CN113117669A - Cryptomelane type manganese dioxide oxidant with three-dimensional structure and preparation method and application thereof - Google Patents
Cryptomelane type manganese dioxide oxidant with three-dimensional structure and preparation method and application thereof Download PDFInfo
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- CN113117669A CN113117669A CN202110428818.3A CN202110428818A CN113117669A CN 113117669 A CN113117669 A CN 113117669A CN 202110428818 A CN202110428818 A CN 202110428818A CN 113117669 A CN113117669 A CN 113117669A
- Authority
- CN
- China
- Prior art keywords
- cryptomelane
- manganese dioxide
- oxidant
- dimensional structure
- type manganese
- Prior art date
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 239000007800 oxidant agent Substances 0.000 title claims abstract description 123
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 42
- 238000010525 oxidative degradation reaction Methods 0.000 claims abstract description 37
- 239000007787 solid Substances 0.000 claims abstract description 30
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 150000000703 Cerium Chemical class 0.000 claims abstract description 15
- 150000001621 bismuth Chemical class 0.000 claims abstract description 15
- 150000002696 manganese Chemical class 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 37
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 36
- YJVBLROMQZEFPA-UHFFFAOYSA-L acid red 26 Chemical compound [Na+].[Na+].CC1=CC(C)=CC=C1N=NC1=C(O)C(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=CC=C12 YJVBLROMQZEFPA-UHFFFAOYSA-L 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 18
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 229940099596 manganese sulfate Drugs 0.000 claims description 11
- 235000007079 manganese sulphate Nutrition 0.000 claims description 11
- 239000011702 manganese sulphate Substances 0.000 claims description 11
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 9
- 229960001826 dimethylphthalate Drugs 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000004098 Tetracycline Substances 0.000 claims description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 229960002180 tetracycline Drugs 0.000 claims description 8
- 235000019364 tetracycline Nutrition 0.000 claims description 8
- 229930101283 tetracycline Natural products 0.000 claims description 8
- 150000003522 tetracyclines Chemical class 0.000 claims description 8
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 7
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 7
- 229940043267 rhodamine b Drugs 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 claims description 6
- 229960001680 ibuprofen Drugs 0.000 claims description 6
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 claims description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 5
- CYDMQBQPVICBEU-UHFFFAOYSA-N chlorotetracycline Natural products C1=CC(Cl)=C2C(O)(C)C3CC4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-UHFFFAOYSA-N 0.000 claims description 5
- 229960004475 chlortetracycline Drugs 0.000 claims description 5
- CYDMQBQPVICBEU-XRNKAMNCSA-N chlortetracycline Chemical compound C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-XRNKAMNCSA-N 0.000 claims description 5
- 235000019365 chlortetracycline Nutrition 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- WPPDXAHGCGPUPK-UHFFFAOYSA-N red 2 Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C=3C4=CC=C5C6=CC=C7C8=C(C=9C=CC=CC=9)C9=CC=CC=C9C(C=9C=CC=CC=9)=C8C8=CC=C(C6=C87)C(C=35)=CC=2)C4=C1C1=CC=CC=C1 WPPDXAHGCGPUPK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 3
- XWZDJOJCYUSIEY-UHFFFAOYSA-L disodium 5-[(4,6-dichloro-1,3,5-triazin-2-yl)amino]-4-hydroxy-3-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].Oc1c(N=Nc2ccccc2)c(cc2cc(cc(Nc3nc(Cl)nc(Cl)n3)c12)S([O-])(=O)=O)S([O-])(=O)=O XWZDJOJCYUSIEY-UHFFFAOYSA-L 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 claims 2
- 229940063650 terramycin Drugs 0.000 claims 2
- 239000000356 contaminant Substances 0.000 claims 1
- 238000004220 aggregation Methods 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 230000001988 toxicity Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 102
- 230000000052 comparative effect Effects 0.000 description 52
- 239000002351 wastewater Substances 0.000 description 43
- 230000015556 catabolic process Effects 0.000 description 29
- 238000006731 degradation reaction Methods 0.000 description 29
- 239000000975 dye Substances 0.000 description 24
- 238000001228 spectrum Methods 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 238000002474 experimental method Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 230000000593 degrading effect Effects 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 9
- 239000012046 mixed solvent Substances 0.000 description 9
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000004100 Oxytetracycline Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229960000625 oxytetracycline Drugs 0.000 description 3
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 description 3
- 235000019366 oxytetracycline Nutrition 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 description 3
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- -1 bisphenol a Chemical compound 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000245665 Taraxacum Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a cryptomelane type manganese dioxide oxidant with a three-dimensional structure and a preparation method and application thereof. The preparation method comprises the following steps: enabling a uniformly mixed reaction system containing potassium permanganate, divalent manganese salt, cerium salt, bismuth salt and acid to react for 5-24 hours at 50-100 ℃ to prepare the cryptomelane type manganese dioxide oxidant with a three-dimensional structure, wherein the molar ratio of the potassium permanganate to the cerium salt to the bismuth salt is 1: 0.015-0.075: 0.012-0.55. The preparation method is simple, high in yield, good in repeatability, low in toxicity of the used raw materials and convenient for large-scale production; the cryptomelane type manganese dioxide oxidant prepared by the invention has a unique central aggregation type cuboid structure and a single cryptomelane crystal phase, can greatly improve the specific surface area and the surface adsorption energy, and can be used as a solid oxidant to realize the direct oxidative degradation of organic pollutants in a water body under a neutral condition.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a cryptomelane type manganese dioxide oxidant with a three-dimensional structure, a preparation method and application thereof, and particularly relates to a cryptomelane type manganese dioxide oxidant with a three-dimensional structure, a preparation method thereof, and application thereof in oxidative degradation of organic pollutants in a water body under a neutral condition.
Background
Cryptomelane type manganese dioxide, manganese oxide octahedral molecular sieve, is a typical one-dimensional nanofiber linear structure material, and is formed by arranging 2x2 manganese oxide hexahedral structural units in a common edge mode to form a pore channel structure containing potassium ions, wherein the pore size is equal to that of a pore channel
Cryptomelane type manganese dioxide exhibits excellent properties in terms of adsorption, catalysis, oxidation, and electrical conductivity because it has mixed valence Mn, abundant surface oxygen vacancies and oxygen species, active lattice oxygen, and easy ion exchange properties. Particularly, the material has the property of easy electron transfer, so that the material is often used as a metal oxide catalytic material in recent years and is used in the processes of VOCs elimination, catalytic oxidation degradation of organic pollutants in water and clean synthesis of organic molecules.
The structure of cryptomelane type manganese dioxide is three-dimensional, so that the mass transfer rate of the material in the catalytic process can be improved, and more active crystal faces and activities can be realizedThe exposure of the site greatly improves the physical and chemical properties, thereby being more beneficial to the application of the catalyst in the field of catalysis. Chinese patent CN107021525B discloses the preparation of a-MnO with three-dimensional nanorod structure by oxidizing manganese salt with a hyperoxidant and potassium sulfate in the presence of sulfuric acid2The method of (1). S.l.suib et al reported that a chromium-containing reagent was used to oxidize manganous salts to obtain three-dimensional taraxacum cryptomelane type manganese dioxide (j.am.chem.soc., 2005, 127, 14184; j.phys.chem.b 2006, 110, 3066) via a high pressure hydrothermal reaction. Although the preparation method of three-dimensional cryptomelane type manganese dioxide is available in recent years, high-toxicity and easily carcinogenic chemical reagents are used, and high-pressure hydrothermal reaction conditions cause low yield and poor repeatability, so that large-scale production is difficult. Therefore, the preparation method of cryptomelane type manganese dioxide with the three-dimensional nano structure still needs to be developed so as to meet the requirements of safe and simple operation, high yield, good repeatability, low toxicity of used raw materials and convenience for large-scale production.
Disclosure of Invention
The invention mainly aims to provide a cryptomelane type manganese dioxide oxidant with a three-dimensional structure and a preparation method thereof, so as to overcome the defects of the prior art.
The invention also aims to provide the cryptomelane type manganese dioxide oxidant with the three-dimensional structure, which can be used as a solid oxidant under a neutral condition without adding an external oxidant, and can be applied to the direct oxidative degradation of common water organic pollutants.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of cryptomelane type manganese dioxide oxidant with a three-dimensional structure, which comprises the following steps:
enabling a uniformly mixed reaction system containing potassium permanganate, divalent manganese salt, cerium salt, bismuth salt and acid to react for 5-24 hours at 50-100 ℃ to prepare cryptomelane type manganese dioxide oxidant with a three-dimensional structure;
wherein the molar ratio of the potassium permanganate to the cerium salt to the bismuth salt is 1 to (0.015-0.075) to (0.012-0.55).
The embodiment of the invention also provides the cryptomelane type manganese dioxide oxidant with the three-dimensional structure, which is prepared by the method, and the cryptomelane type manganese dioxide oxidant has a three-dimensional structure of a central aggregation type cuboid and has a single cryptomelane crystalline phase.
The embodiment of the invention also provides a solid oxidant which comprises the cryptomelane type manganese dioxide oxidant with the three-dimensional structure.
The embodiment of the invention also provides an application of the cryptomelane type manganese dioxide oxidant with the three-dimensional structure or the solid oxidant in oxidative degradation of organic pollutants.
The embodiment of the invention also provides a method for oxidatively degrading organic pollutants, which comprises the following steps:
adopting the cryptomelane type manganese dioxide oxidant with the three-dimensional structure or the solid oxidant;
under the neutral condition, the cryptomelane type manganese dioxide oxidant or the solid oxidant is contacted with a water body at least containing organic pollutants to carry out an oxidative degradation reaction, so that the oxidative degradation of the organic pollutants is realized.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with the existing preparation method of cryptomelane type manganese dioxide with a three-dimensional structure, the preparation method disclosed by the invention is safe and simple in operation method, high in yield, good in repeatability, low in toxicity of used raw materials and convenient for large-scale production;
(2) the cryptomelane type manganese dioxide oxidant with the three-dimensional structure has a unique central aggregation type cuboid structure, the specific surface area and the surface adsorption energy can be greatly improved by a single cryptomelane crystalline phase, more reaction active sites are exposed, the cryptomelane type manganese dioxide oxidant can be used as a solid oxidant, direct oxidative degradation of organic pollutants in common water bodies can be realized under a neutral condition without adding an external oxidant, and a potential solid oxidation material is provided for degradation of the water pollutants under a special anaerobic condition.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an SEM spectrum of a cryptomelane-type manganese dioxide oxidizer having a three-dimensional structure prepared in example 1 of the present invention;
FIG. 2 is a SEvei spectrum of a cryptomelane type manganese dioxide oxidizer of three-dimensional structure prepared in example 2 of the present invention;
FIG. 3 is an XRD spectrum of cryptomelane type manganese dioxide oxidizer of three-dimensional structure prepared in example 3 of the present invention;
FIG. 4 is an XRD spectrum of cryptomelane type manganese dioxide oxidizer of three-dimensional structure prepared in example 4 of the present invention;
FIG. 5 is an SEM photograph of a material A prepared in comparative example 1 of the present invention;
FIG. 6 is an SEM spectrum of a material B prepared in comparative example 2 of the present invention;
FIG. 7 is an SEM photograph of material C prepared in comparative example 3 of the present invention;
FIG. 8 is an SEM spectrum of a material D prepared in comparative example 4 of the present invention;
FIG. 9 is an SEM spectrum of material E prepared in comparative example 5 of the present invention;
FIG. 10 is an SEM photograph of a material F prepared in comparative example 6 of the present invention;
FIG. 11 is an SEM spectrum of a material G prepared in comparative example 7 of the present invention;
FIG. 12 is an SEM photograph of a material H prepared in comparative example 8 of the present invention;
FIG. 13 is an SEM photograph of material I prepared in comparative example 9 of the present invention;
fig. 14 is a graph of the cyclic degradation efficiency of cryptomelane type manganese dioxide oxidant with a three-dimensional structure prepared in example 1 of the present invention for degrading organic pollutants in water.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention provides a technical scheme of the present invention through long-term research and a great deal of practice, wherein potassium permanganate, divalent manganese salt, cerium salt, bismuth salt and inorganic acid are uniformly mixed, and the mixture is stirred and post-treated at a certain temperature to obtain the cryptomelane type manganese dioxide solid oxidant with a unique central aggregation type cuboid three-dimensional structure. The technical solution, its implementation and principles, etc. will be further explained as follows.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of the embodiments of the present invention provides a method for preparing cryptomelane-type manganese dioxide oxidant with a three-dimensional structure, including:
enabling a uniformly mixed reaction system containing potassium permanganate, divalent manganese salt, cerium salt, bismuth salt and acid to react for 5-24 hours at 50-100 ℃ to prepare cryptomelane type manganese dioxide oxidant with a three-dimensional structure;
wherein the molar ratio of the potassium permanganate to the cerium salt to the bismuth salt is 1 to (0.015-0.075) to (0.012-0.55).
In some specific embodiments, the molar ratio of the potassium permanganate to the manganous salt is 1: 1-2.
Furthermore, the molar ratio of the potassium permanganate to the acid is 1: 0.001-4.
In some more specific embodiments, the divalent manganese salt includes any one or a combination of two or more of manganese sulfate, manganese chloride, manganese nitrate, and manganese acetate, and is not limited thereto.
Further, the cerium salt includes any one or a combination of two or more of cerium nitrate, cerium sulfate, cerium acetate, and cerium chloride, and is not limited thereto.
Further, the bismuth salt includes any one or a combination of two or more of bismuth nitrate, bismuth sulfate, and bismuth acetate, and is not limited thereto.
Further, the acid comprises any one or the combination of more than two of nitric acid, sulfuric acid, phosphoric acid and acetic acid.
In some more specific embodiments, the preparation method specifically comprises: and (2) mixing a divalent manganese salt, a cerium salt, a bismuth salt, an acid and water to form a mixed solution, mixing the mixed solution with an aqueous solution containing potassium permanganate to form the uniform mixed reaction system, and carrying out stirring reaction to prepare the cryptomelane type manganese dioxide oxidant with the three-dimensional structure.
In some more specific embodiments, the preparation method further comprises: after the reaction is completed, the obtained mixture is subjected to filtration, washing and drying.
Further, the drying treatment temperature is 80-150 ℃, and the drying treatment time is 5-24 hours.
In some more specific embodiments, the method for preparing the cryptomelane-type manganese dioxide oxidant with the three-dimensional structure specifically comprises the following steps:
stirring and reacting a uniformly mixed reaction system containing potassium permanganate, divalent manganese salt, cerium salt, bismuth salt and inorganic acid at 50-100 ℃ for 5-24 hours to obtain cryptomelane type manganese dioxide oxidant with a three-dimensional structure;
the molar ratio of the potassium permanganate to the divalent manganese salt is 1: 0.001-1: 0.1, the molar ratio of the potassium permanganate to the cerium salt is 1: 0.018-1: 0.075, the molar ratio of the potassium permanganate to the bismuth salt is 1: 0.012-1: 0.04, and the molar ratio of the potassium permanganate to the inorganic acid is 1: 0.001-1: 4;
the cryptomelane type manganese dioxide oxidant with the three-dimensional structure has a central aggregation type cuboid three-dimensional structure and a single cryptomelane crystalline phase, and the specific surface area of the cryptomelane crystalline phase is 140m2/g～220m2/g。
Yet another aspect of an embodiment of the present invention provides cryptomelane-type manganese dioxide oxidant having a three-dimensional structure prepared by the foregoing method, the cryptomelane-type manganese dioxide oxidant having a three-dimensional structure of a central aggregated-type cuboid, and the cryptomelane-type manganese dioxide oxidant having a single cryptomelane crystalline phase.
Further, the specific surface area of the cryptomelane type manganese dioxide oxidant is 140-220 m2The pore diameter of the pores is 4.7-9.1 nm.
In another aspect of the embodiments of the present invention, there is also provided a solid oxidizer including the cryptomelane-type manganese dioxide oxidizer having a three-dimensional structure as described above.
In another aspect of the embodiment of the present invention, an application of the cryptomelane type manganese dioxide oxidant with the three-dimensional structure or the solid oxidant in oxidative degradation of organic pollutants is further provided.
Further, the organic pollutants include one or a combination of two or more of rhodamine B, acid scarlet G, reactive brilliant blue, reactive red 2, methylene blue, tetracycline, aureomycin, oxytetracycline, ibuprofen, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, bisphenol a, and phenol, but are not limited thereto.
Another aspect of an embodiment of the present invention also provides a method for oxidative degradation of organic pollutants, which includes:
adopting the cryptomelane type manganese dioxide oxidant with the three-dimensional structure or the solid oxidant;
under the neutral condition, the cryptomelane type manganese dioxide oxidant or the solid oxidant is contacted with a water body at least containing organic pollutants to carry out an oxidative degradation reaction, so that the oxidative degradation of the organic pollutants is realized.
Further, the time of the oxidative degradation reaction is 1-40 min.
Further, the organic pollutants include one or a combination of two or more of rhodamine B, acid scarlet G, reactive brilliant blue, reactive red 2, methylene blue, tetracycline, aureomycin, oxytetracycline, ibuprofen, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, bisphenol a, and phenol, but are not limited thereto.
Further, the preparation method further comprises the following steps: and after the oxidative degradation reaction is finished, filtering and drying the cryptomelane type manganese dioxide oxidant for recycling.
Further, the recovery treatment comprises filtration and drying treatment, and the oxidability of the cryptomelane type manganese dioxide oxidant after the recovery treatment cannot be lost.
Further, the drying treatment temperature is 50-100 ℃, and the drying treatment time is 5-8 hours.
In conclusion, by the technical scheme, the operation method is safe and simple, the yield is high, the repeatability is good, the used raw materials are low in toxicity, the obtained cryptomelane type manganese dioxide with the three-dimensional structure has a unique center aggregation type cuboid structure, the specific surface area and the surface adsorption energy are greatly improved by a single cryptomelane crystal phase, more reaction active sites are exposed, and the cryptomelane type manganese dioxide can be used as a solid oxidant to degrade organic pollutants such as rhodamine B, acid scarlet G, active brilliant blue, active red 2, methylene blue, tetracycline, aureomycin, oxytetracycline, ibuprofen, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, bisphenol A, phenol and the like under a neutral condition, and has excellent oxidation activity.
In the application, the cryptomelane type manganese dioxide oxidant with the prepared three-dimensional structure is an oxidizing material, the oxidant does not need to be additionally added when organic matters are degraded, the material can be recycled, pollutants are directly degraded with the material effect in principle, and then the cryptomelane type manganese dioxide oxidant is recycled and dried, so that recycling of the cryptomelane type manganese dioxide oxidant is realized.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
(1) Dissolving 0.104mol of manganese sulfate, 0.0056mol of cerium nitrate, 0.0036mol of bismuth nitrate and 6mL of nitric acid in 60mL of deionized water at room temperature, dropwise adding 200mL of deionized water solution containing 0.074mol of potassium permanganate into the mixed solvent, stirring and mixing uniformly, stirring and reacting at 60 ℃ for 24h, filtering, washing with distilled water, and drying at 100 ℃ for 12h to obtain the cryptomelane type manganese dioxide oxidant material with the three-dimensional structure. And (3) material morphology identification: the SEM spectrum of cryptomelane type manganese dioxide oxidant with three-dimensional structure obtained in this example is shown in FIG. 1, and the specific surface area is 205m2/g。
(2) Application of oxidative degradation of organic pollutants in water body
The cryptomelane type manganese dioxide oxidant with the three-dimensional structure prepared in the example is added into 200mg/L of active red 2 dye wastewater, the concentration of the solid oxidant in the wastewater is 2g/L, after stirring and reacting for 60min at room temperature, the degradation rate of the active red 2 dye is 99%, the cryptomelane type manganese dioxide oxidant in the degraded wastewater is filtered and dried at 70 ℃ for 6h for recovery, and then the recovered cryptomelane type manganese dioxide oxidant is recycled to degrade organic pollutants, wherein the degradation efficiency is shown in fig. 14.
Comparative experiment: the cryptomelane type manganese dioxide oxidant with the three-dimensional structure prepared in the example is not added into the wastewater, and the degradation rate is 0% under the same reaction conditions.
Example 2
(1) Dissolving 0.4mol of manganese sulfate, 0.022mol of cerium nitrate, 0.014mol of bismuth nitrate and 24mL of nitric acid in 200mL of deionized water at room temperature, dropwise adding 1L of deionized water solution containing 0.4mol of potassium permanganate into the mixed solvent, stirring and mixing uniformly, stirring and reacting at 100 ℃ for 20h, filtering, washing with distilled water, and drying at 120 ℃ for 2h to obtain the cryptomelane type manganese dioxide oxidant material with a three-dimensional structure. And (3) material morphology identification: the SEM spectrum of cryptomelane type manganese dioxide oxidant material with three-dimensional structure obtained in this example is shown in FIG. 2, and the specific surface area is 203m2/g。
(2) Application of oxidative degradation of organic pollutants in water body
The cryptomelane type manganese dioxide oxidant with the three-dimensional structure prepared in the example is added into 200mg/L of acid scarlet G dye wastewater, the concentration of the solid oxidant in the wastewater is 1.5G/L, and after stirring and reacting for 30min at room temperature, the degradation rate of the acid scarlet G dye is 99%.
Comparative experiment: the cryptomelane type manganese dioxide oxidant with the three-dimensional structure prepared in the example is not added into the wastewater, and the degradation rate is 0% under the same reaction conditions.
Example 3
(1) Dissolving 0.104mol of manganese sulfate, 0.0014mol of cerium nitrate, 0.0009mol of bismuth nitrate and 6mL of nitric acid in 60mL of deionized water at room temperature, dropwise adding 200mL of deionized water solution containing 0.074mol of potassium permanganate into the mixed solvent, stirring and mixing uniformly, stirring and reacting at 100 ℃ for 24h, filtering, washing with distilled water, and drying at 100 ℃ for 12h to obtain the cryptomelane type manganese dioxide oxidant material with a three-dimensional structure. And (3) identifying the crystal form structure of the material: the XRD spectrum of cryptomelane type manganese dioxide oxidant material with three-dimensional structure obtained in this example is shown in FIG. 3, and the specific surface area is 202m2/g。
(2) Application of oxidative degradation of organic pollutants in water body
The cryptomelane type manganese dioxide oxidant with the three-dimensional structure prepared in the embodiment is added into 100mg/L of rhodamine B dye wastewater, the concentration of the solid oxidant in the wastewater is 0.8g/L, and after stirring and reacting for 30min at room temperature, the degradation rate of the rhodamine B dye is 99%.
Example 4
(1) Dissolving 4mol of manganese sulfate, 0.05mol of cerium nitrate, 0.1mol of bismuth nitrate and 200mL of nitric acid in 2.5L of deionized water at room temperature, dropwise adding 8L of deionized water solution containing 3.2mol of potassium permanganate into the mixed solvent, stirring and mixing uniformly, stirring and reacting at 90 ℃ for 24h, filtering, washing with distilled water, and drying at 150 ℃ for 8h to obtain the cryptomelane type manganese dioxide oxidant material with a three-dimensional structure. And (3) identifying the crystal form structure of the material: XR of cryptomelane type manganese dioxide oxidant material having three-dimensional structure obtained in this exampleThe spectrum D is shown in FIG. 4, and the specific surface area is 162m2/g。
(2) Application of oxidative degradation of organic pollutants in water body
The cryptomelane type manganese dioxide oxidant with the three-dimensional structure prepared in the example is added into 500mg/L of methylene blue dye wastewater, the concentration of the solid oxidant in the wastewater is 10g/L, and after the solid oxidant is stirred and reacts for 10min at room temperature, the degradation rate of the methylene blue dye is 99%.
Example 5
(1) Dissolving 0.104mol of manganese sulfate, 0.0028mol of cerium nitrate, 0.0018mol of bismuth nitrate and 6mL of nitric acid in 60mL of deionized water at room temperature, dropwise adding 200mL of deionized water solution containing 0.074mol of potassium permanganate into the mixed solvent, stirring and mixing uniformly, stirring and reacting at 90 ℃ for 24h, filtering, washing with distilled water, and drying at 150 ℃ for 8h to obtain the cryptomelane type manganese dioxide oxidant material with the three-dimensional structure, wherein the specific surface area of the cryptomelane type manganese dioxide oxidant material is 145m2/g。
(2) Application of oxidative degradation of organic pollutants in water body
The cryptomelane type manganese dioxide oxidant with the three-dimensional structure prepared in the example is added into tetracycline waste water of 50mg/L, the concentration of the solid oxidant in the waste water is 1.5g/L, and after stirring and reacting for 60min at room temperature, the tetracycline degradation rate is 79%.
Comparative experiment: the cryptomelane type manganese dioxide oxidant with the three-dimensional structure prepared in the example is not added into the wastewater, and the degradation rate is 0% under the same reaction conditions.
Example 6
(1) Dissolving 1.04mol of manganese sulfate, 0.018mol of cerium nitrate, 0.012mol of bismuth nitrate and 50mL of nitric acid in 500mL of deionized water at room temperature, dropwise adding 2L of deionized water solution containing 0.74mol of potassium permanganate into the mixed solvent, stirring and mixing uniformly, stirring and reacting for 20h at the temperature of 50 ℃, filtering, washing with distilled water, drying for 5h at the temperature of 150 ℃ to obtain cryptomelane type manganese dioxide oxidant material with a three-dimensional structure, wherein the specific surface area of the cryptomelane type manganese dioxide oxidant material is 180m2/g。
(2) Application of oxidative degradation of organic pollutants in water body
The cryptomelane type manganese dioxide oxidant with the three-dimensional structure prepared in the example is added into the ibuprofen waste water with the concentration of 0.8g/L, and after the solid oxidant is stirred and reacts for 60min at room temperature, the tetracycline degradation rate is 85%.
Comparative experiment: the cryptomelane type manganese dioxide oxidant with the three-dimensional structure prepared in the example is not added into the wastewater, and the degradation rate is 0% under the same reaction conditions.
Example 7
(1) Dissolving 0.104mol of manganese sulfate, 0.0056mol of cerium nitrate, 0.0036mol of bismuth nitrate and 6mL of nitric acid in 60mL of deionized water at room temperature, dropwise adding 200mL of deionized water solution containing 0.074mol of potassium permanganate into the mixed solvent, stirring and mixing uniformly, stirring and reacting at 50 ℃ for 20h, filtering, washing with distilled water, and drying at 90 ℃ for 10h to obtain cryptomelane type manganese dioxide oxidant material with a three-dimensional structure, wherein the specific surface area of the cryptomelane type manganese dioxide oxidant material is 168m2/g。
(2) Application of oxidative degradation of organic pollutants in water body
The cryptomelane type manganese dioxide oxidant with the three-dimensional structure prepared in the example was added to dimethyl phthalate wastewater of 50mg/L, the concentration of the solid oxidant in the wastewater was 3.5g/L, and after stirring and reacting at room temperature for 60min, the degradation rate of dimethyl phthalate was 88%.
Comparative experiment: the cryptomelane type manganese dioxide oxidant with the three-dimensional structure prepared in the example is not added into the wastewater, and the degradation rate is 0% under the same reaction conditions.
Example 8
(1) Dissolving 0.104mol of manganese sulfate, 0.0056mol of cerium sulfate, 0.0036mol of bismuth sulfate and 2mL of sulfuric acid in 60mL of deionized water at room temperature, dropwise adding 200mL of deionized water solution containing 0.074mol of potassium permanganate into the mixed solvent, stirring and mixing uniformly, stirring and reacting at 100 ℃ for 18h, filtering, washing with distilled water, and drying at 90 ℃ for 10h to obtain cryptomelane type manganese dioxide oxidant material with a three-dimensional structure, wherein the specific surface area of the cryptomelane type manganese dioxide oxidant material is 195m2/g。
Application of oxidative degradation of organic pollutants in water body
The cryptomelane type manganese dioxide oxidant with the three-dimensional structure prepared in the example is added into bisphenol A wastewater of 20mg/L, the concentration of the solid oxidant in the wastewater is 1.5g/L, and after stirring and reacting for 30min at room temperature, the degradation rate of dimethyl phthalate is 92%.
Comparative experiment: the cryptomelane type manganese dioxide oxidant with the three-dimensional structure prepared in the example is not added into the wastewater, and the degradation rate is 0% under the same reaction conditions.
Example 9
(1) Dissolving 0.2mol of manganese sulfate, 0.008mol of cerium nitrate, 0.005mol of bismuth nitrate and 6mL of nitric acid in 100mL of deionized water at room temperature, dropwise adding 500mL of deionized water solution containing 0.15mol of potassium permanganate into the mixed solvent, stirring and mixing uniformly, stirring and reacting at 70 ℃ for 24h, filtering, washing with distilled water, drying at 100 ℃ for 10h to obtain cryptomelane type manganese dioxide oxidant material with a three-dimensional structure, wherein the specific surface area of the cryptomelane type manganese dioxide oxidant material is 145m2/g。
Application of oxidative degradation of organic pollutants in water body
The cryptomelane type manganese dioxide oxidant with the three-dimensional structure prepared in the example is added into phenol wastewater of 100mg/L, the concentration of the solid oxidant in the wastewater is 2.5g/L, and after stirring and reacting for 120min at room temperature, the degradation rate of dimethyl phthalate is 85%.
Comparative experiment: the cryptomelane type manganese dioxide oxidant with the three-dimensional structure prepared in the example is not added into the wastewater, and the degradation rate is 0% under the same reaction conditions.
Comparative example 1
(1) This comparative example is substantially the same as example 1 except that: cerium nitrate and bismuth nitrate are not added in the step (1), and the finally obtained material is marked as a material A which has the shape of one-dimensional nano fibrous cryptomelane. And (3) material morphology identification: the SEM spectrum of the material A obtained in this comparative example is shown in FIG. 5, and the specific surface area is 67m2/g。
(2) Application of oxidative degradation of organic pollutants in water body
The oxidation performance of material a prepared in this control example was considered using an experiment for degrading acid scarlet G. The material A prepared in the comparative example is added into 200mg/L acid scarlet G dye wastewater, the concentration of the material in the wastewater is 1.5G/L, and after stirring and reacting for 60min at room temperature, the degradation rate of the acid scarlet G dye is 29%.
Comparative example 2
(1) This comparative example is substantially the same as example 1 except that: cerium nitrate is not added in the step (1), and the finally obtained material is marked as a material B which has a one-dimensional nano fibrous shape. And (3) material morphology identification: the SEM spectrum of the material B obtained in this comparative example is shown in FIG. 6, and the specific surface area is 95m2/g。
(2) Application of oxidative degradation of organic pollutants in water body
The oxidation performance of material B prepared in this control example was considered using an experiment for degrading acid scarlet G. The material B prepared in the comparative example is added into 200mg/L acid scarlet G dye wastewater, the concentration of the material in the wastewater is 1.5G/L, and after stirring and reacting for 60min at room temperature, the degradation rate of the acid scarlet G dye is 20%.
Comparative example 3
(1) This comparative example is substantially the same as example 1 except that: bismuth nitrate is not added in the step (1), and the finally obtained material is marked as a material C which has an amorphous shape. And (3) material morphology identification: the SEM spectrum of the material C obtained in this comparative example is shown in FIG. 7.
(2) Application of oxidative degradation of organic pollutants in water body
The oxidation performance of material C prepared in this control example was considered using an experiment for degrading acid scarlet G. The material C prepared in the comparative example is added into 200mg/L acid scarlet G dye wastewater, the concentration of the material in the wastewater is 1.5G/L, and after stirring and reacting for 60min at room temperature, the degradation rate of the acid scarlet G dye is 12%.
Comparative example 4
(1) This comparative example is substantially the same as example 1 except that: and (2) adding 0.056mol of cerium nitrate and 0.036mol of bismuth nitrate into the step (1) to finally obtain a material D which has a nanometer short rod-shaped appearance. And (3) material morphology identification: this comparative example gaveThe SEM spectrum of the material D is shown in FIG. 8, which has a specific surface area of 85m2/g。
(2) Application of oxidative degradation of organic pollutants in water body
The oxidation performance of material D prepared in this control example was considered using an experiment for degrading acid scarlet G. The material D prepared in the comparative example is added into 200mg/L acid scarlet G dye wastewater, the concentration of the material in the wastewater is 1.5G/L, and after stirring and reacting for 60min at room temperature, the degradation rate of the acid scarlet G dye is 15%.
Comparative example 5
(1) In this comparative example, the material a obtained in comparative example 1 was used as a support material, and was immersed in a deionized water solution containing 0.0056mol of cerium nitrate and 0.0036mol of bismuth nitrate for 24 hours, and then filtered to remove the solution, dried, and calcined, to obtain a material denoted as material E having a one-dimensional nano short rod-like morphology with cerium oxide and bismuth oxide nanoparticle clusters supported on the surface. And (3) material morphology identification: the SEM spectrum of the material E obtained in this comparative example is shown in FIG. 9, and the specific surface area is 67m2/g。
(2) Application of oxidative degradation of organic pollutants in water body
The oxidation performance of material E prepared in this control example was considered using an experiment for degrading acid scarlet G. The material E prepared in the comparative example was added to 200mg/L of acid scarlet G dye wastewater, the concentration of the material in the wastewater was 1.5G/L, and after stirring and reacting at room temperature for 60min, the acid scarlet G dye degradation rate was 25%.
Comparative example 6
(1) This comparative example is substantially the same as example 1 except that: and (2) adding 0.0056mol of cerium nitrate and 0.0006mol of bismuth nitrate into the step (1), and finally obtaining a material F which has a mixed shape of a nanometer short rod and an amorphous shape. And (3) material morphology identification: the SEM spectrum of the material F obtained in this comparative example is shown in FIG. 10, and the specific surface area is 135m2/g。
(2) Application of oxidative degradation of organic pollutants in water body
The oxidation performance of material F prepared in this control example was considered using an experiment for degrading acid scarlet G. The material F prepared in the comparative example is added into 200mg/L acid scarlet G dye wastewater, the concentration of the material in the wastewater is 1.5G/L, and after stirring and reacting for 60min at room temperature, the degradation rate of the acid scarlet G dye is 65%.
Comparative example 7
(1) This comparative example is substantially the same as example 1 except that: and (2) adding 0.006mol of cerium nitrate and 0.036mol of bismuth nitrate into the step (1) to finally obtain a material G which has an amorphous morphology. And (3) material morphology identification: the SEM spectrum of the material G obtained in this comparative example is shown in FIG. 11, and the specific surface area is 238m2/g。
(2) Application of oxidative degradation of organic pollutants in water body
The oxidation performance of material F prepared in this control example was considered using an experiment for degrading acid scarlet G. The material G prepared in the comparative example is added into 200mg/L acid scarlet G dye wastewater, the concentration of the material in the wastewater is 1.5G/L, and after stirring and reacting for 60min at room temperature, the degradation rate of the acid scarlet G dye is 15%.
Comparative example 8
(1) This comparative example is substantially the same as example 1 except that: and (2) adding 0.00074mol of cerium nitrate and 0.00074mol of bismuth nitrate into the step (1), and finally obtaining a material marked as a material H with a nano-particle morphology. And (3) material morphology identification: the SEM spectrum of the material H obtained in this comparative example is shown in FIG. 12, and the specific surface area is 75m2/g。
(2) Application of oxidative degradation of organic pollutants in water body
The oxidation performance of material F prepared in this control example was considered using an experiment for degrading acid scarlet G. The material H prepared in the comparative example is added into 200mg/L acid scarlet G dye wastewater, the concentration of the material in the wastewater is 1.5G/L, and after stirring and reacting for 60min at room temperature, the degradation rate of the acid scarlet G dye is 35%.
Comparative example 9
(1) This comparative example is substantially the same as example 1 except that: and (2) adding 0.006mol of cerium nitrate and 0.05mol of bismuth nitrate into the step (1) to finally obtain a material I which has an amorphous morphology. And (3) material morphology identification: this comparisonThe SEM spectrum of the obtained material I is shown in FIG. 13, and the specific surface area is 175m2/g。
(2) Application of oxidative degradation of organic pollutants in water body
The oxidation performance of material F prepared in this control example was considered using an experiment for degrading acid scarlet G. The material I prepared in the comparative example is added into 200mg/L acid scarlet G dye wastewater, the concentration of the material in the wastewater is 1.5G/L, and after stirring and reacting for 60min at room temperature, the degradation rate of the acid scarlet G dye is 18%.
In addition, the present inventors have also conducted experiments with other raw materials and conditions, etc. listed in the present specification, in the manner of example 1 to example 9, and also produced cryptomelane-type manganese dioxide solid oxidizer having a three-dimensional structure with greatly improved specific surface area and oxidation activity.
In conclusion, the operation method is safe and simple, the yield is high, the repeatability is good, the used raw materials are low in toxicity, the obtained cryptomelane type manganese dioxide with the three-dimensional structure has a unique central aggregation type cuboid structure, the specific surface area and the surface adsorption energy are greatly improved due to the single cryptomelane crystal phase, more reaction active sites are exposed, and the cryptomelane type manganese dioxide can be used as a solid oxidant to realize the oxidative degradation of organic pollutants in common water bodies under a neutral condition.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the protection scope of the claims.
Claims (10)
1. A preparation method of cryptomelane type manganese dioxide oxidant with a three-dimensional structure is characterized by comprising the following steps of:
enabling a uniformly mixed reaction system containing potassium permanganate, divalent manganese salt, cerium salt, bismuth salt and acid to react for 5-24 hours at 50-100 ℃ to prepare cryptomelane type manganese dioxide oxidant with a three-dimensional structure;
wherein the molar ratio of the potassium permanganate to the cerium salt to the bismuth salt is 1 to (0.015-0.075) to (0.012-0.55).
2. The method of claim 1, wherein: the molar ratio of the potassium permanganate to the divalent manganese salt is 1: 1-2;
and/or the molar ratio of the potassium permanganate to the acid is 1: 0.001-4.
3. The method of claim 1, wherein: the divalent manganese salt comprises any one or the combination of more than two of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate;
and/or the cerium salt comprises any one or the combination of more than two of cerium nitrate, cerium sulfate, cerium acetate and cerium chloride;
and/or the bismuth salt comprises any one or the combination of more than two of bismuth nitrate, bismuth sulfate and bismuth acetate;
and/or the acid comprises any one or the combination of more than two of nitric acid, sulfuric acid, phosphoric acid and acetic acid.
4. The method according to claim 1, comprising: and (2) mixing a divalent manganese salt, a cerium salt, a bismuth salt, an acid and water to form a mixed solution, mixing the mixed solution with an aqueous solution containing potassium permanganate to form the uniform mixed reaction system, and carrying out stirring reaction to prepare the cryptomelane type manganese dioxide oxidant with the three-dimensional structure.
5. The method of claim 1, further comprising: after the reaction is finished, filtering, washing and drying the obtained mixture;
preferably, the drying treatment temperature is 80-150 ℃ and the drying treatment time is 5-24 h.
6. The cryptomelane-type manganese dioxide oxidant having a three-dimensional structure prepared by the method of any one of claims 1-5, the cryptomelane-type manganese dioxide oxidant having a three-dimensional structure of a central aggregated rectangular body, and the cryptomelane-type manganese dioxide oxidant having a single cryptomelane crystalline phase;
preferably, the specific surface area of the cryptomelane type manganese dioxide oxidant is 140-220 m2The pore diameter of the pores is 4.7-9.1 nm.
7. A solid oxidizing agent characterized by comprising the cryptomelane-type manganese dioxide oxidizing agent of the three-dimensional structure of claim 6.
8. The use of cryptomelane-type manganese dioxide oxidant of the three-dimensional structure of claim 6 or the solid oxidant of claim 7 for the oxidative degradation of organic pollutants;
preferably, the organic pollutants comprise one or a combination of more than two of rhodamine B, acid scarlet G, reactive brilliant blue, reactive red 2, methylene blue, tetracycline, aureomycin, terramycin, ibuprofen, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, bisphenol A and phenol.
9. A method for the oxidative degradation of organic contaminants, comprising:
adopting the cryptomelane type manganese dioxide oxidant with the three-dimensional structure as defined in claim 6 or the solid oxidant as defined in claim 7;
under the neutral condition, the cryptomelane type manganese dioxide oxidant or the solid oxidant is contacted with a water body at least containing organic pollutants to carry out an oxidative degradation reaction, so that the oxidative degradation of the organic pollutants is realized.
10. The method of claim 9, wherein: the organic pollutants comprise one or the combination of more than two of rhodamine B, acid scarlet G, active brilliant blue, active red 2, methylene blue, tetracycline, aureomycin, terramycin, ibuprofen, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, bisphenol A and phenol;
and/or, the preparation method further comprises the following steps: after the oxidative degradation reaction is finished, filtering and drying the cryptomelane type manganese dioxide oxidant for recycling; preferably, the drying treatment temperature is 50-100 ℃, and the drying treatment time is 5-8 h.
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