CN107020091A - It is a kind of that there is visible light-responded Ag4(GeO4) photochemical catalyst and its preparation method and application - Google Patents
It is a kind of that there is visible light-responded Ag4(GeO4) photochemical catalyst and its preparation method and application Download PDFInfo
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- CN107020091A CN107020091A CN201710187956.0A CN201710187956A CN107020091A CN 107020091 A CN107020091 A CN 107020091A CN 201710187956 A CN201710187956 A CN 201710187956A CN 107020091 A CN107020091 A CN 107020091A
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- visible light
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 229910005833 GeO4 Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000001699 photocatalysis Effects 0.000 claims abstract description 27
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 23
- 238000007146 photocatalysis Methods 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 13
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 12
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 12
- 239000011734 sodium Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 239000002352 surface water Substances 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 239000003651 drinking water Substances 0.000 claims 1
- 235000020188 drinking water Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 239000000975 dye Substances 0.000 abstract description 9
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 2
- 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 abstract 1
- 239000000047 product Substances 0.000 description 40
- 239000000243 solution Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- FNIHDXPFFIOGKL-UHFFFAOYSA-N disodium;dioxido(oxo)germane Chemical compound [Na+].[Na+].[O-][Ge]([O-])=O FNIHDXPFFIOGKL-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 10
- 230000003287 optical effect Effects 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011835 investigation Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000003643 water by type Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
-
- 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
-
- 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
Abstract
There is visible light-responded Ag the invention discloses a kind of4(GeO4) photochemical catalyst preparation method, step is as follows：(1) under stirring, germanic acid sodium solution is slowly added dropwise in silver nitrate solution, continues to stir, forms precursor solution；(2) precursor solution is moved in reactor, 10 14h is reacted under conditions of 110 130 DEG C, after the completion of reaction, suction filtration is dried, that is, obtains Ag4(GeO4) photochemical catalyst.Ag prepared by the present invention4(GeO4) photochemical catalyst has visible light-responded, being formed has higher photocatalytic activity after photochemical catalyst, compare and be adapted in photocatalysis field practical application degradable organic pollutant and decompose aquatic products oxygen.Through experimental studies have found that Ag4(GeO4) catalysis material shows preferable photocatalysis performance, and aquatic products oxygen 200umol/g is decomposed within 1 hour in radiation of visible light for photochemical catalyst made from photocatalysis Decomposition aquatic products oxygen.Can be degraded in 20 minutes 98% methylene blue organic dyestuff.
Description
Technical field
The present invention relates to catalysis material preparing technical field, more particularly to visible light-responded Ag4(GeO4) light
Catalyst and its preparation method and application.
Background technology
The solar energy of low-density for being difficult to collect can be changed into what high density was easily utilized using semiconductor light-catalyst
Electric energy and chemical energy, it has also become one of most active research field in the world in recent years.Especially in photochemical catalyzing and profit
The unique advantage shown with photooxidative degradation pollutant control environment aspect causes the extensive concern of countries in the world scientist,
Therefore extensive theoretical and experimental study is carried out to it will have very important strategy and realistic meaning.
At present in all problems of restriction photocatalysis technology practical application, it is most important that improve photochemical catalyst to luminous energy
Utilization ratio.Ultraviolet light accounts for all energy 3~4% in solar spectrum, and visible ray accounting is but more than 40%, therefore,
The visible light-responded photochemical catalyst of research and development is a research emphasis for improving Solar use efficiency, with critically important reason
By and practical significance.
In various photocatalyst materials, titanium dioxide has the advantages that cheap, nontoxic, oxidability is strong, stability is good,
It is one of current most study and most widely used semiconductor light-catalyst.But by titanium dioxide greater band gap, only to ultraviolet
Photoresponse, this leverages it in the commercial promise using solar energy degradable organic pollutant.Currently, it is seen that optical drive
The research of novel photocatalyst is concentrated mainly on two aspects：On the one hand, by being carried out to traditional photocatalysis material of titanium dioxide
It is modified, to realize its effective work under visible light, such as metal ion mixing, nonmetallic ion-doped, ion implanting etc.；
On the other hand, the catalysis material of design research and development various novel visibles response, such as bismuth series photocatalyst, based on Cu2O's urges
Agent etc., is also an important research direction.Therefore, develop it is new there is very strong absorption in visible region, and with compared with
The catalysis material of strong photocatalytic activity, tool is of great significance.
The content of the invention
For above-mentioned the deficiencies in the prior art, there is visible light-responded Ag it is an object of the invention to provide a kind of4
(GeO4) photochemical catalyst and its preparation method and application.The photochemical catalyst of the present invention has very strong absorption in visible region,
And with stronger photocatalytic activity, including photocatalysis Decomposition aquatic products oxygen and photocatalytically degradating organic dye methylene blue.
To achieve the above object, the present invention is adopted the following technical scheme that：
The first aspect of the present invention has visible light-responded Ag there is provided a kind of4(GeO4) photochemical catalyst preparation method,
Step is as follows：
(1) under stirring, germanic acid sodium solution is slowly added dropwise in silver nitrate solution, continues to stir, forms presoma
Solution；
(2) precursor solution is moved in reactor, 10-14h is reacted under conditions of 110-130 DEG C, after the completion of reaction, taken out
Filter, dries, that is, obtains Ag4(GeO4) photochemical catalyst.
It is preferred that, in step (1), the concentration of germanic acid sodium solution is 0.06-0.07mol/L；Preferably 0.0625mol/L.
The concentration of silver nitrate solution is 0.2-0.3mol/L；Preferably 0.25mol/L.
It is preferred that, in step (1), the volume ratio that germanic acid sodium solution and silver nitrate solution are added is 1:1.Sodium germanate and nitric acid
The addition of silver can influence the Ag prepared4(GeO4) photochemical catalyst structure composition, addition of the present invention to sodium germanate and silver nitrate
Investigation is optimized in amount, as a result finds, sodium germanate and silver nitrate are (0.06-0.07) in molar ratio：(0.2-0.3) is incorporated as
Preferably, target product can farthest be generated；When sodium germanate and silver nitrate are 1 in molar ratio:During 4 addition, Ag4(GeO4) light
The yield highest of catalyst.
It is preferred that, in step (1), the time for continuing to stir is 20-40min；Preferably 30min.It can be changed by stirring
The contact situation of kind reactant, improves the thermodynamics and kineticses condition of reaction, reaction is smoothed out.The present invention is right
Mixing time is optimized, and as a result finds, if mixing time is too short, reactant it is insufficient contact；If mixing time mistake
It is long, then generated time is on the one hand extended, production cost is added, on the other hand, mixing time is long may also to influence anti-
Answer the crystalline structure of product.Found through multiple comparison test, mixing time is advisable with 20-40min.
It is preferred that, in step (2), the temperature of reaction is 120 DEG C, and the reaction time is 12h.Carrying out heat treatment to presoma can
To change the crystal phase structure of product, and the crystal phase structure of product and its photocatalytic activity are closely related.The present invention is to heat treatment
Temperature optimizes investigation, as a result finds, the temperature of reaction less than 110 DEG C or can not generate crystalline phase of the present invention higher than 130 DEG C
The pure phase product of structure.
It is preferred that, in step (2), the reactor is polytetrafluoro reactor.
Ag prepared by the above method4(GeO4) photochemical catalyst is also protection scope of the present invention.
There is provided above-mentioned Ag for the second aspect of the present invention4(GeO4) application of the photochemical catalyst in photocatalysis Decomposition aquatic products oxygen.
There is provided above-mentioned Ag for the third aspect of the present invention4(GeO4) photochemical catalyst is in degraded air, waste water, surface water or drinks
The application in organic pollution in water.
Beneficial effects of the present invention：
(1) Ag prepared by the present invention4(GeO4) photochemical catalyst have it is visible light-responded, formed photochemical catalyst after have it is higher
Photocatalytic activity, compare and be adapted in photocatalysis field practical application degradable organic pollutant and decompose aquatic products oxygen.Through reality
Test research and find Ag4(GeO4) catalysis material shows preferable photocatalysis performance, for made from photocatalysis Decomposition aquatic products oxygen
Photochemical catalyst decomposes aquatic products oxygen 200umol/g in 1 hour in radiation of visible light.Can be degraded in 20 minutes 98% methylene blue
Organic dyestuff.
(2) Ag of the invention4(GeO4) to prepare synthetic method condition simple for photochemical catalyst, first with sodium germanate and silver nitrate
For raw material, presoma is formed, then thermally treated reactive crystallization, form thermodynamically stable Ag4(GeO4) photochemical catalyst, reaction
Mild condition, is more suitable for large-scale production and practical application, with higher commercial applications prospect.
Brief description of the drawings
The Figure of description for constituting the part of the application is used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its illustrate be used for explain the application, do not constitute the improper restriction to the application.
Fig. 1 is Ag of the present invention4(GeO4) X ray picture.
Fig. 2 is the optical absorption map of product of the present invention.
Fig. 3 schemes for the SEM of product of the present invention.
Fig. 4 is the photochemical catalyst and silver oxide and C of product of embodiment of the present invention formation3N4For Photocatalytic Activity for Degradation
Organic dyestuff methylene blue comparison diagram；In figure, 1：C3N4, 2：Ag2O, 3：Ag4(GeO4)。
Fig. 5 is that the photochemical catalyst of product of embodiment of the present invention formation is used for photocatalysis Decomposition aquatic products oxygen yield figure.
Embodiment
It is noted that described further below is all exemplary, it is intended to provide further instruction to the application.Unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
As background technology is introduced, exploitation it is new there is very strong absorption in visible region, and with stronger light
The catalysis material of catalytic activity, tool is of great significance.Based on this, the present invention proposes a kind of with visible light-responded
Ag4(GeO4) photochemical catalyst.
There is visible light-responded Ag there is provided a kind of in a kind of embodiment of the application4(GeO4) photochemical catalyst
Preparation method, step is as follows：
(1) under stirring, germanic acid sodium solution is slowly added dropwise in silver nitrate solution, continues to stir, forms presoma
Solution；
(2) precursor solution is moved in reactor, 10-14h is reacted under conditions of 110-130 DEG C, after the completion of reaction, taken out
Filter, dries, that is, obtains Ag4(GeO4) photochemical catalyst.
As preferred scheme, in step (1), the concentration of germanic acid sodium solution is 0.06-0.07mol/L；Preferably
0.0625mol/L.The concentration of silver nitrate solution is 0.2-0.3mol/L；Preferably 0.25mol/L.
As preferred scheme, in step (1), the volume ratio that germanic acid sodium solution and silver nitrate solution are added is 1:1.Germanic acid
The addition of sodium and silver nitrate can influence the Ag prepared4(GeO4) photochemical catalyst structure composition, the present invention to sodium germanate and nitric acid
Investigation is optimized in the addition of silver, as a result finds, sodium germanate and silver nitrate are (0.06-0.07) in molar ratio：(0.2-
0.3) add and be advisable, can farthest generate target product；When sodium germanate and silver nitrate are 1 in molar ratio:During 4 addition,
Ag4(GeO4) photochemical catalyst yield highest.
As preferred scheme, in step (1), the time for continuing to stir is 20-40min；Preferably 30min.By stirring
The contact situation of reactant can be improved by mixing, and improved the thermodynamics and kineticses condition of reaction, reaction is smoothed out.
The present invention mixing time is optimized, as a result find, if mixing time is too short, reactant it is insufficient contact；If stirring
Overlong time is mixed, then on the one hand extends generated time, production cost is added, on the other hand, mixing time is long may be also
The crystalline structure of reaction product can be influenceed.Found through multiple comparison test, mixing time is advisable with 20-40min.
As preferred scheme, in step (2), the temperature of reaction is 120 DEG C, and the reaction time is 12h.Presoma is carried out
Heat treatment can change the crystal phase structure of product, and the crystal phase structure of product and its photocatalytic activity are closely related.The present invention is right
The temperature of heat treatment optimizes investigation, as a result finds, the temperature of reaction is less than 110 DEG C or this can not be generated higher than 130 DEG C
The pure phase product of invention crystal phase structure.
As preferred scheme, in step (2), the reactor is polytetrafluoro reactor.
It is described that there is visible light-responded Ag in a kind of embodiment of the application4(GeO4) photochemical catalyst system
Preparation Method is as follows：
(1) first by 2.5 mMs of sodium germanate (Na2GeO3) and 10 mMs of silver nitrates be dissolved in 40 milliliters of deionizations respectively
In water.
(2) stirring half an hour forms precursor solution.
(3) obtained mixed solution is fitted into 100 milliliters of polytetrafluoro reactor, reacted 12 hours under 120 degrees Celsius.
(4) after the completion of reacting, suction filtration is dried to obtain Ag after Temperature fall4(GeO4) photochemical catalyst.
In order that the technical scheme of the application can clearly be understood by obtaining those skilled in the art, below with reference to tool
The embodiment of body describes the technical scheme of the application in detail.
Test material used is the conventional test material in this area in the embodiment of the present invention, can pass through commercial channel
It is commercially available.
Embodiment 1：Ag4(GeO4) photochemical catalyst preparation
Comprise the following steps that：
By 2.5 mMs of sodium germanate (Na2GeO3) and 10 mMs of silver nitrates be dissolved in respectively in 40 ml deionized waters.
Under stirring, germanic acid sodium solution is slowly added dropwise in silver nitrate solution, stirring half an hour forms precursor solution.By what is obtained
Mixed solution is fitted into 100 milliliters of polytetrafluoro reactor, is reacted 12 hours under 120 degrees Celsius.After the completion of reaction, Temperature fall
Afterwards, suction filtration is dried to obtain Ag4(GeO4) photochemical catalyst.
Fig. 1 is crystalline A g manufactured in the present embodiment4(GeO4) X-ray diffractogram, as shown in Figure 1, by 12 hour water
After heat treatment, product shows preferable crystallinity, and composition is Ag4(GeO4), there is not obvious miscellaneous peak.
Fig. 2 is the optical absorption map of final product obtained by the present embodiment, and as shown in Figure 2, the product has in visible region
Very strong absorption.
Fig. 3 schemes for the SEM of the present embodiment products therefrom, the Ag obtained as shown in Figure 34(GeO4) product be small nanometer rods
Assemble the pumiceous texture formed.
Application examples 1：Photocatalytically degradating organic dye is tested
1. test method：
Photocatalytically degradating organic dye test is carried out in common 100mL glass beakers under normal temperature and pressure.Light source is selected
300W xenon lamps equipped with optical filter so that optical source wavelength is more than 420nm.The photocatalytic activity of sample is evaluated with methylene blue.
Weigh the 50mg Ag of the preparation of embodiment 14(GeO4) sample dispersion is in 50ml methylene blue B solutions (20mg/L).Photocatalysis is anti-
Before should testing, lucifuge magnetic agitation 30min makes methylene blue after catalyst surface reaches adsorption equilibrium, thang-kng every 10min
3ml is sampled, centrifuges, takes supernatant measurement of ultraviolet-visible spectrophotometer absorbance.
2. result of the test：
The result of photocatalytically degradating organic dye methylene blue is as shown in figure 4, as shown in Figure 4, photocatalysis under visible light
Agent through photocatalytically degradating organic dye methylene blue test, photochemical catalyst can 20 minutes by methylene blue B degrade 98%, its light
Catalytic activity is higher than silver oxide and C3N4。
Application examples 2：Photocatalysis Decomposition aquatic products oxygen is tested
1. test method：
The test of photocatalysis Decomposition aquatic products oxygen is gone forward side by side in the glass container system for being connected with (5 DEG C) closings of recirculated cooling water
OK, vacuum condition is -97KPa.The light source irradiated at top selects the 300W xenon lamps equipped with optical filter so that optical source wavelength is more than
420nm.Tested after thang-kng every 0.5h, the peak area value measured by gas chromatograph is converted into the yield of oxygen.
2. result of the test：
Photocatalysis Decomposition aquatic products oxygen is tested as shown in figure 5, as seen from the figure, under visible light 1 hour decomposition water of photochemical catalyst
Produce 200 μm of ol/g of oxygen efficiency.
Comparative example 1：
The mol ratio that sodium germanate in embodiment 1 and silver nitrate are added is adjusted to 1：2, remaining be the same as Example 1.
Comparative example 2：
The mol ratio that sodium germanate in embodiment 1 and silver nitrate are added is adjusted to 1：6, remaining be the same as Example 1.
Product prepared by comparative example 1 and comparative example 2 carries out X-ray diffraction analysis and light absorption analysis respectively, as a result sends out
Existing, compared with product prepared by embodiment 1, the crystallinity of product prepared by comparative example 1 and comparative example 2 is not good enough, has substantially
Miscellaneous peak；In addition, the absorbability in visible region is substantially less than the product of the preparation of embodiment 1.
Comparative example 3：
The reaction temperature of precursor mixed solution is adjusted to 100 DEG C, remaining operation be the same as Example 1.
Comparative example 4：
The reaction temperature of precursor mixed solution is adjusted to 140 DEG C, remaining operation be the same as Example 1.
Product prepared by comparative example 3 and comparative example 4 carries out X-ray diffraction analysis, as a result finds, comparative example 3 and contrast
Example 4 can not generate the pure phase product of the crystal phase structure of the embodiment of the present invention 1.
Photocatalytic degradation is carried out to product prepared by comparative example 1-4 using the method for application examples 1 and application examples 2 respectively organic
Dye test and the test of photocatalysis Decomposition aquatic products oxygen.As a result find, the photocatalytic degradation of product prepared by comparative example 1-4 has engine dyeing
The ability of material is substantially less than product (ability of the comparative example 1-4 product in 20 minutes degradation of methylene blue B of the preparation of embodiment 1
Up to 90%)；The ability of its photocatalysis Decomposition aquatic products oxygen is also significantly lower than product (the comparative example 1-4 production of the preparation of embodiment 1
It is 140 μm of ol/g that thing, which decomposes the peak efficiency of aquatic products oxygen for 1 hour).
The preferred embodiment of the application is the foregoing is only, the application is not limited to, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of have visible light-responded Ag4(GeO4) photochemical catalyst preparation method, it is characterised in that step is as follows：
(1) under stirring, germanic acid sodium solution is slowly added dropwise in silver nitrate solution, continues to stir, forms precursor solution；
(2) precursor solution is moved in reactor, 10-14h is reacted under conditions of 110-130 DEG C, after the completion of reaction, suction filtration,
Dry, that is, obtain Ag4(GeO4) photochemical catalyst.
2. preparation method according to claim 1, it is characterised in that in step (1), the concentration of germanic acid sodium solution is
0.06-0.07mol/L；The concentration of silver nitrate solution is 0.2-0.3mol/L.
3. preparation method according to claim 2, it is characterised in that in step (1), the concentration of germanic acid sodium solution is
0.0625mol/L；The concentration of silver nitrate solution is 0.25mol/L.
4. preparation method according to claim 1, it is characterised in that in step (1), germanic acid sodium solution and silver nitrate solution
The volume ratio of addition is 1:1.
5. preparation method according to claim 1, it is characterised in that in step (1), the time for continuing to stir is 20-
40min；Preferably 30min.
6. preparation method according to claim 1, it is characterised in that in step (2), the temperature of reaction is 120 DEG C, reaction
Time is 12h.
7. preparation method according to claim 1, it is characterised in that in step (2), in step (2), the reactor is
Polytetrafluoro reactor.
8. the Ag that the preparation method described in claim any one of 1-7 is prepared4(GeO4) photochemical catalyst.
9. the Ag described in claim 84(GeO4) application of the photochemical catalyst in photocatalysis Decomposition aquatic products oxygen.
10. the Ag described in claim 84(GeO4) photochemical catalyst is organic in degraded air, waste water, surface water or drinking water
Application in pollutant.
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|---|---|---|---|---|
| CN102989488A (en) * | 2012-12-20 | 2013-03-27 | 中国石油大学(华东) | Silver iodide photocatalyst, preparation method and application thereof |
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| CN105964250A (en) * | 2016-06-08 | 2016-09-28 | 山东大学 | Ag10Si4O13 photocatalyst with visible-light response and preparation method and application thereof |
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2017
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| CN102989488A (en) * | 2012-12-20 | 2013-03-27 | 中国石油大学(华东) | Silver iodide photocatalyst, preparation method and application thereof |
| CN103586024A (en) * | 2013-11-22 | 2014-02-19 | 武汉理工大学 | Preparation method for hollow ball or spheroidal Ag2ZnGeO4 photocatalyst |
| CN105964250A (en) * | 2016-06-08 | 2016-09-28 | 山东大学 | Ag10Si4O13 photocatalyst with visible-light response and preparation method and application thereof |
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