CN106622383A - Prussian blue/tungsten trioxide composite photocatalyst and preparation method and application thereof - Google Patents
Prussian blue/tungsten trioxide composite photocatalyst and preparation method and application thereof Download PDFInfo
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- CN106622383A CN106622383A CN201610851322.6A CN201610851322A CN106622383A CN 106622383 A CN106622383 A CN 106622383A CN 201610851322 A CN201610851322 A CN 201610851322A CN 106622383 A CN106622383 A CN 106622383A
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- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 30
- 239000013225 prussian blue Substances 0.000 title claims abstract description 18
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 6
- 238000004043 dyeing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000007639 printing Methods 0.000 claims description 6
- 206010013786 Dry skin Diseases 0.000 claims description 5
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 239000000975 dye Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 5
- 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 abstract description 5
- 229940012189 methyl orange Drugs 0.000 abstract description 5
- 238000005215 recombination Methods 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- 230000031700 light absorption Effects 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005234 chemical deposition Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- -1 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 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
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
- B01J27/24—Nitrogen compounds
- B01J27/26—Cyanides
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- General Health & Medical Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a PB/WO3 composite photocatalyst and a preparation method and application thereof. The method includes steps: in sodium tungstate precursor solution, taking K4Fe(CN)6.3H2O and FeCl3 in a stoichiometric ratio of 3:4 as reactants to generate PB (Prussian blue) particles; subjecting a mixed system formed by the PB particles and the sodium tungstate precursor solution to ethanol-water solvent thermal reaction to obtain the PB/WO3 composite photocatalyst after 4-hour low-temperature reaction at 100 DEG C. According to research results, by the PB/WO3 composite photocatalyst, WO3 visible light absorption range is widened, semiconductor photon-generated carrier recombination is inhibited effectively, and activity of a composite system in photocatalytic degradation of organic dyes is improved evidently. Under the synergistic action of trace hydrogen peroxide, the kinetic constant in methyl orange degradation is 19.0 times of that of pure WO3. The preparation method has advantages of simplicity, low cost, energy saving and the like. Performances of the composite photocatalyst are evidently improved, and problems of weak catalytic performances and severe limitation on practical application of existing pure WO3 are solved.
Description
Technical field
The invention belongs to environmental protection technical field, is related to a kind of preparation method of photochemical catalyst, and in particular to one kind is adopted
With first simple chemical deposition then solvent hot preparation PB/WO3The method of composite photo-catalyst.
Background technology
With the continuous aggravation of process of industrialization, water pollution becomes one of today's society problem demanding prompt solution.It is heterogeneous
Photocatalysis is used as a kind of effective technology, it is possible to use sunlight irradiation, in the presence of a catalyst, to organic matter depth oxygen is carried out
Change, energy saving and free from environmental pollution, thus have great application prospect.
China's tungsten resource reserves are enriched, and rank first in the world, thus WO3Source it is relatively extensive.As a kind of n-type semiconductor,
Its band-gap energy is 2.4-2.8eV, can respond the visible ray of 460-500 nm, is a kind of visible-light-responsive photocatalyst.In recent years
To attract wide attention in applications such as photochemistry, photochemical catalyst, luminescence generated by light, gas sensing properties.In a large number for WO3It is micro-nano
The research of structure shows that the semiconductor presents good photocatalytic activity in terms of degraded organic compound.But for the list
One system, however it remains following several problems for needing to solve：One is that it absorbs threshold value only about 470 nm, the utilization to solar energy
Rate is still relatively low；Two is WO3Conduction band positions about 0.5 ~ 0.7V with respect to O2/O2-Potential（-0.046V）Polarization, is unfavorable for oxygen
The one-electron reduction of gas, causes the recombination rate of photo-generate electron-hole in semiconductor quickly, makes photo-quantum efficiency relatively low.
The presence of the two problems makes WO3The further raising of photocatalytic activity is restricted.Therefore, WO is widened3Visible light-responded model
Enclose, promote efficiently separating and transfer for photo-generate electron-hole, be the key issue for needing to solve in the current catalyst research.
Hydrogen peroxide (H2O2) strong oxygen is produced in oxidizing process with the Fenton reagent of the mixed solution composition of ferrous ion
Agent OH, the degradable gas chromatography including including dyestuff, thus it is widely used in the process of harmful organic substance.So
And traditional Fenton technology can only be carried out in acid condition, the Fe when pH is higher2+Precipitation is easily generated, the iron cement of generation can cause two
Secondary pollution, increases processing cost, while OH can be suppressed to generate, terminates Fenton's reaction, limits its application and promotes.Therefore, seek
Look for and be conducive to the iron supported catalyst for improving Fenton's reaction condition to become current study hotspot.Prussian blue chemical formula composition
For Fe4[Fe(CN)6]3, existing Fe in its composition2+There is Fe again3+, wherein, Fe3+/Fe2+Standard electrode EMF be 0.771V, than
WO3The potential of conduction band（0.5 ~ 0.7V) corrigendum, therefore Fe3+WO can be captured3Electronics on conduction band, so that WO3Light induced electron
Efficiently separated with hole；The Fe for being formed simultaneously2+The H that can be added into again2O2It is oxidized to Fe3+ , it is achieved thereby that between ion
Conversion and cycle, constitute a class Fenton's reaction.
Based on above-mentioned thinking, we devise WO3With Prussia's composite photo-catalyst, and from energy saving, environmental protection
Angle set out, a kind of simple to operate, with low cost and efficient NEW TYPE OF COMPOSITE photochemical catalyst is explored, with important theory
And practical significance.
The present invention is in line with simplified preparation technology, energy saving and puies forward high performance angle, by simple chemical deposition then
The method of solvent heat realizes PB and WO3Compound, the discovery PB and WO of semiconductor3 Mol ratio 0.0005:1～0.1:1
In the range of photocatalytic activity significantly improve, wherein mol ratio be 0.03:Photocatalytic activity when 1 is optimal, its kinetic constant
For 0.4546min-1, reach pure WO319.0 times of sample.
The content of the invention
For achieving the above object, the invention discloses a kind of Prussian blue PB/WO3Composite photo-catalyst, it is characterised in that
It is by PB and WO3Composition；Wherein PB and WO3 Mol ratio be 0.001:1~0.05:1；PB refers in the composite photo-catalyst
Be mol ratio be 3:4 K4Fe(CN)6·3H2O and FeCl3The product that reaction is obtained；WO3Refer to tungstic acid.Wherein most
Good PB and WO3 Mol ratio be 0.03:1.
The present invention further discloses Prussian blue PB/WO3The preparation method of composite photo-catalyst, it is characterised in that by such as
Lower step is carried out：
Weigh a certain amount of Na2WO4·2H2O adds 5mL ethanol, magnetic force to stir in the ptfe autoclave liner of 25mL
15min is mixed, 2mlNaCl solution is added dropwise in reactor, continue magnetic agitation 15min, then by 5mL 1.5 × 10-6~1.5
×10-4The K of mol/L4Fe(CN)6·3H2O and 5ml 2.0 × 10-6~2.0×10-4The FeCl of mol/L3The aqueous solution is slowly dropped into
In above-mentioned mixed solution, it is 0.5 ~ 2.0 that stirring 10-15min adds 3M HCl to adjust pH value of solution, continue to stir 20 ~ 40 min after
60 ~ 200 DEG C of 2 ~ 12h of isothermal reaction, after being cooled to room temperature, by precipitation and centrifugal separation, washing, 60 DEG C of dryings, collect gained powder
End obtains the PB/WO of serial different composite ratio3Composite photo-catalyst, PB and WO in described composite photo-catalyst3Mol ratio
0.001:1~0.05:1.It is preferred that PB and WO3Mol ratio is 0.03:1.Volume ratio of alcohol to water example is in the preparation method of the present invention
1:2.4, reaction temperature is 100-120 DEG C.
The present invention further discloses Prussian blue PB/WO3Application of the composite photo-catalyst in terms of degradating organic dye.Its
In degradating organic dye refer to contained refractory organicses aromatic compounds aspect in degraded printing and dyeing and paper machine room sewer
Application.The composite photo-catalyst shows good catalytic performance in terms of degradating organic dye.The preparation method for being adopted
For the simple chemical deposition then hot method of alcohol-water mixed solvent, gained sample has excellent photocatalysis performance, these advantages indications
Applications well prospect of the photochemical catalyst in field of industrial waste water treatment.
Description of the drawings：
It is as follows to the properity characterization result of gained part photocatalyst：
Fig. 1 is XRD, EDS collection of illustrative plates of different samples；Wherein A is the XRD spectrum of serial difference sample：(a) WO3；(b) PB/
WO3-0.03；(c) PB；Obviously compared to pure WO3, the diffraction maximum of composite photo-catalyst is at a fairly low, illustrates composite photo-catalyst
Degree of crystallinity is poor, it is not easy to clearly detect WO by the sign3With the presence of PB.Therefore further electronics has been carried out to sample
Power spectrum（EDX）Sign, as shown in Figure 1B, except WO3In two kinds of elements of W and O outside, clearly detect from energy spectrum diagram general
The presence of Fe elements in Shandong scholar basket, shows that product is Prussian blue and WO3The composite photo-catalyst of formation；B is PB/WO3 -0.03
The EDS collection of illustrative plates of composite photo-catalyst；
Fig. 2 is WO3, PB and PB/WO3The UV-Vis DRS spectrum of different composite ratio； WO3Precipitous absorption spectrum shape
Shape illustrates it from native band gap transition, although also show certain absorption in visible region, but due to its band-gap energy about
2.64eV, therefore band edge only about 470 nm are absorbed, the absorption to visible region is still relatively fewer.And the absorption spectrum ranges of PB are very
Width, has stronger absorption in the whole ultraviolet-visible wave band of 200-800 nm.When by PB and WO3After compound, PB/WO3Complex light
The obvious red shift of absorption band edge of catalyst.And with the increase of PB compositely proportionals, degree of absorption of the material in visible region
Strengthen.UV-Vis DRS spectrum shows that the compound of PB has effectively widened WO3Absorption to visible ray such that it is able to
More efficiently utilize solar energy；
Fig. 3 is the WO before and after PB is compound under 410nm ultraviolet excitations3Fluorescence spectrum；Fluorescence spectrum is commonly used to investigate semiconductor
The migration of middle photo-generated carrier and recombination process, the decrease of fluorescence intensity means that the recombination probability of carrier is reduced.WO3
500-580 nm show wider yellow green fluorescence emission band, wherein the most hyperfluorescence peak of 525 nm belong to excite electronics from
Valence band is returned in the transition of conduction band, the energy discharged so as to cause photo-generate electron-hole compound.WO3After the compound PB of Jing, fluorescence
Peak shape is front basically identical with compound, but fluorescence intensity has declined, especially PB/WO3The peak intensity of -0.03 sample reduces obvious,
Illustrate that the compound of PB can effectively suppress the compound of electron-hole.But PB and WO3Mol ratio too high (0.05:1) when, complex light is urged
The fluorescence intensity of agent strengthens on the contrary again, and this excessive is mutually lacked because too high PB contents mean to introduce in the material
Fall into, and it can become the complex centre of photo-generated carrier.Therefore, in certain compositely proportional, the compound of PB can effectively press down
WO processed3Middle light induced electron and the combination probability in hole, so as to improve photo-quantum efficiency.
Fig. 4 is 5 mg different composite ratios PB/WO3Photochemical catalyst under 500W Xe lamp irradiation, the ml of photocatalytic degradation 10
10-5 The performance comparison figure of the MO solution of M；Wherein（a）Degradation efficiency；（b）Light-catalyzed reaction speed constant；Blank assay shows
In the presence of without photochemical catalyst, Jing after 10min irradiation, only about 1.2% MO there occurs degraded to MO, illustrate illumination
Impact can be ignored；WO3Absorption to dye molecule is little, nor affects on the performance comparison of serial photochemical catalyst.In peroxidating
Compare serial WO under the collaboration of hydrogen3The performance of based photocatalyst can be seen that WO after compound PB3Photochemical catalyst, activity it is bright
It is aobvious to improve, and show with the raising of PB elements compounding ratios, catalytic degradation efficiency was increased substantially before this, then and slightly
The trend of reduction, but be significantly better than that without compound WO3.In pure WO3In the presence of, it is to the degradation rate of MO after illumination 10min
22.7%；PB/WO3- 0.01 sample increases substantially to 74.1% after illumination 10min to the degradation rate of MO；And work as PB/WO3Mole
Than being increased to 0.03:When 1, through same exposure time, the absorbance of MO is almost reduced to zero, shows that dyestuff is degraded substantially
Completely.Further increase PB and WO3Mol ratio be 0.04:When 1, the degradation rate of MO is 83.3% in the equal time.According to accurate one
Order reaction dynamics（Fig. 4 b）, pure WO3Degradation reaction speed constant be 0.02386 min-1, and PB/WO3- 0.03 speed
Constant is 0.4546 min-1, it is 19.0 times of compound front sample, show optimal photocatalytic activity.Therefore PB/WO is selected3Rub
You are than being 0.03:1 is best complex ratio.
Specific embodiment：
In order to the present invention is explained further, there is provided following preparation method embodiments.The statement of following examples does not limit this
Bright, one of skill in the art can make improvements and change, described such modifications and variations according to the spirit of the present invention
It is regarded as in the new scope of the present invention.Various raw materials such as Na of the present invention2WO4·2H2O, NaCl, HCl have
It is commercially available.
Embodiment 1
Weigh a certain amount of Na2WO4·2H2O adds 5mL ethanol, magnetic force to stir in the ptfe autoclave liner of 25ml
10 min are mixed, 2ml NaCl solutions are added dropwise in reactor, continue magnetic agitation 15min, then by 5ml 1.5 × 10-6
The K of mol/L4Fe(CN)6·3H2O and 5ml 2.0 × 10-6The FeCl of mol/L3Solution is slowly dropped into above-mentioned mixed solution, is stirred
After mixing 10min, add 3MHCl to adjust the pH of solution to be about 1, continue to stir 20 min after 100 DEG C of isothermal reaction 4h, be cooled to
After room temperature, by precipitation and centrifugal separation, washing, 60 DEG C of dryings, you can obtain mol ratio for 0.001:1 PB/WO3Photochemical catalyst.
Embodiment 2
Weigh a certain amount of Na2WO4·2H2O adds 5mL ethanol, magnetic force to stir in the ptfe autoclave liner of 25ml
12min is mixed, 2mlNaCl solution is added dropwise in reactor, continue magnetic agitation 15min, then by 5ml 4.5 × 10-5 mol/
The K of L4Fe(CN)6·3H2O and 5ml 6.0 × 10-5The FeCl of mol/L3Solution is slowly dropped into above-mentioned mixed solution, stirring
After 12min, add 3MHCl to adjust the pH of solution to be about 0.5, continue to stir 30 min after 100 DEG C of isothermal reaction 4h, be cooled to
After room temperature, by precipitation and centrifugal separation, washing, 60 DEG C of dryings, you can obtain mol ratio for 0.03:1 PB/WO3Photochemical catalyst.
Embodiment 3
Weigh a certain amount of Na2WO4·2H2O adds 5mL ethanol, magnetic force to stir in the ptfe autoclave liner of 25ml
15min is mixed, 2mlNaCl solution is added dropwise in reactor, continue magnetic agitation 15min, then by 5ml 7.5 × 10-5 mol/
The K of L4Fe(CN)6·3H2O and 5ml 1.0 × 10-4The FeCl of mol/L3Solution is slowly dropped into above-mentioned mixed solution, stirring
After 15min, add 3MHCl to adjust the pH of solution to be about 1.5, continue to stir 40 min after 100 DEG C of isothermal reaction 4h, be cooled to
After room temperature, by precipitation and centrifugal separation, washing, 60 DEG C of dryings, you can obtain mol ratio for 0.05:1 PB/WO3Photochemical catalyst.
Embodiment 4
The degraded example of the refractory organicses aromatic compounds contained in printing and dyeing workshop institute sewer：
Methyl orange is the conventional difficult degradation aromatics orange of printing and dyeing industry, is taken containing methyl orange dye from printing and dyeing workshop
The waste water 500mL of 3.27mg/L, adds PB and WO3Mol ratio is 0.03:1 PB/WO3The mg of photochemical catalyst 250, then instill certain
The hydrogen peroxide of amount, magnetic agitation reaches suction-desorption equilibrium, Jing 500W xenon lamp moulds in XPA-7 type photochemical reaction instrument camera bellows
After intending the min of solar radiation 10, it is separated by filtration immediately, the degradation rate for surveying supernatant absorbance calculating MO is 99.5%, and equal bar
Pure WO under part3Photocatalytic degradation efficiency be only 22.7%.
Embodiment 3
The optimal PB/WO of selected performance30.03:1 sample, to other dyestuffs in addition to methyl orange including orange and Ponceaux
The light degradation experiment under the same terms has been carried out respectively, and and without compound WO3Sample is contrasted, the data obtained list
It is as follows：
PB/WO is can be seen that from upper table data3- 0.03 not only to the degradation efficiency of methyl orange apparently higher than without compound
WO3, degraded orange to dyestuff and Ponceaux shows same advantage.Illustrate the composite photo-catalyst in the invention in degraded
Printing and dyeing workshop is arranged and had a good application prospect really in the sewage containing refractory organicses aromatic compounds.
Claims (7)
1. a kind of Prussian blue PB/WO3Composite photo-catalyst, it is characterised in that it is by PB and WO3Composition；Wherein PB and WO3 's
Mol ratio is 0.001:1~0.05:1；PB refers to mol ratio for 3 in the composite photo-catalyst:4 K4Fe(CN)6·3H2O
And FeCl3The product that reaction is obtained；WO3Refer to tungstic acid.
2. high-performance described in claim 1 is Prussian blue/WO3Composite photo-catalyst, wherein PB and WO3 Mol ratio be
0.03:1。
3. Prussian blue PB/WO described in claim 13The preparation method of composite photo-catalyst, it is characterised in that enter as follows
OK：
Weigh a certain amount of Na2WO4·2H2O adds 5mL ethanol, magnetic force to stir in the ptfe autoclave liner of 25mL
15min is mixed, 2mlNaCl solution is added dropwise in reactor, continue magnetic agitation 15min, then by 5mL 1.5 × 10-6~1.5
×10-4The K of mol/L4Fe(CN)6·3H2O and 5ml 2.0 × 10-6~2.0×10-4The FeCl of mol/L3The aqueous solution is slowly dropped into
In above-mentioned mixed solution, it is 0.5 ~ 2.0 that stirring 10-15min adds 3M HCl to adjust pH value of solution, continue to stir 20 ~ 40 min after
60 ~ 200 DEG C of 2 ~ 12h of isothermal reaction, after being cooled to room temperature, by precipitation and centrifugal separation, washing, 60 DEG C of dryings, collect gained powder
End obtains the PB/WO of serial different composite ratio3Composite photo-catalyst, PB and WO in described composite photo-catalyst3Mol ratio
0.001:1~0.05:1.
4. the preparation method described in claim 3, wherein PB and WO3Mol ratio is 0.03:1.
5. the preparation method described in claim 3, wherein volume ratio of alcohol to water example are 1:2.4, reaction temperature is 100-120 DEG C.
6. Prussian blue PB/WO described in claim 13Application of the composite photo-catalyst in terms of degradating organic dye.
7. the application described in claim 6, degradating organic dye therein is referred in degraded printing and dyeing and paper machine room sewer
Application in terms of contained refractory organicses aromatic compounds.
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| CN107153311A (en) * | 2017-06-06 | 2017-09-12 | 中国科学院上海硅酸盐研究所 | Based on tungstic acid and Prussian blue double-function device |
| CN108579656A (en) * | 2018-03-23 | 2018-09-28 | 天津师范大学 | Prussian blue has the nano particle and its preparation method and application of face-centred cubic structure |
| CN111871407A (en) * | 2020-09-05 | 2020-11-03 | 兰州理工大学 | All-tungsten PbWO4/WO3Preparation method and application of Z-type composite photocatalytic material |
| CN112062157A (en) * | 2020-09-11 | 2020-12-11 | 华东理工大学 | Preparation method of tungsten trioxide with inverse opal structure and application of tungsten trioxide in photo-Fenton catalysis |
| CN115703077A (en) * | 2021-08-10 | 2023-02-17 | 中国科学院大连化学物理研究所 | PB @ MoS 2 Application of catalyst in heterogeneous Fenton-like reaction |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107153311A (en) * | 2017-06-06 | 2017-09-12 | 中国科学院上海硅酸盐研究所 | Based on tungstic acid and Prussian blue double-function device |
| CN108579656A (en) * | 2018-03-23 | 2018-09-28 | 天津师范大学 | Prussian blue has the nano particle and its preparation method and application of face-centred cubic structure |
| CN108579656B (en) * | 2018-03-23 | 2021-03-16 | 天津师范大学 | Prussian blue nano-particles with face-centered cubic structure and preparation method and application thereof |
| CN111871407A (en) * | 2020-09-05 | 2020-11-03 | 兰州理工大学 | All-tungsten PbWO4/WO3Preparation method and application of Z-type composite photocatalytic material |
| CN112062157A (en) * | 2020-09-11 | 2020-12-11 | 华东理工大学 | Preparation method of tungsten trioxide with inverse opal structure and application of tungsten trioxide in photo-Fenton catalysis |
| CN112062157B (en) * | 2020-09-11 | 2022-11-08 | 华东理工大学 | Preparation method of tungsten trioxide with inverse opal structure and application of tungsten trioxide in photo-Fenton catalysis |
| CN115703077A (en) * | 2021-08-10 | 2023-02-17 | 中国科学院大连化学物理研究所 | PB @ MoS 2 Application of catalyst in heterogeneous Fenton-like reaction |
| CN115703077B (en) * | 2021-08-10 | 2024-05-14 | 中国科学院大连化学物理研究所 | PB@MoS2Application of catalyst in heterogeneous Fenton-like reaction |
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