CN109647383A - A kind of nanometer of silver silicate photochemical catalyst and the preparation method and application thereof - Google Patents
A kind of nanometer of silver silicate photochemical catalyst and the preparation method and application thereof Download PDFInfo
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- CN109647383A CN109647383A CN201910080341.7A CN201910080341A CN109647383A CN 109647383 A CN109647383 A CN 109647383A CN 201910080341 A CN201910080341 A CN 201910080341A CN 109647383 A CN109647383 A CN 109647383A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910052709 silver Inorganic materials 0.000 title abstract description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title abstract description 7
- 239000004332 silver Substances 0.000 title abstract description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Substances OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 89
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 54
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000006731 degradation reaction Methods 0.000 claims abstract description 13
- 230000015556 catabolic process Effects 0.000 claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 8
- 231100000719 pollutant Toxicity 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 abstract description 14
- 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 description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 6
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000005286 illumination Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000010668 complexation reaction Methods 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 10
- 238000010532 solid phase synthesis reaction Methods 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- 238000010792 warming 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
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 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 description 1
- 229910003243 Na2SiO3·9H2O Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 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 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing 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
- 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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
Abstract
The present invention provides a kind of nanometer of silver silicate photochemical catalysts and the preparation method and application thereof, belong to photocatalytic semiconductor material preparation technical field.The present invention is using ethyl orthosilicate, silver nitrate as raw material, the nanometer Ag that composition is accurate, partial size is less than 50nm, good dispersion is prepared as teos hydrolysis catalyst and silver ion complexation agent, using Complex Type sol-gel technique combination heat treatment process in citric acid10Si4O13Photochemical catalyst.Embodiment statistics indicate that, nanometer Ag provided by the invention10Si4O13The partial size of photochemical catalyst is 5~20nm；It is 1g/L in catalyst content, when illumination 45min, 94.35% is reached to the degradation rate that concentration is 20mg/L methylene blue solution Methylene Blue；It can be widely applied for photocatalytic pollutant degradation.
Description
Technical field
The present invention relates to photocatalytic semiconductor material preparation technical field more particularly to a kind of nanometer of silver silicate photochemical catalysts
And the preparation method and application thereof.
Background technique
In recent years, with the development of industry, the discharge of dyestuff and industrial wastewater causes environmental pollution constantly to aggravate, serious prestige
Coerce people's health.Environmental problem is one of the main problem that current social is faced.Photocatalysis technology has in degradation of contaminant
Broad application prospect；The advantages that its is simple to operation, reaction condition is mild, without secondary pollution is by extensive concern.
Silver-based material has unique electron structure, and narrow so as to cause its band gap, light abstraction width extends to visible light
Area, light utilization efficiency with higher.Ag10Si4O13It is a up-and-coming novel visible driving photochemical catalyst.
Ag10Si4O13With relatively narrow band gap, and since the oriented alignment of internal polar molecules has so as to cause with built in field
The inhibition of effect is to the compound of photo-generated carrier, to improve photocatalysis performance.Current Ag10Si4O13Preparation method (precipitation method,
Solid phase method) it is all made of excessive AgNO3And Na2SiO3·9H2O is directly mixed, then washes away the side being heat-treated after unreacted silver nitrate
Method, product purity is high, partial size big (1~2 μm) and the uneven, small (0.36m of specific surface area2/ g), poor dispersion.
Nanoparticle has large specific surface area, strong adsorption, active site mostly with carrier mobility apart from the advantages such as short, has
Conducive to further increasing photocatalytic activity.In addition, polarized electric field range is within 100nm, to make full use of polarized electric field
Promote the separation of photo-generated carrier, diameter of particle should be not more than 100nm.Therefore, nanometer Ag is studied10Si4O13The system of photochemical catalyst
Preparation Method is particularly necessary.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of nanometer of silver silicate photochemical catalyst and preparation method thereof with answer
With.Nanometer Ag provided by the invention10Si4O13The partial size < 50nm of photochemical catalyst has biggish specific surface area and preferable point
Property is dissipated, can be widely applied for photocatalytic pollutant degradation.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of nanometer Ags10Si4O13The preparation method of photochemical catalyst, comprising the following steps:
(1) citric acid, dehydrated alcohol and ethyl orthosilicate are mixed, obtains mixed solution；
(2) the mixed solution and dripping water obtained in the step (1), is aged after stirring, obtains silica sol；
(3) silica sol that the step (2) obtains is mixed with silver nitrate, carries out complex reaction, dries, obtain after standing
To presoma；
(4) presoma that the step (3) obtains is heat-treated, obtains the nanometer Ag10Si4O13Photochemical catalyst.
Preferably, the molar ratio of the ethyl orthosilicate and citric acid is 1:0.1~3.
Preferably, the molar ratio of the dehydrated alcohol and citric acid is 20:0.1~3.
Preferably, the molar ratio of the ethyl orthosilicate and water is 1:4~6.
Preferably, the molar ratio of the ethyl orthosilicate and silver nitrate is 1:2.5.
Preferably, the time of the ageing is 5~15 days.
Preferably, the time of the standing is 12h.
Preferably, the temperature of the heat treatment is 350~450 DEG C, and the time is 4~6h.
The present invention also provides nanometer Ags made from preparation method described in above-mentioned technical proposal10Si4O13Photochemical catalyst, it is described
Nanometer Ag10Si4O13The partial size < 50nm of photochemical catalyst.
The present invention also provides nanometer Ags described in above-mentioned technical proposal10Si4O13Photochemical catalyst is in photocatalytic pollutant degradation
In application.
The present invention provides a kind of nanometer Ags10Si4O13The preparation method of photochemical catalyst, comprising the following steps: (1) by lemon
Acid, dehydrated alcohol and ethyl orthosilicate mixing, obtain mixed solution；(2) mixed solution and dripping obtained in the step (1)
Water is aged after stirring, obtains silica sol；(3) silica sol that the step (2) obtains is mixed with silver nitrate, is carried out
Complex reaction dries after standing, obtains presoma；(4) presoma that the step (3) obtains is heat-treated, obtains institute
State nanometer Ag10Si4O13Photochemical catalyst.
The present invention replaces sodium metasilicate to avoid the introducing of sodium ion as silicon source using ethyl orthosilicate, and is preparing silicic acid
In colloidal sol, using citric acid as catalyst, avoid introducing foreign ion using inorganic acid, so that extra element only has in system
C, H, O, N (come from AgNO3) element；In heat treatment process, after extra C, H, O, N element processing, obtained sample purity is more
It is high.Meanwhile as complexing agent, ethyl orthosilicate and citric acid monodentate ligand, silester in heat treatment process occur for citric acid
Between generate steric effect, effectively inhibit reunite.In addition, the addition of citric acid, can prevent from directly generating precipitating, in liquid
Under, Ag+With Si4+It is effectively complexed on citric acid, forms crystallite dimension smaller Ag when heat treatment10Si4O13Photochemical catalyst.With
Solid phase method, the precipitation method are compared, and preparation method provided by the invention, which eliminates, is washed with deionized step, have prevented final products
The loss of middle effective element (Si, Ag), so that Ag10Si4O13Photochemical catalyst yield is high；It is accurate to form simultaneously, and crystallite dimension is smaller,
The high free from admixture ion of sample purity.Embodiment statistics indicate that, nanometer Ag provided by the invention10Si4O13The partial size of photochemical catalyst
It is 1g/L in catalyst content for 20~50nm, when illumination 45min, the degradation rate that concentration is 20mg/L methylene blue is reached
94.35%.
Further, the present invention controls Ag by adjusting the additive amount of citric acid+With Si4+Complexing, to reach thin
Change the effect of crystal grain；Silver nitrate and silester press theoretical stoichiometric ratio batching control product Ag10Si4O13Composition it is accurate,
Purity is high.
Detailed description of the invention
Fig. 1 is 1 gained nanometer Ag of embodiment10Si4O13The X-ray diffraction spectrogram of photochemical catalyst；
Fig. 2 is 1 gained nanometer Ag of embodiment10Si4O13The UV absorption band gap map of photochemical catalyst；
Fig. 3 is 1 gained nanometer Ag of embodiment10Si4O13The TEM of photochemical catalyst schemes；
Fig. 4 is 1 gained nanometer Ag of embodiment10Si4O13The photocatalytic degradation efficiency curve of photochemical catalyst.
Specific embodiment
The present invention provides a kind of nanometer Ags10Si4O13The preparation method of photochemical catalyst, comprising the following steps:
(1) citric acid, dehydrated alcohol and ethyl orthosilicate are mixed, obtains mixed solution；
(2) water is added dropwise in the mixed solution that the step (1) obtains, is aged after stirring, obtains silica sol；
(3) silica sol that the step (2) obtains is mixed with silver nitrate, carries out complex reaction, dries, obtain after standing
To presoma；
(4) presoma that the step (3) obtains is heat-treated, obtains the nanometer Ag10Si4O13Photochemical catalyst.
The present invention mixes citric acid, dehydrated alcohol and ethyl orthosilicate, obtains mixed solution.In the present invention, described
The molar ratio of ethyl orthosilicate and citric acid is preferably 1:0.1~3, further preferably 1:0.5~2.5, more preferably 1:1.0
~2.0.In the present invention, the molar ratio of the dehydrated alcohol and citric acid is preferably 20:0.1~3, and further preferably 20:
0.5~2.5, more preferably 20:1.0~2.0.In invention, the citric acid, dehydrated alcohol and ethyl orthosilicate are mixed suitable
Sequence preferably first mixes citric acid with dehydrated alcohol, obtains solution；Then above-mentioned solution is mixed with ethyl orthosilicate, is obtained
Mixed solution.The present invention is not specifically limited the mixed time and mode, as long as above-mentioned substance can be made to mix.
After obtaining mixed solution, the present invention is aged after stirring in the mixed solution and dripping water, it is molten to obtain silicic acid
Glue.In the present invention, the molar ratio of the ethyl orthosilicate and water is preferably 1:4~6, further preferably 1:4.5~5.5.
In the present invention, the rate of addition of the water is preferably 0.04mL/s.In the present invention, the water preferably includes distilled water.?
In the present invention, the dropwise addition process preferably carries out under stirring conditions；The revolving speed of the stirring is preferably 300r/min.
In the present invention, the revolving speed of the stirring is preferably 300r/min；The time of the stirring is preferably 1h；It is described to stir
The time mixed after water droplet adds timing.In the present invention, the time of the ageing is preferably 5~15 days.In the present invention
In, the ageing preferably carries out under conditions of sealing.
Water droplet is added in mixed solution by the present invention, ethyl orthosilicate can be made slowly to hydrolyze；When teos hydrolysis,
If the rate of addition of water is too fast or water is too many, there will be flocculent deposit generations；So being by the rate of addition control of water
0.04mL/s is added dropwise, can just obtain the silica sol of stable transparent.Meanwhile citric acid is urged for teos hydrolysis
Agent promotes the hydrolysis of ethyl orthosilicate；In addition, ageing can further promote the hydrolysis of ethyl orthosilicate, make positive silicic acid second
Ester hydrolysis is completed, and purity is high and the accurate photochemical catalyst of composition are advantageously formed.
After obtaining silica sol, the present invention mixes the silica sol with silver nitrate, carries out complex reaction, dries after standing
It is dry, obtain presoma.In the present invention, the molar ratio of the ethyl orthosilicate and silver nitrate is preferably 1:2.5.In the present invention
In, the silver nitrate is added preferably in the form of silver nitrate solution；The concentration of the silver nitrate solution is preferably 0.4g/mL.
In the present invention, the temperature of the complex reaction is preferably 20~30 DEG C；The time of the complex reaction is preferably
1h.In the present invention, the complex reaction preferably carries out under stirring conditions；The revolving speed of the stirring is preferably 300r/
min。
In the present invention, the time of the standing is preferably 12h.In the present invention, the temperature of the drying is preferably 100
DEG C, the time is preferably for 24 hours.After drying, the present invention preferably grinds drying product, and the present invention does not have the parameter of the grinding
There is special restriction, as long as keeping presoma powdered.
The complexing agent that citric acid is complexed as silver ion and silica sol in the present invention, can make silver ion complexation in silicic acid
On, it is hydrolyzed so as to avoid silver ion and generates precipitating, the presence of citric acid can form it into stable complex compound.
After obtaining presoma, the presoma is heat-treated by the present invention, obtains the nanometer Ag10Si4O13Photocatalysis
Agent.In the present invention, the temperature of the heat treatment is preferably 350~450 DEG C, and further preferably 380~430 DEG C, more preferably
It is 390~400 DEG C；The time of the heat treatment is preferably 4~6h.In the present invention, the pressure of the heat treatment is preferably normal
Pressure.In the present invention, the heating rate for being warming up to the temperature of the heat treatment is preferably 5 DEG C/min.
Heat treatment of the invention makes Ag10Si4O13Crystallization forms the good Ag of crystallinity10Si4O13Crystal；And by presoma
Present in extra C, H, O, N (come from AgNO3) element, it sufficiently vapors away, to leave pure phase Ag10Si4O13Photochemical catalyst.
The present invention compares sodium metasilicate using ethyl orthosilicate as silicon source, avoids the introducing of sodium ion, and use citric acid
As catalyst, avoid introducing foreign ion using inorganic acid, so that extra element only has C, H, O, N in system；It is heat treated
Cheng Zhong, after extra C, H, O, N element processing, so that sample purity is higher.Meanwhile citric acid is as complexing agent, positive silicic acid second
Monodentate ligand occurs for ester and citric acid, generates steric effect between silester in heat treatment process, effectively inhibits to reunite.Separately
Outside, the addition of citric acid can prevent from directly generating precipitating, in the liquid state, Ag+With Si4+Effective complexing is on citric acid, heat
Crystallite dimension smaller Ag is formed when processing10Si4O13Photochemical catalyst.Compared with solid phase method, the precipitation method, method of the invention is omitted
Step is washed with deionized, has prevented the loss of effective element in final products (Si, Ag), so that Ag10Si4O13Photocatalysis
Agent yield is high；It is accurate to form simultaneously, and crystallite dimension is smaller, the high free from admixture ion of sample purity.
The present invention also provides the nanometer Ags that preparation method described in above-mentioned technical proposal obtains10Si4O13Photochemical catalyst, it is described
Nanometer Ag10Si4O13The partial size < 50nm of photochemical catalyst.
The present invention also provides nanometer Ags described in above-mentioned technical proposal10Si4O13Photochemical catalyst is in photocatalytic pollutant degradation
In application.In the present invention, the pollutant preferably includes dyestuff, and the dyestuff preferably includes methylene blue or methyl orange.
In the present invention, the application preferably includes following steps: by the nanometer Ag10Si4O13Photochemical catalyst and pollution
Object mixing carries out catalytic degradation in the case where illumination.
The present invention is to the nanometer Ag10Si4O13The dosage of photochemical catalyst and pollutant, the intensity of illumination and catalytic degradation
Condition does not have special restriction, and those skilled in the art select according to actual needs.
Due to nanometer Ag provided by the invention10Si4O13Photochemical catalyst has small superior particle size, large specific surface area and dispersibility
Good advantage, can be widely used in photocatalyst for degrading pollutant field.
Nanometer silver silicate photochemical catalyst provided by the invention and the preparation method and application thereof is carried out below with reference to embodiment
Detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) 0.43g citric acid is mixed with 5.2mL dehydrated alcohol, stirring is to being completely dissolved；1mL ethyl orthosilicate is added
Enter to above-mentioned solution, obtains mixed solution；
(2) in above-mentioned mixed solution and dripping 0.33mL distilled water (rate of addition 0.04mL/s), after stirring 1h, sealing
Ageing 15 days, obtains silica sol；
(3) 1.9g AgNO is weighed3It is mixed with 5mL distilled water, obtains silver nitrate solution；By gained silver nitrate solution with
The mixing of 6.53mL silica sol, carries out complex reaction 1h, stands 12h, be put into the drying of 100 DEG C of baking ovens for 24 hours, grinding, obtain forerunner
Body；
(4) presoma is subjected to heat treatment 5h in normal pressure, 400 DEG C, obtains nanometer Ag10Si4O13Photochemical catalyst.
Embodiment 2
(1) 0.258g citric acid is mixed with 5.2mL dehydrated alcohol, stirring is to being completely dissolved；1mL ethyl orthosilicate is added
Enter to above-mentioned solution, obtains mixed solution；
(2) it in above-mentioned mixed solution and dripping 0.33mL distilled water (rate of addition 0.04mL/s), is sealed after stirring 1h
Ageing 15 days, obtains silica sol；
(3) by 1.9g AgNO3It is mixed with 5mL distilled water, obtains silver nitrate solution；By gained silver nitrate solution with
The mixing of 6.53mL silica sol, carries out complex reaction 1h, after standing 12h, be put into the drying of 100 DEG C of baking ovens for 24 hours, grinding, before obtaining
Drive body；
(4) presoma is heat-treated 5h under the conditions of normal pressure, 400 DEG C, obtains nanometer Ag10Si4O13Photochemical catalyst.
Embodiment 3
(1) 0.086g citric acid is mixed with 5.2mL dehydrated alcohol, stirs to being completely dissolved, 1mL ethyl orthosilicate is added
Enter into above-mentioned solution, obtains mixed solution；
(2) it in above-mentioned mixed solution and dripping 0.33mL distilled water (rate of addition 0.04mL/s), is sealed after stirring 1h
Ageing 15 days, obtains silica sol；
(3) 1.9g AgNO is weighed3It is mixed with 5mL distilled water, obtains silver nitrate solution；By gained silver nitrate solution with
The mixing of 6.53mL silica sol, carries out complex reaction 1h, after standing 12h, is put into 100 DEG C of baking oven drying for 24 hours, grinding, before obtaining
Drive body；
(4) presoma is heat-treated 5h at normal pressure, 400 DEG C, obtains nanometer Ag10Si4O13Photochemical catalyst.
Comparative example 1
Ag is prepared using solid phase method10Si4O13, the preparation method comprises the following steps: first in molar ratio 3:1 weighs silver nitrate and nine water silicons acid
Sodium, mixed grinding, until mixture becomes uniform yellow；Mixture is moved in beaker, addition goes in distilled water to stir
10min allows unreacted silver nitrate to be dissolved in distilled water, filters to isolate precipitating, and with distilled water and ethyl alcohol to precipitating
Each cleaning 3 times；Precipitating after washing is placed in and is dried to obtain amorphous precursor body at room temperature；Then presoma is placed in crucible and is set
In Muffle furnace, 400 DEG C are warming up to 5 DEG C/min of heating rate, 4h is kept the temperature, is cooled to room temperature, obtains solid phase method preparation
Ag10Si4O13。
Fig. 1 is 1 gained nanometer Ag of embodiment10Si4O13The X-ray diffraction spectrogram of photochemical catalyst, as can be seen from Figure 1: this
Invention gained Ag10Si4O13Crystallinity is high, and without any impurity peak, sample purity is high.
Fig. 2 is 1 gained nanometer Ag of embodiment10Si4O13The UV absorption band gap map of photochemical catalyst, as can be seen from Figure 2:
Nanometer Ag10Si4O13The band gap of photochemical catalyst is in 1.78eV or so.
Fig. 3 is 1 gained nanometer Ag of embodiment10Si4O13The TEM of photochemical catalyst schemes, as can be seen from Figure 3: nanometer
Ag10Si4O13Photochemical catalyst can directly react that change sample crystallite dimension that method is prepared be nm rank having a size of nm rank.
1 gained nanometer Ag of Example respectively10Si4O13Photochemical catalyst, 1 gained Ag of comparative example10Si4O13With it is commercially available
TiO20.1g is mixed with the aqueous solution of methylene blue that 100mL concentration is 20mg/L respectively, (filter is added in xenon lamp in 300W xenon lamp
Mating plate filters 420nm ultraviolet light below) irradiation under, carry out catalytic degradation；Obtain 1 gained nanometer Ag of embodiment10Si4O13Light is urged
Agent, 1 gained Ag of comparative example10Si4O13With commercially available TiO2Photocatalytic degradation efficiency curve, as shown in Figure 4.It can from Fig. 4
Out: at identical conditions, sol-gal process reaches 94.35% in degradation rate of the 45min to methylene blue, and solid phase method can only
It is degraded to 84.28%, and TiO2Degradation rate be only 45.68%.Illustrate nanometer Ag provided by the invention10Si4O13Photochemical catalyst
Have the characteristics that partial size is small, dispersion degree is high, large specific surface area, it is possible to provide reaction site more than solid phase method preparation
Ag10Si4O13。
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of nanometer Ag10Si4O13The preparation method of photochemical catalyst, which comprises the following steps:
(1) citric acid, dehydrated alcohol and ethyl orthosilicate are mixed, obtains mixed solution；
(2) the mixed solution and dripping water obtained in the step (1), is aged after stirring, obtains silica sol；
(3) silica sol that the step (2) obtains is mixed with silver nitrate, carries out complex reaction, is dried after standing, before obtaining
Drive body；
(4) presoma that the step (3) obtains is heat-treated, obtains the nanometer Ag10Si4O13Photochemical catalyst.
2. preparation method according to claim 1, which is characterized in that the molar ratio of the ethyl orthosilicate and citric acid is
1:0.1~3.
3. preparation method according to claim 1, which is characterized in that the molar ratio of the dehydrated alcohol and citric acid is
20:0.1~3.
4. preparation method according to claim 1, which is characterized in that the molar ratio of the ethyl orthosilicate and water is 1:4
~6.
5. preparation method according to claim 1, which is characterized in that the molar ratio of the ethyl orthosilicate and silver nitrate is
1:2.5.
6. preparation method according to claim 1, which is characterized in that the time of the ageing is 5~15 days.
7. preparation method according to claim 1, which is characterized in that the time of the standing is 12h.
8. preparation method according to claim 1, which is characterized in that the temperature of the heat treatment is 350~450 DEG C, when
Between be 4~6h.
9. nanometer Ag made from any one of claim 1~8 preparation method10Si4O13Photochemical catalyst, which is characterized in that institute
State nanometer Ag10Si4O13The partial size < 50nm of photochemical catalyst.
10. nanometer Ag as claimed in claim 910Si4O13Application of the photochemical catalyst in photocatalytic pollutant degradation.
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| US20120322648A1 (en) * | 2011-06-15 | 2012-12-20 | Samsung Electronics Co., Ltd. | Visible light sensitive photocatalyst, method of producing the same, and electrochemical water decomposition cell, water decomposition system, and organic material decomposition system each including the same |
| CN104003411A (en) * | 2014-05-16 | 2014-08-27 | 北京科技大学 | Preparation method of lithium silicate porous material used for absorption of high temperature CO2 |
| 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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| US20120322648A1 (en) * | 2011-06-15 | 2012-12-20 | Samsung Electronics Co., Ltd. | Visible light sensitive photocatalyst, method of producing the same, and electrochemical water decomposition cell, water decomposition system, and organic material decomposition system each including the same |
| CN104003411A (en) * | 2014-05-16 | 2014-08-27 | 北京科技大学 | Preparation method of lithium silicate porous material used for absorption of high temperature CO2 |
| 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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