio of silicon to aluminum is 1 to 5, that is, the molar number of silicon is 1 to 5 times that of aluminum. The silicon precursor is one of sodium silicate, tetramethylsilane, tetraethoxysilane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethoxysilane, vinyltriethoxysilane or vinyltri(2-methoxyethoxy)silane. The aluminum precursor is one of aluminum sulfate, aluminum chloride, aluminum iodide, aluminum nitrate or aluminum sulfate.

[0026] Step 2 (S2): perform an alkali fusion reaction and a hydrolysis reaction in sequence; add at least one alkaline substance to the silicon / aluminum mixture obtained in step 1 and perform an alkali fusion reaction to obtain an alkali fusion reactant; then add deionized water to the alkali fusion reactant and perform a hydrolysis reaction to obtain a hydrolysis solution. In the second step, the alkaline substance is one or more combinations of strong alkaline substances such as sodium hydroxide and potassium hydroxide, and the alkaline substance is 1 to 4 times the weight of the silicon / aluminum mixture. For example, if the weight of the silicon / aluminum mixture is 1 gram, the weight of the alkaline substance can be 1 gram to 4 grams. The alkali fusion reaction is to uniformly stir and mix the silicon / aluminum mixture and the alkaline substance, put them in a crucible, and react at 350°C to 600°C. The reaction time is 30 to 90 minutes. After the reaction time is over, the alkali fusion reactant is obtained. The hydrolysis reaction is to add the alkali molten reactant to deionized water to adjust the weight concentration of 1-5 wt% alkali molten aqueous solution, then put the alkali molten aqueous solution into a closed tank, and put it into an oven at a temperature of 105°C-140°C for hydrolysis reaction. After the hydrolysis reaction, the hydrolysis solution is obtained.

[0027] Step 3 (S3): preparing a nano-platinum-loaded porous zeolite particle; adding at least one interfacial agent to the hydrolysis solution obtained in step 2, adding chloroplatinic acid (Hexachloro-Platinic; its chemical formula is H2PtCl6) to the hydrolysis solution, and then adding a sulfuric acid solution to adjust the pH value of the hydrolysis solution, and finally subjecting the hydrolysis solution to a hydrothermal reaction. After the hydrothermal reaction is completed, removing the liquid portion, and obtaining a nano-platinum-loaded porous zeolite (silicon / zinc element) particle, such as Figure 1 As shown, a plurality of nano-platinum particles 2 are carried on zeolite particles 1; wherein, after removing the liquid portion, the solid obtained is placed in an oven at 450°C to 600°C for 2.5 to 5 hours of baking, and the product is a powder of nano-platinum-loaded porous zeolite particles (silicon / zinc elements). The hydrothermal reaction is to place the hydrolysis solution in a closed container and then place it in an oven, the oven temperature is set to 105°C to 125°C, and the hydrothermal reaction time is 16 to 24 hours. In the third step, the concentration of the interfacial agent in the hydrolysis solution is between 0.05 and 0.5 wt%. In the third step, the concentration of chloroplatinic acid in the hydrolysis solution is between 0.005 and 0.03 wt%. In the third step, sulfuric acid is added to adjust the pH value of the hydrolysis solution, and the pH value is between 9 and 11. The interfacial agent is one or a combination of the following: sodium dodecylbenzenesulfonate (SDBS), polydiallyldimethylammonium chloride (PDDA), t-Octylphenoxypolyethoxyethanol (Triton X-100), cetyltrimethylammonium bromide (CTAB), sodium dodecylsulfate (SDS), polyethylene glycol monostearate (PEG-MS), n-dodecyltrimethyl-ammonium chloride (DTAC), cetyltrimethylammonium bromide (DTAB), potassium hydrogen phthalate, etc.

[0028] Step 4 (S4): grafting the nano-platinum-loaded porous zeolite particles; performing a rinsing procedure on the nano-platinum-loaded porous zeolite particles obtained in step 3, and then performing a grafting molecule procedure after the rinsing procedure is completed and dried; wherein the grafting molecule procedure is to first prepare at least one or more grafting molecules and dissolve them in an organic solvent to obtain a grafting molecule solution, and then add the nano-platinum-loaded porous zeolite (silicon / zinc element) particles (powder) to the grafting molecule solution, at which time one end of the grafting molecule is a silane group, so that the silicon atom of the silane group will bond with the oxygen atom of the silicon group on the surface of the nano-platinum-loaded porous zeolite particles to form a siloxane bond, that is, the nano-platinum-loaded porous zeolite particles with long carbon chain molecules grafted on the surface are obtained, such as Figure 2As shown, a plurality of nano-platinum particles 2 are carried on the zeolite particles 1, and a plurality of long carbon chain molecules 3 are grafted on the surface of the zeolite particles 1. The rinsing procedure is to rinse the nano-platinum-loaded porous zeolite particles with deionized water for at least 5 to 10 times; then, rinse with 99% or more methanol for 5 to 10 times; then, rinse with 1% to 10% dilute hydrochloric acid aqueous solution for 5 to 10 times; finally, rinse with deionized water for at least 5 to 10 times; after completion, place in an oven for drying, and pass nitrogen or inert gas in the oven for 10 to 30 minutes until the nano-platinum-loaded porous zeolite particles are completely dried. In the fourth step, one or more grafted molecules are dissolved in an organic solvent to prepare a grafted molecule solution with a concentration of 0.1 to 5 Mm. In the fourth step, nano-platinum-loaded porous zeolite particles (powder) are added to the grafting molecule solution, the weight concentration of which is between 1wt% and 10wt%, and the mixing time is between 24 hours and 72 hours. The grafting molecule is one or a combination of 3-mercaptopropyltrimethoxysilane (MPTMS), 3-aminopropyltriethoxysilane (APTMS), N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (APTES), 3-(2,3-glycidoxypropyltrimethoxysilane (GPTMS), 3-(methacryloyloxy)propyltrimethoxysilane (MCOPTMS). The organic solvent is one of dimethylsulfoxide (DMSO), dimethylformamide (DMF), N,N-dimethyl acetamid (DMAC), tetrahydrofuran (THF), etc.

[0029] Thus, by using the above-mentioned preparation method, the surface of the nano-platinum-supported porous zeolite particles can be grafted to grow long carbon chain molecules. Since the colloid or polymer colloid is a hydrocarbon, the surface of the nano-platinum-supported porous zeolite particles is grafted with a plurality of long carbon chain molecules, so that the nano-platinum-supported porous zeolite particles can be closely bonded with the colloid or polymer colloid. The polymer colloid can be acrylic resin, epoxy resin, acrylate, cyanoacrylate, methacrylate, melamine, etc.

[0030] When the nano-platinum-loaded porous zeolite particles grafted with long carbon chain molecules disclosed in the present invention are further applied, the powder of the nano-platinum-loaded porous zeolite particles grafted with long carbon chain molecules can be added to a polymer colloid (such as UV glue). Since the polymer colloids are all hydrocarbons, the nano-platinum-loaded porous zeolite particles grafted with long carbon chain molecules on the surface can be stably combined with the polymer colloid to make a coating, paint or adhesive with long-lasting deodorizing and antibacterial effects, which is then coated on the board or wall, so that the board or wall can still achieve the deodorizing and antiviral effects after multiple water washings, and completely solves the problem that the existing deodorizing coating is only prepared by the traditional physical bonding and embedding method. Once washed with water, the zeolite particles are very easy to physically disappear, resulting in the loss of the desired effects such as deodorizing.

[0031] Please refer to the attachment 1 in the attachment for the present invention to try to add nano-platinum-loaded porous zeolite particles grafted with long carbon chain molecules to a polymer colloid for coating on a plate for H1N1 virus antibacterial test results. The aging test results for 10 years show that the coating with the nano-platinum-loaded porous zeolite particles grafted with long carbon chain molecules of the present invention has an antiviral activity value of >3.37 and an antiviral activity rate of >99.96%; thus, a long-lasting antibacterial effect is indeed achieved.

[0032] Please refer to Attachment 2 of the Attachments, which shows that the present invention attempts to apply nano-platinum-loaded porous zeolite particles grafted with long carbon chain molecules to a polymer colloid, and then applies the nano-platinum-loaded porous zeolite particles to a plate for formaldehyde, ammonia, and hydrogen sulfide residue testing. The aging test results after 10 years show that the formaldehyde removal rate is 94.6%, the ammonia removal rate is 92.8%, and the hydrogen sulfide removal rate is 90.9%; thus, a long-lasting deodorizing effect is indeed achieved.

[0033] Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

Claims

1. A method for preparing nano-platinum-supported porous zeolite particles grafted with long carbon chain molecules, characterized in that: The preparation method comprises the following steps: S1. preparing a silicon / aluminum mixture: taking a silicon precursor and an aluminum precursor and mixing them to obtain the silicon / aluminum mixture; S2, sequentially performing an alkali fusion reaction and a hydrolysis reaction: adding at least one alkaline substance to the silicon / aluminum mixture and performing the alkali fusion reaction to obtain an alkali fusion reactant, and then adding deionized water to the alkali fusion reactant and performing the hydrolysis reaction to obtain a hydrolysis solution; S3, preparing a nano-platinum-loaded porous zeolite particle: adding at least one interfacial agent to the hydrolysis solution, adding chloroplatinic acid to the hydrolysis solution, adding sulfuric acid solution to adjust the pH value of the hydrolysis solution, and finally subjecting the hydrolysis solution to a hydrothermal reaction. After the hydrothermal reaction is completed, removing the liquid portion, thus obtaining the nano-platinum-loaded porous zeolite particle; S4, grafting the nano-platinum-loaded porous zeolite particles: the nano-platinum-loaded porous zeolite particles are subjected to a rinsing procedure, and then a grafting molecule procedure is performed after the rinsing procedure is completed. The grafting molecule procedure is to first prepare at least one grafting molecule and dissolve it in an organic solvent to obtain a grafting molecule solution, and the nano-platinum-loaded porous zeolite particles are added to the grafting molecule solution. At this time, one end of the grafting molecule is a silane group, so that the silicon atom of the silane group will bond with the oxygen atom of the silicon group on the surface of the nano-platinum-loaded porous zeolite particles to form a siloxane bond, that is, the nano-platinum-loaded porous zeolite particles with long carbon chain molecules grafted on the surface are obtained.

2. A method for preparing nano-platinum-loaded porous zeolite particles grafted with long carbon chain molecules as claimed in claim 1, characterized in that: In the silicon / aluminum mixture, the molar number of silicon is 1 to 5 times that of aluminum; the silicon precursor is one of sodium silicate, tetramethylsilane, tetraethoxysilane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethoxysilane, vinyltriethoxysilane or vinyltri(2-methoxyethoxy)silane; and the aluminum precursor is one of aluminum sulfate, aluminum chloride, aluminum iodide, aluminum nitrate or aluminum sulfate.

3. A method for preparing nano-platinum-supported porous zeolite particles grafted with long carbon chain molecules as claimed in claim 1, characterized in that: The alkaline substance is one of sodium hydroxide and potassium hydroxide or a combination of more than one of them, and the alkaline substance is 1 to 4 times the weight of the silicon / aluminum mixture.

4. A method for preparing nano-platinum-loaded porous zeolite particles grafted with long carbon chain molecules as claimed in claim 1, characterized in that: The concentration of the interfacial agent in the hydrolysis solution is between 0.05 and 0.5 wt %; and the concentration of the chloroplatinic acid in the hydrolysis solution is between 0.005 and 0.03 wt %.

5. A method for preparing nano-platinum-supported porous zeolite particles grafted with long carbon chain molecules as claimed in claim 1, characterized in that: The interface agent is one or a combination of the following: sodium dodecylbenzene sulfonate, polydiallyldimethylammonium chloride, polyethylene glycol octylphenyl ether, hexadecyltrimethylammonium bromide, sodium dodecyl sulfate, ethylene glycol stearate, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide or potassium hydrogen phthalate.

6. A method for preparing nano-platinum-loaded porous zeolite particles grafted with long carbon chain molecules as claimed in claim 1, characterized in that: In S3, the sulfuric acid solution is added to adjust the pH value of the hydrolysis solution, and the pH value is between 9 and 11.

7. A method for preparing nano-platinum-supported porous zeolite particles grafted with long carbon chain molecules as claimed in claim 1, characterized in that: The grafted molecule is dissolved in the organic solvent to prepare a grafted molecule solution with a concentration of 0.1-5 Mm.

8. A method for preparing nano-platinum-loaded porous zeolite particles grafted with long carbon chain molecules as claimed in claim 1, characterized in that: The grafted molecule is one or a combination of mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, 3-(2,3-epoxypropyloxy)propyltrimethoxysilane or 3-(methacryloyloxy)propyltrimethoxysilane.

9. A method for preparing nano-platinum-supported porous zeolite particles grafted with long carbon chain molecules as claimed in claim 1, characterized in that: The organic solvent is one of dimethyl sulfoxide, dimethylformamide, acetyl dimethylamine or tetrahydrofuran.

10. A method for preparing nano-platinum-loaded porous zeolite particles grafted with long carbon chain molecules as claimed in claim 1, characterized in that: The powder of the nano-platinum-loaded porous zeolite particles with long carbon chain molecules grafted on the surface is further added into a polymer colloid to make a coating, paint, glue, etc.

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