CN106366102A - Waugh-type manganese molybdate included in dysprosium-isonicotinic acid, and preparation method and application thereof - Google Patents
Waugh-type manganese molybdate included in dysprosium-isonicotinic acid, and preparation method and application thereof Download PDFInfo
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- CN106366102A CN106366102A CN201610641621.7A CN201610641621A CN106366102A CN 106366102 A CN106366102 A CN 106366102A CN 201610641621 A CN201610641621 A CN 201610641621A CN 106366102 A CN106366102 A CN 106366102A
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- dysprosium
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- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 26
- 239000011572 manganese Substances 0.000 title claims abstract description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 25
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- NCFKYZGQOULHRT-UHFFFAOYSA-N C(C1=CC=NC=C1)(=O)O.[Dy] Chemical compound C(C1=CC=NC=C1)(=O)O.[Dy] NCFKYZGQOULHRT-UHFFFAOYSA-N 0.000 title abstract 2
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims abstract description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 11
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000012153 distilled water Substances 0.000 claims description 20
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 20
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 19
- 238000013019 agitation Methods 0.000 claims description 19
- DVENVBCPDCQQGD-UHFFFAOYSA-N dysprosium(3+);trinitrate Chemical compound [Dy+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DVENVBCPDCQQGD-UHFFFAOYSA-N 0.000 claims description 15
- 229960000583 acetic acid Drugs 0.000 claims description 13
- 239000012362 glacial acetic acid Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000012467 final product Substances 0.000 claims description 9
- 241000972773 Aulopiformes Species 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 235000019515 salmon Nutrition 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- WXLFIFHRGFOVCD-UHFFFAOYSA-L azophloxine Chemical compound [Na+].[Na+].OC1=C2C(NC(=O)C)=CC(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=C1N=NC1=CC=CC=C1 WXLFIFHRGFOVCD-UHFFFAOYSA-L 0.000 abstract description 29
- 235000012739 red 2G Nutrition 0.000 abstract description 29
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 6
- 238000011160 research Methods 0.000 abstract description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 52
- 230000001699 photocatalysis Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- 238000002835 absorbance Methods 0.000 description 11
- 230000008859 change Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000975 dye Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 238000006552 photochemical reaction Methods 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- LQYSRXGPAGSDSK-UHFFFAOYSA-N dysprosium;nitric acid Chemical compound [Dy].O[N+]([O-])=O LQYSRXGPAGSDSK-UHFFFAOYSA-N 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- -1 manganese molybdic acid salt Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- GVKCHTBDSMQENH-UHFFFAOYSA-L phloxine B Chemical compound [Na+].[Na+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 GVKCHTBDSMQENH-UHFFFAOYSA-L 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical group CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- CQPFMGBJSMSXLP-ZAGWXBKKSA-M Acid orange 7 Chemical compound OC1=C(C2=CC=CC=C2C=C1)/N=N/C1=CC=C(C=C1)S(=O)(=O)[O-].[Na+] CQPFMGBJSMSXLP-ZAGWXBKKSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 101150050192 PIGM gene Proteins 0.000 description 1
- 241000719193 Seriola rivoliana Species 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000002864 food coloring agent Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000016768 molybdenum Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic System without C-Metal linkages
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- B01J35/39—
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The invention relates to Waugh-type manganese molybdate included in dysprosium-isonicotinic acid. The Waugh-type manganese molybdate has a chemical formula of (NH4)3[Dy(Hina)2(H2O)6][MnIVMo9O32].7H2O. The Waugh-type manganese molybdate is prepared from manganese acetate, dysprosium nitrate, isonicotinic acid, hydrogen peroxide with a concentration of 30%, glacial acetate acid and ammonium heptamolybdate through a reaction in an aqueous solution. The preparation method is simple, easy to operate and low in cost; and crystals are fast in growth and high in yield. Experimental and research results show that the Waugh-type manganese molybdate exerts good photocatalytic degradation effect on azophloxine and provide experimental basis for application of polyoxomolybdate to photocatalytic degradation of organic dyestuffs.
Description
Technical field
The invention belongs to many molybdenums oxygen hydrochlorate technical field of chemical material preparation is and in particular to what a kind of dysprosium .gamma.-pyridinecarboxylic acid comprised
Waugh type manganese molybdic acid salt production process and its application in terms of organic dyestuff light degradation, this compound utilizes manganese acetate, nitric acid
Dysprosium .gamma.-pyridinecarboxylic acid, 30% hydrogen peroxide, glacial acetic acid and ammonium heptamolybdate react under aqueous conditions and are obtained.
Background technology
Polyacid compound also known as polyoxometallate, be by high price early transition metal ion (as moⅵ, wⅵ, vⅴ,
ndⅴ, taⅴDeng) with oxygen high polymeric formed the inorganic polymer cluster compound with spacial framework.Because of its oxygen-enriched table
Face, controlled structure, size, the Nomenclature Composition and Structure of Complexes multiformity and uniqueness redox active so that they catalysis, glimmering
The fields such as light, magnetic, medicine are greatly paid close attention to.As 2008, coronado etc. reported with single molecular magnetses behavior
The isopolytungstate [erw that comprises of monokaryon rare earth10o36]9–(referring to m. a. aldamen, j. m. clemente-juan,
e. coronado, et al,j. am. chem. soc, 2008,130, 8874).2010, boskovic etc. studied
Hybrid inorganic-organic multinuclear terbium replaces arsenowolframic acid salt k4li4h4[tb8(pic)6(h2o)22(b-β-asw8o30)4(wo2
(pic))6]·58h2O fluorescent characteristic (referring to c. ritchie, e. g. moore, c. boskovic, et al,angew. chem. int. ed.2010,49, 7702).2015, Wang En ripple seminar reported with photocatalysis water oxygen
Change the multinuclear nickel substituted tungstosilicate na of performance24[ni12(oh)9(co3)3(po4)(siw9o34)3]·56h2o、na25[ni13
(h2o)3(oh)9(po4)4(siw9o34)3]·50h2O and na50[ni25(h2o)2oh)18(co3)2(po4)6(siw9o34)6]·
85h2O(referring to x. b. han, y. g. li, e. b. wang, et al,j. am. chem. soc.2015,137,
5486).Especially, polyacid compound belongs to nanoscale molecular sill, and optical physicss activity is high, stable chemical nature, both aerobics
Change reduction catalystses activity and have Louis acid catalysis activity, reaction condition is gentle, not etching apparatus, and there is good light and urge
Change performance, administer in organic wastewater in photocatalytic method and have a wide range of applications and environment protection significance.As 1989,
The reported first such as papaconstantinou phosphotungstate [pw12o40]3–Degrading chlorophenol, monoxone etc. under ultraviolet light
The result of study of organic contamination is (referring to e. papaconstantinou.chem. soc. rev.1989,18, 1).2000
Year, ferry etc. reports with h2napw12o40、h4siw12o40And h3pmo12o40For catalyst, have studied them to 1,2- dichloro
The Photocatalytic Degradation Property of benzene is (referring to r. r. ozer, j. l. ferry.j. phys. chem. b2000,104,
9444).2003, hori etc. utilized homogeneous catalyst h3pw12o40Achieve under room temperature condition and 500w high voltage mercury lamp irradiation
To perfluor substituted carboxylic acid cf3cooh、c2f5cooh、c3f7Cooh and c4f9Cooh photocatalytic Degradation is (referring to h. hori, y.
takano, k. koike, et al.environ. sci. technol. 2003,37, 418).At present, organic dyestuff
(being mainly derived from weaving, cosmetics, food color, printing and pharmaceutical industry) has become a kind of environmental pollution of generally existing
Thing, causes serious harm to water environment.Thus, it is found that carrying out having in catalytic degradation waste water with finding suitable photocatalyst
Engine dyeing material and then reach improve water quality purpose applied research become in the urgent need to task.As 2002, arslan-
The homogeneous catalyst silico-tungstic acid h such as alaton4siw12o40/ phosphotungstate na2hpw12o40Successfully degrade azo dye acid
Orange 7(is referring to i. arslan-alaton, j. l. ferry.dyes. pigm. 2002,54, 25).2010, Li Yang
Light etc. has synthesized, using ion full-boiled process, the transition metal having good photodegradation to rhodamine b and has comprised silicotungstate [emim]9na8[(siw9o34)3{fe3(μ2-oh)2(μ3-o)}3(wo4)]·0.5h2o (emim = 1-ethyl-3-meth-
Ylimidazole) (referring to w. l. chen, b. w. chen, y. g. li, et al.j. solid. state. chem.2010,183, 310).So far, there is not yet the waugh type manganese molybdate comprising with regard to dysprosium .gamma.-pyridinecarboxylic acid and its light are urged
Change the research report of performance.
Content of the invention
Present invention aim at providing waugh type manganese molybdate of comprising of a kind of dysprosium .gamma.-pyridinecarboxylic acid and preparation method thereof and should
With.
For achieving the above object, the present invention adopts the following technical scheme that
The waugh type manganese molybdate that a kind of dysprosium .gamma.-pyridinecarboxylic acid comprises, its chemical formula is: (nh4)3[dy(hina)2(h2o)6]
[mnivmo9o32]·7h2o.
The waugh type manganese molybdate that above-mentioned dysprosium .gamma.-pyridinecarboxylic acid comprises is obtained using traditional aqua-solution method synthesis, its preparation
Method specifically includes following steps:
1) prepare solution a: under agitation ammonium heptamolybdate is dissolved in distilled water and adjusts ph to 4.5-5.5, thereto
Sequentially add manganese acetate, the h of .gamma.-pyridinecarboxylic acid, Dysprosium trinitrate and concentration 30%2o2, stir 20 min under room temperature to form uniform mixing
Phase, heats 1 h in the water-bath being subsequently placed in 90 ± 2 DEG C, take out and filtered while hot, obtain final product solution a；
2) prepare solution b: under agitation Dysprosium trinitrate is dissolved in glacial acetic acid and the mixed solvent of distilled water, stirs under room temperature
Mix 30 min and form uniform mixed phase, obtain final product solution b；
3) under agitation solution b is added in solution a, 15 mins are stirred at room temperature to form uniform mixed phase, then put
Heat 2 h in 60 ± 2 DEG C of water-bath, take out and filtered while hot, filtrate separates out salmon pink acicular crystal after standing 1 h, filters,
Drying at room temperature, obtains final product target compound.
Wherein, it is possible that a small amount of crystallite in placement process, therefore, step 3) than more preferably scheme is solution a:
Add a small amount of distilled water in advance and heated and stirred makes the crystallite in solution a dissolve in solution a, stop heating after dissolving, then
Under agitation solution b is added in solution a again.
Specifically, ammonium heptamolybdate, manganese acetate .gamma.-pyridinecarboxylic acid, Dysprosium trinitrate, the h of concentration 30% in described step 1)2o2And distilled water
Mol ratio be 1.0 0.3 0.4 0.6 1.0 0.15 0.17 9.1 18.2 685.9；Namely (nh4)6(mo7o24)·
4h2o、mn(ch3coo)2·4h2o、c5h4ncooh、dy(no3)3·6h2O, the h of concentration 30%2o2Mol ratio with distilled water.Institute
State step 2) in the mol ratio of Dysprosium trinitrate, glacial acetic acid and distilled water be 1.0 3.9 52.2 57.5 831.6, namely dy
(no3)3·6h2o、ch3Cooh and the mol ratio of distilled water.Raw material ammonium heptamolybdate in the present invention, manganese acetate .gamma.-pyridinecarboxylic acid, nitric acid
Dysprosium, the h of concentration 30%2o2, and glacial acetic acid all can directly buy ordinary commercial products.
Application in photocatalytically degradating organic dye for the waugh type manganese molybdate that above-mentioned dysprosium .gamma.-pyridinecarboxylic acid comprises, especially
Potential application in terms of photocatalytic degradation azophloxine.
The present invention adopt simple aqua-solution method, using manganese acetate, Dysprosium trinitrate .gamma.-pyridinecarboxylic acid, mass concentration 30% dioxygen
Water, glacial acetic acid and ammonium heptamolybdate are prepared for the waugh type manganese that target compound dysprosium .gamma.-pyridinecarboxylic acid comprises under certain mol ratio
Molybdate.The water bath that 90 ± 2 DEG C of step 1) is conducive to waugh type polyanion [mnivmo9o32]6−Formation, for preparation
Target compound provides precondition.Additionally, the water bath of 60 ± 2 DEG C of step 1) can also effectively improve each reaction group
The reactivity divided, can improve the stability of target compound simultaneously.
The present invention is determined to the crystal structure of target compound and characterizes, and its cell parameter is as follows:
Compound (nh4)3[dy(hina)2(h2o)6][mnivmo9o32]·7h2O is rhombic system, and space group ispbca, structure cell
Parametera=19.0233 (6),b=22.7722 (7),c=24.1995 (7),α=90 °,β=90 °,γ =
90 °,v=10483.3(6) å3,z=8,r 1=0.0506,wr 2= 0.1147.
The structure of target compound is described as follows: its molecular cell comprises 1 waugh type [mnivmo9o32]6–Anion, 1
Individual [dy (hina)2(h2o)6]3+Ion, 3 nh4 +Ion and 7 crystalline water molecules (see a in Fig. 1).Wherein waugh type
[mnivmo9o32]6–Polyanion has 1 mno6Octahedra center, 3 moo6Octahedron be arranged in a triangle by with
The mno at center6One plane of octahedra coplanar composition.Then 2 mo that side is connected altogether3o13Three metal clusters are located at 4 eight respectively
The upper and lower of the plane that face body is constructed, is hadd 3hSymmetric polyanionic [mnivmo9o32]6–.In [dy (hina)2
(h2o)6]3+Dy in ion3+The carbonylic oxygen atom of ion and 2 .gamma.-pyridinecarboxylic acid is coordinated and is formed with the oxygen atom ligand of 6 waters of coordination
The distortion trigondodecahedron configuration (see b in Fig. 1) of eight-coordinate.
The present invention is characterized to the infrared spectrum (see figure 2) of target compound and ultraviolet spectra (see figure 3).
To target compound, the application in terms of photocatalytic degradation azophloxine has carried out studying and calculating the present invention
The photocatalytic conversion rate of azophloxine (y =(a 0 -a t )/a 0 ×100%=(c 0 -c t )/c 0 )×100%.Result of study table
Bright: compound shows preferable photocatalytic Degradation to azophloxine.Especially in low ph value, target compound is
Make also azophloxine can be had under visible light good photocatalytic Degradation.
For inquiring into the photocatalytic Degradation to azophloxine for the target compound, we explore mesh under different condition
The mark impact to azophloxine photocatalytic Degradation for the compound.The xpa- photochemistry being produced by Xujiang Electromechanical Plant, Nanjing, China is anti-
Ying Yi is as reaction kit, and carries out record analyses with ultraviolet-visual spectrometer to Photocatalytic Degradation Process.
Assess target compound using 300 w mercury lamp/500 w xenon lamp simulation ultraviolet light/sunlights to azo fluorescence Fructus Persicae
Red photocatalytic Degradation.Azophloxine is one of important representative of azo dye, is widely used for the dyeing of fabric.By
In azophloxine dye structure stablize traditional physical chemistry biologic treating technique can not effectively process this dyestuff give up
Water.And polyacid has the property of the semi-conducting materials such as similar titanium dioxide, obtain extensively as a kind of photocatalyst of green
Research.Additionally, detect the change of the absorbance of azophloxine by ultraviolet-visual spectrometer.Because absorbance with dense
Degree is directly proportional, such that it is able to measure the photocatalysis of azophloxine by the change of the absorbance of detection azophloxine
Degraded change.
The Photocatalytic activity of target compound of the present invention has important to the research of polyoxometallate photocatalytic activity
Meaning, is that polyoxometallate provides experimental basis as the feasibility of new photocatalyst.Compared to the prior art, this
Bright have the advantage that
1) result of study that the present invention provides is grinding of the waugh type manganese molybdate photocatalytic activity that the first dysprosium .gamma.-pyridinecarboxylic acid comprises
Study carefully, to manganese molybdate, or even application in terms of sewage disposal containing azo dye for the polyoxometallate provides experimental basis；
2) target compound of the present invention can understand its architectural feature exactly by x- ray single crystal diffraction；
3) target compound of the present invention has good photocatalytic Degradation to azophloxine；
4), simply it is easy to operation, yield is high and cost is relatively low for target compound preparation method of the present invention, before having potential application
Scape.
Brief description
Fig. 1 is the molecular cell of target compound and the coordination environment of rare earth ion, for understanding the knot of its photocatalytic activity
Fruit provides precondition；
Fig. 2 is target compound infrared spectrogram, shows mo o (935 cm in target compound−1With 902 cm−1Belong to ν
(mo–ot) stretching vibration absworption peak；681 cm−1, 594 cm−1Belong to ν (mo obMo) stretching vibration absworption peak)；mn–o
(542 cm−1Belong to mn o absworption peak) and hydrone (3400 cm−1Belong to the stretching vibration absworption peak of o h in hydrone)
Eigen vibration absorption band；
Fig. 3 is the ultraviolet spectrogram of target compound；207 nm belong to otThe p π d π charge transfer transition of → mo, 232 nm
Belong to obThe p π d π charge transfer transition of → mo；
Fig. 4 is the aqueous solution ph stable region of target compound, shows that the aqueous solution ph stable region of target compound is 2.4
4.8；
Fig. 5 is the Photocatalytic Degradation Process curve to azophloxine for the target compound；This figure illustrates this compound to azo
Phloxine has good photocatalytic Degradation；
Fig. 6 is the impact to azophloxine photocatalytic degradation conversion ratio for the target compound of different content.In figure can be seen that
Amount with target compound is gradually increased photocatalytic degradation efficiency and is gradually increased, after the amount of target compound reaches 70 mg,
With the increase of target compound, azophloxine photocatalytic degradation conversion ratio reduces；
Fig. 7 is the impact of target compound antithesis nitrogen phloxine photocatalytic degradation conversion ratio under the conditions of different ph.In figure can be seen that
With the rising of ph, azophloxine photocatalytic degradation conversion ratio reduces.
Specific implementation method
Below by way of specific embodiment, the invention will be further described, but protection scope of the present invention is not limited thereto.
Embodiment 1:
The waugh type manganese molybdate that a kind of dysprosium .gamma.-pyridinecarboxylic acid comprises, its chemical formula is: (nh4)3[dy(hina)2(h2o)6]
[mnivmo9o32]·7h2o.
The waugh type manganese molybdate that above-mentioned dysprosium .gamma.-pyridinecarboxylic acid comprises is obtained using traditional aqua-solution method synthesis, its preparation
Method specifically includes following steps:
1) prepare solution a: in 25 ml beakers, under agitation ammonium heptamolybdate (2.002 g, 1.62 mmol) is dissolved
Adjust its ph to 5.0 in distilled water and with glacial acetic acid, then sequentially add thereto manganese acetate (0.120 g, 0.49
Mmol) .gamma.-pyridinecarboxylic acid (0.156 g, 1.27 mmol), Dysprosium trinitrate (0.120 g, 0.26 mmol) and 0.45 ml 30%
h2o2, stir 20 min under room temperature to form uniform mixed phase, be subsequently placed in heating 1h in 90 ± 2 DEG C of water-bath, take out while hot
It is filled in 50 ml beakers, obtain final product solution a；
2) prepare solution b: in 25 ml beakers, under agitation Dysprosium trinitrate (0.511 g, 1.12 mmol) is dissolved into 2
In the mixed solvent of ml glacial acetic acid and 10 ml distilled water, stir 30 min under room temperature and form uniform mixed phase ie in solution b;
3) add 15 ml distilled water heated and stirred in solution a, so that the crystallite in solution a is dissolved, after dissolving, stop heating simultaneously
Under agitation solution b is added in solution a, 15 mins are stirred at room temperature to form uniform mixed phase, are subsequently placed in 60 ± 2
DEG C water-bath in heat 2 h, take out and filtered while hot, filtrate separates out salmon pink acicular crystal after standing 1 h, filters, and room temperature is done
Dry, obtain target compound, 0.73 g(yield 70%).
Embodiment 2:
The waugh type manganese molybdate that a kind of dysprosium .gamma.-pyridinecarboxylic acid comprises, its chemical formula is: (nh4)3[dy(hina)2(h2o)6]
[mnivmo9o32]·7h2o.
The waugh type manganese molybdate that above-mentioned dysprosium .gamma.-pyridinecarboxylic acid comprises is obtained using traditional aqua-solution method synthesis, its preparation
Method specifically includes following steps:
1) prepare solution a: in 25 ml beakers, under agitation ammonium heptamolybdate (2.002 g, 1.62 mmol) is dissolved
Adjust its ph to 5.0 in distilled water and with glacial acetic acid, then sequentially add thereto manganese acetate (0.120 g, 0.49
Mmol) .gamma.-pyridinecarboxylic acid (0.156 g, 1.27 mmol), Dysprosium trinitrate (0.120 g, 0.26 mmol) and 0.45 ml 30%
h2o2, stir 20 min under room temperature to form uniform mixed phase, be subsequently placed in heating 1h in 90 ± 2 DEG C of water-bath, take out while hot
It is filled in 50 ml beakers, obtain final product solution a；
2) prepare solution b: in 25 ml beakers, under agitation Dysprosium trinitrate (0.305 g, 0.668 mmol) is dissolved into
In the mixed solvent of 2 ml glacial acetic acid and 10 ml distilled water, stir 30 min under room temperature and form uniform mixed phase ie in solution b;
3) add 15 ml distilled water heated and stirred in solution a, so that the crystallite in solution a is dissolved, after dissolving, stop heating simultaneously
Under agitation solution b is added in solution a, 15 mins are stirred at room temperature to form uniform mixed phase, are subsequently placed in 60 ± 2
DEG C water-bath in heat 2 h, take out and filtered while hot, filtrate separates out salmon pink acicular crystal after standing 1 h, filters, and room temperature is done
Dry, obtain target compound, 0.42 g(yield 40%).
Embodiment 3:
The waugh type manganese molybdate that a kind of dysprosium .gamma.-pyridinecarboxylic acid comprises, its chemical formula is: (nh4)3[dy(hina)2(h2o)6]
[mnivmo9o32]·7h2o.
The waugh type manganese molybdate that above-mentioned dysprosium .gamma.-pyridinecarboxylic acid comprises is obtained using traditional aqua-solution method synthesis, its preparation
Method specifically includes following steps:
1) prepare solution a: in 25 ml beakers, under agitation ammonium heptamolybdate (2.002 g, 1.62 mmol) is dissolved
Adjust its ph to 5.0 in distilled water and with glacial acetic acid, then sequentially add thereto manganese acetate (0.120 g, 0.49
Mmol) .gamma.-pyridinecarboxylic acid (0.156 g, 1.27 mmol), Dysprosium trinitrate (0.120 g, 0.26 mmol) and 0.45 ml 30%
h2o2, stir 20 min under room temperature to form uniform mixed phase, be subsequently placed in heating 1h in 90 ± 2 DEG C of water-bath, take out while hot
It is filled in 50 ml beakers, obtain final product solution a；
2) prepare solution b: in 25 ml beakers, under agitation Dysprosium trinitrate (1.187 g, 2.60 mmol) is dissolved into 2
In the mixed solvent of ml glacial acetic acid and 10 ml distilled water, stir 30 min under room temperature and form uniform mixed phase ie in solution b;
3) add 15 ml distilled water heated and stirred in solution a, so that the crystallite in solution a is dissolved, after dissolving, stop heating simultaneously
Under agitation solution b is added in solution a, 15 mins are stirred at room temperature to form uniform mixed phase, are subsequently placed in 60 ± 2
DEG C water-bath in heat 2 h, take out and filtered while hot, separate out salmon pink acicular crystal after filtrate standing 1h, filter, room temperature is done
Dry, obtain target compound, 0.75 g(yield 72%).
Application experiment 1
By the new azophloxine solution (6 × 10 prepared-5mol·l–1) it is dispensed into (1 He in the quartz test tube of 2 50 ml
2).No. 1 test tube, as blank, adds 10 mg embodiment 1 target compound in No. 2 test tubes.There is provided light with 300w mercury lamp
Source, carries out photocatalysis experiment on xpa- photochemical reaction instrument.First No. 1 test tube and No. 2 test tubes are placed on photochemical reaction
Magnetic agitation 30 min under dark condition on instrument, makes solution mix homogeneously, and is tested respectively after stirring with ultraviolet-visual spectrometer
The absorbance (being designated as 0 min) of solution.Open light source, test its extinction respectively every the solution that 30 min take out about 3 ml
Degree.Calculate the photocatalytic conversion rate of azophloxine according to following formula, result is shown in Fig. 5 a, 5b.
The photocatalytic conversion rate of azophloxine=[(absorbance during illumination 0 min (a 0 )-light application time t min
When absorbance (a t ))/illumination 0 min when absorbance (a 0 )]×100 %.
As shown in Figure 5: target compound (nh4)3[dy(hina)2(h2o)6][mnivmo9o32]·7h2O is to azo fluorescence Fructus Persicae
Red have good photocatalytic Degradation.
Application experiment 2
By the new azophloxine solution (6 × 10 prepared-5mol·l–1) be dispensed into (1 in the quartz test tube of 7 50 ml
7).No. 1 test tube as blank, add in 2 No. 7 test tubes respectively 10 mg, 30 mg, 50 mg, 70 mg, 90 mg, 110
Mg embodiment 1 target compound.There is provided light source with 300w mercury lamp, xpa- photochemical reaction instrument carries out photocatalysis experiment.Will
1 No. 7 test tubes are placed on magnetic agitation 30 min under dark condition on photochemical reaction instrument, make solution mix homogeneously, and with purple
Outer visible spectrophotometer test stirring respectively after solution absorbance (being designated as 0 min).Open light source, take out every 30 min big
The solution of about 3 ml tests its absorbance respectively.Calculate the photocatalytic conversion rate of azophloxine according to formula, result is shown in
Fig. 6.
As shown in Figure 6: with the increase of target compound amount, the photocatalytic conversion rate of azophloxine raises, and works as mesh
When mark compound is 70 mg, the photocatalytic conversion rate highest of azophloxine.After target compound is more than 70 mg, azo
The photocatalytic conversion rate of phloxine declines.So target compound is that during 70 mg, photocatalysis effect is best.
Application experiment 3
By the new azophloxine solution (6 × 10 prepared-5mol·l–1) be dispensed into (1 in the quartz test tube of 4 50 ml
4).No. 1 test tube, as blank, adds 70 mg embodiment 1 target compound respectively in 2 No. 4 test tubes, and respectively him
Ph dilute hydrochloric acid be transferred to 2.6,3.5 and 4.4.There is provided light source with 300w mercury lamp, xpa- photochemical reaction instrument carries out light
Catalysis experiments.1 No. 4 test tubes are placed on magnetic agitation 30 min under dark condition on photochemical reaction instrument, so that solution is mixed all
Even, and the absorbance (being designated as 0 min) of solution after stirring is tested respectively with ultraviolet-visual spectrometer.Open light source, every certain
Time take out about 3 ml solution test its absorbance respectively.Turn according to the photocatalysis that formula calculates azophloxine
Rate, result is shown in Fig. 7.
As shown in Figure 7: when ph is 2.6, target compound is best to the degradation effect of azophloxine.
Claims (5)
1. the waugh type manganese molybdate that a kind of dysprosium .gamma.-pyridinecarboxylic acid comprises, its chemical formula is: (nh4)3[dy(hina)2(h2o)6]
[mnivmo9o32]·7h2o.
2. the preparation method of the waugh- type manganese molybdate that dysprosium .gamma.-pyridinecarboxylic acid described in claim 1 comprises is it is characterised in that include
Following steps:
1) prepare solution a: under agitation ammonium heptamolybdate is dissolved in distilled water and adjusts ph to 4.5-5.5, thereto
Sequentially add manganese acetate, the h of .gamma.-pyridinecarboxylic acid, Dysprosium trinitrate and concentration 30%2o2, stir 20 min under room temperature to form uniform mixing
Phase, heats 1 h in the water-bath being subsequently placed in 90 ± 2 DEG C, take out and filtered while hot, obtain final product solution a；
2) prepare solution b: under agitation Dysprosium trinitrate is dissolved in glacial acetic acid and the mixed solvent of distilled water, stirs under room temperature
Mix 30 min and form uniform mixed phase, obtain final product solution b；
3) under agitation solution b is added in solution a, 15 mins are stirred at room temperature to form uniform mixed phase, then put
Heat 2 h in 60 ± 2 DEG C of water-bath, take out and filtered while hot, filtrate separates out salmon pink acicular crystal after standing 1 h, filters,
Drying at room temperature, obtains final product target compound.
3. the preparation method of the waugh type manganese molybdate that dysprosium .gamma.-pyridinecarboxylic acid as claimed in claim 2 comprises is it is characterised in that described
Ammonium heptamolybdate, manganese acetate .gamma.-pyridinecarboxylic acid, Dysprosium trinitrate, the h of concentration 30% in step 1)2o2Mol ratio with distilled water is 1.0 0.3
0.4 0.6 1.0 0.15 0.17 9.1 18.2 685.9；Described step 2) in Dysprosium trinitrate, the rubbing of glacial acetic acid and distilled water
That ratio is 1.0 3.9 52.2 57.5 831.6.
4. the waugh type manganese molybdate that the dysprosium .gamma.-pyridinecarboxylic acid described in claim 1 comprises answering in photocatalytically degradating organic dye
With.
5. the waugh type manganese molybdate that the dysprosium .gamma.-pyridinecarboxylic acid described in claim 1 comprises is glimmering in photocatalytically degradating organic dye azo
Application during light is pink.
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| CN113795742A (en) * | 2019-01-25 | 2021-12-14 | 意大利科技研究基金会 | Contrast solution for characterizing biological samples by electron microscopy or correlated microscopy |
| CN115041228A (en) * | 2022-07-22 | 2022-09-13 | 西安石油大学 | Organic-inorganic hybrid material based on Waugh type manganese molybdenum heteropoly acid and synthetic method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113795742A (en) * | 2019-01-25 | 2021-12-14 | 意大利科技研究基金会 | Contrast solution for characterizing biological samples by electron microscopy or correlated microscopy |
| CN113795742B (en) * | 2019-01-25 | 2024-04-09 | 意大利科技研究基金会 | Contrast solution for characterizing biological samples by electron microscopy or correlation microscopy |
| CN109999827A (en) * | 2019-04-19 | 2019-07-12 | 苏州大学 | The copper mesh of a kind of manganese molybdate cladding and its applied to the separation of oil hydrosol and the degradation of organic pollutants |
| CN115041228A (en) * | 2022-07-22 | 2022-09-13 | 西安石油大学 | Organic-inorganic hybrid material based on Waugh type manganese molybdenum heteropoly acid and synthetic method thereof |
| CN115041228B (en) * | 2022-07-22 | 2024-03-26 | 西安石油大学 | Organic-inorganic hybrid material based on Waugh type manganese-molybdenum heteropoly acid and synthesis method thereof |
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