CN101934219B - Porous carbon material having effects of long-acting nanometer antibacterium and accelerant, and preparation method thereof - Google Patents
Porous carbon material having effects of long-acting nanometer antibacterium and accelerant, and preparation method thereof Download PDFInfo
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- CN101934219B CN101934219B CN2009101500668A CN200910150066A CN101934219B CN 101934219 B CN101934219 B CN 101934219B CN 2009101500668 A CN2009101500668 A CN 2009101500668A CN 200910150066 A CN200910150066 A CN 200910150066A CN 101934219 B CN101934219 B CN 101934219B
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Abstract
The invention provides a porous carbon material having effects of long-acting nanometer antibacterium and accelerant, and a preparation method thereof. The method comprises the steps that zinc oxide nano particles and silver salt are added into a water solution, the water solution is retained at a first temperature, the water solution is formed by mixing water, alkaline liquor, ammonia water or ammonia, water-soluble acryl powder, an aqueous adhesive and the like, the silver salt is transformed to silver amide coordination ions, the zinc oxide nano particles and the silver amide coordination ions are uniformly dispersed by water-soluble acryl, and an adhesive is covered on the surfaces of the zinc oxide nano particles and the silver amide coordination ions; the main body of the porous carbon material is baked to a second temperature, then is immersed in the water solution to achieve the penetration of the zinc oxide nano particles and the silver amide coordination ions into the holes of the porous carbon material body; the formaldehyde or the glucose is added to reduce the silver amide coordination ions to silver nano particles; and the porous carbon material is dried to realize the stable adherence of the zinc oxide nano particles and the silver nano particles on the surface of the carbon material and on the inner walls of the poles. The porous carbon material has the effectsof long-acting antibacterium, corrosion resistance and accelerant.
Description
Technical field
The present invention is porous carbon material of a kind of tool long-acting type nano-antibacterial and effect of catalyst and preparation method thereof.
Background technology
Before 18th century, the human absorption property of promptly finding charcoal, and be used in sugared decolouring; During 20th century, because of succeeding in developing of activated carbon (activated carbon) manufacturing technology, activated carbon replaces charcoal then; And be widely used in gradually in the industry, activated carbon has excellent characterization of adsorption, can be as the base material of gas or the absorption of various matter selective; Of many uses, remove widely various industry and adopt, as: in the production technology of chemicals, food and pharmaceuticals in order to carry out outside the purposes such as purifying products, decolouring, detoxification, dechlorination and solvent recovery; In recent years, the new line of social enviroment protection consciousness also makes activated carbon be used in the environmental protection fields such as purifying of wastewater treatment, exhaust-gas treatment, water purification, pure qi (oxygen) or other gas in a large number; Therefore, the active of activated carbon market mainly is the driving of environmental protection subject under discussion, especially; The processing that water and air pollutes, this phenomenon is obvious especially in advanced country, the environmental regulation harsh country of healing; The consumption of activated carbon is also bigger, and the consumption of other conventional use, annually also increases with 2～3% ratio.
The principal component of activated carbon is a carbon, and is mixed with material chemical combination such as a spot of hydrogen, oxygen, nitrogen, sulphur and forms, and is the complicated porous material of black and surface; Structure is formed six rings of carbon, and particle shape can have the irregular particle of 6～120 mesh granularities by cylindrical coarse granule to the fine powder particle; Particle diameter is generally 1～6mm; Length is about 0.7～4 times of particle diameter, activated carbon odorless, tasteless, water insoluble and organic solvent; The organic polymer material there is very strong absorption affinity, and the micro constitutent in the liquid phase, pigment, odorous substance etc. are had the removal ability of height.Nearly all carbonaceous material all can pass through different procedures and process activated carbon, and procedure comprises carbonization (Carbonization) technology and activation (Activation) technology, and wherein carbonization technique is that raw material is heated; Dry under 170 to 600 degree Celsius, make about 80% carbonization of original organic matter, carbonization is under the condition of anoxic and high temperature, to carry out; With structure with raw material pyrolysis (Pyrolysis) formation many ceasmas property, most non-carbon between the carbon period, as: hydrogen and oxygen; Can be removed and become escaping gas by the cracking program of raw material, because the combination of the carbon atom of carbide belongs to the laminated structure of aromatic ring; Very irregular, so can form some cracks, these cracks can form more flourishing pore space structure in the postorder activating process; Owing on the formed hydrocarbon of carbonization technique can the carbon atom attached to the active carbon edge, stopped up the part crack, and then influenced its adsorption capacity; So must increase the formation of hole by follow-up activating process; Activating process is to utilize steam or chemical substance to remove tar material and the pyrolysis product of carbonisation savings in fissured structure, and utilizes CO and the H that produces in the priming reaction
2The mist of forming; Burning heating carbide to suitable temperature (800 to 1000 degree Celsius approximately); But with the wherein all decomposed substances of burn off, produce flourishing pore space structure and huge specific area, make it possess very strong adsorption capacity; Therefore, activated carbon should be referred to as the carbonaceous material through activating process.As for bamboo carbon or be equipped with carbon material such as long carbon; Owing to be to separate by the plant carbon heat-transmission to form,, itself promptly possessed flourishing pore space structure and huge specific area so need not extra activating process; Form very strong adsorption capacity; So the present invention following chat and " porous carbon material ", general reference activated carbon, the bamboo carbon or the particle of material such as long carbon fully close first Chen Ming.
Generally speaking, the adsorption capacity of porous carbon material is broadly divided into following two kinds:
(1) adhesive ability: there are very many small holes porous carbon material the inside, and its specific area is bigger, and the hole of promptly representing porous carbon material the more; Adhesive ability better, so after getting into the hole of porous carbon material when impurity, will be stuck in the hole and can't get out; Also can not impurity be washed out with general method for washing, because, no matter liquid, gaseous state or solid-state impurity; Generally all have different size, but have only identical with the hole of porous carbon material, could hole attached to porous carbon material in; Too big or too little person is then not all right for particle diameter; Therefore, organic matters such as the bacterium that particle diameter is too little in water or the air, mould and virus still can pass through the hole of porous carbon material, and can't be attached in porous carbon material;
(2) attraction power: porous carbon material surface positively charged, thus can attract some electronegative small materials, as: organic matters such as bacterium, mould and virus; Though porous carbon material itself is renewable; Generally under high pressure 100BAR and 300 degree Celsius, can the material that adsorb in the porous carbon material be driven out of, be referred to as " desorption "; But the adsorption capacity of handling the porous carbon material of regeneration through desorption is merely original 40～60%.
In recent years, along with the progress of material progress, water in the human habitat and air-polluting problem are also serious day by day, and various water purification catridge, air filter screen and mouth mask have become in household and the office in order to improve the indispensable running stores of water and air quality.Especially, the TaiWan, China located in subtropical zone belongs to the weather kenel of moist high temperature all the year round; Organic matters such as bacterium, mould and virus are multiplied especially easily, and therefore, the water purification catridge in water cleaning systems, air conditioner ventilating system and the mouth mask, air filter screen and filter material must be cleared up regularly and change; Otherwise; These water purification catridges, air filter screen and mouth mask can become the hotbed that grows mould, bacterium and germ in water and the air on the contrary, and the harm to health causes should not be underestimated in fact.
In view of this, in recent years, many dealers have been applied to porous carbon material in the design and manufacturing of filter materials such as water purification catridge, air filter screen and mouth mask; In the hope of by the powerful adsorption capacity of porous carbon material, adsorbed water and airborne various suspended particulates, but; Because microorganisms such as mould, bacterium and germ are that volume is minimum in the suspended particulates; And be prevalent in occurring in nature, so, unquestionable; Harm (as: causing allergy, infection or toxic reaction) to human body causes is also quick and obvious, even produces fatefulue lethality.The filter material that the porous carbon material that is widely used is now processed, though ability adsorbed water and airborne particulates and microorganism; Itself does not but possess antibiotic and sterilization effects fully; So the organic matters such as bacterium, mould and virus that some particle diameter is too little still can pass through the hole of porous carbon material, to the harm that human body causes, other; When the suspended particulates of accumulation absorption in the porous carbon material and microorganism reach some; Can lose the clean effect of its due filter to the greatest extent, and become the hotbed that mould, bacterium and germ grow because of the accumulating of organic suspension particulate and microorganism on the contrary.
Therefore, how to design a kind of porous carbon material of novelty, the feasible filter materials of processing with this porous carbon material such as water purification catridge, air filter screen and mouth mask; Outside decapacitation adsorbed water and airborne particulates and the microorganism; Still can produce photocatalyst and catalysis having under light or the unglazed environment, realize organic degradeds such as bacterium, virus and moulds; To produce excellent antibiotic and sterilization effect, promptly become the important topic that the present invention inquires in this desire.
Summary of the invention
Because the problems that filter materials such as aforementioned conventional water purification catridge, air filter screen and mouth mask exist; The inventor is through the permanent research and experiment of making great efforts; Finally development and Design goes out porous carbon material of a kind of tool long-acting type nano-antibacterial of the present invention and effect of catalyst and preparation method thereof; In the hope of making outside the various filter material decapacitation adsorbed water and airborne particulates and microorganism that this porous carbon material processes, still can possess antibiotic and sterilization effects.
An object of the present invention is to be to provide the preparation method of the porous carbon material of a kind of tool long-acting type nano-antibacterial and effect of catalyst.
Another object of the present invention is the porous carbon material that is to provide a kind of tool long-acting type nano-antibacterial and effect of catalyst.
The invention provides a kind of preparation method of porous carbon material; Said method is an osmotic effect of utilizing action of thermal difference to produce; Make the water-soluble fluid power that contains zinc oxide nano-particle and ammonification silver complex ion (complex ions) successfully infiltrate the surface of porous carbon material main body and the hole of inner dense distribution; With at this porous carbon material after high temperature drying is handled white drying; On its surface and the hole inwall form the nanoparticle composite membrane of zinc oxide and silver, make this porous carbon material possess antibiotic, the anticorrosion and effect of catalyst of long-acting type.Specifically, the preparation method of porous carbon material of the present invention is with zinc oxide nano-particle and silver salt powder (as: silver nitrate (AgNO
3), silver acetate (CH
3COOAg) etc.),, be added in the aqueous solution with a predetermined percentage by weight; The two is evenly mixed in this aqueous solution; And making this aqueous solution remain on first temperature, this aqueous solution is by compositions such as water (as: deionized water or pure water etc.), alkali lye (like the KOH or the NaOH aqueous solution), ammoniacal liquor (or ammonia), water-soluble acryl powder and water-soluble adhesive agents, according to predetermined percentage by weight; Evenly mix; Said alkali lye is that silver salt is transformed into silver hydroxide, because silver hydroxide can form brown precipitate in the aqueous solution, can't be evenly dispersed in the aqueous solution; So still must in the aqueous solution, add ammoniacal liquor (or ammonia), changing into the precipitating ion with silver hydroxide is the silver-colored complex ion (Ag (NH of ammonification
3)
+ 2); Said water-soluble acryl powder is a water soluble dispersing agent; Its effect is after being dissolved in the water; Zinc oxide nano-particle and ammonification silver complex ion evenly and dispersedly is suspended in the aqueous solution, and the effect of said water-soluble adhesive agent is when zinc oxide nano-particle and ammonification silver complex ion evenly is mixed to the aqueous solution, can be coated on the surface of zinc oxide nano-particle and ammonification silver complex ion; With porous carbon material main body (as: activated carbon, bamboo carbon or be equipped with traditional porous carbon material such as long carbon; These carbon materials are the raw materials that are used as in the method for the present invention; Form the porous carbon material with zinc oxide and Nano silver grain of the present invention through method processing of the present invention; Distinguish for porous carbon material that this is not contained as yet zinc oxide and Nano silver grain and the porous carbon material that has zinc oxide and Nano silver grain through method processing back of the present invention in the technical scheme of the present invention; The spy is called " porous carbon material main body " with porous carbon material that this does not contain the nano particle of zinc oxide and silver as yet) toast (for example inserting a baking oven) to second temperature; Wherein this second temperature is greater than first temperature, and temperature range is at 20～80 degree Celsius; This porous carbon material main body is immersed in the said aqueous solution; Carry out the stirring of a scheduled time; Making can be because of action of thermal difference between this porous carbon material main body and the aqueous solution; And the generation osmotic effect makes the said aqueous solution be able to successfully infiltrate through the surface of this porous carbon material main body and the hole of inner dense distribution, makes zinc oxide nano-particle and ammonification silver complex ion to infiltrate described hole along with the aqueous solution; Next, in the aqueous solution, add the formaldehyde (HCHO) or the glucose of a predetermined weight percent, and continue to stir a scheduled time, the ammonification silver complex ion that makes formaldehyde or glucose can will infiltrate in this porous carbon material main body hole is reduced into Nano silver grain; The porous carbon material that has zinc oxide nano-particle and Nano silver grain in this porous carbon material main body hole is taken out in this aqueous solution; Carrying out high temperature drying handles; With behind this porous carbon material bone dry; Make the water-soluble adhesive agent that zinc oxide nano-particle and Nano silver grain in the described hole can its surperficial institute coating of mat; Stably, form the nanoparticle composite membrane of zinc oxide and silver, make that this porous carbon material possesses that long-acting type is antibiotic, sterilization, anticorrosion and effect of catalyst attached to the surface and the hole inwall of this porous carbon material main body.
The invention provides the porous carbon material of a kind of tool long-acting type nano-antibacterial and effect of catalyst, it comprises: a porous carbon material main body, its surface and in be intensively distributed with hole; Water-soluble adhesive agent is distributed in said porous carbon material body surfaces and the interior hole thereof, and under the state of this porous carbon material bone dry, can be attached to the wall of this porous carbon material body surfaces and interior hole thereof; And zinc oxide nano-particle and Nano silver grain, through said water-soluble adhesive agent evenly distribute and wall attached to porous carbon material body surfaces and interior hole thereof on.Among the present invention; Zinc oxide nano-particle and Nano silver grain are the water-soluble adhesive agents of its surperficial institute coating of mat; Stably, forever combine, form the nanoparticle composite membrane of zinc oxide and silver with this porous carbon material main body attached to the surface and the hole inwall of porous carbon material main body.Like this, when this porous carbon material is used to make water purification catridge, air filter screen, mouth mask or other filter material, the cellular structure characteristic of this porous carbon material itself; Except can adsorbed water or airborne particulates and microorganism, the nanoparticle composite membrane of the zinc oxide of this porous carbon material body surfaces and hole inwall and silver also can have under light or the unglazed state; Realization is to the antibiotic and bactericidal effect of organic microbials such as bacterium, mould and virus; In addition and since this porous carbon material have can not develop immunity to drugs, plurality of advantages such as avirulence, non-stimulated anaphylaxis and the influence of acid and alkali base number, and have that long-acting type is antibiotic, effects such as sterilization, mildew-resistant and deodorizing; So after being made into various filter material; Only need regularly to be cleaned, can use repeatedly, meet requirements of green environmental protection.
For making the reader further understanding and understanding arranged to the object of the invention, technical characterictic and effect thereof, specially now lift an embodiment, and cooperate graphicly, be described in detail as follows.
Description of drawings
Fig. 1 is a manufacture craft sketch map of the present invention; And
Fig. 2 is the part section microcosmic sketch map that utilizes a porous carbon equipment structure of manufacture craft made of the present invention.
The primary clustering symbol description:
20 porous carbon materials, 21 holes, 31 zinc oxide nano-particles
32 Nano silver grains, 33 water-soluble adhesive agents
The specific embodiment
Nano silver grain makes whole surface area significantly increase because of fine particles, and active the change greatly very easily discharges active silver ion; Attracting the sulfydryl on the zymoprotein in the bacterial body, and with its rapid combination, the enzyme that contains sulfydryl is lost activity, cause bacterial death; And positively charged silver ion can adsorb after touching electronegative microbial cell each other, and puncture cells of microorganisms outer wall makes the inner sex change of microorganism; Reduce energy for growth, let the cell can't metabolism and breeding, until death, in addition; After bacterium was killed by silver ion, silver ion can dissociate out from the bacterium that dies again, continued other bacterium that lives is cooked the action of repetition, till all bacteriums are eliminated; So Nano silver grain need not the illumination activation, promptly has excellent antibiotic and sterilization effect, but more mould fungus inhibition growth effectively reaches anti-corrosion function.Zinc oxide nano-particle also because of its crystallite dimension and light wave quite or littler, dimensional effect causes the interval of its conduction band and valence band to increase, and its light absorpting ability is significantly strengthened; Therefore; Penetrate down in illumination,, or have photon above the semiconductor gap energy when a photon with certain energy; When injecting the semi-conductor electricity minor structure of zinc oxide nano-particle; An electronics in the semiconducting crystal can be from the valence to the conduction band, the positively charged hole OH that stays the next one to have powerful oxidability, the hydrone (H in electric hole and water and air
2When O) meeting, can pass through photochemical reaction, grab the electronics of hydroxy in the hydrone; At this moment, the hydroxy that loses electronics becomes non-persistent hydroxyl free radical (OH) at once, and in a single day non-persistent hydroxyl free radical runs into external or when being attached to the organic matter on the zinc oxide nano-particle; Can make and oneself tend towards stability, like this by the mode of grabbing the other side's electronics; These organic matters are promptly oxidized, and become water and carbon dioxide, are dissipated in the water and air; So zinc oxide nano-particle can be realized to organic degradeds such as mould, bacterium and viruses, to kill mould, bacterium and virus as strong oxidizer.According to the above, Nano silver grain and zinc oxide nano-particle have all that long-acting type is antibiotic, sterilization, can not develop immunity to drugs, plurality of advantages such as avirulence, non-stimulated anaphylaxis and the influence of acid and alkali base number.
The present invention promptly utilizes the characteristic of Nano silver grain and zinc oxide nano-particle; And with materials such as zinc oxide nano-particle and Nano silver grains; Be applied to the manufacturing process of porous carbon material; Make the various filter material (as: water purification catridge, air filter screen, mouth mask or other filter material) that porous carbon material of the present invention is processed, when being mounted to installation site dark in air conditioner ventilating system or the water cleaning systems, outside the suspended particulates and microorganism in decapacitation absorbed air and the water; Also can mat zinc oxide nano-particle and Nano silver grain on it respectively having under light or the unglazed state, realize organic antibiotic and sterilization effects such as bacterium, virus and moulds.In the present invention; In order to make porous carbon material can produce the antibiotic and sterilization effect of long-acting type; Zinc oxide nano-particle and Nano silver grain can be infiltrated in the cellular structure of porous carbon material fully, and preparation method of the present invention comprises the following steps, consults shown in Figure 1:
(101) with zinc oxide nano-particle and silver salt powder (as: silver nitrate (AgNO
3) and silver acetate (CH
3COOAg) etc.) with a predetermined percentage by weight; Be added in the aqueous solution; The two is evenly mixed in this aqueous solution; And making this aqueous solution remain on first temperature, this aqueous solution is evenly to be mixed according to predetermined percentage by weight by compositions such as water, alkali lye (like the KOH or the NaOH aqueous solution), ammoniacal liquor (or ammonia), water-soluble acryl (acrylic) powder and water-soluble adhesive agents; Said alkali lye is according to chemical formula, and silver salt is transformed into silver hydroxide (AgOH):
AgNO
3(aq)+KOH
(aq)→AgOH
(ppt)+K
++NO
3 -，
Because silver hydroxide can form brown precipitate in the aqueous solution; Can't be evenly dispersed in the aqueous solution; So must in the aqueous solution, add ammoniacal liquor (or ammonia) among the present invention, with according to chemical formula, it is ammonification silver complex ion (Ag (NH that the precipitating ion of silver hydroxide is changed into
3)
+ 2):
AgOH
(ppt)+2NH
4OH
(aq)→Ag(NH
3)
2 + (aq)+OH
-+2H
2O；
Said water-soluble acryl powder is a water soluble dispersing agent, and its effect is after being dissolved in the water, and zinc oxide nano-particle and ammonification silver complex ion evenly and dispersedly is suspended in the aqueous solution; The effect of said water-soluble adhesive agent is when zinc oxide nano-particle and ammonification silver complex ion is mixed into the aqueous solution, can evenly be coated on the surface of zinc oxide nano-particle and ammonification silver complex ion;
(102) porous carbon material main body (as: activated carbon, bamboo carbon or be equipped with the particle of material such as long carbon) is inserted a baking oven and be baked to second temperature; Wherein this second temperature must be less than 400 degree Celsius; And need greater than said first temperature, and temperature range is at 20～80 degree Celsius;
(103) this porous carbon material main body is immersed in the said aqueous solution; Carry out the stirring of a scheduled time; Making can be because of action of thermal difference between this porous carbon material main body and the aqueous solution; And the generation osmotic effect makes the said aqueous solution be able to successfully infiltrate through the surface of this porous carbon material main body and the hole of inner dense distribution, makes zinc oxide nano-particle and ammonification silver complex ion to infiltrate described hole along with this aqueous solution;
(104) formaldehyde (HCHO) or the glucose of interpolation one predetermined weight percent in the said aqueous solution; And continue to stir a scheduled time; Make that formaldehyde (HCHO) or glucose can be according to chemical formula, the ammonification silver complex ion with infiltrating in this porous carbon material main body hole is reduced into Nano silver grain:
2Ag(NH
3)
2 + (aq)+HCHO
(l)+2OH
-→2Ag
(ppt)+HCOO
-+NH
4 ++3NH
3(g)+H
2O；
(105) this porous carbon material (having had zinc oxide nano-particle and Nano silver grain in the porous carbon material main body hole) is taken out in the said aqueous solution; Carrying out high temperature drying handles; Consult shown in Figure 2; With behind these porous carbon material 20 bone dries; Make the water-soluble adhesive agent 33 that zinc oxide nano-particle 31 and Nano silver grain 32 in the described hole 21 can its surperficial institute coatings of mat,, form the nanoparticle composite membrane of zinc oxide and silver at this porous carbon material body surfaces and inside holes 21 inwalls stably attached to the surface and inside holes 21 inwalls of this porous carbon material main body.
Because; In preparation method of the present invention; Zinc oxide nano-particle and Nano silver grain are the water-soluble adhesive agents of its surperficial institute coating of mat; Stably, make zinc oxide nano-particle and Nano silver grain forever to combine, and make this porous carbon material possess antibiotic, anticorrosion and catalyst (catalysis) effect of long-acting type with this porous carbon material main body attached to the surface of porous carbon material main body and the hole inwall of interior dense distribution thereof.Therefore, when this porous carbon material is used to make water purification catridge, air filter screen, mouth mask or other filter material, the cellular structure characteristic of this porous carbon material itself; Except ability filtering water or airborne impurity and dirt; The nanoparticle composite membrane of the zinc oxide of this porous carbon material body surfaces and hole inwall and silver also can have under light or the unglazed state, realizes organic antibiotic and bactericidal effects such as bacterium, mould and viruses; Since this porous carbon material have can not develop immunity to drugs, avirulence, non-stimulated anaphylaxis, need not the illumination activation and plurality of advantages such as acid and alkali base number influence; And have that long-acting type is antibiotic, effects such as sterilization, mildew-resistant and deodorizing, so can after being made into various filter material, only need regularly to be cleaned; Can use repeatedly, meet requirements of green environmental protection.
In a most preferred embodiment of the present invention; The said aqueous solution is by water, zinc oxide nano-particle, water miscible silver salt powder (silver nitrate and/or silver acetate), water-soluble acryl powder, water-soluble adhesive agent, ammoniacal liquor (or ammonia) and alkali lye compositions such as (like the KOH or the NaOH aqueous solution); (weight with the said aqueous solution is benchmark according to following percentage by weight; Each component sum is 100%), evenly mix:
(1) water: like deionized water or pure water etc., its percentage by weight is 80%～99%;
(2) nano particle of zinc oxide: its percentage by weight is 0.2%～10%, in this embodiment, is the particle that earlier zinc oxide is ground to form nanometer (nanometer) size, and 1 nanometer equals part per billion meter (10
-9Meter), or the particle of nanoscale size, promptly be about 1～100 nanometer, the nano particle between between molecule and inferior micron;
(3) water miscible silver salt powder (as: silver nitrate (AgNO
3), silver acetate (CH
3COOAg) etc.): its percentage by weight is 0.001%～5%, and the water soluble silver salt powder has can be dissolved in the aqueous solution fully, and in the aqueous solution, discharges the characteristic of ammonification silver complex ion;
(4) alkali lye: the aqueous solution that is potassium hydroxide or NaOH; Its percentage by weight is 0.001%～5%; Can in the process that the aqueous solution is stirred, silver salt be transformed into silver hydroxide, because; Silver hydroxide can form brown precipitate in the aqueous solution, so can't be evenly dispersed in the aqueous solution;
(5) ammoniacal liquor (or ammonia): its (amounting to into general commercially available ammonia concn meter) percentage by weight is 0.005%～25%, can be in the process that the aqueous solution is stirred, and it is ammonification silver complex ion (Ag (NH that the precipitating ion of silver hydroxide is changed into
3)
+ 2), because ammonification silver complex ion has the characteristic of oxyphie again, thus very easily with zinc oxide nano-particle on the oxygen key tie, and in the modulated process of this aqueous solution, equably attached to the surface of zinc oxide nano-particle;
(6) water-soluble acryl powder: its percentage by weight is 2%～30%; Wherein this water-soluble acryl powder is a water soluble dispersing agent; Its effect is after being dissolved in the water; Zinc oxide nano-particle and ammonification silver complex ion evenly and dispersedly is suspended in the aqueous solution, and in this embodiment, this water-soluble acryl powder is a polyacrylic acid derivative (Polyacrylic acid derivative); Zinc oxide nano-particle and ammonification silver complex ion is dispersed in the aqueous solution; And the phenomenon of unlikely generation deposition or alluvial caking, like this, said zinc oxide nano-particle and ammonification silver complex ion could successfully infiltrate the described hole of porous carbon material body surfaces and interior dense distribution thereof with the aqueous solution; And
(7) water-soluble adhesive agent: its percentage by weight is 0.2%～10%; This water-soluble adhesive agent is in order to be coated on even and the zinc oxide nano-particle of dispersion and the surface of ammonification silver complex ion in the aqueous solution; In this embodiment; Said water-soluble adhesive agent comprises and gathers urine ester resin (Urethane polymer), N-methyl ratio is coughed up ketone (N-Methyl Pyrrolidinone) and triethylamine compositions such as (Triethylamine); Behind the hole with the surface that successfully infiltrates through this porous carbon material main body at zinc oxide nano-particle and ammonification silver complex ion along with this aqueous solution and inner dense distribution; Can handle and during bone dry through high temperature drying at this porous carbon material; Make zinc oxide nano-particle reach this water-soluble adhesive agent of its surperficial institute coating of Nano silver grain mat that forms by oxidation,, form the nanoparticle composite membrane of zinc oxide and silver stably attached to the surface and the hole inwall of this porous carbon material main body; Make zinc oxide nano-particle and Nano silver grain forever to combine, produce the effect of antibiotic, the anticorrosion and catalyst of long-acting type with this porous carbon material main body.
In this most preferred embodiment, first temperature of the said aqueous solution can be normal temperature or low temperature, between 10～25 degree promptly Celsius; Second temperature of said porous carbon material particle (porous carbon material main body) then is between 30～105 degree Celsius, and the temperature range of the two remains between 20～80 degree Celsius, like this; When this porous carbon material main body is dumped in this aqueous solution, when carrying out at least ten minutes whipping process, can be between this porous carbon material main body and the aqueous solution because of action of thermal difference; And the generation osmotic effect; Make this water-soluble fluid power successfully infiltrate the surface of this porous carbon material main body and the hole of inner dense distribution, the air in these holes is extruded, so; In whipping process; Understand the huge micro-bubble of quantity of in this aqueous solution, emerging, and then make zinc oxide nano-particle and ammonification silver complex ion to infiltrate described hole, next along with this aqueous solution; (weight with the said aqueous solution is benchmark, with C in this aqueous solution, to add percentage by weight and be formaldehyde (HCHO) or 0.002%～0.1% glucose of 0.001%～0.05% (weight with the said aqueous solution is benchmark)
6H
12O
6H
2The amount meter of O), and continues to stir at least 30 minutes, make formaldehyde or glucose can infiltrate the hole of this porous carbon material main body; And with its in ammonification silver complex ion generation chemical reaction, make ammonification silver complex ion be reduced into Nano silver grain, and firmly on the surface attached to zinc oxide nano-particle; At last; The porous carbon material that has zinc oxide nano-particle and Nano silver grain in this porous carbon material main body hole is taken out in this aqueous solution, under the high temperature of 80～200 degree Celsius, carry out dried; After treating this porous carbon material bone dry; Zinc oxide nano-particle in the described hole and Nano silver grain can its surperficial institute coating of mat water-soluble adhesive agent, stably attached to the surface and the inside holes inwall of this porous carbon material main body, form the nanoparticle composite membrane of zinc oxide and silver.In aforementioned most preferred embodiment of the present invention; Through experiment proof repeatedly; Please consult shown in Figure 2ly again, the percentage by weight that zinc oxide nano-particle 31 in the said nanoparticle composite membrane and Nano silver grain are 32 can produce best antibiotic and sterilization effect to organic matters such as bacterium, virus and moulds with 5: 1～60: 1.
The above is merely of the present invention one best specific embodiment, and characteristic of the present invention is not limited thereto, the personnel of any skilled in field of the present invention, can think easily and variation or modification, all should be encompassed in protection scope of the present invention.
Claims (18)
1. the preparation method of the porous carbon material of tool long-acting type nano-antibacterial and effect of catalyst, this method comprises:
Zinc oxide nano-particle and silver salt powder are added in the aqueous solution, the two are evenly mixed in this aqueous solution, and make this aqueous solution remain on first temperature, said first temperature is 10～25 degree Celsius; Wherein this aqueous solution is evenly to be mixed by the composition that comprises water, alkali lye, ammoniacal liquor, water-soluble acryl powder and water-soluble adhesive agent; Said alkali lye is that silver salt is transformed into silver hydroxide; Said ammoniacal liquor is that the precipitating ion with silver hydroxide changes into is ammonification silver complex ion; Said water-soluble acryl powder is a water soluble dispersing agent; Its effect is after being dissolved in the water, and zinc oxide nano-particle and ammonification silver complex ion evenly and dispersedly is suspended in the aqueous solution, and said water-soluble adhesive agent comprises and gathers urine ester resin, N-methyl ratio is coughed up ketone and triethylamine; Its effect is when zinc oxide nano-particle and ammonification silver complex ion is mixed into this aqueous solution, can evenly be coated on the surface of zinc oxide nano-particle and ammonification silver complex ion;
Porous carbon material main body is baked to second temperature; Said second temperature is 30～105 degree Celsius, and wherein the temperature range of this second temperature and first temperature is enough to make said water-soluble fluid power successfully to infiltrate the surface of this porous carbon material main body and the hole of inner dense distribution because of action of thermal difference;
Porous carbon material main body is immersed in the said aqueous solution; Stir; Making can be because of action of thermal difference between this porous carbon material main body and the aqueous solution; Produce osmotic effect, make the said aqueous solution be able to successfully infiltrate through the surface of porous carbon material main body and the hole of inner dense distribution, make zinc oxide nano-particle and ammonification silver complex ion to infiltrate described hole along with this aqueous solution;
In this aqueous solution, add formaldehyde or glucose, proceed to stir, the ammonification silver complex ion that makes formaldehyde or glucose can will infiltrate in this porous carbon material main body hole is reduced into Nano silver grain; And
The porous carbon material that has zinc oxide nano-particle and Nano silver grain in this porous carbon material main body hole is taken out in this aqueous solution; Carry out dried; With behind this porous carbon material bone dry; Make water-soluble adhesive agent that zinc oxide nano-particle and Nano silver grain in the described hole can its surperficial institute coating of mat stably attached to the surface and the inside holes inwall of this porous carbon material main body, form the nanoparticle composite membrane of zinc oxide and silver at this porous carbon material body surfaces and inside holes inwall.
2. preparation method as claimed in claim 1, wherein said water are deionized water or pure water.
3. preparation method as claimed in claim 2, wherein said silver salt powder is silver nitrate or silver acetate.
4. preparation method as claimed in claim 3, wherein said alkali lye comprises potassium hydroxide or NaOH.
5. preparation method as claimed in claim 1, the percentage by weight of wherein said water are 80%～99%.
6. preparation method as claimed in claim 5, the percentage by weight of wherein said zinc oxide nano-particle are 0.2%～10%.
7. preparation method as claimed in claim 6, the percentage by weight of wherein said silver salt powder are 0.001%～5%.
8. preparation method as claimed in claim 7, the percentage by weight of wherein said alkali lye are 0.001%～5%.
9. preparation method as claimed in claim 8, the percentage by weight of wherein said ammoniacal liquor are 0.005%～25%.
10. preparation method as claimed in claim 9, the percentage by weight of wherein said water-soluble acryl powder are 2%～30%.
11. preparation method as claimed in claim 10, the percentage by weight of wherein said water-soluble adhesive agent are 0.2%～10%.
12. preparation method as claimed in claim 11, wherein said porous carbon material main body are dipped into the time of stirring in the said aqueous solution and were at least ten minutes.
13. preparation method as claimed in claim 12, wherein said formaldehyde or the glucose percentage by weight in the said aqueous solution is respectively 0.001%～0.05% or 0.002%～0.1%.
14. preparation method as claimed in claim 13, wherein said formaldehyde or glucose are added into the time of proceeding to stir in the said aqueous solution and were at least 30 minutes.
15. preparation method as claimed in claim 14 is under the high temperature of 80～200 degree Celsius, to carry out dried after wherein said porous carbon material takes out in the aqueous solution.
16. preparation method as claimed in claim 15, zinc oxide nano-particle in the wherein said nanoparticle composite membrane and the percentage by weight between Nano silver grain are 5: 1～60: 1.
17. the porous carbon material of tool long-acting type nano-antibacterial and effect of catalyst, it is made according to the described preparation method of claim 1 and obtains, and it comprises:
One porous carbon material main body, its surface and in be intensively distributed with hole;
Water-soluble adhesive agent; Comprise and gather urine ester resin, N-methyl ratio is coughed up ketone and triethylamine; Said water-soluble adhesive agent is distributed in said porous carbon material body surfaces and the interior hole thereof; And under the state of this porous carbon material bone dry, can be attached to the wall of this porous carbon material body surfaces and interior hole thereof; And
Zinc oxide nano-particle and Nano silver grain, through said water-soluble adhesive agent evenly distribute and wall attached to porous carbon material body surfaces and interior hole thereof on.
18. porous carbon material as claimed in claim 17, the percentage by weight between wherein said zinc oxide nano-particle and Nano silver grain is 5: 1～60: 1.
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| CN107737578B (en) * | 2017-11-12 | 2021-02-19 | 慕林健康负氧离子医用建材(深圳)集团有限公司 | Preparation method of anion antibacterial adsorption material composition |
| CN113578016B (en) * | 2021-06-30 | 2022-06-07 | 南京凯创协同纳米技术有限公司 | Preparation method of micro-nano zinc deodorant for pig farm |
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