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CN107051549B - Double-heterostructure photochemical catalyst and its application and preparation method - Google Patents

Double-heterostructure photochemical catalyst and its application and preparation method Download PDF

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CN107051549B
CN107051549B CN201710172916.9A CN201710172916A CN107051549B CN 107051549 B CN107051549 B CN 107051549B CN 201710172916 A CN201710172916 A CN 201710172916A CN 107051549 B CN107051549 B CN 107051549B
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tio
double
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photochemical catalyst
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CN107051549A (en
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胡陈果
刘建林
张翠玲
王雪
奚伊
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Chongqing University
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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

Double-heterostructure photochemical catalyst and its application and preparation method
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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