CN106000433B - A kind of Bi (III) metal oxygen cluster inorganic skeleton and preparation method and application - Google Patents
A kind of Bi (III) metal oxygen cluster inorganic skeleton and preparation method and application Download PDFInfo
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- CN106000433B CN106000433B CN201610329253.2A CN201610329253A CN106000433B CN 106000433 B CN106000433 B CN 106000433B CN 201610329253 A CN201610329253 A CN 201610329253A CN 106000433 B CN106000433 B CN 106000433B
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 57
- 239000001301 oxygen Substances 0.000 title claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 239000002184 metal Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 14
- 229910020881 PMo12O40 Inorganic materials 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 239000000975 dye Substances 0.000 claims description 51
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 23
- 238000010521 absorption reaction Methods 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 125000002091 cationic group Chemical group 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000011017 operating method Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims 4
- 239000011259 mixed solution Substances 0.000 claims 2
- 210000000988 bone and bone Anatomy 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 abstract description 14
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 14
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 238000002474 experimental method Methods 0.000 abstract description 6
- 238000001907 polarising light microscopy Methods 0.000 abstract description 6
- 229920006324 polyoxymethylene Polymers 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 238000011160 research Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 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 description 38
- 229960000907 methylthioninium chloride Drugs 0.000 description 37
- 229940043267 rhodamine b Drugs 0.000 description 37
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 36
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 28
- 229940012189 methyl orange Drugs 0.000 description 28
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 229940122361 Bisphosphonate Drugs 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004663 bisphosphonates Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- -1 rare earth ion Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
- B01J27/192—Molybdenum with bismuth
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to photocatalysis technology field, specifically a kind of Bi (III) metal oxygen cluster inorganic skeleton and preparation method and application, and use it for photocatalytically degradating organic dye field.The chemical formula of the inorganic skeleton is：{PMo12O40Bi2(H2O)2}·4H2O.Bi (III) metal oxygen cluster inorganic skeleton of the present invention is prepared by solvent-thermal method, and technique is simple, and purity is high, and repeatability is good, and China's bismuth aboundresources, and polyacid materials safety is nontoxic, inexpensively and is easy to get, through Bi（Ⅲ）The metal oxygen cluster of modification, its catalytic activity are significantly improved, so the metal oxygen cluster of bismuth-containing is for photocatalysis, this research field has very wide prospect.Bi (III) metal oxygen cluster inorganic skeleton, it is not ground, it can be directly used for photocatalytic degradation experiment, and it can be completely separated by simple filtering, reusable edible rate is high, the defects such as traditional POMs photochemical catalysts hardly possible is separated, active component is easy to run off, cyclic utilization rate is low are overcome, are easy to be industrially used.
Description
Technical field
The invention belongs to photocatalysis technology field, specifically a kind of Bi (III)-metal oxygen cluster inorganic skeleton and its preparation side
Method and application, and use it for photocatalytically degradating organic dye field.
Background technology
With the continuous development of industrial economy, environmental pollution turns into a great problem that today's society need to be solved urgently.And
The processing of waste water is also as one of important research content of chemists.In water pollution, organic dyestuff due to
The characteristics such as bio-degradable is poor, toxicity is big, be not easy to fade, complicated component, it is always a great problem of wastewater treatment.Because of these
Dyestuff is all toxic to animals and humans, so seeking a kind of biodegrading process efficiently, economic becomes particularly important.And pass
The processing methods such as the absorption method of system, membrane separation process, Coagulation Method are undesirable to the degradation effect of these dyestuffs, and actual application
It is middle in the presence of certain difficulty, in this context, people generate keen interest to photocatalysis technology.This technology is available can
See that light or ultraviolet light carry out photocatalytically degradating organic dye, can be CO by the thorough mineralising of toxic dye in water2、H2O and others
Inorganic molecules or ion, and non-secondary pollution, efficiency high, it is expected to turn into one of main method of degraded toxic dye.
At present, the photochemical catalyst for commonly using degradating organic dye has semi-conductor type metal oxide or sulfide (such as TiO2、
ZnO, CdS etc.), compound (BiOX, X=Cl, Br or I containing Bi；BiPO4) and polyoxometallate (POMs).Wherein, TiO2
Because stable chemical performance, catalytic activity is high, safe and non-toxic the advantages that receive much attention.But because solidification is with separating difficult, absorption ripple
The factors such as long narrow range, the recombination rate of carrier are high, photochemical catalyst is easy to run off, limit its application in practice.And POMs
Because reactivity is high, stability is strong, various structures, property are controllable, strong oxidation-reduction quality, it is safe and non-toxic the advantages that always in light
Catalytic field receives much concern, and existing lot of documents proves that POMs is a kind of effective photochemical catalyst, and its photochemical activity comes from
Their unique cage structures (referring to：Wang S S,Yang G Y.Recent Advances in Polyoxometalate-
Catalyzed Reactions[J].Chemical reviews,2015,115(11):4893-4962.).But traditional is more golden
Category oxygen hydrochlorate because band gap wide between high water solubility and HOMO-LUMO make it that most of polyacid cyclic utilization rate is low, live by photocatalysis
Property is poor, limits its extensive use as catalyst.In recent years, people by polyacid by loading to the big solid of specific surface area
Material is (such as：TiO2、ZrO2、SiO2Deng) or introduce scattered organic ligand, organometallic components etc. to traditional heteropoly acid progress
Modification, and then the electronic structure for changing polyacid improves its photocatalytic activity.At present, the modification unit of introducing is mainly concentrated
In the organic coordination compound segment of various transition metal or rare earth ion (referring to：Zheng S T,Yang G Y.Recent
Advances in paramagnetic-TM-substituted polyoxometalates (TM=Mn, Fe, Co, Ni, Cu)
[J].Chemical Society Reviews,2012,41(22):7623-7646、Dolbecq A,Mialane P,
Secheresse F,et al.Functionalized polyoxometalates with covalently linked
bisphosphonate,N-donor or carboxylate ligands:from electrocatalytic to
optical properties[J].Chemical Communications,2012,48(67):8299-8316.), and utilize
Compound prepared by bismuth and metal oxygen cluster reaction is also seldom.Bi (III) is because comprising a pair of lone electrons, the formation to target compound
Stereochemical influence can be produced, helps to construct the topological structure of novelty；And bismuth-containing compound is because of Bi6sAnd O2pTrack it is miscellaneous
Change, there is narrow band gap and catalytic activity is high；Finally, bismuth resource in China's is relatively abundanter, accounts for the 84% of world's gross reserves, so preparing
The metal oxygen cluster catalysis material of bismuth-containing, there is certain researching value, for exploitation China's bismuth resource there is important reality to anticipate
Justice.
The content of the invention
The present invention is directed to above present situation, there is provided a kind of Bi (III)-metal oxygen cluster inorganic skeleton and preparation method thereof is with answering
With.Research is found：The bismuth-containing metal oxygen cluster is used for photo-catalytic degradation of methyl-orange (MO), methylene blue (MB), rhodamine B
(RhB) the nitrogenous organic dyestuff such as, its degradation rate can be completely separated in 1h up to more than 90%, and by simple filtering,
Reusable edible rate is high, overcomes the difficult separation of traditional POMs photochemical catalysts, active component is easy to run off, cyclic utilization rate is low etc. lacks
Fall into.The simple technical method, economy, it is easy to be industrially used.Tested by photocatalysis performance, find the bismuth-containing metal oxygen cluster again
There is higher absorption property to nitrogenous organic dyestuff of cationic such as methylene blue (MB), rhodamine Bs (RhB).
To achieve the above object of the invention, the present invention is achieved by the following technical solutions：A kind of Bi (III)-metal oxygen
Cluster inorganic skeleton, its chemical formula are：{PMo12O40Bi2(H2O)2}·4H2O, its crystallographic system belong to anorthic system, space group P-1,
Cell parameter is：α=106.5111 °, β=100.8001 °, γ
=111.9686 °.
In addition the invention provides the preparation method of the inorganic skeleton, i.e.,：Precise Bi (NO3)3·5H2O、
H3PMo12O40It is dissolved in absolute ethyl alcohol, forms 0.005mol/L Bi (NO3)3With 0.004mol/L H3PMo12O40Mixing it is molten
Liquid, it is 3 to add with mixed liquor volume:10 concentration is 1.0mol/L HNO3Solution, at room temperature magnetic agitation 15min；
Then the mixed liquor is transferred in reactor, is reacted 3 days at 150 DEG C, be finally down to room temperature with 5 DEG C/h, obtain black rod
Shape or little particle crystal, filter, wash and collect, and obtain inorganic skeleton compound.
The bismuth-containing metal oxygen cluster of above-mentioned preparation has higher stability and strong photocatalytic activity.By it is ultraviolet-can
See that spectrum (referring to Fig. 2) analysis can obtain, the compound has obvious absworption peak in ultra-violet (UV) band, calculates band gap and is about
2.88ev, laid a good foundation (referring to Fig. 3) to study its photocatalysis performance.
Further, nitrogenous have in ultraviolet catalytic degraded the invention provides the Bi (III)-metal oxygen cluster inorganic skeleton
Application in engine dyeing material.When it is implemented, the operating method of the application is：HNO is added in nitrogenous organic dye solution3Solution
It is 2.5 to adjust pH, adds inorganic skeleton, the magnetic agitation under dark condition；After be placed under ultraviolet light and irradiate, and be stirred continuously, it is real
The degraded of existing nitrogenous organic dyestuff.
Finally, the invention provides the Bi (III)-metal oxygen cluster inorganic skeleton in the nitrogenous organic of Liquidity limit type
Application in dyestuff.When it is implemented, the operating method of the application is：Added in the nitrogenous organic dyestuff of cationic inorganic
Skeleton, the magnetic agitation under dark condition, realize the absorption of the nitrogenous organic dyestuff of cationic.
Bi (III)-metal oxygen cluster inorganic skeleton provided by the invention and preparation method and application, compared with prior art,
Have the advantage that and effect：
(1) at present, the metal oxygen cluster crystal majority by Bi (III) modifications reported is omission type structure, and is based on
{ the PMo of Keggin-type12The compound of unit does not occur also, and this is first and is used for the nitrogenous organic dyestuff of photocatalytic degradation
Example, there is certain innovative significance and researching value.
(2) Bi (III)-metal oxygen cluster inorganic skeleton of the present invention is prepared by solvent-thermal method, technique letter
Single, purity is high, and repeatability is good, and China's bismuth aboundresources, and polyacid materials safety is nontoxic, inexpensively and is easy to get, and is modified through Bi (III)
Metal oxygen cluster, its catalytic activity is significantly improved, so the metal oxygen cluster of bismuth-containing is used for photocatalysis this research field
There is very wide prospect.
(3) Bi (III)-metal oxygen cluster inorganic skeleton of the present invention in 1h to methyl orange (MO), methylene blue
(MB), the nitrogenous degradation of organic dyes rate such as rhodamine B (RhB) is all very high, up to more than 90%, it was demonstrated that it is as a kind of light
Catalyst, it is broad to the selectivity ratios for substrate of degrading, there is universality in the field, contribute to actual application.
(4) Bi (III)-metal oxygen cluster inorganic skeleton of the present invention, it is not ground, it can be directly used for photocatalytic degradation
Experiment, and can be completely separated by simple filtering, reusable edible rate is high, overcomes difficult point of traditional POMs photochemical catalysts
From, the defect such as active component is easy to run off, cyclic utilization rate is low, it is easy to be industrially used.
(5) nitrogenous organic dyestuff (methylene of Bi (the III)-metal oxygen cluster inorganic skeleton of the present invention to cationic
Blue (MB), rhodamine B (RhB)) there is stronger adsorption capacity, available for this field of absorption degradation dyestuff.
Brief description of the drawings
Fig. 1 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton structure chart (coloured picture referring to examination as to substances with reference to provide
Material).
Fig. 2 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton UV-visible spectrum.
Fig. 3 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton (α h ν)1/2The band gap calculation changed with energy (h ν)
Figure.
Fig. 4 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton degraded methyl orange (MO) UV-visible spectrum.
Fig. 5 is blank and adds methyl orange (MO) C/C after framework material0With the variation diagram in reaction time.
Fig. 6 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton degradation of methylene blue (MB) ultraviolet-visible spectrum
Figure.
Fig. 7 is blank and adds methylene blue (MB) C/C after framework material0With the variation diagram in reaction time.
Fig. 8 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton rhodamine B degradation (RhB) ultraviolet-visible spectrum
Figure.
Fig. 9 is blank and adds rhodamine B (RhB) C/C after framework material0With the variation diagram in reaction time.
Figure 10 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton degraded methyl orange (MO) recycles block diagram.
Figure 11 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton PXRD figures.1 represents that inorganic skeleton circulates 3 times in figure
Peak shape figure afterwards, 2 represent the obtained inorganic skeleton peak shape figure of experiment, and 3 represent inorganic skeleton monocrystalline simulation peak shape figure.
Figure 12 is the absorbance standard curve figure of the methylene blue (MB) of various concentrations.
Figure 13 is Linear Fit Chart of methylene blue (MB) absorbance with change in concentration.
Figure 14 is the absorbance standard curve figure of the rhodamine B (RhB) of various concentrations.
Figure 15 is Linear Fit Chart of rhodamine B (RhB) absorbance with change in concentration.
Figure 16 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton absorption methylene blue (MB) (uncomfortable pH) it is ultraviolet-
Visible ray spectrogram.
Figure 17 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton absorption methylene blue (MB) (pH=2.5) it is ultraviolet-
Visible ray spectrogram.
Figure 18 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton absorption rhodamine B (RhB) (uncomfortable pH) it is ultraviolet-
Visible ray spectrogram.
Figure 19 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton absorption rhodamine B (RhB) (pH=2.5) it is ultraviolet-
Visible ray spectrogram.
Figure 20 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton absorption methyl orange (MO) (uncomfortable pH) it is ultraviolet-can
See spectrogram.
Figure 21 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton absorption methyl orange (MO) (pH=2.5) it is ultraviolet-can
See spectrogram.
Figure 22 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton absorption methylene blue (MB) (uncomfortable pH) 0h and 3h when
The color contrast figure of dye solution (coloured picture is referring to examination as to substances reference).
Figure 23 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton absorption methylene blue (MB) (pH=2.5) 0h and 3h
When dye solution color contrast figure (coloured picture is referring to examination as to substances reference).
Figure 24 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton absorption rhodamine B (RhB) (uncomfortable pH) 0h and 3h when
The color contrast figure of dye solution (coloured picture is referring to examination as to substances reference).
Figure 25 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton absorption rhodamine B (RhB) (pH=2.5) 0h and 3h
When dye solution color contrast figure (coloured picture is referring to examination as to substances reference).
Figure 26 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton absorption methyl orange (MO) (uncomfortable pH) 0h and 3h when contaminate
Expect the color contrast figure of solution (coloured picture is referring to examination as to substances reference).
Figure 27 is Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton absorption methyl orange (MO) (pH=2.5) 0h and 3h when
The color contrast figure of dye solution (coloured picture is referring to examination as to substances reference).
Embodiment
In order that technical solution of the present invention, advantage, purpose become apparent from, one is entered to it below in conjunction with accompanying drawing, embodiment
Walk explanation.
Embodiment 1, Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton preparation：
Precise 0.0243g (0.05mmol) Bi (NO3)3·5H2O, 0.07301g's (0.04mmol)
H3PMo12O40, mixing is dissolved in 10ml anhydrous ethanol solvent, then adds 3ml, and concentration is 1.0mol/L HNO3Solution, in room temperature
Lower magnetic agitation 15min.The mixed liquor is transferred in 20ml reactors, reacted 3 days at 150 DEG C, finally with 5 DEG C/h
Room temperature is down to, with distilled water, washes of absolute alcohol, filtering, dry black is bar-shaped or little particle crystal.
Embodiment 2, Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton crystallographic structure parameter
Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton crystal structure determination that embodiment 1 obtains is as follows：Micro-
The monocrystalline that suitable dimension is selected under mirror carries out x-ray crystal structure analysis.The X ray diffracting data of crystal is used using Germany
Bruker Smart-Apex CCD faces detection X-ray single crystal diffractometer is collected, using Mo-K αTarget, room temperature
Measure.Data are reduced using SHELXTL-97 programs and structure elucidation.The predominant crystal data of inorganic skeleton is shown in Table
1。
The crystallographic structure parameter of the inorganic skeleton of table 1.
The experimental implementation of the nitrogenous organic dyestuff of embodiment 3, photocatalytic degradation：
(1) it is 2 × 10 to distinguish compound concentration first-5Mol/L methyl orange MO (6.5466mg), methylene blue MB
(7.4780mg), rhodamine B are the nitrogenous organic dye solutions such as RhB (9.5802mg), in case using.
(2) Bi (III)-metal oxygen cluster (PM is added12O40) degradation experiment after inorganic skeleton：Above-mentioned prepare is pipetted respectively
Organic dye solution 100ml in large beaker, with 1.0mol/L HNO3It is 2.5 that solution, which adjusts pH, adds load weighted 20mg
Sample, under dark surrounds, magnetic agitation 30min, to ensure the adsorption equilibrium between organic dyestuff and sample.Put afterwards
Irradiate certain time, and be stirred continuously under 30W uviol lamp, take 3ml solution to be analyzed for ultraviolet-visible luminosity per 10min,
So that it is determined that its degradation rate.
(3) blank assay：The above-mentioned organic dye solution 100ml prepared is pipetted respectively in large beaker, with 1.0mol/L
HNO3It is 2.5 that solution, which adjusts pH, under dark surrounds, magnetic agitation 30min, is placed under 30W uviol lamp and irradiates afterwards
Certain time, and be stirred continuously, take 3ml solution to be analyzed for ultraviolet-visible luminosity per 10min, so that it is determined that its degradation rate.By
Fig. 5,7 and 9 understand that under ultra violet lamp, (methyl orange MO, methylene blue MB, rhodamine B are blank degradating organic dye
RhB) less than 10% in its degradation rate 1h, and the degradation rate added after the inorganic skeleton, up to more than 90% in 1h, thus may be used
, the inorganic skeleton has certain catalytic action for these three organic dyestuff of degrading.
(4) Bi (III)-metal oxygen cluster (PM12O40) inorganic skeleton recycles experiment：After completing above-mentioned steps (2),
I.e. dyestuff it is degradable after, it is filtered, washing, collect the bismuth-containing metal oxygen cluster.Pipette the above-mentioned organic dyestuff prepared respectively again
Solution 100ml is in large beaker, with 1.0mol/L HNO3It is 2.5 that solution, which adjusts pH, and the bismuth-containing metal oxygen after 20mg is collected
Cluster is added in beaker, under dark surrounds, magnetic agitation 30min, to ensure the adsorption equilibrium between organic dyestuff and sample.It
It is placed under 30W uviol lamp and irradiates certain time afterwards, and be stirred continuously, takes 3ml solution to be used for ultraviolet-visible per 10min
Photometric analysis, so that it is determined that its degradation rate.By that analogy, circulate 3 times, determine its stability.As shown in Figure 10, followed by 3 times
After ring, the photocatalytic activity of the inorganic skeleton degradating organic dye does not lose significantly；After (Figure 11) is circulated 3 times in PXRD figures
The peak shape of peak shape and monocrystalline simulation substantially coincide, it can thus be concluded that, the inorganic skeleton structural integrity, be a kind of more stable drop
Solve the photochemical catalyst of organic dyestuff.
The experimental implementation of embodiment 4, the nitrogenous organic dyestuff of absorption：
(1) it is 2 × 10 to distinguish compound concentration first-5Mol/L methyl orange MO (6.5466mg), methylene blue MB
(7.4780mg), rhodamine B are the nitrogenous organic dye solutions such as RhB (9.5802mg), in case using.
(2) the above-mentioned organic dye solution 25ml prepared is pipetted respectively in beaker, adds load weighted 5.0mg samples,
Continuing magnetic force stirs 3h under dark surrounds, takes 3ml solution to be analyzed for ultraviolet-visible luminosity, primarily determines that its adsorbance is big
It is small.From Figure 16,18,20,22,24 and 26：Nitrogenous organic dyestuff (methylene blue of the inorganic skeleton for cationic
(MB), rhodamine B (RhB)) there is larger adsorbance, and then inhaled for the nitrogenous organic dyestuff (methyl orange (MO)) of anionic
Attached amount is almost nil.
(3) drafting of standard curve：For the dyestuff that adsorbance is larger, i.e. methylene blue (MB), rhodamine B (RhB), divide
Not Pei Zhi various concentrations (2,4,6,8,10,12,14mg/L) solution, survey the absorbance of its maximum absorption wave strong point, draw dense
Linear relationship between degree and absorbance, finally according to formula Qe=V (C0-Ce)/m(Qe：Adsorbance；V：The volume of dye solution；
C0：The initial concentration of dye solution；Ce：Concentration after dye solution 3h；m：The quality of adsorbent) try to achieve adsorbance.By Figure 12 extremely
15 understand that the inorganic skeleton is 42.79mgg to the adsorbance of methylene blue (MB)-1, and to rhodamine B (RhB) adsorbance
For 43.84mgg-1。
(4) influence experiment of the pH value to adsorbance size：The above-mentioned organic dye solution 25ml prepared is pipetted respectively in burning
In cup, with 1.0mol/L HNO3It is 2.5 that solution, which adjusts pH, adds load weighted 5.0mg samples, the continuing magnetic force under dark surrounds
3h is stirred, takes 3ml solution to be analyzed for ultraviolet-visible luminosity, finally studies influences of the pH to adsorbance size.By Figure 16 to 27
Understand, pH is influenceed less, and for methylene blue (MB), in pH=for methyl orange (MO), the adsorbance of rhodamine B (RhB)
When 2.5, absorption 17.80% is only capable of, adsorbance during well below uncomfortable pH (i.e. pH=7.0).
Claims (6)
1. a kind of Bi (III)-metal oxygen cluster inorganic skeleton, it is characterised in that its chemical formula is：{PMo12O40Bi2(H2O)2}·
4H2O, its crystallographic system belong to anorthic system, space group P-1, and cell parameter is：A=9.7857, b=10.6361, c=
12.2790, α=106.5111o, β=100.8001o, γ=111.9686o；The preparation method of described inorganic skeleton,
Through the following steps that realize：
Precise Bi (NO3)3·5H2O、H3PMo12O40It is dissolved in absolute ethyl alcohol, forms 0.005mol/L Bi (NO3)3With
0.004mol/L H3PMo12O40Mixed solution, add with mixed liquor volume be 3:10 concentration is 1.0mol/L
HNO3Solution, at room temperature magnetic agitation 15min；Then the mixed liquor is transferred in reactor, reacted 3 days at 150 DEG C,
Room temperature finally is down to 5 DEG C/h, obtains that black is bar-shaped or little particle crystal, filters, wash and collect, obtain inorganic skeleton
Compound.
2. a kind of preparation method of Bi (III)-metal oxygen cluster inorganic skeleton, what it was prepared is inorganic bone as claimed in claim 1
Frame, it is characterised in that through the following steps that realize：
Precise Bi (NO3)3·5H2O、H3PMo12O40It is dissolved in absolute ethyl alcohol, forms 0.005mol/L Bi (NO3)3With
0.004mol/L H3PMo12O40Mixed solution, add with mixed liquor volume be 3:10 concentration is 1.0mol/L
HNO3Solution, at room temperature magnetic agitation 15min；Then the mixed liquor is transferred in reactor, reacted 3 days at 150 DEG C,
Room temperature finally is down to 5 DEG C/h, obtains that black is bar-shaped or little particle crystal, filters, wash and collect, obtain inorganic skeleton
Compound.
3. the Bi of claim 1 or 2 (III)-metal oxygen cluster inorganic skeleton is degraded in ultraviolet catalytic in nitrogenous organic dyestuff
Using.
4. application according to claim 3, it is characterised in that the operating method of the application is：
HNO is added in nitrogenous organic dye solution3It is 2.5 that solution, which adjusts pH, adds inorganic skeleton, the magnetic agitation under dark condition；
After be placed under ultraviolet light and irradiate, and be stirred continuously, realize the degraded of nitrogenous organic dyestuff.
5. the Bi of claim 1 or 2 (III)-metal oxygen cluster inorganic skeleton is in the nitrogenous organic dyestuff of Liquidity limit type
Using.
6. application according to claim 5, it is characterised in that the operating method of the application is：
Inorganic skeleton is added in the nitrogenous organic dyestuff of cationic, the magnetic agitation under dark condition, realizes cationic
The absorption of nitrogenous organic dyestuff.
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| CN104402938A (en) * | 2014-11-24 | 2015-03-11 | 江苏科技大学 | Polyoxometalate Ni complex composite material as well as preparation method and application thereof |
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| CN104402938A (en) * | 2014-11-24 | 2015-03-11 | 江苏科技大学 | Polyoxometalate Ni complex composite material as well as preparation method and application thereof |
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