CN109126789A - A kind of photocatalysis hydrogen production Z-type photochemical catalyst and its preparation method and application - Google Patents
A kind of photocatalysis hydrogen production Z-type photochemical catalyst and its preparation method and application Download PDFInfo
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- CN109126789A CN109126789A CN201811135985.3A CN201811135985A CN109126789A CN 109126789 A CN109126789 A CN 109126789A CN 201811135985 A CN201811135985 A CN 201811135985A CN 109126789 A CN109126789 A CN 109126789A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 67
- 239000001257 hydrogen Substances 0.000 title claims abstract description 65
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 65
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 43
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 230
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 claims abstract description 190
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 186
- 238000000034 method Methods 0.000 claims abstract description 55
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 131
- 239000000243 solution Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 19
- 238000004528 spin coating Methods 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
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- 238000000227 grinding Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- HDEPFLVKWKPGFZ-UHFFFAOYSA-N Cl(=O)(=O)O.[Pt] Chemical compound Cl(=O)(=O)O.[Pt] HDEPFLVKWKPGFZ-UHFFFAOYSA-N 0.000 claims description 3
- PSCMQHVBLHHWTO-UHFFFAOYSA-K Indium trichloride Inorganic materials Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 3
- 229910019804 NbCl5 Inorganic materials 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001548 drop coating Methods 0.000 claims description 3
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- 238000001179 sorption measurement Methods 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 229960004756 ethanol Drugs 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 19
- 239000011941 photocatalyst Substances 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 8
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- 230000002186 photoactivation Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
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- 229910052738 indium Inorganic materials 0.000 description 3
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- 230000003647 oxidation Effects 0.000 description 3
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- 229910052727 yttrium Inorganic materials 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
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- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
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- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
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- 229960000583 acetic acid Drugs 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
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- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
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- 229910001449 indium ion Inorganic materials 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
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- 239000003345 natural gas Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical group [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6484—Niobium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The present invention relates to a kind of photocatalysis hydrogen production Z-type photochemical catalysts and its preparation method and application.The present invention utilizes plated film-demoulding method synthesizing new high-efficiency composite photocatalyst Er3+:Y3Al5O12@Nb2O5/Pt/In2O3, the compound of light induced electron and hole can be efficiently separated, Pt can speed up electronics transfer, Er as conductive channel3+:Y3Al5O12Visible light can be absorbed and be translated into ultraviolet photoactivation wide bandgap N b2O5.By Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Applied in photocatalysis hydrogen production, there is very high photocatalytic hydrogen production activity.
Description
Technical field
The invention belongs to the synthetic methods and catalyst of photocatalysis field more particularly to novel photocatalyst in photocatalysis system
Application in hydrogen.
Background technique
With the increase of population and the fast development of world economy, energy consumption will be continued growing, the period of energy shortage
To occur earlier.Coal, the large-scale development of the conventional fossil fuels such as oil and natural gas and utilization cause these non-renewable
Energy carrier is reduced and is consumed rapidly.Green is explored, is efficiently had become in the world mostly with the new energy carrier of sustainable substitution
The hot topic of number researcher.Due to high fuel value, pollution-free and low-carbon, hydrogen is that energy field brings new vitality.
On the one hand, solar energy resources are abundant, free to use, no transportation cost, no pollution to the environment.On the other hand, 72% earth table
Face is covered with water.Therefore, realize that decomposing aquatic products hydrogen is a necessity and important research topic by using solar energy.
Since Fujishima and Honda is since discovery photoelectrocatalysis hydrogen manufacturing in 1972 is from water decomposition, researcher is to visit
The research of the photochemical catalyst of rope efficient stable is made that significant contribution.For example, by doped metal ion and nonmetallic ion come
Adjust the absorption region of photochemical catalyst.The co-catalyst being deposited in photocatalyst surface can efficiently separate light induced electron and
Hole, to enhance photocatalytic activity.The suitable p-n heterojunction being made of N-type and P-type semiconductor is due to position of energy band relationship
The potential difference of generation can efficiently separate charge.However, the efficiency for the photocatalysis hydrogen that water decomposition generates is still very low.It is crucial
The reason is that light-catalyzed reaction lacks powerful driving force, light source underutilization and light induced electron and hole are easy compound.2006
Year, it was recently reported that first all solid state Z-type photochemical catalyst.From that time, Z-type photochemical catalyst causes extensive concern.Pass through choosing
Suitable semiconductor building Z-type photochemical catalyst is selected, can effectively inhibit the compound of light induced electron and hole, widen photochemical catalyst
Optical response range improves the driving capability of photocatalytic redox reaction.It is difficult although Z-type photochemical catalyst has the advantages that these
To obtain the real Z-type photocatalytic system with high activity.That is, in traditional preparation method, for example, mechanical mixture
(M-M) method, the quantity for obtaining real Z-type photocatalyst composite particle are considerably less.Moreover, photocatalyst granular of the same race is poly-
Collection accounts for significant proportion, causes the activity of entire photocatalytic system low.
Summary of the invention
In order to solve the Complex Problem of electrons and holes, the present invention has synthesized a kind of Z-type light using plated film demoulding (C-D) method
Catalyst (Er3+:Y3Al5O12@Nb2O5/Pt/In2O3) for efficiently separating compound, the Pt conduct conduction of light induced electron and hole
Channel can speed up electronics transfer, Er3+:Y3Al5O12Visible light can be absorbed and be translated into ultraviolet photoactivation broad-band gap
Nb2O5.The composite photo-catalyst Er finally synthesized3+:Y3Al5O12@Nb2O5/Pt/In2O3, it is applied in photocatalysis hydrogen production,
With very high photocatalytic hydrogen production activity.
The technical solution adopted by the present invention is that: a kind of photocatalysis hydrogen production Z-type photochemical catalyst, the photocatalysis hydrogen production Z-type
Photochemical catalyst is Er3+:Y3Al5O12@Nb2O5/Pt/In2O3。
Preferably, above-mentioned a kind of photocatalysis hydrogen production Z-type photochemical catalyst, the Er3+:Y3Al5O12@Nb2O5/Pt/
In2O3In, the weight percentage of Pt is 0.5%；Er3+:Y3Al5O12Weight percentage be 15.0%；In molar ratio,
Nb2O5:In2O3=1:1.
A kind of preparation method of photocatalysis hydrogen production Z-type photochemical catalyst, includes the following steps:
1) by Er3+:Y3Al5O12@Nb2O5Colloidal sol is coated in template by spin-coating method under 1800 turns and grows 20-30s,
Dry 30-40min forms Er in triplicate at 80 DEG C3+:Y3Al5O12@Nb2O5Film；
2) by chloric acid platinum solution drop coating in Er3+:Y3Al5O12@Nb2O5On film, Pt particle is deposited on by ionic adsorption method
Er3+:Y3Al5O12@Nb2O5On film, Er is formed3+:Y3Al5O12@Nb2O5/ Pt film；
3) by In2O3Colloidal sol is coated in Er by spin-coating method under 1800 turns3+:Y3Al5O12@Nb2O5On/Pt film, growth
20-30s, dry 30-40min forms Er in triplicate at 80 DEG C3+:Y3Al5O12@Nb2O5/Pt/In2O3Film；
4) load there is into Er3+:Y3Al5O12@Nb2O5/Pt/In2O3The template of film is heat-treated 1.0- at 400-600 DEG C
3.0h, after cooling, demoulds, and grinding obtains target product Er3+:Y3Al5O12@Nb2O5/Pt/In2O3。
Preferably, the preparation method of above-mentioned a kind of photocatalysis hydrogen production Z-type photochemical catalyst, the Er3+:Y3Al5O12@
Nb2O5The preparation method of colloidal sol includes the following steps: aqueous citric acid solution being added dropwise to NbCl5Ethanol solution in, stirring
Er is added after 5-10min3+:Y3Al5O12Continue to stir 30-40min, be aged at room temperature, forms Er3+:Y3Al5O12@Nb2O5Colloidal sol.
Preferably, the preparation method of above-mentioned a kind of photocatalysis hydrogen production Z-type photochemical catalyst, the In2O3The preparation of colloidal sol
Method includes the following steps: that under stiring, the mixed solution of deionized water, ethylene glycol and dehydrated alcohol is added dropwise to
InCl3Glacial acetic acid solution in, after mixing evenly, citric acid is added, gained mixed solution is flowed back 2-3h at 50 DEG C, it is cooling
To room temperature and aging, In is obtained2O3Colloidal sol.
Application of the above-mentioned Z-type photochemical catalyst in photocatalysis hydrogen production.Method is as follows: in the aqueous solution containing methanol,
Above-mentioned photocatalysis hydrogen production Z-type photochemical catalyst Er is added3+:Y3Al5O12@Nb2O5/Pt/In2O3, in 25 DEG C of temperature and pressure
Under 101325Pa, 300min is irradiated with the xenon lamp of 300W.
Photocatalysis hydrogen production Z-type photochemical catalyst Er of the invention3+:Y3Al5O12@Nb2O5/Pt/In2O3Under visible light illumination
The process analysis procedure analysis of photocatalytic hydrogen production by water decomposition: Z-type photocatalytic system is by In2O3, Er3+:Y3Al5O12@Nb2O5With Pt nanoparticle
Composition, wherein Pt nanoparticle is located at In2O3And Er3+:Y3Al5O12@Nb2O5Between.Due to In2O3Valence band be relatively close to potential
For Nb2O5Conduction band, ideal Z-type photocatalytic system can be by In2O3And Nb2O5Composition.Especially Nb2O5Electronics on conduction band can
To enter In by Pt nanoparticle2O3Valence band effectively inhibit Nb then with hole-recombination2O5And In2O3Middle light induced electron
It is compound with hole.As Z-type Er3+:Y3Al5O12@Nb2O5/Pt/In2O3When photochemical catalyst is by radiation of visible light, due to its band gap
It is narrow, In2O3It can directly be excited by visible light to form light induced electron and hole.In addition, visible light passes through Er3+:Y3Al5O12Turn
It is changed to high energy UV, excites wide bandgap N b2O5, generate light induced electron and hole.Due to In2O3Valence band be relatively close to potential
For Nb2O5Conduction band, therefore Nb2O5Electronics on conduction band can enter In by Pt nanoparticle2O3Valence band, and it is multiple with hole
It closes.In2O3Electronics and Nb on conduction band2O5Hole in valence band carries out redox reaction respectively.Nb2O5Hole in valence band can
Using Oxidation of Methanol as sacrifice agent, promote In2O3Electron reduction on conduction band is hydrogen.Thus, it will be seen that in presence of methyl alcohol,
Z-type Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Photocatalysis hydrogen production can be effectively performed in photochemical catalyst.
Beneficial effects of the present invention:
Composite photo-catalyst Er prepared by the present invention3+:Y3Al5O12@Nb2O5/Pt/In2O3Not only there is traditional Z-type light to urge
The advantages of agent, and more it is worth noting that i.e. coating demoulding (C-D) is square the invention proposes a kind of new preparation method
Method, for obtaining a high proportion of Z-type photocatalyst granular.The advantages of based on Z-type photochemical catalyst, have by this compulsive method
Effect combines different catalysts particle that can greatly improve the ratio of high activity Z-type photocatalyst composite particle, and it is multiple to reduce non-Z-type
Close the quantity of particle.In turn, the activity of entire photocatalytic system can be improved.In addition, can be by some works by this method
It is fixed between two photocatalyst granulars for the noble metal granule pressure of conductive channel, to form improved Z-type photocatalysis body
System.
Detailed description of the invention
Fig. 1 a is In2O3X-ray powder diffraction (XRD) figure.
Fig. 1 b is Nb2O5X-ray powder diffraction (XRD) figure.
Fig. 1 c is Er3+:Y3Al5O12X-ray powder diffraction (XRD) figure.
Fig. 1 d is Er3+:Y3Al5O12@Nb2O5/In2O3(M-M) X-ray powder diffraction (XRD) figure.
Fig. 1 e is Er3+:Y3Al5O12@Nb2O5/In2O3(C-D) X-ray powder diffraction (XRD) figure.
Fig. 1 f is Er3+:Y3Al5O12@Nb2O5/Pt/In2O3(C-D) X-ray powder diffraction (XRD) figure.
Fig. 2 is In2O3,Nb2O5,Er3+:Y3Al5O12And Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Scanning electron microscope
(SEM) figure.
Fig. 3 is Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Transmission electron microscope (TEM) figure.
Fig. 4 is Er3+:Y3Al5O12@Nb2O5/Pt/In2O3X-ray energy dispersion spectrum (EDX) figure.
Fig. 5 a is Er3+:Y3Al5O12@Nb2O5/Pt/In2O3X-ray photoelectron spectroscopy (XPS) figure.
Fig. 5 b is x-ray photoelectron spectroscopy (XPS) figure of In (3d),
Fig. 5 c is x-ray photoelectron spectroscopy (XPS) figure of Nb (3d).
Fig. 5 d is x-ray photoelectron spectroscopy (XPS) figure of Er (4d).
Fig. 5 e is x-ray photoelectron spectroscopy (XPS) figure of Y (3d).
Fig. 5 f is x-ray photoelectron spectroscopy (XPS) figure of Al (2p).
Fig. 5 g is x-ray photoelectron spectroscopy (XPS) figure of O (1s).
Fig. 5 h is x-ray photoelectron spectroscopy (XPS) figure of Pt (4f).
Fig. 6 a is In2O3,Nb2O5And Er3+:Y3Al5O12@Nb2O5/In2O3UV-vis diffusing reflection spectrum (DRS) figure.
Fig. 6 b is In2O3Band gap estimate figure.
Fig. 6 c is Nb2O5Band gap estimate figure.
Fig. 7 a is In2O3Fourier Transform Infrared Spectroscopy (FT-IR) figure.
Fig. 7 b is Nb2O5Fourier Transform Infrared Spectroscopy (FT-IR) figure.
Fig. 7 c is Er3+:Y3Al5O12Fourier Transform Infrared Spectroscopy (FT-IR) figure.
Fig. 7 d is Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Fourier Transform Infrared Spectroscopy (FT-IR) figure.
Fig. 8 is In2O3,Nb2O5,Er3+:Y3Al5O12@Nb2O5/In2O3(M-M),Er3+:Y3Al5O12@Nb2O5/In2O3(C-
) and Er D3+:Y3Al5O12@Nb2O5/Pt/In2O3(C-D) luminescence generated by light (PL) spectrogram.
Fig. 9 a is Er3+:Y3Al5O12@Nb2O5/In2O3(M-M),Er3+:Y3Al5O12@Nb2O5/In2O3(C-D) and Er3+:
Y3Al5O12@Nb2O5/Pt/In2O3(C-D) electro-chemical test.
Fig. 9 b is Er3+:Y3Al5O12@Nb2O5/In2O3(M-M),Er3+:Y3Al5O12@Nb2O5/In2O3(C-D) and Er3+:
Y3Al5O12@Nb2O5/Pt/In2O3(C-D) electro-chemical test.
Figure 10 a is the influence diagram that distinct methods prepare catalyst to photocatalysis hydrogen production.
Figure 10 b is the influence diagram that different heat treatment temperature prepares catalyst to photocatalysis hydrogen production.
Figure 10 c is the influence diagram for the different heat treatment time preparing catalyst to photocatalysis hydrogen production.
Figure 10 d is access times to photochemical catalyst Er3+:Y3Al5O12@Nb2O5/Pt/In2O3The shadow of photocatalytic hydrogen production activity
Ring figure.
Figure 11 is Z-type photochemical catalyst Er3+:Y3Al5O12@Nb2O5/Pt/In2O3The mechanism figure of photocatalysis hydrogen production.
Specific embodiment
A kind of photocatalysis hydrogen production Z-type photochemical catalyst Er of embodiment 13+:Y3Al5O12@Nb2O5/Pt/In2O3
(1) preparation method
1, Er is prepared3+:Y3Al5O12Powder
Under stiring, by 2.27g Y2O3With 0.01g Er2O3It is dissolved in hot HNO appropriate3In solution, Y (NO is obtained3)3
With Er (NO3)3Mixed solution.Then, 12.62g Al (NO is added under magnetic stirring3)3·9H2O, and obtain homogeneous solution.
Later, 33.93g solid citric acid is also added in the mixture solution.Continue agitating solution and is heated at 50-60 DEG C
Until being successfully formed vitreosol.Then, colloidal sol is heated for 24 hours at 80 DEG C, and becomes xerogel.Gel is cold in air
But after, it is ground into uniform powder.Obtained precursor is calcined into 2.0h at 1100 DEG C in Muffle furnace, to remove residual
Organic component and nitrate ion.Finally, being cooled to room temperature agglutinating matter in air.Completely after cooling, Er is obtained3+:
Y3Al5O12The particle of nano-scale.
2, Er is prepared3+:Y3Al5O12@Nb2O5Colloidal sol
By 7.4g NbCl5It is dissolved in 10.0mL dehydrated alcohol, and stirs 30min at 70 DEG C, be marked as solution A.
17.2g citric acid is dissolved in 10.0mL deionized water, solution B is marked as.Solution B is added dropwise in solution A, is stirred
0.5g Er is added after mixing 5-10min3+:Y3Al5O12Continue to stir 30-40min, be aged at room temperature, forms Er3+:Y3Al5O12@
Nb2O5Colloidal sol.
3, In is prepared2O3Colloidal sol
By 8.0g InCl3It is added in 10.0mL glacial acetic acid, is then vigorously stirred 30min, is marked as solution A.It will
3.0mL deionized water and 2.0mL ethylene glycol are added in 5.0mL dehydrated alcohol, then stir 30min, are labeled as solution B.?
Under stirring, solution B is slowly dropped into solution A.Finally, 1.2g citric acid is added in mixture solution.Acquired solution is turned
It moves in three-neck flask, and the 2.5h that flows back at 50 DEG C.By solution cooling and aging at room temperature, light yellow In is obtained2O3It is molten
Glue.
4, mechanical mixing (M-M) prepares Er3+:Y3Al5O12@Nb2O5/In2O3
By 20mg In2O3Colloidal sol directly with 20mg Er3+:Y3Al5O12@Nb2O5Colloidal sol mixing, ultrasonic disperse 1.0h.So
Afterwards, mixed sols is heated, drying for 24 hours, forms xerogel at 80 DEG C.After xerogel is cooled down in air, wear into uniformly
Powder.Powder is heat-treated 2.0h at 500 DEG C, cooling, grinding obtains Z-type Er3+:Y3Al5O12@Nb2O5/In2O3Light is urged
Agent.
5, plated film-demoulding method (C-D) prepares Er3+:Y3Al5O12@Nb2O5/In2O3
By Er3+:Y3Al5O12@Nb2O5Colloidal sol is coated by spin-coating method under 1800 turns and grows 20s on the glass substrate, and 80
Dry 30min, spin coating process in triplicate, obtain Er at DEG C3+:Y3Al5O12@Nb2O5Film.And then by In2O3Colloidal sol, 1800
Turn the lower spin-coating method that passes through in Er3+:Y3Al5O12@Nb2O520s is grown on film, it is 30 minutes dry at 80 DEG C.Spin coating process repeats three
It is secondary.Load there is into Er3+:Y3Al5O12@Nb2O5/In2O3The glass substrate of film is in 500 DEG C of heat treatment 2.0h.Finally, by demoulding,
Milled processed obtains Z-type Er3+:Y3Al5O12@Nb2O5/In2O3Photochemical catalyst.
6, plated film-demoulding method (C-D) prepares Er3+:Y3Al5O12@Nb2O5/Pt/In2O3
By Er3+:Y3Al5O12@Nb2O5Colloidal sol is coated by spin-coating method under 1800 turns and grows 20s on the glass substrate, and 80
Dry 30min at DEG C.Spin coating process in triplicate, forms Er3+:Y3Al5O12@Nb2O5Film.
By chloric acid platinum solution drop coating in Er3+:Y3Al5O12@Nb2O5On film, Pt particle is deposited on by ionic adsorption method
Er3+:Y3Al5O12@Nb2O5On film, Er is formed3+:Y3Al5O12@Nb2O5/ Pt film.
By In2O3Colloidal sol is coated in Er by spin-coating method under 1800 turns3+:Y3Al5O12@Nb2O5On/Pt film, growth
20s, it is 30 minutes dry at 80 DEG C, in triplicate, form Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Film.
Load there is into Er3+:Y3Al5O12@Nb2O5/Pt/In2O3The glass substrate of film respectively different temperatures (400 DEG C, 500
DEG C and 600 DEG C) and different time (1.0h, 2.0h and 3.0h) under be heat-treated.It after cooling, demoulds, grinding obtains not respectively
With the target product Er for the treatment of temperature and different disposal time3+:Y3Al5O12@Nb2O5/Pt/In2O3。
(2) it detects
(1)In2O3, Nb2O5, Er3+:Y3Al5O12, Er3+:Y3Al5O12@Nb2O5/In2O3(M-M and C-D) and Er3+:
Y3Al5O12@Nb2O5/Pt/In2O3(C-D) X-ray powder diffraction (XRD)
In is had studied by X-ray diffraction (XRD)2O3, Nb2O5, Er3+:Y3Al5O12, Er3+:Y3Al5O12@Nb2O5/In2O3
(M-M and C-D) and Er3+:Y3Al5O12@Nb2O5/Pt/In2O3(C-D) crystal structure, as a result as shown in Fig. 1 a- Fig. 1 f.Fig. 1 a
Show the diffraction maximum at 2 θ=21.75 °, 30.66 °, 35.47 °, 51.12 ° and 60.73 °, they correspond respectively to In2O3
Lattice plane ((211), (222), (400), (440) and (622)).The diffraction maximum and cubic structure type In of well-crystallized2O3's
Standard card JCPDS#06-0416 data are consistent.As shown in Figure 1 b, the Nb of synthesis2O5Diffraction maximum be located at 22.68 ° (001),
28.61 ° (180), 36.75 ° (181), 46.30 ° (002), 50.59 ° (380) and 55.31 ° (202), with Nb2O5Standard card
JCPDS#30-0873 data are consistent.The sample of XRD diagram display preparation is the Nb of high-purity2O5Nano particle, and it is not any
Niobium oxide phase (such as the NbO and NbO of other valence states2).In figure 1 c, the Er of synthesis3+:Y3Al5O12Main diffraction peak be located at
27.77 ° (321), 29.72 ° (400), 33.34 ° (420), 36.62 ° (422), 41.14 ° (521), 46.56 ° (532),
55.09 ° (640) and 61.78 ° (800), with Y3Al5O12Standard card JCPDS#33-0040 data it is almost the same.Spike shows
The Er with very high-crystallinity is successfully synthesized3+:Y3Al5O12.However, for some main diffraction maximums, with Y3Al5O12's
Standard card data are compared to there is slight movement, this shows during the preparation process, a small amount of Er3+Ion is instead of a part of Y3 +Ion, hence into Y3Al5O12Internal crystal framework.Fig. 1 d and Fig. 1 e respectively illustrate the Er of M-M method and the preparation of C-D method3+:
Y3Al5O12@Nb2O5/In2O3XRD spectrum.From XRD spectrum it will be clear that Er3+:Y3Al5O12, In2O3And Nb2O5Feature
Diffraction maximum shows that the sample prepared by M-M and C-D preparation method contains these oxide particles.However, although passing through M-M
The sample of method preparation gives In2O3(30.66 °) and Nb2O5The characteristic peak of (28.61 °), but these characteristic diffraction peaks are opposite
It is independent, and almost with pure In2O3And Nb2O5Peak it is identical.This shows most of In2O3And Nb2O5It does not combine closely one
It rises.For the Er of C-D method preparation3+:Y3Al5O12@Nb2O5/In2O3, in Fig. 1 e, weak diffraction maximum appears in 28.61 °, belongs to solution
From Nb2O5.In addition, new strong and wide diffraction maximum appears in 30.52 °, this may be due to In2O3And Nb2O5Diffraction maximum
Relative displacement, show In2O3And Nb2O5It is closely linked.In Fig. 1 f, it can find and characteristic identical in Fig. 1 e.
In addition, the characteristic peak of Pt can also be seen at 39.83 °, 46.48 ° and 68.03 ° positions respectively.They and Pt standard card JCPDS#
01-1194 data are consistent.Moreover, all characteristic diffraction peaks are all with high-intensitive sharp peak.Surface C-D Er3+:
Y3Al5O12@Nb2O5/Pt/In2O3With very high crystallinity.Also, In2O3And Nb2O5It can be closely linked, Pt
The particle of nano-scale is located at In2O3And Nb2O5Between, form a high proportion of modified Z-type photochemical catalyst.
(2)In2O3, Nb2O5, Er3+:Y3Al5O12And Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Scanning electron microscope
(SEM)
In2O3(a),Nb2O5(b),Er3+:Y3Al5O12(c) and Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Different times magnifications
The pattern and structure of number 1:1.0 μm (d-1), 2:500 (d-2) nm and 3:200nm (d-3) assess (Fig. 2) by SEM.Fig. 2's
(a) in, In2O3Cubic structure, size range 200-300nm is presented in particle.In (b) of Fig. 2, Nb2O5Sample, which is shown, to be provided
There is the morphology of the aggregate of large scale and regular layer structure.Er as up-conversion luminescence agent3+:Y3Al5O12Form such as Fig. 2
(c) shown in.Obviously, Er3+:Y3Al5O12Particle is that some long axis are 50nm, and short axle is the ellipsoid of 30nm.(d) of Fig. 2 is shown
The Z-type Er that is prepared by C-D method3+:Y3Al5O12@Nb2O5/Pt/In2O3The SEM image of the different scale of photochemical catalyst.From
(d-1 (1.0 μm)) of Fig. 2 are as can be seen that Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Nanoparticle aggregate is together.These are poly-
The partial size of collective is about 1.0 μm.In (d-2 (500nm)) of Fig. 2, the Er of each aggregation3+:Y3Al5O12@Nb2O5/Pt/In2O3
Particle is by relatively small In2O3And Er3+:Y3Al5O12@Nb2O5Particle composition.Further expansion ratio, in Fig. 2 (d-3
(200nm)) in, it can clearly be seen that In2O3And Er3+:Y3Al5O12@Nb2O5It combines closely.In addition, in In2O3It is deposited on surface
In some molecules, can be confirmed as Pt nano particle.This also indicates that the particle of many Pt nano-scales should be located at Er3+:
Y3Al5O12@Nb2O5And In2O3Between.Judge from SEM image, the present invention successfully uses C-D method to be prepared for Z-type Er3+:
Y3Al5O12@Nb2O5/Pt/In2O3Photochemical catalyst.
(3)Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Transmission electron microscope (TEM)
It is deeply observed by TEM and high-resolution TEM (HRTEM) further progress, as shown in Figure 3.(a) can from Fig. 3
To find out, the photochemical catalyst of preparation is made of four parts.Wherein, darker part is Nb2O5, and in Nb2O5The centre of particle
Black portions with irregular spherical shape are Er3+:Y3Al5O12Nano particle.Shallower color part is In2O3.In addition, In2O3
And Nb2O5Small dark ball between particle is the particle of Pt nano-scale.In addition, being seen as shown in (b) in Fig. 3 by HRTEM
Examine Er3+:Y3Al5O12@Nb2O5/Pt/In2O3In four parts crystal structure, and by measure spacing of lattice confirm theirs
Relationship.In the centre of image, it can be seen that the lattice fringe of one group of 0.390nm corresponds to Nb2O5(001) face (JCPDS#
30-0873).The 0.295nm lattice fringe in the image upper right corner is attributed to a cube In2O3(222) plane (JCPDS#06-0416).This
Outside, Er is also observed in the picture3+:Y3Al5O120.265nm lattice fringe, this is attributed to Y3Al5O12(420) lattice plane
(JCPDS#33-0040).With the Nb in image2O5Adjacent 0.198nm lattice fringe belongs to (200) face (JCPDS#01- of Pt
1194).From figure 3, it can be seen that Z-type Er can be confirmed further3+:Y3Al5O12@Nb2O5/Pt/In2O3The group of photochemical catalyst
At the correlation with four parts.
(4)Er3+:Y3Al5O12@Nb2O5/Pt/In2O3X-ray energy dispersion spectrum (EDX) figure
In order to determine the Z-type Er of preparation3+:Y3Al5O12@Nb2O5/Pt/In2O3The element of photochemical catalyst forms, and has studied it
Energy dispersion X-ray spectrum (EDX).As shown in figure 4, the Er of preparation3+:Y3Al5O12@Nb2O5/Pt/In2O3By Er, Y, Al, Nb,
Pt, In and O element composition.It can consider that In, the strong characteristic peak of Nb and O element are present in In2O3And Nb2O5In.Er, Y, Al and O
The characteristic peak of element confirms Er3+:Y3Al5O12It has successfully been added to as up-conversion luminescence agent in the Z-type photochemical catalyst of preparation.This
Outside, it has also been found that the diffraction maximum of Pt atom, this further demonstrates that the presence of Pt atom.These observation results and XRD, SEM
It is almost the same with the result of TEM.
(5)Er3+:Y3Al5O12@Nb2O5/Pt/In2O3, In (3d), Nb (3d), Er (4d), Y (3d), Al (2p), O (1s)
With x-ray photoelectron spectroscopy (XPS) figure of Pt (4f)
Z-type Er is had studied by x-ray photoelectron spectroscopy (XPS)3+:Y3Al5O12@Nb2O5/Pt/In2O3Photochemical catalyst
Basic composition and valence bond structure, as shown in Fig. 5 a- Fig. 5 h.Wherein, Fig. 5 a shows the Z-type Er of preparation3+:Y3Al5O12@Nb2O5/
Pt/In2O3The XPS spectrum of photochemical catalyst.This shows that the sample of preparation contains Er, Y, Al, Nb, Pt, In and O element.In figure 5b
It can be attributed to In 3d respectively at the peak that 444.6eV and 452.1eV are observed5/2With In 3d3/2, they are the spies of trivalent indium ion
Levy oxidation state.Two characteristic peaks in the Nb 3d spectrum of Fig. 5 c middle high-resolution are respectively 207.7eV and 210.46eV, can be distinguished
Belong to Nb 3d5/2With Nb 3d3/2Spin(-)orbit peak shows all niobium atoms all with Nb5+Form be present in this composite wood
In material.Fig. 5 d, Fig. 5 e, Fig. 5 f and Fig. 5 g indicate 168.3eV (Er4d5/2), 158.1eV (Y 3d5/2), 160.1eV (Y 3d3/2),
74.3eV(Al 2p3/2), 74.5eV (Al 2p1/2) and 531.4eV (O 1s), they and Er3+:Y3Al5O12The close phase of composition
It closes.Fig. 5 g shows three peaks of oxygen species.It is attributed to O-Nb key positioned at first peak of 530.6eV, and positioned at 531.4eV's
Second peak may be In2O3Lattice Oxygen.The oxygen atom of absorption can be belonged at the third peak that 532.2eV is observed.Scheming
In 5h, two peaks of Pt 4f can descend discovery in the combination of 71.3eV and 74.0eV respectively, it was confirmed that the presence of metal platinum.
(6)In2O3, Nb2O5And Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Ultraviolet-visible diffuse reflectance spectrum (DRS) with
In2O3And Nb2O5Band gap estimate figure
In is measured by UV-vis diffusing reflection spectrum2O3, Nb2O5And Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Optics inhale
It receives, and uses absorbance and wavelength data calculating In based on Kubelka-Munk function2O3And Nb2O5Band gap.It can from Fig. 6 a
To find out, In2O3Absorption edge is shown at 450nm, this proves the In of preparation2O3Some visible light can be absorbed.Nb2O5It is aobvious
The absorption belt edge of 355nm is shown, this shows the Nb of preparation2O5Ultraviolet light can only be absorbed.Due to Er3+:Y3Al5O12Presence,
Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Absorption spectrum tail portion it is significantly raised at 450-800nm.Should the result shows that, Er3+:
Y3Al5O12Visible light can be absorbed and be converted into ultraviolet light, to activate wide bandgap N b2O5Semiconductor, as shown in Figure 6 a.
Fig. 6 b and Fig. 6 c, according to Kubelka-Munk ((α h ν)2=c (h ν-Eg)) formula, pass through extrapolation (α h ν)2Linear segment and energy
Spirogram estimates In2O3And Nb2O5Band gap.Wherein α, c, ν and h are absorbance, constant, frequency and Planck's constant respectively.Meter
Obtained In2O3And Nb2O5Band gap respectively may be about 2.82eV and 3.32eV, it is similar to the value being previously reported.
(7)In2O3, Nb2O5, Er3+:Y3Al5O12And Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Fourier-transform infrared light
It composes (FT-IR)
In order to prove the chemical information of bonding structure in sample, the In of preparation2O3, Nb2O5, Er3+:Y3Al5O12And Er3+:
Y3Al5O12@Nb2O5/Pt/In2O3FT-IR spectrum as shown in Fig. 7 a- Fig. 7 d.From Fig. 7 a it can be seen that in 540cm-1,
565cm-1And 600cm-1There is the phonon vibration that three sharp absorption peaks can be attributed to In-O key in place, this is suggested the formation of
Cube In2O3.In fig.7b, two of Nb-O group very wide stretching vibration absorption bands are respectively in 642cm-1And 864cm-1,
Show Nb2O5Sample has prepared.Fig. 7 c gives the Er of preparation3+:Y3Al5O12FT-IR spectrum.In 482cm-1, 512cm-1And 567cm-1The absorption peak at place belongs to Al-O6The stretching and bending vibration of-Al, in 698cm-1And 793cm-1The absorption peak at place is
It stretches and curved Al-O4The vibration of-Al and 729cm-1The absorption peak at place corresponds to Y-O key.In figure 7d, it can be found that
In2O3, Nb2O5And Er3+:Y3Al5O12All characteristic absorption peaks, but some peaks have slight movement and enhancing.It can push away
It is disconnected, In2O3And Nb2O5It is combined together and Er3+:Y3Al5O12By Nb2O5Cladding.Meanwhile 3400cm can be confirmed-1Neighbouring width
Absorption band corresponds to the stretching vibration of-OH hydrogen bond.In 1600cm-1The obvious of place absorbs the moisture for being attributable to the absorption of-OH group
The deformation vibration of son.
(8)In2O3, Nb2O5, Er3+:Y3Al5O12@Nb2O5/In2O3(M-M), Er3+:Y3Al5O12@Nb2O5/In2O3(C-D)
And Er3+:Y3Al5O12@Nb2O5/Pt/In2O3(C-D) luminescence generated by light (PL) spectrum
In order to study separation of charge and transfer characteristic, the sample of preparation has carried out PL test, as the result is shown in fig. 8.It is many
Well known, high photocatalytic activity is since photo-generate electron-hole is to efficiently separating.Briefly, the low PL of photochemical catalyst
Emissive porwer shows that the recombination rate in light induced electron and hole is low, this shows high photocatalytic activity in turn.When preparation
In2O3And Nb2O5When being excited under the light of 310nm wavelength, for two strong PL emission peak present in 470nm, this shows In2O3With
Nb2O5Recombination rate with higher light induced electron and hole.With In2O3And Nb2O5It compares, passes through two kinds of differences (M-M and C-D)
The Z-type photochemical catalyst of method preparation all shows relatively low PL emissive porwer under identical smooth excitation wavelength.This shows Z-type
The light induced electron of photochemical catalyst and the significant reduction of the recombination rate in hole.It is worth noting that, the Z-type Er prepared using C-D method3+:
Y3Al5O12@Nb2O5/Pt/In2O3Photochemical catalyst has minimum PL emissive porwer in all samples.On the one hand, the preparation side C-D
Method can effectively improve high activity Z-type Er3+:Y3Al5O12@Nb2O5/Pt/In2O3The ratio of photocatalyst granular.On the other hand,
Nb2O5Electronics on conduction band can be quickly transferred to In by Pt nano particle2O3Valence band, recombined with hole.This is effectively
Ground inhibits the In of photogenerated2O3And Nb2O5Electron-hole pair it is compound.Therefore Z-type Er3+:Y3Al5O12@Nb2O5/Pt/
In2O3Photochemical catalyst can show high photocatalytic activity.
(9)Er3+:Y3Al5O12@Nb2O5/In2O3(M-M), Er3+:Y3Al5O12@Nb2O5/In2O3(C-D) and Er3+:
Y3Al5O12@Nb2O5/Pt/In2O3(C-D) electro-chemical test
Optical electro-chemistry measurement is commonly used in the excitation and transfer of photogenerated charge carriers in qualitative research photocatalysis.In Fig. 9 a
In, to understand the electron-transport behavior in the photochemical catalyst prepared, electrochemical impedance spectroscopy result is in the form of nyquist diagram
It is existing.Lesser electric arc size generally means that the surface of photochemical catalyst has low charge transfer resistance.Obviously, with C-D legal system
Standby Z-type Er3+:Y3Al5O12@Nb2O5/Pt/In2O3The arc radius of photochemical catalyst is minimum.In other words, Z-type Er3+:Y3Al5O12@
Nb2O5/Pt/In2O3Photochemical catalyst has minimum interfacial charge transfer resistance, leads to the high separating efficiency of electrons and holes.Phase
Than under, the Z-type Er that is prepared by M-M method3+:Y3Al5O12@Nb2O5/In2O3Photochemical catalyst has maximum arc radius, therefore,
It has highest interfacial charge transfer resistance, leads to the low separative efficiency of electrons and holes.
In order to further appreciate that these by distinct methods prepare photocatalytic system in photogenerated charge separative efficiency and
Electrodes transfer behaviour tests the transient photocurrents response of the photochemical catalyst of preparation.As shown in figure 9b, all to lamp on and off
When sample show relatively stable and reversible photoresponse under visible light illumination, be repeated once within every 20 seconds, bias be+
0.62V.When lit, photoelectric current sharply increases, and then returns to its reset condition immediately after lamp goes out.It is prepared by M-M method
Z-type Er3+:Y3Al5O12@Nb2O5/In2O3Photochemical catalyst shows low-down photoelectric current.Also, since there is no Pt nanometers
Particle is as electron channel, the Z-type Er of C-D method preparation3+:Y3Al5O12@Nb2O5/In2O3Also relatively low photoelectric current is shown.
However, the Z-type Er prepared by C-D method3+:Y3Al5O12@Nb2O5/Pt/In2O3Show very strong photoelectric current.The result into
One step confirms, can greatly improve high activity Z-type Er by using C-D method3+:Y3Al5O12@Nb2O5/Pt/In2O3Photocatalysis
The ratio of agent particle.It leads to the enhancing of whole photocatalytic activity.In contrast, the Z-type Er of C-D method preparation3+:Y3Al5O12@
Nb2O5/Pt/In2O3Photoelectric current be much higher than C-D method preparation Er3+:Y3Al5O12@Nb2O5/In2O3(without Pt as conductive logical
Road) photoelectric current.This is because the presence of Pt nano particle makes Nb2O5Electronics on conduction band can be quickly transferred to In2O3's
Then valence band is recombined with hole.Obviously, photoelectric current analysis is consistent with the result of PL and electrochemical impedance spectroscopy.
2 Er of embodiment3+:Y3Al5O12@Nb2O5/Pt/In2O3Application in photocatalysis hydrogen production
Experimental method: photocatalysis hydrogen generates experiment in 500mL Pyrex reactor assembly, in 25 DEG C of temperature and pressure
It is carried out under 101325Pa.In the typical light-catalyzed reaction for hydrogen generator, the sample of preparation is being contained under constant stirring
Have in the aqueous solution of methanol and is put into Photoreactor.Before radiation of visible light, reaction system is led into argon gas 30 minutes to remove
The air of dissolution.Then pass through the light cutoff filter from 300W Xe lamp (LX-300, Deruifeng hardware electrical company, China)
For device with radiation of visible light the system 4.0 hours, which was looped around the side of Photoreactor.Pass through Cold Mirrors (CM-1) and water filter
Combination control irradiation optical wavelength.For radiation of visible light, by optical filter (L42) be assembled to above-mentioned light source (420 < λ <
800nm)。
(1) distinct methods prepare influence of the catalyst to photocatalysis hydrogen production
Influence of the different preparation methods to the hydrogen production activity of the Z-type photochemical catalyst of preparation is as shown in Figure 10 a.It can be found that
The hydrogen yield of these three Z-type photochemical catalysts increases with the increase of irradiation time.However, two Z prepared with C-D method
The hydrogen output for the Z-type photochemical catalyst that the hydrogen yield of type photochemical catalyst is prepared much higher than with M-M method.This shows that C-D method can be with
The ratio of high activity Z- type photocatalyst composite particle is greatly improved, and reduces non-Z- type photocatalyst granular as by-product
Quantity.That is, C-D method can promote the activity of Z-type photocatalytic system.For C-D method preparation Z-type photochemical catalyst,
It is important to point out that Z-type Er of the Pt nano particle as conductive channel3+:Y3Al5O12@Nb2O5/Pt/In2O3Photochemical catalyst
Hydrogen output is significantly larger than Z-type Er3+:Y3Al5O12@Nb2O5/In2O3.This is because Pt nanoparticle passes through C-D as conductive channel
Method is forced to be fixed on Nb2O5And In2Between O particle, effective Z-type photocatalytic system is formed.Therefore, in this Z-type Er3+:
Y3Al5O12@Nb2O5/Pt/In2O3In photocatalytic system, Nb2O5Electronics on conduction band can be quickly transferred to In2In the valence band of O,
In conjunction with hole.In conclusion using the Z-type Er of the available high activity of C-D method3+:Y3Al5O12@Nb2O5/Pt/In2O3Light
Catalyst system, the presence of Pt nanoparticle can accelerate the separation in light induced electron and hole.
(2) different heat treatment temperature prepares influence of the catalyst to photocatalysis hydrogen production
Figure 10 b shows heat treatment temperature to the Z-type Er of preparation3+:Y3Al5O12@Nb2O5/Pt/In2O3The system of photochemical catalyst
The influence of hydrogen activity.As can be seen that for three heat treatment temperatures, Z-type Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Photochemical catalyst
Hydrogen yield increase with the increase of irradiation time.However, with the increase of heat treatment temperature, in any irradiation time,
Hydrogen yield all significantly increases (from 400 DEG C to 500 DEG C) and then slightly reduces (from 500 DEG C to 600 DEG C).As Z-type Er3+:
Y3Al5O12@Nb2O5/Pt/In2O3When photochemical catalyst calcines 2.0h at 500 DEG C, it is seen that the amount of photocatalysis hydrogen production reaches maximum value.
Therefore, high temperature appropriate advantageously forms Z-type Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Photochemical catalyst.But even if temperature into
One step increases, and the activity of the photochemical catalyst of preparation is also almost unchanged.It can be confirmed that 500 DEG C are to prepare Z-type Er3+:Y3Al5O12@
Nb2O5/Pt/In2O3The optimum treatment temperature of photochemical catalyst, hydrogen output is up to 384 μm of olg-1。
(3) the different heat treatment time prepares influence of the catalyst to photocatalysis hydrogen production
Figure 10 c shows heat treatment time to the Z-type Er of preparation3+:Y3Al5O12@Nb2O5/Pt/In2O3The light of photochemical catalyst
The active influence of catalyzing manufacturing of hydrogen.Similarly, the hydrogen yield of the Z-type photochemical catalyst of three heat treatment times is with irradiation time
Increase and increases.Furthermore, it is possible to find, as Z-type Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Photochemical catalyst is calcined at 500 DEG C
When 1.0h, it shows highest photocatalytic activity.That is, with the increase of heat treatment time, in any irradiation time
Hydrogen yield all reduce.This shows for Z-type Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Photochemical catalyst is only heat-treated in 1.0h
After could obtain high activity.Moreover, photocatalytic activity can slightly decline after the heat treatment of long period.This is because
At relatively high temperature, long-term heat treatment can cause the aggregation of Pt nano particle.Therefore, for 500 DEG C of temperature, the calcining of 1.0h
It is to form high activity Z-type Er3+:Y3Al5O12@Nb2O5/Pt/In2O3The desired heat treatment time of photochemical catalyst, hydrogen output are reachable
410μmol·g-1.It is not only does this facilitate and improves Z-type Er3+:Y3Al5O12@Nb2O5/Pt/In2O3The photocatalytic activity of photochemical catalyst,
And also avoid longer heat treatment time.
(4) access times are to photochemical catalyst Er3+:Y3Al5O12@Nb2O5/Pt/In2O3The influence of photocatalytic hydrogen production activity
Finally, using the time to the Z-type Er of preparation3+:Y3Al5O12@Nb2O5/Pt/In2O3The photocatalysis hydrogen production of photochemical catalyst
Active influence is as shown in fig. 10d.For photocatalytic system, highlight catalytic active is the key that assessment photochemical catalyst.In addition, light
Catalyst is another key factor for evaluating stability using the time.In in this section, each circulation experiment when
Between be 4.0h, then at 80 DEG C be heat-treated 1.0h to be activated after, recycle photochemical catalyst to carry out identical circulation experiment.
As can be seen that after each repetition is tested, Z-type Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Under the hydrogen yield of photochemical catalyst slightly has
Drop, but still keep high level.Certainly, a high proportion of Z-type Er is being prepared by C-D method3+:Y3Al5O12@Nb2O5/Pt/In2O3Light
While catalyst, some be suitably modified to keep stable highlight catalytic active is needed.
Er3+:Y3Al5O12@Nb2O5/Pt/In2O3The principle of photocatalysis hydrogen production are as follows: as shown in figure 11, Z-type photocatalytic system
By In2O3, Er3+:Y3Al5O12@Nb2O5It is formed with Pt nanoparticle, wherein Pt nanoparticle is located at In2O3And Er3+:Y3Al5O12@
Nb2O5Between.Due to In2O3Valence band be relatively close to potential be Nb2O5Conduction band, ideal Z-type photocatalytic system can be by In2O3
And Nb2O5Composition.Especially Nb2O5Electronics on conduction band can enter In by Pt nanoparticle2O3Valence band, then with hole
It is compound, effectively inhibit Nb2O5And In2O3Middle light induced electron and hole it is compound.As Z-type Er3+:Y3Al5O12@Nb2O5/Pt/
In2O3When photochemical catalyst is by radiation of visible light, since its band gap is narrow, In2O3It can directly be excited by visible light to form photoproduction electricity
Son and hole.In addition, visible light passes through Er3+:Y3Al5O12High energy UV is converted to, wide bandgap N b is excited2O5, generate photoproduction electricity
Son and hole.Due to In2O3Valence band be relatively close to potential be Nb2O5Conduction band, therefore Nb2O5Electronics on conduction band can pass through
Pt nanoparticle enters In2O3Valence band, and and hole-recombination.In2O3Electronics and Nb on conduction band2O5Hole difference in valence band
Carry out redox reaction.Nb2O5Hole in valence band can promote In using Oxidation of Methanol as sacrifice agent2O3Electronics on conduction band
It is reduced to hydrogen generation.Thus, it will be seen that in presence of methyl alcohol, Z-type Er3+:Y3Al5O12@Nb2O5/Pt/In2O3Photochemical catalyst
Photocatalysis hydrogen production can be effectively performed.
Claims (7)
1. a kind of photocatalysis hydrogen production Z-type photochemical catalyst, it is characterised in that: the photocatalysis hydrogen production Z-type photochemical catalyst is Er3+:
Y3Al5O12@Nb2O5/Pt/In2O3。
2. a kind of photocatalysis hydrogen production Z-type photochemical catalyst according to claim 1, it is characterised in that: the Er3+:
Y3Al5O12@Nb2O5/Pt/In2O3In, the weight percentage of Pt is 0.5%；Er3+:Y3Al5O12Weight percentage be
15.0%；In molar ratio, Nb2O5:In2O3=1:1.
3. a kind of preparation method of photocatalysis hydrogen production Z-type photochemical catalyst of any of claims 1 or 2, which is characterized in that including such as
Lower step:
1) by Er3+:Y3Al5O12@Nb2O5Colloidal sol, under 1800 turns by spin-coating method be coated in template on, grow 20-30s, 80 DEG C
Lower dry 30-40min forms Er in triplicate3+:Y3Al5O12@Nb2O5Film；
2) by chloric acid platinum solution drop coating in Er3+:Y3Al5O12@Nb2O5On film, Pt particle is deposited on by Er by ionic adsorption method3+:
Y3Al5O12@Nb2O5On film, Er is formed3+:Y3Al5O12@Nb2O5/ Pt film；
3) by In2O3Colloidal sol is coated in Er by spin-coating method under 1800 turns3+:Y3Al5O12@Nb2O5On/Pt film, 20- is grown
30s, dry 30-40min forms Er in triplicate at 80 DEG C3+:Y3Al5O12@Nb2O5/Pt/In2O3Film；
4) load there is into Er3+:Y3Al5O12@Nb2O5/Pt/In2O3The template of film is heat-treated 1.0-3.0h at 400-600 DEG C, cold
But it after, demoulds, grinding obtains target product Er3+:Y3Al5O12@Nb2O5/Pt/In2O3。
4. a kind of preparation method of photocatalysis hydrogen production Z-type photochemical catalyst according to claim 3, which is characterized in that described
Er3+:Y3Al5O12@Nb2O5The preparation method of colloidal sol includes the following steps: aqueous citric acid solution being added dropwise to NbCl5's
In ethanol solution, Er is added after stirring 5-10min3+:Y3Al5O12Continue to stir 30-40min, be aged at room temperature, forms Er3+:
Y3Al5O12@Nb2O5Colloidal sol.
5. a kind of preparation method of photocatalysis hydrogen production Z-type photochemical catalyst according to claim 3, which is characterized in that described
In2O3The preparation method of colloidal sol includes the following steps: under stiring, and the mixing of deionized water, ethylene glycol and dehydrated alcohol is molten
Liquid is added dropwise to InCl3Glacial acetic acid solution in, after mixing evenly, be added citric acid, by gained mixed solution at 50 DEG C
Flow back 2-3h, is cooled to room temperature simultaneously aging, obtains In2O3Colloidal sol.
6. application of the Z-type photochemical catalyst of any of claims 1 or 2 in photocatalysis hydrogen production.
7. application according to claim 6, which is characterized in that method is as follows: in the aqueous solution containing methanol, power is added
Benefit require 1 or 2 described in photocatalysis hydrogen production Z-type photochemical catalyst Er3+:Y3Al5O12@Nb2O5/Pt/In2O3, in 25 DEG C of temperature and pressure
Under power 101325Pa, 300min is irradiated with the xenon lamp of 300W.
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| JP2012091143A (en) * | 2010-10-28 | 2012-05-17 | National Institute Of Advanced Industrial Science & Technology | Environment-resistant visible light responsive photocatalyst film structure and photocatalyst promoter |
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