CN107051549B - Double-heterostructure photochemical catalyst and its application and preparation method - Google Patents
Double-heterostructure photochemical catalyst and its application and preparation method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 121
- 229910052923 celestite Inorganic materials 0.000 claims abstract description 73
- 239000000463 material Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 229910001868 water Inorganic materials 0.000 claims abstract description 23
- 229910002370 SrTiO3 Inorganic materials 0.000 claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 22
- 230000015556 catabolic process Effects 0.000 claims abstract description 20
- 238000006731 degradation reaction Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 238000001782 photodegradation Methods 0.000 claims abstract description 13
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 10
- 231100000719 pollutant Toxicity 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- 239000010931 gold Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 239000010944 silver (metal) Substances 0.000 claims description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229910000018 strontium carbonate Inorganic materials 0.000 description 11
- 239000004809 Teflon Substances 0.000 description 10
- 229920006362 Teflon® Polymers 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000005649 metathesis reaction Methods 0.000 description 6
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 229910002367 SrTiO Inorganic materials 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- BRSVJNYNWNMJKC-UHFFFAOYSA-N [Cl].[Au] Chemical compound [Cl].[Au] BRSVJNYNWNMJKC-UHFFFAOYSA-N 0.000 description 1
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 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
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- MACBSXIPRLPFDJ-UHFFFAOYSA-N oxygen(2-) platinum(2+) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Pt+2] MACBSXIPRLPFDJ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
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- 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
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C01B2203/1041—Composition of the catalyst
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Abstract
The invention discloses a kind of double-heterostructure photochemical catalyst and its application and preparation methods, are TiO2/ metal/SrSO4Double-heterostructure material.It is applied on light degradation pollutant and photodegradation water hydrogen manufacturing.Preparation method includes the following steps: step (1), heterojunction structure TiO2/SrSO4The synthesis of material, with nanometer SrTiO3For raw material, excessive sulfuric acid solution is added, is put into container after mixing evenly, then is put into togerther in reaction kettle and reacts with container, obtained sample clean is dry;Step (2), double-heterostructure material TiO2/Ag/SrSO4Synthesis: by gained heterojunction structure TiO2/SrSO4Material is added in deionized water, and precious metal solution is then added and is uniformly mixed, according to weight ratio, noble metal and TiO2/SrSO4The weight ratio of material is 1:2-64, is reacted under ultraviolet lighting, is cleaned and dried to obtain product after having reacted.The present invention greatly facilitates the separation of photo-generate electron-hole pairs, and due to SrSO4The reasons such as special construction, greatly improve the ability of its light degradation pollutant and photodegradation water hydrogen manufacturing.
Description
Technical field
The present invention relates to a kind of double-heterostructure photochemical catalyst and its application and preparation methods, belong to catalyst field.
Background technique
Environmental pollution and energy crisis have become two hang-ups for restricting human social development.Titanium dioxide (TiO2)
It is a kind of wide bandgap semiconductor, with 3.2 electron-volts of band-gap energy (anatase), has been widely studied.Nano-TiO2
(P25) as photochemical catalyst because of its higher photocatalytic activity, nontoxic, chemical stability and cheapness in degradable organic pollutant
Aspect has been obtained to compare and has been widely applied, certain P25 there is also being difficult to recycle and reuse, photo-generate electron-hole it is compound to it
The problems such as reduction of photocatalytic activity.In the Photocatalytic Degradation Property for how improving nano material, people have done a large amount of scientific research
Work.Currently, inhibiting the aspect of the recombination of photo-generate electron-hole pair to carry out, mainly mainly from making the band gap of nano material narrow
Doping including metal ion and nonmetallic ion, the dye sensitization of nano-material surface, the deposition of noble silver, gold, platinum etc.
Deng.
From in the 1970s, having utilized the sun since the hydrogen manufacturing of Fujishima and Honda discovery platinum titanium dioxide electrodes
It is always a focus of attention that water, which can be decomposed, this might mean that solar energy can be directly changed into chemical energy, and cleaning can be again
Raw hydrogen fuel.Up to the present, a large amount of research promotes the development of semiconductor catalyst hydrogen, and photodegradation water hydrogen manufacturing is believed general
And that day of application will not be too far.However it is compound due to photo-generate electron-hole pairs, almost all of semiconductor material does not all have
There is relatively high hydrogen manufacturing performance.Equally, the deposition of noble silver, gold, platinum etc., especially platinum are deposited on semiconductor surface, can be very
The big performance for improving its photodegradation water hydrogen manufacturing.But be also exactly the valuableness of noble metal, largely aspect limits light point
Solve the popularization and application of water hydrogen manufacturing.
Summary of the invention
It is applied on light degradation pollutant and photodegradation water hydrogen manufacturing in order to solve the above technical problem, the present invention provides a kind of
Double-heterostructure photochemical catalyst, the present invention also provides the preparation methods of this kind of double-heterostructure photochemical catalyst, improve light
The performance of catalysis and light degradation pollutant, low manufacture cost.
In order to realize above-mentioned first purpose, technical scheme is as follows: a kind of double-heterostructure photochemical catalyst is
TiO2/ metal/SrSO4Double-heterostructure material.
Using the above scheme, because of SrSO4Band gap is wide, is not suitable as catalysis material, and therefore, people will not generally
SrSO4As photochemical catalyst, but inventor has found that after being added to metal, TiO2/SrSO4Photocatalytic
It can be greatly improved.Meanwhile the present invention is being added to SrSO4The light degradation catalysis of double-heterostructure material obtained afterwards
Performance is also than simple TiO2The effect of/metal is good, plays unexpected effect.
It is preferred: Ag or Pt or Au or Pd or their alloy.That is the alloy material of Ag or Pt or Au or Pd
Above-mentioned double-heterostructure photochemical catalyst is in light degradation pollutant, the hydrogen manufacturing of photoelectric decomposition water, the hydrogen manufacturing of electrolysis water and light
Application on hydrogen production by water decomposition.
Present invention facilitates the separation of photo-generate electron-hole pairs, also, find the island knot due to strontium sulfate after study
Structure dissociates in (001) and (210) face, and has the reasons such as elecrtonegativity, so that the double-heterostructure material is in photocatalytic degradation
There is good application prospect in terms of pollutant and the hydrogen manufacturing of photodegradation water.
The working principle of the double-heterostructure material is as shown in Figure 3 (with TiO2/Ag/SrSO4For): illumination makes TiO2
A large amount of photo-generate electron-hole pairs are generated, electronics is easy to transfer and gathers on Argent grain, after three kinds of materials, SrSO4Lead
Band can be slightly below TiO2, since local surface plasma resonance (LSPR) effect of silver is transferred to SrSO4On.TiO2Hole
And SrSO4Electrons and absorption H2O/OH-And O2Generate OH, O2 -And HO2Last light degradation pollutant or
Photodegradation water hydrogen manufacturing.
The double-heterostructure material and corresponding several heterojunction structures that we compare Ag of the present invention (are respectively as follows: TiO2/
Ag/SrSO4、TiO2/SrSO4、TiO2/Ag、TiO2) material light degradation methylene blue degradation situation, light intensity is in experiment
100mW/cm2, methylene blue is that 50mL concentration is 10-5mol·L-1, material therefor 20mg.It can be seen that from FIG. 1 a that this hair
Bright double-heterostructure material TiO2/Ag/SrSO4, can be in 25 minutes with good photocatalytic degradation capability, degradation 97%
Correspondence methylene blue solution.TiO2/SrSO4Photocatalytic degradation capability it is worst, than simple TiO2Photocatalytic Degradation Property
Difference.Because of SrSO4Band gap is wide, is not suitable as catalysis material, and therefore, people are not generally by SrSO4As photochemical catalyst, but
It is the TiO inventor has found that after being added to noble metal2/SrSO4Photocatalysis performance obtained very big mention
It is high.Meanwhile the present invention is being added to SrSO4The light degradation catalytic performance of double-heterostructure material obtained is also than simple afterwards
TiO2The effect of/Ag is good, plays unexpected effect.
We are to double-heterostructure material (Ag and TiO of the invention2/SrSO4The weight ratio 1:16 of material) do repetition examination
It tests, the photocatalytic degradation efficiency of four reuses is respectively 97.0%, 95.6%, 93.8% and 91.9%, illustrates its tool
There are good stability and reusable property.
By double-heterostructure material TiO of the invention2/Ag/SrSO4(Ag and TiO2/SrSO4The weight ratio 1:16 of material)
For photodegradation water hydrogen manufacturing, it can be seen that double-heterostructure material TiO2/Ag/SrSO4Energy with good photodegradation water hydrogen manufacturing
Power.It is 260 μm of ol/h/g that it, which produces hydrogen rate, much larger than the P25 (19 of one of the best hydrogen manufacturing material of similarity condition Publication about Document report
μm ol/h/g), and it is seen that it is with preferable stability and reusable property.
In order to realize above-mentioned second purpose, the technical scheme is that a kind of system of the double-heterostructure photochemical catalyst
Preparation Method includes the following steps:
Step (1), heterojunction structure TiO2/SrSO4The synthesis of material, with nanometer SrTiO3For raw material, according to stoichiometry,
Excessive sulfuric acid solution is added, is put into container after mixing evenly, then is put into togerther in reaction kettle and reacts with container, after having reacted
It takes out, is cleaned and dried to obtain sample;
Step (2), double-heterostructure material TiO2/ metal/SrSO4Synthesis: by gained heterojunction structure TiO2/SrSO4Material
Material is added in deionized water or alcohol, and metallic solution is then added and is uniformly mixed, according to weight ratio, metal and TiO2/
SrSO4The ratio of material is 1:2-64, is reacted under ultraviolet lighting or ultraviolet-visible, is cleaned and dried to obtain after having reacted
TiO2/ metal/SrSO4Double-heterostructure product.
In above scheme: the metallic solution is silver nitrate or chloroplatinic acid or gold chloride or four ammino palladium dichloride solutions.
In above scheme: in step (2), Ag or Pt or Au or Pd and TiO2/SrSO4The weight ratio of material is 1:2-32.
In above scheme: in step (2), Ag or Pt or Au or Pd and TiO2/SrSO4The weight ratio of material is 1:4-16.
In step (1), the concentration of sulfuric acid solution is 0.05-2M.
Figure 4 and 5 are respectively the XRD diagram and structure of the invention and corresponding of structure of the invention and corresponding single heterojunction structure
FESEM, EDS and the TEM of single heterojunction structure scheme.Illustrating the material synthesized by us really is exactly the novel double-heterostructure material
TiO2/Ag/SrSO4And corresponding single heterojunction structure material.
Fig. 1 b, when showing ultraviolet light, when the weight ratio that Ag is added is 1:16, the weight ratio of Ag is after practical synthesis
1%, the double-heterostructure material TiO prepared2/Ag/SrSO4Photocatalytic degradation effect is best.It can also be seen that and work as from Fig. 1 b
When not adding Ag, degradation rate is only fifties percent, and effect is poor.
In above scheme: in step (2), the reaction time is 0.2- under 10-3000W ultraviolet light or UV, visible light illumination
6h。
In above scheme: nanometer SrTiO3Preparation: in the reaction vessel be added molar ratio be SrCO3: TiO2=0.1-
10:1, while deionized water and alkali is added, it is put into reaction kettle reaction, cooling is taken out after having reacted, collects sample, clean into
Property, it is dried to obtain required SrTiO3Micro nanocrystalline.
In above scheme, in preparation nanometer SrTiO3When, every 1mmol SrCO3Deionized water 2-5mL is added, alkali used is
Potassium hydroxide and the compound alkali of sodium hydroxide, 180-220 DEG C of reaction temperature.
In above scheme, every 1mmol SrCO3Deionized water 2-5mL is added.The nanometer SrTiO for being prepared out3Micro-nano
The brilliant particle of rice is most uniform.
The utility model has the advantages that double-heterostructure material TiO of the invention2/ metal/SrSO4, greatly facilitate photo-generate electron-hole
Pair separation, and due to SrSO4The reasons such as special construction, greatly improve its light degradation pollutant and photodegradation water hydrogen manufacturing
Ability.It compares corresponding single heterojunction structure, in situation of the same race, can be polluted with less noble metal with better light degradation
The ability of object and photodegradation water hydrogen manufacturing.The experimental performance that photo-generate electron-hole pairs participate in reaction can be improved.
Detailed description of the invention
Fig. 1 is the experimental result picture of degradation of methylene blue of the present invention, and a is this double-heterostructure material of the present invention and correspondence
Several heterojunction structures material light degradation methylene blue degradation situation lab diagram, b be Ag additional amount to photocatalysis
The comparison diagram of the influence of degradation property, c are the realization effect picture that material of the present invention is recycled and reused for photocatalytic pollutant degradation.
Fig. 2 is the result lab diagram of material photodegradation water hydrogen manufacturing of the present invention.
Fig. 3 is Catalysis Principles schematic diagram of the invention.
Fig. 4 is the XRD diagram of the present invention and corresponding single heterojunction structure.
Fig. 5 is FESEM, EDS and the TEM figure of the present invention and corresponding single heterojunction structure.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples:
Embodiment 1
SrTiO3The synthesis of nano cubic block: the compound alkali (5.12g of 9g is added in the Teflon jar of three 25mL
KOH and 3.88g NaOH), 1mmol SrCO3, 1mmol commercial titanium dioxide, be then respectively adding 2mL, 3mL, 5mL deionization
Water is put into reaction kettle, reacts 48 hours under conditions of 200 DEG C, after cooling, collects gained sample, with deionized water clean to
Neutrality, it is 3 hours dry under the conditions of 55 DEG C, obtain required SrTiO3Micro nanocrystalline.By it was found that, add water be 3mL when, obtain
The SrTiO arrived3Nano cubic block partial size is most uniform.
Embodiment 2
SrTiO3The synthesis of nano cubic block: the compound alkali (5.12g of 9g is added in the Teflon jar of two 25mL
KOH and 3.88g NaOH), 1mmol SrCO3, 1mmol commercial titanium dioxide, then be separately added into 3mL deionized water, be put into reaction
Kettle reacts 48 hours under conditions of 180 DEG C and 220 DEG C respectively, after cooling, collects gained sample, with deionized water clean to
Neutrality, it is 3 hours dry under the conditions of 55 DEG C, obtain required SrTiO3Micro nanocrystalline.
Embodiment 3
SrTiO3The synthesis of nano cubic block: the compound alkali (5.12g of 9g is added in the Teflon jar of two 25mL
KOH and 3.88g NaOH), 0.1mmol SrCO3, 1mmol commercial titanium dioxide, then be separately added into 3mL deionized water, be put into anti-
Kettle is answered, is reacted 48 hours under conditions of 180 DEG C and 220 DEG C respectively, after cooling, gained sample collected, is cleaned with deionized water
It is 3 hours dry under the conditions of 55 DEG C to neutrality, obtain required SrTiO3Micro nanocrystalline.
Embodiment 4
SrTiO3The synthesis of nano cubic block: the compound alkali (5.12g of 9g is added in the Teflon jar of two 25mL
KOH and 3.88g NaOH), 10mmol SrCO3, 1mmol commercial titanium dioxide, then be separately added into 3mL deionized water, be put into anti-
Kettle is answered, is reacted 48 hours under conditions of 180 DEG C and 220 DEG C respectively, after cooling, gained sample collected, is cleaned with deionized water
It is 3 hours dry under the conditions of 55 DEG C to neutrality, obtain required SrTiO3Micro nanocrystalline.
By any SrTiO made from embodiment 1 or embodiment 2 or embodiment 3 and embodiment 43Micro nanocrystalline either city
The nanometer SrTiO bought on face3For synthesizing double-heterostructure material TiO under same synthesis condition2/Ag/SrSO4, to product
Final performance influence it is little.
Embodiment 5
Heterojunction structure TiO2/SrSO4Synthesis, using metathesis reaction: will be according to the amount of embodiment 1 (1mmol SrCO3、
1mmol commercial titanium dioxide) made from SrTiO3The 1M H of micro nanocrystalline addition 10mL2SO4In, it is put into 25mL after mixing evenly
Teflon jar in, be put into reaction kettle, reacted 12 hours under conditions of 200 DEG C, after cooling, collect gained sample, cleaning
To neutrality, TiO is dried to obtain under the conditions of 55 DEG C2/SrSO4。
Double-heterostructure material TiO2/Ag/SrSO4Synthesis: using ultraviolet light reduction silver: respectively in six beakers
In be put into heterojunction structure TiO obtained by 50mg2/SrSO4Material is separately added into the 0.1M of 30mL deionized water and different volumes
AgNO3, so that corresponding weight ratio Ag:SrSO4/TiO2Respectively 1:16,1:2,1:32,1:8,1:4,1:64 are stirred
Ultraviolet lamp that is even, being about 100W with light intensity, distance 15cm irradiate 2 hours.It finally collects respectively, cleaning to neutrality is dried to obtain
Required sample.
Embodiment 6
Heterojunction structure TiO2/SrSO4Synthesis will be according to the amount of embodiment 1 (1mmol SrCO using metathesis reaction3、
1mmol commercial titanium dioxide) made from SrTiO3The 0.5M H of micro nanocrystalline addition 20mL2SO4In, it is put into after mixing evenly
In the Teflon jar of 25mL, it is put into reaction kettle, is reacted 12 hours under conditions of 180 DEG C, after cooling, collects gained sample,
Cleaning is dried to obtain TiO under the conditions of 55 DEG C to neutrality2/SrSO4。
Embodiment 7
Heterojunction structure TiO2/SrSO4Synthesis, using metathesis reaction, the amount same as Example 6 that will be bought on the market
Nanometer SrTiO3The 2M H of 8mL is added2SO4In, it is put into the Teflon jar of 25mL after mixing evenly, is put into reaction kettle,
It is reacted 12 hours under conditions of 220 DEG C, after cooling, collect gained sample, clean to neutrality, be dried to obtain under the conditions of 55 DEG C
TiO2/SrSO4。
Experiment discovery: heterojunction structure TiO made from embodiment 5, embodiment 6 and embodiment 72/SrSO4Performance it is suitable.
Embodiment 8
Heterojunction structure TiO2/SrSO4Synthesis, using metathesis reaction: will be according to the amount of embodiment 1 (1mmol SrCO3、
1mmol commercial titanium dioxide) made from SrTiO3The 1M H of micro nanocrystalline addition 10mL2SO4In, it is put into 25mL after mixing evenly
Teflon jar in, be put into reaction kettle, reacted 12 hours under conditions of 200 DEG C, after cooling, collect gained sample, cleaning
To neutrality, TiO is dried to obtain under the conditions of 55 DEG C2/SrSO4。
Double-heterostructure material TiO2/Pt/SrSO4Synthesis: using ultraviolet light restore platinum: respectively in six beakers
In be put into heterojunction structure TiO obtained by 50mg2/SrSO4Material is separately added into the 0.1M chlorine platinum of 30mL deionized water and different volumes
Acid, so that corresponding weight ratio Pt:SrSO4/TiO2Respectively 1:16,1:2,1:32,1:8,1:4,1:64 are used after stirring 30 minutes
The ultraviolet lamp that light intensity is about 1000W, distance 15cm irradiate 0.2 hour.It finally collects respectively, cleaning to neutrality is dried to obtain institute
Need sample.
Embodiment 9
Heterojunction structure TiO2/SrSO4Synthesis, using metathesis reaction: will be according to the amount of embodiment 1 (1mmol SrCO3、
1mmol commercial titanium dioxide) made from SrTiO3The 1M H of micro nanocrystalline addition 10mL2SO4In, it is put into 25mL after mixing evenly
Teflon jar in, be put into reaction kettle, reacted 12 hours under conditions of 200 DEG C, after cooling, collect gained sample, cleaning
To neutrality, TiO is dried to obtain under the conditions of 55 DEG C2/SrSO4。
Double-heterostructure material TiO2/Au/SrSO4Synthesis: using ultraviolet light restore Au/: respectively in six beakers
In be put into heterojunction structure TiO obtained by 50mg2/SrSO4Material is separately added into the 0.1M chlorine gold of 30mL dehydrated alcohol and different volumes
Acid, so that corresponding weight ratio Au:SrSO4/TiO2Respectively 1:16,1:2,1:32,1:8,1:4,1:64 are used after stirring 30 minutes
The ultraviolet lamp that light intensity is about 100W, distance 15cm irradiate 2 hours.It finally collects respectively, cleaning to neutrality is dried to obtain required sample
Product.
Embodiment 10
Heterojunction structure TiO2/SrSO4Synthesis, using metathesis reaction: will be according to the amount of embodiment 1 (1mmol SrCO3、
1mmol commercial titanium dioxide) made from SrTiO3The 1M H of micro nanocrystalline addition 10mL2SO4In, it is put into 25mL after mixing evenly
Teflon jar in, be put into reaction kettle, reacted 12 hours under conditions of 200 DEG C, after cooling, collect gained sample, cleaning
To neutrality, TiO is dried to obtain under the conditions of 55 DEG C2/SrSO4。
Double-heterostructure material TiO2/Pd/SrSO4Synthesis: using ultraviolet light restore palladium: respectively in six beakers
In be put into heterojunction structure TiO obtained by 50mg2/SrSO4Material is separately added into tetra- ammonia of 0.1M of 30mL deionized water and different volumes
Network palladium chloride, so that corresponding weight ratio Pd:SrSO4/TiO2Respectively 1:16,1:2,1:32,1:8,1:4,1:64, stirring 30
After minute, the ultraviolet lamp for being about 10W with light intensity, distance 15cm irradiates 6 hours.It finally collects respectively, cleaning is to neutral dry
To required sample.
The present invention is not limited to above-mentioned specific embodiment, it should be understood that those skilled in the art are without creativeness
Labour, which according to the present invention can conceive, makes many modifications and variations.In short, all technician in the art are according to this
The design of invention passes through the available technical side of logical analysis, reasoning, or a limited experiment on the basis of existing technology
Case, all should be within the scope of protection determined by the claims.
Claims (8)
1. a kind of preparation method of double-heterostructure photochemical catalyst, it is characterised in that: the double-heterostructure photochemical catalyst is
TiO2/ metal/SrSO4Double-heterostructure material, includes the following steps:
Step (1), heterojunction structure TiO2/SrSO4The synthesis of material, with nanometer SrTiO3It is added for raw material according to stoichiometry
Excessive sulfuric acid solution, is put into container after mixing evenly, then is put into togerther in reaction kettle and reacts with container, takes after having reacted
Out, it is cleaned and dried to obtain sample;
Step (2), double-heterostructure material TiO2/ metal/SrSO4Synthesis: by gained heterojunction structure TiO2/SrSO4Material adds
Enter in deionized water or alcohol, metallic solution is then added and is uniformly mixed, according to weight ratio, metal and TiO2/SrSO4Material
The ratio of material is 1:2-64, is reacted under ultraviolet lighting or ultraviolet-visible, is cleaned and dried to obtain TiO after having reacted2/ gold
Category/SrSO4Double-heterostructure product.
2. the preparation method of double-heterostructure photochemical catalyst according to claim 1, it is characterised in that: the metal be Ag or
Pt or Au or Pd or their alloy.
3. the preparation method of double-heterostructure photochemical catalyst according to claim 2, it is characterised in that: in step (2), Ag or
Pt or Au or Pd and TiO2/SrSO4The weight ratio of material is 1:2-32.
4. the preparation method of double-heterostructure photochemical catalyst according to claim 3, it is characterised in that: in step (2), Ag or
Pt or Au or Pd and TiO2/SrSO4The weight ratio of material is 1:4-16.
5. the preparation method of double-heterostructure photochemical catalyst according to claim 1, it is characterised in that: the metallic solution is
Silver nitrate or chloroplatinic acid or gold chloride or four ammino palladium dichloride solutions.
6. the preparation method of double-heterostructure photochemical catalyst according to claim 1, it is characterised in that: in step (2),
10-3000W ultraviolet light or UV, visible light illumination lower reaction time are 0.2-6h.
7. the preparation method of double-heterostructure photochemical catalyst according to claim 1, it is characterised in that: nanometer SrTiO3System
Standby: it is SrCO that molar ratio is added in the reaction vessel3: TiO2=0.1-10:1, while deionized water and alkali is added, it is put into reaction
Kettle reaction takes out cooling after having reacted, collects sample, cleans to neutrality, be dried to obtain required SrTiO3Micro nanocrystalline.
8. a kind of application of double-heterostructure photochemical catalyst, which is characterized in that any the method system of claim 1-7 will be used
The TiO obtained2/ metal/SrSO4Double-heterostructure material light degradation pollutant, the hydrogen manufacturing of photoelectric decomposition water, the hydrogen manufacturing of electrolysis water and
Application in photodegradation water hydrogen manufacturing.
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