CN112998011A - Strong-oxidizing antibacterial disinfection material and preparation method and application thereof - Google Patents
Strong-oxidizing antibacterial disinfection material and preparation method and application thereof Download PDFInfo
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- CN112998011A CN112998011A CN202110207754.4A CN202110207754A CN112998011A CN 112998011 A CN112998011 A CN 112998011A CN 202110207754 A CN202110207754 A CN 202110207754A CN 112998011 A CN112998011 A CN 112998011A
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000004659 sterilization and disinfection Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 110
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000003930 superacid Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 17
- 230000001954 sterilising effect Effects 0.000 claims abstract description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 68
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 42
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 41
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 38
- 229910052593 corundum Inorganic materials 0.000 claims description 37
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- 239000000645 desinfectant Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001179 sorption measurement Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- 241000894006 Bacteria Species 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 241000700605 Viruses Species 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 claims description 7
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- 239000012855 volatile organic compound Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 230000000840 anti-viral effect Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 241000204003 Mycoplasmatales Species 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 230000009977 dual effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000001590 oxidative effect Effects 0.000 description 10
- 239000002131 composite material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 210000002421 cell wall Anatomy 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 241000228245 Aspergillus niger Species 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191963 Staphylococcus epidermidis Species 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000249 desinfective effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N peroxyacetic acid Substances CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000219495 Betulaceae Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004895 Lipoproteins Human genes 0.000 description 1
- 108090001030 Lipoproteins Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241001430197 Mollicutes Species 0.000 description 1
- 241000204031 Mycoplasma Species 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 241001052560 Thallis Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- -1 amino, carboxyl Chemical group 0.000 description 1
- 230000037358 bacterial metabolism Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- SKFIUGUKJUULEM-UHFFFAOYSA-N butan-1-ol;zirconium Chemical compound [Zr].CCCCO SKFIUGUKJUULEM-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000007102 metabolic function Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/02—Sulfur; Selenium; Tellurium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention provides an HY molecular sieve antibacterial disinfection material loaded with super acid, which is characterized by comprising an HY molecular sieve and super acid loaded on the surface of the HY molecular sieve, wherein the mass ratio of the HY molecular sieve to the super acid is 10:1-100: 1. The super acid loaded HY molecular sieve antibacterial and disinfection material provided by the invention can be used for directly carrying out in-situ oxidation disinfection after the mycoplasma is adsorbed, has obvious antibacterial action (including dual functions of bacteriostasis and sterilization), has the antibacterial rate and the antiviral rate of more than 99%, and is simple and efficient in process, green and environment-friendly. The preparation method of the superacid-loaded HY molecular sieve antibacterial and disinfection material is simple in process and easy to prepare in a large scale.
Description
Technical Field
The invention relates to the field of chemistry, in particular to an HY molecular sieve antibacterial disinfection material loaded with super acid, and a preparation method and application thereof.
Background
With the increasing environmental pollution, various bacteria, mold, viruses and the like have great influence and harm on human life for microorganisms, and the oxidative disinfectant is the most common disinfection and sterilization measure. The oxidant disinfectant is also called peroxide disinfectant, and mainly depends on the strong oxidizing ability to kill microorganisms. Through oxidation reaction, the bacterial strain can directly react with amino, carboxyl and sulfydryl in thalli or protease to damage cell structures or inhibit metabolic functions, so that bacteria die; or the bacterial metabolism system is damaged through oxidation, so that the metabolism is out of balance, and the bacteria die; or through oxidation-reduction reaction, the metabolism of bacteria is accelerated, and the growth process is damaged to cause death. Common oxidative disinfectants are: NaClO, Cl2、H2O2、O3、 Na2O2、HClO、K2MnO4Peroxyacetic acid, oxone, and the like.
Such disinfectants are usually prepared into disinfectants with a certain concentration, and are used for disinfecting instruments, furniture and clothes in a spraying mode, so that the disinfectants can cause certain damage to the skin when being directly contacted with a human body, can cause irreparable influence on human organs and cell tissues after being inhaled into the human body, and are not suitable for large-area indoor air purification. Therefore, the development of new air purification materials is a necessary choice facing the current situation.
CN102000597A discloses a method for preparing a composite solid super acid, which adopts a molecular sieve as a carrier and quickly impregnates and deposits load TiO under the condition of ultrasonic wave2Then washing and concentrating by a ceramic membrane separation device without filtering and drying, and then directly carrying out the next step of loading SO4 2-And finally, carrying out solid-liquid separation, drying and roasting to obtain the composite solid super acidic catalyst. CN106076401A discloses a superacid supported HZSM-5 molecular sieve catalyst, i.e. a superacid TiO is loaded on the surface of an HZSM-5 molecular sieve2·H2SO4、ZrO2·H2SO4、TiO2·H2S2O8Or ZrO2·H2S2O8One or a composition thereof, and also discloses the application of the catalyst in the process of preparing low-carbon olefin by catalytic cracking of naphtha.
Disclosure of Invention
The molecular sieve is usually from TO4Tetrahedrons form crystalline inorganic solids with microporous structures (pore sizes typically less than 2nm) with excellent adsorption, catalysis, and ion exchange properties. In addition, the molecular sieve can be subjected to nano-scale compounding with other catalytic activities (such as compounds or compounds with strong oxidizing property), so that adsorption and strong catalytic oxidizing property are organically combined, and a synergistic catalytic material with stronger performance is obtained. The solid catalytic material is non-toxic and free of secondary pollution, is insoluble in water and organic solvents, can be prepared into particles or compounded with various carriers, is expected to be widely applied to epidemic-resistant products and daily air and water purification products, realizes the adsorption and inactivation of viruses, and improves the protection level.
The technical problem solved by the invention is as follows: the common oxidative disinfectant in the prior art is NaClO and Cl2、H2O2The disinfectant is usually prepared into a disinfectant with a certain concentration, instruments, furniture and clothes are disinfected in a spraying mode, a person can be damaged by directly contacting the disinfectant, the disinfectant can cause irreparable influence on human organs and cell tissues after being inhaled into the human body, the action time is usually only 0.5 hour, and bacteria or viruses can be continuously propagated after the disinfectant is out of work, so that the disinfectant is not suitable for long-acting purification and disinfection of large-area indoor air.
Specifically, the present invention provides the following technical solutions.
The invention provides an HY molecular sieve antibacterial disinfection material loaded with super acid, which comprises an HY molecular sieve and super acid loaded on the surface of the HY molecular sieve, wherein the mass ratio of the HY molecular sieve to the super acid is 10:1-100: 1.
Preferably, SiO in the HY molecular sieve2And Al2O3In a molar ratio of 40 to 1000, preferably 80 to 120, and/or the VOCsThe adsorption capacity of the components is more than or equal to 10.0 percent.
Preferably, the super acid comprises MnO2·H2SO4，ZrO2·H2SO4，Al2O3·H2SO4， TiO2·H2SO4，MnO2·H2S2O8，ZrO2·H2S2O8，Al2O3·H2S2O8And TiO2·H2S2O8One or more kinds of them, preferably, MnO2·H2SO4。
The invention also provides a preparation method of the antibacterial and disinfectant material, which comprises the following steps:
step 1: mixing a silicon source, an aluminum source and a template agent for treatment to obtain the HY molecular sieve;
step 2: MnO formation by chemical liquid phase deposition2、ZrO2、Al2O3And TiO2One or more than two precursors are deposited on the surface of the HY molecular sieve to obtain a material with MnO on the surface2、ZrO2、Al2O3And/or TiO2The HY molecular sieve of (4);
and step 3: the surface obtained in the step 2 contains MnO2、ZrO2、Al2O3And/or TiO2And vulcanizing the HY molecular sieve to obtain the superacid-loaded HY molecular sieve antibacterial and disinfection material.
Preferably, in the step 2, the MnO2、ZrO2、Al2O3And/or TiO2The content of (B) is 0.1-20 wt%, preferably 1-5 wt% of the total mass of the antibacterial and disinfectant material.
Preferably, the silicon source in step 1 is one or more selected from sodium silicate, silica sol, silicon dioxide and tetraethyl silicate,
preferably, the aluminium source is selected from NaAlO2，Al(NO3)3，Al2O3And Al (OH)3One or more than two of the above;
more preferably, the template agent is selected from one or more of tetraethylammonium hydroxide, sodium hydroxide and tetraethylammonium bromide;
further preferably, the mass ratio of the silicon source, the aluminum source and the template agent is 2:1: 0.25.
Preferably, the step 1 comprises mixing the template and part of the aluminum source for heat treatment,
preferably, the heat treatment temperature is 25-40 ℃, the heat treatment time is 10-24h, and the guiding agent is obtained,
more preferably, the silicon source, part of the aluminum source and the guiding agent are mixed and crystallized at the crystallization temperature of 80-180 ℃ for 10-24h, and the Y powder is obtained after drying at the temperature of 40-100 ℃.
Preferably, the Y powder obtained in the step 1 is sequentially subjected to acid washing, hydrothermal overtemperature treatment and/or high-temperature roasting to obtain an HY molecular sieve;
preferably, the acid used for acid washing comprises one or more of nitric acid, hydrochloric acid and sulfuric acid, and the acid washing temperature is 50-100 ℃;
more preferably, the temperature of the hydrothermal overtemperature treatment is 450-700 ℃, and the flow rate is 5-50 mL/h;
further preferably, the high-temperature roasting degree is 450-650 ℃, and the time is 1-5 h.
Preferably, said MnO in said step 22、ZrO2、Al2O3And/or TiO2The precursor is selected from one or two of sodium permanganate, tetrabutyl titanate, sodium aluminate, tetrabutyl zirconate and manganese nitrateThe above;
preferably, the precursor is dissolved in absolute ethyl alcohol, an HY molecular sieve is added into the absolute ethyl alcohol solution containing the precursor,
more preferably, the mass ratio of the HY molecular sieve to the precursor is 10-100.
Preferably, in the step 2, after the HY molecular sieve is added into the anhydrous ethanol solution containing the precursor, the method further comprises the step of heating and stirring, wherein the heating temperature is 60-80 ℃, and the stirring time is 0.5-2 h;
preferably, the stirring process comprises the drying and roasting processes, the roasting temperature is 500-600 ℃, and the roasting time is 1-5h, so that the MnO contained on the surface is obtained2、ZrO2、Al2O3Or TiO2The HY molecular sieve.
Preferably, the surface obtained in step 3 from step 2 contains MnO2、ZrO2、 Al2O3And/or TiO2The HY molecular sieve is added into a sulfur-containing solution, and the surface contains MnO2、 ZrO2、Al2O3And/or TiO2The mass ratio of the HY molecular sieve to the sulfur-containing solution is 10-100; preferably 20 to 40, and/or further comprises a stirring step, wherein the stirring time is 0.5 to 24 hours; preferably for a period of 2-3 hours,
more preferably, the stirring process comprises the drying and roasting processes, the roasting temperature is 500-600 ℃, and the roasting time is 1-5h, so as to obtain the superacid supported HY molecular sieve antibacterial and disinfection material;
further preferably, the SO4 2-Or S2O8 2-The content of (B) is 0.005-2 wt% of the total mass of the catalyst.
Preferably, the sulfur-containing solution is one or more of sulfuric acid, ammonium sulfate, persulfuric acid and ammonium persulfate, and the concentration is 2-20 wt%, preferably 5-10 wt%.
The invention also provides the superacid-loaded HY molecular sieve antibacterial disinfection material prepared by the preparation method.
The invention also provides application of the superacid-loaded HY molecular sieve antibacterial and disinfection material in the aspect of antibacterial and disinfection, and preferably, the application is efficient inactivation of bacterial viruses at room temperature under the condition of no illumination.
The beneficial effects obtained by the invention are as follows: the super acid loaded HY molecular sieve antibacterial and disinfection material provided by the invention can be used for directly carrying out in-situ oxidation disinfection after the mycoplasma is adsorbed, has obvious antibacterial action (including dual functions of bacteriostasis and sterilization), has the antibacterial rate and the antiviral rate of more than 99%, and is simple and efficient in process, green and environment-friendly. The preparation method of the superacid-loaded HY molecular sieve antibacterial and disinfection material is simple in process and easy to prepare in a large scale.
Detailed Description
The technical scheme adopted by the patent for solving the technical problem is as follows: firstly, a molecular sieve porous material with strong water absorption and high adsorption performance is obtained through a synthesis technology, and then a solid super acid component is loaded on a molecular sieve to obtain a composite material with high adsorption capacity and strong oxidation activity.
The preparation method of the multifunctional molecular sieve loading material comprises the following steps:
in order to synthesize the HY molecular sieve with strong hydrophobicity and high adsorption capacity, the HY molecular sieve with high silica-alumina ratio is prepared by regulating and controlling the raw material formulas of a silicon source, an aluminum source and the like in a hydrothermal synthesis method. And then the silicon-aluminum ratio is greatly improved by regulating and controlling the conditions of modification processes such as ion exchange, hydrothermal overtemperature, acid washing, roasting and the like and the proportion of used reagents, so that the HY molecular sieve material with strong hydrophobicity and high adsorption capacity is prepared.
In order to prepare the superacid supported HY molecular sieve catalyst, firstly, a layer of MnO with controllable quality is deposited on the outer surface of HY molecular sieve crystal grains by regulating and controlling the raw material formula in a chemical liquid phase deposition method2、ZrO2、Al2O3Or TiO2. Then, the vulcanization is completed in a sulfur-containing solution (sulfuric acid, ammonium sulfate, persulfuric acid, or an aqueous ammonium persulfate solution). MnO is realized by adjusting the concentration of the sulfur-containing solution and the vulcanization time2、ZrO2、Al2O3Or TiO2The super strong acidification of different degree, and then at HY molecular sieve surface, form the super acid that a layer of can be regulated and control, realize the promotion to HY molecular sieve catalytic activity.
As described above, the present invention discloses for the first time: by the combination of synthesis and loading methods, the superacid is successfully and controllably loaded on the outer surface of an HY molecular sieve crystal grain, and the multifunctional molecular sieve composite material which is hydrophobic, has high adsorption capacity and can inactivate bacteria and viruses at room temperature and under the condition of no illumination is prepared. The solid material is non-toxic and free of secondary pollution, is insoluble in water and organic solvents, can be prepared into particles or compounded with various carriers, is expected to be widely applied to epidemic-resistant products and daily air and water purification products, realizes the adsorption and inactivation of viruses, and improves the protection level.
The present patent provides a molecular sieve based oxidizing antibacterial disinfectant material with excellent adsorption performance and strong oxidizing property, which firstly adsorbs the particles of bacteria, viruses and other mycoplasmas to the surface of the material by adsorption, and then chemically reacts lipoproteins in the cell walls of the mycoplasmas or phospholipids and proteins in the cell membranes by strong oxidizing property, so that the cell walls and cells of the bacteria are destroyed (so-called bacteriolysis), the permeability of the cell membranes is increased, and the substances in the cells flow out to lose the activity. Or destroy and decompose cell wall, rapidly diffuse into cell, and oxidize intracellular enzyme or RNA, DNA, thereby killing mycoplasma.
The invention provides a method for synthesizing an HY molecular sieve, which has strong hydrophobicity and high adsorption capacity.
Preferably, the HY molecular sieve with strong hydrophobicity and high adsorbability is prepared from water glass (or silica sol, SiO)2) As a silicon source, NaAlO is used2(or Al (NO)3)3、Al2O3) The HY molecular sieve is an aluminum source, tetraethyl ammonium hydroxide (TEAOH) (or NaOH) is used as a template agent, the mass of the tetraethyl ammonium hydroxide (TEAOH) (or NaOH) is 2:1:0.25, and the HY molecular sieve with high silicon-aluminum ratio, strong hydrophobicity and high adsorption performance is obtained by a dealuminizing and silicon-supplementing modification method such as a hydrothermal synthesis method, ion exchange, hydrothermal superstability and acid washing.
The second aspect of the invention provides an HY molecular sieve composite material loaded with super acid, which is loaded with super acid on the surface of an HY molecular sieve.
Preferably, the super acid is MnO2·H2SO4、ZrO2·H2SO4、Al2O3·H2SO4、 TiO2·H2SO4、MnO2·H2S2O8、ZrO2·H2S2O8、Al2O3·H2S2O8、TiO2·H2S2O8One or a combination of, wherein MnO is2、ZrO2、Al2O3Or TiO2The content of (A) is 0.1-20 wt% of the total mass of the catalyst, and SO4 2-Or S2O8 2-The content of (B) is 0.005-2 wt% of the total mass of the catalyst.
The third aspect of the invention provides a preparation method of the superacid supported HY molecular sieve composite material, which comprises the following steps:
(1) MnO formation by chemical liquid phase deposition2、ZrO2、Al2O3Or TiO2The precursor is deposited on the surface of an HY molecular sieve, and is further dried and roasted to obtain the material with the MnO on the surface2、ZrO2、Al2O3Or TiO2The HY molecular sieve of (4);
(2) the surface obtained in the step (1) contains MnO2、ZrO2、Al2O3Or TiO2And carrying out vulcanization treatment on the HY molecular sieve, and further drying and roasting to obtain the superacid supported HY molecular sieve catalyst.
In a preferred embodiment of the third aspect of the invention, the following detailed steps are included:
(1) dissolving 0.03-3 g of permanganate, titanate, meta-aluminate or zirconate in 100-500 mL of absolute ethyl alcohol, adding 2-10 g of HY molecular sieve into the solution, stirring for about 0.5-2 hours, filtering, drying the obtained solid, and roasting at 500-600 ℃ for 1Cooling naturally to room temperature for 5 hours to obtain the product with MnO on the surface2、ZrO2、 Al2O3Or TiO2The HY molecular sieve of (4);
(2) the surface obtained in the step (1) contains MnO2、ZrO2、Al2O3Or TiO2And adding the HY molecular sieve into 50-500 mL of sulfur-containing solution, stirring for 0.5-24 hours, filtering, drying the obtained solid, roasting at 500-600 ℃ for 1-5 hours, and naturally cooling to room temperature to obtain the superacid-loaded multifunctional HY molecular sieve material.
Preferably, the sulfur-containing solution is an aqueous solution of sulfuric acid, ammonium sulfate, persulfuric acid or ammonium persulfate, and the concentration of the aqueous solution is 2-20 wt%.
The invention provides the application of the super acid supported HY molecular sieve composite material in adsorption and in-situ sterilization.
In order to better understand the present invention, the following examples are included to further illustrate the present invention.
The manufacturers of the raw materials and equipment used in the present example, and the equipment and analysis method used in the product analysis are described below, wherein the chemical substances are not indicated as being chemically pure grades of conventional reagents.
Among them, information on the raw materials used in examples and comparative examples is shown in table 1 below.
TABLE 1 information on materials and instruments used in the present invention
| Raw materials | Purity of | Manufacturer of the product |
| NaOH | 97％ | SHANGHAI MACKLIN BIOCHEMICAL Co.,Ltd. |
| NaAlO2 | 98％ | SHANGHAI MACKLIN BIOCHEMICAL Co.,Ltd. |
| Sodium silicate | 30％ | SHANGHAI MACKLIN BIOCHEMICAL Co.,Ltd. |
| HNO3 | 0.1M | SHANGHAI MACKLIN BIOCHEMICAL Co.,Ltd. |
| Sodium permanganate | 40％ | Hangzhou Jianfei chemical Co Ltd |
| Anhydrous ethanol | ≥99.5％ | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Ammonium sulfate | 99.0％ | Xuzhou Songyu chemical technology Limited |
| Zirconium Butanol | 28％ | TIANJIN KWANGFU FINE CHEMICAL INDUSTRY Research Institute |
| Al(OH)3 | NULL | Bailingwei Tech Co Ltd |
| Sulfuric acid | 0.1N | Sigma-Aldrich Sigma Alder |
| Tetrabutyl titanate | ≥99.0％ | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
Examples
Example 1: preparation of HY molecular sieve with strong hydrophobicity and high adsorption capacity
(1) Preparing a guiding agent: mixing 3.8g NaOH, 2.1g NaAlO2Mixing with 15.2g deionized water in a 100mL beaker, stirring until the solution is completely dissolved, weighing 21.5g sodium silicate, mixing with the solution, stirring with a rotor under magnetic force, and aging for 24h at 25 ℃.
(2) Preparing mother liquor: 110g of water glass and the guiding agent are mixed and rapidly stirred (magnetic rotor stirring); weighing 85.4g of water and 10.7g of sodium aluminate, stirring and dissolving completely at room temperature, pouring the solution, quickly stirring for 20min, subpackaging the mixed solution into 2 hydrothermal synthesis reaction kettles, crystallizing for 16h at 100 ℃, filtering, washing and drying at 80 ℃ to obtain a NaY powder product.
(3) Modification: 15.0g of NaY molecular sieve and 150mL of HNO with the concentration of 0.4moL/L3And placing the solution into a 250mL flask, stirring and carrying out acid washing at 80 ℃, and after the acid washing is finished, sequentially carrying out hydrothermal superstability (temperature is 600 ℃, flow rate is 20mL/h) and high-temperature roasting (550 ℃, 2h) to obtain the hydrophobic molecular sieve.
Example 2: MnO2·H2SO4Preparation of HY Supported
0.25g of sodium permanganate was dissolved in 125mL of a mixed solvent of absolute ethanol and water (the volume ratio of water to ethanol was 1:4), 5g of the HY molecular sieve described in example 1 was added to the solution, and the mixture was heated at 70 ℃ and stirred for about 2 hours. Next, the solution was filtered, dried, and then calcined at 550 ℃ for 3 hours.
100mL of a 10 wt% aqueous ammonium sulfate solution was taken, and the calcined sample was added to the solution, followed by stirring at room temperature for about 8 hours. Next, the solution was filtered, dried, and then calcined at 550 ℃ for 3 hours to obtain MnO2·H2SO4Supported HY molecular sieve (sample 2), HY molecular sieve and super acid MnO in sample 22·H2SO4The mass ratio of (A) to (B) is 100: 3.
example 3: ZrO (ZrO)2·H2SO4Preparation of HY Supported
Under the condition of protecting gas and excluding air, 0.30g of zirconium butoxide is dissolved in 125mL of absolute ethanol, 5g of HY molecular sieve in example 1 is added to the solution, and the solution is heated to 70 ℃ and stirred for about 2 hours. Next, the solution was filtered, dried, and then calcined at 500 ℃ for 4 hours.
100mL of a 2 wt% aqueous solution of sulfuric acid was taken, and the calcined sample was added to the solution, followed by stirring at room temperature for about 1 hour. Next, the solution was filtered, dried, and then calcined at 500 ℃ for 4 hours to obtain ZrO2·H2SO4Supported HY molecular Sieve (sample 3), HY molecular Sieve and superacid ZrO in sample 32·H2SO4The mass ratio of (A) to (B) is 100: 3.
example 4: al (Al)2O3·H2SO4Preparation of HY Supported
Mixing 0.15gAl (OH)3Dissolved in 125mL of a mixed solvent of absolute ethanol and water (the volume ratio of water to ethanol is 1:4), 5g of the HY molecular sieve in example 1 was added to the solution, and the mixture was heated at 70 ℃ and stirred for about 2 hours. Next, the solution was filtered, dried, and then calcined at 580 ℃ for 2.5 hours.
100mL of a 2 wt% aqueous solution of sulfuric acid was taken, and the calcined sample was added to the solution, followed by stirring at room temperature for about 8 hours. Then, the mixture is filtered and driedThe solution is then calcined at 580 ℃ for 2.5 hours to obtain Al2O3·H2SO4Supported HY molecular sieve (sample 4), HY molecular sieve and super acidic Al in sample 42O3·H2SO4The mass ratio of (A) to (B) is 100: 3.
example 5: TiO 22·H2SO4Preparation of HY Supported
0.15g of tetrabutyl titanate was dissolved in 125mL of absolute ethanol, 5g of the HY molecular sieve of example 1 was added to the solution, and the mixture was heated at 70 ℃ and stirred for about 2 hours. Next, the solution was filtered, dried, and then calcined at 600 ℃ for 2 hours.
100mL of a 10 wt% aqueous ammonium sulfate solution was taken, and the calcined sample was added to the solution, followed by stirring at room temperature for about 8 hours. Next, the solution was filtered, dried, and then calcined at 600 ℃ for 2 hours to obtain TiO2·H2SO4Supported HY molecular Sieve (sample 5), HY molecular Sieve and super acid TiO in sample 52·H2SO4The mass ratio of (A) to (B) is 100: 1.
comparative example 1 Pd Supported ceramic catalyst
Mixing Al (OH)3Mixing with dispersant in the ratio of 2 to 1 to obtain the dipping stock solution. The honeycomb ceramic was immersed therein for about 2 hours, taken out, dried at 120 ℃ for 2 hours, and fired at 550 ℃ for 3 hours, and the above operation was repeated. Placing the honeycomb ceramic carrier after dip coating in 1g/L Ce (NO)3)3Soaking in the solution for 2 hr, drying at 120 deg.C for 2 hr, calcining at 550 deg.C for 3 hr, and soaking in PdCl with pH of 82Drying and roasting the solution to prepare the final catalyst.
Comparative example 2
0.25g of sodium permanganate was dissolved in 125mL of a mixed solvent of absolute ethanol and water (the volume ratio of water to ethanol was 1:4), 5g of the HY molecular sieve described in example 1 was added to the solution, and the mixture was heated to 50 ℃ and stirred for about 2 hours. Next, the solution was filtered, dried, and then calcined at 550 ℃ for 3 hours.
100mL of a 10 wt% aqueous ammonium sulfate solution was taken, and the calcined sample was added to the solutionTo the solution, it was then stirred at room temperature for about 8 hours. Next, the solution was filtered, dried, and then calcined at 550 ℃ for 3 hours to obtain MnO2·H2SO4Supported HY molecular sieve (sample D2).
Comparative example 3
Under the condition of protecting gas and excluding air, 0.30g of zirconium butoxide is dissolved in 125mL of absolute ethanol, 5g of HY molecular sieve in example 1 is added to the solution, and the solution is heated to 70 ℃ and stirred for about 2 hours. Next, the solution was filtered, dried, and then calcined at 500 ℃ for 4 hours.
20mL of a 2 wt% aqueous solution of sulfuric acid was taken, and the calcined sample was added to the solution, followed by stirring at room temperature for about 1 hour. Next, the solution was filtered, dried, and then calcined at 500 ℃ for 4 hours to obtain ZrO2·H2SO4Supported HY molecular sieve (sample D3).
Comparative example 4
Mixing 0.015g Al (OH)3Dissolved in 125mL of a mixed solvent of absolute ethanol and water (the volume ratio of water to ethanol is 1:4), 5g of the HY molecular sieve in example 1 was added to the solution, and the mixture was heated at 70 ℃ and stirred for about 2 hours. Next, the solution was filtered, dried, and then calcined at 580 ℃ for 2.5 hours.
100mL of a 2 wt% aqueous solution of sulfuric acid was taken, and the calcined sample was added to the solution, followed by stirring at room temperature for about 8 hours. Next, the solution was filtered, dried, and then calcined at 580 ℃ for 2.5 hours to obtain Al2O3·H2SO4Supported HY molecular sieve (sample D4).
Application example: evaluation of antibacterial Properties
The antibacterial performance test method in each embodiment of the invention is as follows:
1. antibacterial inspection basis and method: the antibacterial performance detection method of the nano inorganic material G B/T21510-20081 appendix A.
2. Virus purification rate test basis and method: the antibacterial performance detection method of the nano inorganic material G B/T21510-20081 appendix A.
The material was not diluted and the sterility test time was 24 hours.
The test results are shown in table 2.
TABLE 2 HY MOLECULAR SIEVE-SUPER ACID COMPOSITE MATERIAL ANTIBIOTIC AND DISINFECTING PERFORMANCE TEST RESULTS
As can be seen from the data in table 2, the superacid HY-loaded molecular sieves prepared in examples 2 to 5 (samples 2 to 5) have the killing rate on staphylococcus albus and escherichia coli of more than 99%, the killing rate on aerobiotic bacteria of more than 98%, the killing rate on aspergillus niger of more than 99%, and the antiviral rate on H1N1 virus of more than or equal to 99.99%, while the killing rate on staphylococcus albus and escherichia coli of comparative examples 2 to 4 are less than 79%, the killing rate on aerobiotic bacteria of less than 79%, the killing rate on aspergillus niger of less than 80%, and the antiviral rate on H1N1 virus of less than 66%.
Compared with the samples obtained in comparative examples 1 to 4, the super acid supported HY molecular sieve (samples 2 to 5) prepared in examples 2 to 5 has remarkable antibacterial and disinfectant effects. As mentioned above, the HY molecular sieve supported by the super acid is characterized in that in order to improve the antibacterial rate to bacteria and the purification rate to viruses, the outer surface of an HY molecular sieve crystal grain is supported by a super acid shell layer, so that the modified HY molecular sieve improves the catalytic activity and simultaneously has high adsorption capacity. Compared with other HY modification processes, the superacid supported HY molecular sieve disclosed by the invention has the advantages of simple process flow for preparing the catalyst, less related medicines, low price and economic advantage in cost aspect.
The foregoing is considered as illustrative and not restrictive in character, and that various modifications, equivalents, and improvements made within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (14)
1. An HY molecular sieve antibacterial disinfection material loaded with super acid is characterized by comprising an HY molecular sieve and super acid loaded on the surface of the HY molecular sieve, wherein the mass ratio of the HY molecular sieve to the super acid is 10:1-100: 1.
2. The antibacterial and disinfectant material according to claim 1, wherein the HY molecular sieve is SiO2And Al2O3Is 40-1000, preferably 80-120, and/or the adsorption capacity of the VOCs component is greater than or equal to 10.0%.
3. The antibacterial sterilizing material of claim 1 or 2, wherein the super acid comprises MnO2·H2SO4，ZrO2·H2SO4，Al2O3·H2SO4，TiO2·H2SO4，MnO2·H2S2O8，ZrO2·H2S2O8，Al2O3·H2S2O8And TiO2·H2S2O8One or more kinds of them, preferably, MnO2·H2SO4。
4. A method for preparing the antibacterial sterilizing material according to any one of claims 1 to 3, comprising the steps of:
step 1: mixing a silicon source, an aluminum source and a template agent for treatment to obtain the HY molecular sieve;
step 2: MnO formation by chemical liquid phase deposition2、ZrO2、Al2O3And TiO2One or more than two precursors are deposited on the surface of the HY molecular sieve to obtain a material with MnO on the surface2、ZrO2、Al2O3And/or TiO2The HY molecular sieve of (4);
and step 3: the surface obtained in the step 2 contains MnO2、ZrO2、Al2O3And/or TiO2And vulcanizing the HY molecular sieve to obtain the superacid-loaded HY molecular sieve antibacterial and disinfection material.
5. The production method according to claim 4, wherein, in the step 2, the MnO2、ZrO2、Al2O3And/or TiO2The content of (B) is 0.1-20 wt%, preferably 1-5 wt% of the total mass of the antibacterial and disinfectant material.
6. The production method according to claim 4 or 5, wherein the silicon source in step 1 is one or more selected from the group consisting of sodium silicate, silica sol, silica and tetraethyl silicate,
preferably, the aluminium source is selected from NaAlO2，Al(NO3)3，Al2O3And Al (OH)3One or more than two of the above;
more preferably, the template agent is selected from one or more of tetraethylammonium hydroxide, sodium hydroxide and tetraethylammonium bromide;
further preferably, the mass ratio of the silicon source, the aluminum source and the template agent is 2:1: 0.25.
7. The preparation method according to any one of claims 4 to 6, wherein the step 1 comprises mixing and heat treating the template and part of the aluminum source,
preferably, the heat treatment temperature is 25-40 ℃, the heat treatment time is 10-24h, and the guiding agent is obtained,
more preferably, the silicon source, part of the aluminum source and the guiding agent are mixed and crystallized at the crystallization temperature of 80-180 ℃ for 10-24h, and the Y powder is obtained after drying at the temperature of 40-100 ℃.
8. The preparation method of claim 7, wherein the Y powder obtained in the step 1 is sequentially subjected to acid washing, hydrothermal overtemperature treatment and/or high-temperature roasting to obtain an HY molecular sieve;
preferably, the acid used for acid washing comprises one or more of nitric acid, hydrochloric acid and sulfuric acid, and the acid washing temperature is 50-100 ℃;
more preferably, the temperature of the hydrothermal overtemperature treatment is 450-700 ℃, and the flow rate is 5-50 mL/h;
further preferably, the high-temperature roasting degree is 450-650 ℃, and the time is 1-5 h.
9. The production method according to any one of claims 4 to 8, wherein the MnO in the step 22、ZrO2、Al2O3And/or TiO2The precursor of (A) is selected from one or more than two of sodium permanganate, tetrabutyl titanate, sodium aluminate, tetrabutyl zirconate and manganese nitrate;
preferably, the precursor is dissolved in absolute ethyl alcohol, an HY molecular sieve is added into the absolute ethyl alcohol solution containing the precursor,
more preferably, the mass ratio of the HY molecular sieve to the precursor is 10-100.
10. The preparation method according to claim 9, wherein the step 2 further comprises heating and stirring after adding the HY molecular sieve into the anhydrous ethanol solution containing the precursor, wherein the heating temperature is 60-80 ℃, and the stirring time is 0.5-2 h;
preferably, the stirring process comprises the drying and roasting processes, the roasting temperature is 500-600 ℃, and the roasting time is 1-5h, so that the MnO contained on the surface is obtained2、ZrO2、Al2O3Or TiO2The HY molecular sieve.
11. The production method according to any one of claims 4 to 10, wherein the surface obtained in step 3 in step 2 contains MnO2、ZrO2、Al2O3And/or TiO2The HY molecular sieve is added into a sulfur-containing solution, and the surface contains MnO2、ZrO2、Al2O3And/or TiO2The mass ratio of the HY molecular sieve to the sulfur-containing solution is 10-100;preferably 20 to 40, and/or further comprises a stirring step, wherein the stirring time is 0.5 to 24 hours; preferably for a period of 2-3 hours,
more preferably, the stirring process comprises the drying and roasting processes, the roasting temperature is 500-600 ℃, and the roasting time is 1-5h, so as to obtain the superacid supported HY molecular sieve antibacterial and disinfection material;
further preferably, the SO4 2-Or S2O8 2-The content of (B) is 0.005-2 wt% of the total mass of the catalyst.
12. The production method according to claim 11, wherein the sulfur-containing solution is one or more of sulfuric acid, ammonium sulfate, persulfuric acid and ammonium persulfate, and the concentration is 2 to 20 wt%, preferably 5 to 10 wt%.
13. The superacid supported HY molecular sieve antibacterial and disinfectant material prepared by the preparation method of any one of claims 4-12.
14. The super acid supported HY molecular sieve antibacterial disinfection material as claimed in claim 1 is applied to antibacterial disinfection, preferably, the application is to efficiently inactivate bacteria and viruses at room temperature under the condition of no illumination.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110756160A (en) * | 2019-11-05 | 2020-02-07 | 北京泷涛环境科技有限公司 | Modified molecular sieve, preparation method, material and use method |
| CN112057960A (en) * | 2020-09-08 | 2020-12-11 | 北京泷涛环境科技有限公司 | Purifying composite material with air antibacterial and purifying functions and preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110756160A (en) * | 2019-11-05 | 2020-02-07 | 北京泷涛环境科技有限公司 | Modified molecular sieve, preparation method, material and use method |
| CN112057960A (en) * | 2020-09-08 | 2020-12-11 | 北京泷涛环境科技有限公司 | Purifying composite material with air antibacterial and purifying functions and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023032367A1 (en) * | 2021-08-31 | 2023-03-09 | 住友化学株式会社 | Anti-viral material |
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