CN111266099A - Series of inorganic antibacterial mildew-proof monatomic catalysts and preparation method thereof - Google Patents
Series of inorganic antibacterial mildew-proof monatomic catalysts and preparation method thereof Download PDFInfo
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- 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
Abstract
The invention belongs to the field of catalysts, and particularly relates to a series of inorganic antibacterial and mildewproof monatomic catalysts and a preparation method thereof. The invention discloses a series of inorganic antibacterial mildew-proof monatomic catalysts, wherein each monatomic catalyst consists of a carrier and transition metal, and the carrier is any one of an inorganic calcium-based carrier, an inorganic silicon-based carrier, an inorganic aluminum-based carrier and an inorganic titanium-based carrier; the transition metal is selected from one or more of a first transition metal and a second transition metal; the transition metal is anchored in the form of a single atom at a defect site on the surface of the support. The catalyst can efficiently activate oxygen in air or water without other auxiliary conditions, generate active oxygen species, oxidize cell membranes, proteins, genetic substances and the like of bacteria, and kill the bacteria. The monatomic catalyst has a stable structure, is not consumed, can be repeatedly used, has no pollution to the environment, and has no side effect on organisms.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a series of inorganic antibacterial and mildewproof monatomic catalysts and a preparation method thereof.
Background
At present, the global environmental pollution problem is increasingly serious, the healthy survival and development of human beings are damaged, and the pollution treatment problem is urgent. The environmental pollution is mainly divided into air pollution, soil pollution and water pollution. The microorganisms such as bacteria and viruses not only consume a large amount of energy and resources, but also seriously harm the health of people, so that the development of novel, practical and long-acting broad-spectrum antibacterial and mildew-proof materials has great significance.
In recent years, the single-atom catalysis has rapidly developed into the most popular frontier field in the field of catalytic science, is widely applied to the fields of energy, materials, chemical engineering, medical treatment, biology and the like, and has raised a hot trend in the scientific field. Compared with a nano-scale catalyst, the single-atom catalyst takes a single atom as an active center, the utilization rate of a catalytic active material reaches 100%, and the catalyst cost is greatly reduced. The active sites of the monatomic catalyst are clear and uniform, and the monatomic catalyst has high activity and high selectivity. The single-atom catalysis successfully enters ten research achievements in the 2016 year chemical and chemical fields of the American chemical society, and the 20 scientific and technical problems released by the 2019 year China science society are successfully entered in this year, so that the method is popular in China and the world scientific research fields.
Because the application of the monatomic catalyst is very wide, different applications have different requirements for the monatomic catalyst, and the existing monatomic catalyst is difficult to meet the requirements of antibacterial and mildewproof application, the exploration and development of the monatomic catalyst with antibacterial and mildewproof functions has very important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a series of monatomic catalysts for antibacterial and mildewproof applications.
In order to achieve the purpose, the invention discloses a series of inorganic antibacterial and mildewproof monatomic catalysts, wherein the monatomic catalysts consist of carriers and transition metals, and the carriers are any one of inorganic calcium-based carriers, inorganic silicon-based carriers, inorganic aluminum-based carriers and inorganic titanium-based carriers; the transition metal is selected from one or more of a first transition metal and a second transition metal; the transition metal is anchored in the form of a single atom at a defect site on the surface of the support.
Preferably, the inorganic calcium-based carrier is any one of calcium carbonate, calcium phosphate, calcium silicate, and hydroxyapatite.
Preferably, the inorganic silicon-based carrier is any one of diatomite, kaolin, nano silica and fumed silica, the chemical component of the diatomite is mainly SiO2, and the crystal chemical formula of the kaolin is 2SiO 2. Al2O 3. 2H 2O.
Preferably, the inorganic aluminum-based carrier is any one of alumina and kaolin.
Preferably, the inorganic titanium-based carrier is any one of titanium dioxide, nano titanium dioxide and degussa P25.
Preferably, the transition metal is selected from one or more of Fe, Co, Ni, Cu, Ag, Mn and Zn, and the mass ratio of the transition metal contained in the catalyst to the carrier is 1: 20-1: 200.
Further, the invention also discloses a preparation method of the antibacterial and mildewproof monatomic catalyst, and the specific technical scheme is as follows: a series of inorganic antibacterial and mildewproof monatomic catalysts comprise the following steps:
1) carrying out ultrasonic and stirring mixing on the transition metal salt solution and the carrier;
2) removing the solvent of the product obtained in the step 1), and grinding to obtain solid powder;
3) heating the solid powder obtained in the step 2), cooling and grinding to obtain the required catalyst.
Preferably, the concentration of the metal salt solution in the step 1) is 5-200 g/L, the metal salt is any one of chloride, nitrate and sulfate, the solvent of the solution is any one of water, an organic solution and a water-organic mixed solvent, and the stirring time is 12-48 h.
Preferably, the heating treatment in the step 3) is heating for 2-4 hours at 50-1000 ℃ in air or argon atmosphere, and the grinding time is 20-40 min.
Compared with the traditional antibacterial material, the monatomic catalyst has more excellent antibacterial performance. The monatomic catalyst does not need any auxiliary condition, can efficiently activate oxygen in the air to generate active oxygen species and oxidize bacterial membranes, proteins, genetic substances and the like of bacteria to kill cells, has a stable structure, can be repeatedly used, has no pollution to the environment, and has no side effect on organisms.
Drawings
FIG. 1 shows the antibacterial effect of different doses of catalyst on Staphylococcus aureus;
FIG. 2 shows the antibacterial effect of different doses of catalyst on E.coli;
FIG. 3 shows the antibacterial effect of different doses of catalyst on Salmonella;
FIG. 4 shows the antibacterial effect of different series of inorganic supported monatomic catalysts (catalyst content 2000ppm) on Staphylococcus aureus, Escherichia coli, and Salmonella;
FIG. 5 shows the broad-spectrum antibacterial effect of the practical application scenarios of different series of inorganic carrier monatomic catalysts (catalyst content 2000 ppm);
fig. 6 shows the antibacterial performance versus time curves for a monatin catalyst, oxone (dupont fencoll) and benzalkonium chloride (sinkiang grandro).
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited to the scope of the examples. These examples are intended to illustrate the invention only and are not intended to limit the scope of the invention. In addition, various modifications may occur to those skilled in the art upon reading the present disclosure, and such equivalent variations are within the scope of the present invention as defined in the appended claims.
Example 1
Step 1, adding 5g/L of ferric chloride aqueous solution into diatomite (inorganic silicon-based carrier), wherein the mass ratio of transition metal to carrier is 1:20, carrying out ultrasonic 30min under the condition of 100kHz on the obtained solution to disperse uniformly, and then stirring the mixed solution for 12h at 100 r/min;
step 2, heating the mixed solution obtained in the step 1 to the boiling point of water, volatilizing at high temperature, evaporating the solvent to dryness, and fully grinding for 0.5 hour at the rotating speed of 50r/min by using a ball mill to obtain solid powder;
and 3, heating the solid powder obtained in the step 2 for 2 hours under the conditions of air atmosphere and 400 ℃, cooling to room temperature, grinding for 20 minutes at the rotating speed of 50r/min by using a ball mill to obtain the required catalyst, wherein transition metals contained in the prepared catalyst are anchored on defect sites on the surface of the carrier in a monoatomic mode.
Example 2
Step 1, adding 10g/L of copper chloride aqueous solution into calcium carbonate (inorganic calcium-based carrier), wherein the mass ratio of transition metal to carrier is 1:50, performing ultrasonic treatment on the obtained solution for 30min under the condition of 100kHz to uniformly disperse, and then stirring the mixed solution for 20h at the speed of 150 r/min;
step 2, heating the mixed solution obtained in the step 1 to the boiling point of water, volatilizing at high temperature, evaporating the solvent to dryness, and fully grinding for 1 hour at the rotating speed of 100r/min by using a ball mill to obtain solid powder;
and 3, heating the solid powder obtained in the step 2 for 3 hours under the conditions of air atmosphere and temperature of 200 ℃, cooling to room temperature, grinding for 30 minutes at the rotating speed of 100r/min by using a ball mill to obtain the required catalyst, wherein transition metals contained in the prepared catalyst are anchored on defect sites on the surface of the carrier in a monoatomic mode.
Example 3
Step 1, adding 200g/L of water and ethanol (volume ratio is 1: 1) solution of cobalt chloride into alumina (inorganic aluminum-based carrier), wherein the mass ratio of transition metal to carrier is 1:200, performing ultrasonic 30min to disperse uniformly on the obtained solution under the condition of 100kHz, and then stirring the mixed solution for 48h at 200 r/min;
step 2, heating the mixed solution obtained in the step 1 to the boiling point of the mixed solution, volatilizing at high temperature, evaporating the solvent to dryness, and fully grinding for 3 hours at the rotating speed of 500r/min by using a ball mill to obtain solid powder;
and 3, heating the solid powder obtained in the step 2 for 4 hours under the conditions of argon atmosphere and 800 ℃, cooling to room temperature, grinding for 40 minutes at the rotating speed of 500r/min by using a ball mill to obtain the required catalyst, wherein transition metals contained in the prepared catalyst are anchored on defect sites on the surface of the carrier in a monoatomic mode.
Example 4
Step 1, adding 10g/L nickel chloride and 10g/L zinc chloride aqueous solution into titanium dioxide (inorganic titanium-based carrier), wherein the mass ratio of transition metal to carrier is 1:30, the mass ratio of two transition metals is 1:1, performing ultrasonic 30min under the condition of 100kHz of the obtained solution to disperse uniformly, and then stirring the mixed solution for 48h at 100 r/min;
step 2, heating the mixed solution obtained in the step 1 to the boiling point of water, volatilizing at high temperature, evaporating the solvent to dryness, and fully grinding for 2 hours at the rotating speed of 300r/min by using a ball mill to obtain solid powder;
and 3, heating the solid powder obtained in the step 2 for 2.5 hours under the conditions of air atmosphere and 600 ℃, cooling to room temperature, grinding for 25 minutes at the rotating speed of 200r/min by using a ball mill to obtain the required catalyst, wherein transition metals contained in the prepared catalyst are anchored on defect sites on the surface of the carrier in a monoatomic mode.
Example 5
Step 1, adding 50g/L zinc nitrate and 50g/L ferric nitrate aqueous solution into calcium silicate (inorganic calcium-based carrier), wherein the mass ratio of transition metal to carrier is 1:60, the mass ratio of two transition metals is 1:2, carrying out ultrasonic treatment on the obtained solution under the condition of 100kHz for 30min to uniformly disperse, and then stirring the mixed solution for 25h at the speed of 150 r/min;
step 2, heating the mixed solution obtained in the step 1 to the boiling point of water, volatilizing at high temperature, evaporating the solvent to dryness, and fully grinding for 1.5 hours at the rotating speed of 250r/min by using a ball mill to obtain solid powder;
and 3, heating the solid powder obtained in the step 2 for 3 hours under the conditions of air atmosphere and 300 ℃, cooling to room temperature, grinding for 35 minutes at the rotating speed of 300r/min by using a ball mill to obtain the required catalyst, wherein transition metals contained in the prepared catalyst are anchored on defect sites on the surface of the carrier in a monoatomic mode.
Example 6
Step 1, adding 50g/L cobalt chloride, 50g/L copper chloride and 100g/L silver nitrate aqueous solution into nano silicon oxide (inorganic silicon-based carrier), wherein the mass ratio of transition metal to carrier is 1:20, and the mass ratio of cobalt, copper and silver is 1:2:3, carrying out ultrasonic 30min on the obtained solution under the condition of 100kHz to uniformly disperse the obtained solution, and then stirring the mixed solution for 12h at 200 r/min;
step 2, heating the mixed solution obtained in the step 1 to the boiling point of water, volatilizing at high temperature, evaporating the solvent to dryness, and fully grinding for 0.5 hour at the rotating speed of 500r/min by using a ball mill to obtain solid powder;
and 3, heating the solid powder obtained in the step 2 for 2 hours under the conditions of argon atmosphere and 700 ℃, cooling to room temperature, grinding for 20 minutes at the rotating speed of 500r/min by using a ball mill to obtain the required catalyst, wherein transition metals contained in the prepared catalyst are anchored on defect sites on the surface of the carrier in a monoatomic mode.
Example 7
Step 1, adding 150g/L ferric sulfate and 150g/L copper sulfate aqueous solution into kaolin (an inorganic aluminum-based carrier), wherein the mass ratio of transition metal to the carrier is 1:150, and the mass ratio of the two transition metals is 1:1, carrying out ultrasonic treatment on the obtained solution under the condition of 100kHz for 30min to uniformly disperse the solution, and then stirring the mixed solution at the speed of 100r/min for 48 h;
step 2, heating the mixed solution obtained in the step 1 to the boiling point of water, volatilizing at high temperature, evaporating the solvent to dryness, and fully grinding for 3 hours at the rotating speed of 400r/min by using a ball mill to obtain solid powder;
and 3, heating the solid powder obtained in the step 2 for 2 hours under the conditions of argon atmosphere and 50 ℃, cooling to room temperature, grinding for 40min at the rotating speed of 400r/min by using a ball mill to obtain the required catalyst, wherein transition metals contained in the prepared catalyst are anchored on defect sites on the surface of the carrier in a monoatomic mode.
Example 8
Step 1, adding 150g/L ferric chloride, 160g/L copper chloride water and ethanol solution into nano titanium dioxide (inorganic titanium-based carrier), wherein the mass ratio of transition metal to carrier is 1:200, and the mass ratio of two transition metals is 1:1, the volume ratio of water to ethanol is 1:1, carrying out ultrasonic treatment on the obtained solution under the condition of 100kHz for 30min to uniformly disperse the solution, and then stirring the mixed solution at the speed of 100r/min for 48 h;
step 2, heating the mixed solution obtained in the step 1 to the boiling point of the mixed solvent, volatilizing at high temperature, evaporating the solvent to dryness, and fully grinding for 3 hours at the rotating speed of 500r/min by using a ball mill to obtain solid powder;
and 3, heating the solid powder obtained in the step 2 for 4 hours under the conditions of argon atmosphere and 750 ℃, cooling to room temperature, grinding for 40 minutes at the rotating speed of 500r/min by using a ball mill to obtain the required catalyst, wherein transition metals contained in the prepared catalyst are anchored on defect sites on the surface of the carrier in a monoatomic mode.
Example 9
Step 1, adding 200g/L of zinc nitrate methanol solution into hydroxyapatite (inorganic calcium-based carrier), wherein the mass ratio of transition metal to carrier is 1:200, performing ultrasonic treatment on the obtained solution for 30min under the condition of 100kHz to uniformly disperse, and then stirring the mixed solution for 48h at 200 r/min;
step 2, heating the mixed solution obtained in the step 1 to the boiling point of methanol, volatilizing at high temperature, evaporating the solvent to dryness, and fully grinding for 3 hours at the rotating speed of 500r/min by using a ball mill to obtain solid powder;
and 3, heating the solid powder obtained in the step 2 for 4 hours under the conditions of argon atmosphere and temperature of 1000 ℃, cooling to room temperature, grinding for 40 minutes at the rotating speed of 500r/min by using a ball mill to obtain the required catalyst, wherein transition metals contained in the prepared catalyst are anchored on defect sites on the surface of the carrier in a monoatomic mode.
Example 10
Step 1, adding 5g/L silver nitrate acetone solution into fumed silica (inorganic silicon-based carrier), wherein the mass ratio of transition metal to carrier is 1:20, performing ultrasonic 30min to disperse uniformly on the obtained solution under the condition of 100kHz, and then stirring the mixed solution for 12h at 100 r/min;
step 2, heating the mixed solution obtained in the step 1 to the boiling point of acetone, volatilizing at high temperature, evaporating the solvent to dryness, and fully grinding for 0.5 hour at the rotating speed of 50r/min by using a ball mill to obtain solid powder;
and 3, heating the solid powder obtained in the step 2 for 2 hours under the conditions of argon atmosphere and 180 ℃, cooling to room temperature, grinding for 20 minutes at the rotating speed of 50r/min by using a ball mill to obtain the required catalyst, wherein transition metals contained in the prepared catalyst are anchored on defect sites on the surface of the carrier in a monoatomic mode.
Example 11
A series of monatomic catalysts prepared in preparation examples 1 to 10 were subjected to antibacterial experimental tests:
step 1, preparing bacteria (staphylococcus aureus, escherichia coli and salmonella) which are freshly cultured for 18-24h, washing down the lawn with 5ml PBS solution (0.03mol/L) to prepare bacterial suspension, diluting the bacterial suspension with PBS to the required concentration (dropping 100 mu L on a control sample, recovering 1 × 10 bacteria number4-9×104cfu/patch);
step 2, respectively weighing a certain amount of catalyst and a control sample, dispersing the catalyst and the control sample in PBS to prepare sample solutions (the concentrations are 0, 1000ppm, 2000ppm, 3000ppm, 4000ppm and 5000ppm respectively), and putting the sample solutions into a 250ml conical flask;
step 3, fixing the conical flask on a shaking table, and shaking for 1h at 300 r/min;
and 4, after 0 hour and 1 hour of oscillation respectively, taking 0.5mL of sample liquid or sample liquid diluted by PBS appropriately, inoculating the sample liquid into a plate by an agar pouring method, and performing colony counting after culturing for 18-24 hours in a constant temperature box of 36-37 ℃.
The test is repeated for 3 times, and the bacteriostasis rate is calculated according to the formula:
X＝(A-B)/A×100％
in the formula:
x-antimicrobial Rate,%;
a-average colony number before oscillation of the sample to be tested;
b-average number of colonies after shaking the sample.
As shown in figures 1-3, under the condition of 2000ppm, the removal rate of each monatomic catalyst on staphylococcus aureus, escherichia coli and salmonella can reach more than 99%. As shown in FIG. 4, the monatomic catalysts prepared by different series of inorganic carriers all show an antibacterial rate of more than 99%, and the excellent antibacterial performance of a series of inorganic antibacterial mildew-proof monatomic catalysts prepared by the method is proved again.
Example 12
A series of monatomic catalysts prepared in preparation examples 1 to 10 were subjected to an actual application scenario antibacterial experiment test:
step 1, selecting scenes such as actual living fish pond water, river water, landscape lake and the like which are rich in various bacteria for testing, respectively taking 1L of raw water, precipitating for 30 minutes, taking 100mL of raw water, adding 100mL of purified water for dilution, taking 200mL of raw water as bacteria-containing raw water in total, wherein the colony count is 1 multiplied by 103-5×103cfu/tablet.
Step 2, respectively weighing a certain amount of catalyst and a control sample, dispersing the catalyst and the control sample in the raw water (the concentrations are 0, 1000ppm, 2000ppm, 3000ppm, 4000ppm and 5000ppm respectively), and putting the raw water and the control sample into a 250ml conical flask;
step 3, fixing the conical flask on a shaking table, and shaking for 1h at 300 r/min;
and 4, after 0 hour and 1 hour of oscillation respectively, taking 1mL of sample solution, inoculating the sample solution into a plate by an agar pouring method, and performing colony counting after culturing for 18-24 hours in a constant temperature box of 36-37 ℃.
The test is repeated for 3 times, and the bacteriostasis rate is calculated according to the formula:
X＝(A-B)/A×100％
in the formula:
x-antimicrobial Rate,%;
a-average colony number before oscillation of the sample to be tested;
b-average number of colonies after shaking the sample.
As shown in FIG. 5, the broad-spectrum antibacterial performance of different series of inorganic carrier monatomic catalysts shows 99% of antibacterial rate in practical application scenarios.
Example 13
A series of monatomic catalysts prepared in preparation examples 1-10 are compared with a traditional antibacterial material, the traditional material is selected to be potassium hydrogen persulfate (Dupont Weike) and benzalkonium chloride (New Zealand Sunno) for comparison, the antibacterial performance of the catalysts is monitored in real time, and the experimental method is consistent with that of example 12. As shown in fig. 6, under the same conditions, all three products showed about 80% of antibacterial rate after 1 h. However, Dupont Weir may gradually lose effectiveness after 12 hours; the new zealand granduno shows 99% of antibacterial rate in 12h and can last for 5 days, and then gradually loses effect; compared with the two antibacterial agents, each monatomic catalytic antibacterial agent shows 99% of antibacterial rate within 12 hours, and the antibacterial rate of more than 99% can be maintained and can continue to function after continuous detection for 30 days.
Example 14
A series of monatomic catalysts prepared in preparation examples 1-10 were recovered, and the performance of the catalysts was tested in a cyclic manner.
Step 1, the experiment was performed according to the experimental method described in example 12;
step 2, centrifugally recovering the catalyst, washing with water and ethanol for three times, vacuum-drying at 80 ℃, and then performing the test again according to the example 12;
and 3, repeating the operation of the step 2 for more than 100 times.
Each monatomic catalyst shows a removal rate of more than 99% to various bacteria, and the monatomic catalyst is repeatedly recycled for more than 100 times without attenuation of antibacterial performance.
Claims (9)
1. A series of inorganic antibacterial mildew-proof monatomic catalysts are characterized in that the monatomic catalysts consist of carriers and transition metals, and the carriers are any one of inorganic calcium-based carriers, inorganic silicon-based carriers, inorganic aluminum-based carriers and inorganic titanium-based carriers; the transition metal is selected from one or more of a first transition metal and a second transition metal; the transition metal is anchored in the form of a single atom at a defect site on the surface of the support.
2. The antibacterial and antifungal monatomic catalyst as set forth in claim 1, wherein the inorganic calcium-based carrier is any one of calcium carbonate, calcium phosphate, calcium silicate, and hydroxyapatite.
3. The antibacterial and mildewproof monatomic catalyst of claim 1, wherein the inorganic silicon-based carrier is any one of diatomite, kaolin, nano-silica and fumed silica.
4. The single-atom catalyst as claimed in claim 1, wherein the inorganic aluminum-based carrier is one of alumina and kaolin.
5. The antibacterial and mildewproof monatomic catalyst of claim 1, wherein the inorganic titanium-based carrier is any one of titanium dioxide, nano titanium dioxide and degussa P25.
6. The antibacterial and mildewproof monatomic catalyst according to any one of claims 1 to 5, wherein the transition metal is one or more selected from Fe, Co, Ni, Cu, Ag, Mn and Zn, and the mass ratio of the transition metal to the carrier in the catalyst is 1:20 to 1: 200.
7. A process for preparing the monatomic catalyst of any one of claims 1 to 6, which comprises the steps of:
1) carrying out ultrasonic and stirring mixing on the transition metal salt solution and the carrier;
2) removing the solvent of the product obtained in the step 1), and grinding to obtain solid powder;
3) heating the solid powder obtained in the step 2), cooling and grinding to obtain the required catalyst.
8. The antibacterial and mildewproof monatomic catalyst according to claim 7, wherein the concentration of the metal salt solution in the step 1) is 5-200 g/L, the metal salt is any one of chloride, nitrate and sulfate, the solvent of the solution is any one of water, an organic solution and a water-organic mixed solvent, and the stirring time is 12-48 h.
9. The antibacterial and mildewproof monatomic catalyst of claim 7, wherein the heating treatment in the step 3) is heating for 2-4 hours at a temperature of 50-1000 ℃ in an air or argon atmosphere, and the grinding time is 20-40 min.
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