CN107051451A - The dendritic heterojunction structure photochemical catalyst and preparation method of a kind of wide spectrum driving - Google Patents
The dendritic heterojunction structure photochemical catalyst and preparation method of a kind of wide spectrum driving Download PDFInfo
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- CN107051451A CN107051451A CN201710216201.9A CN201710216201A CN107051451A CN 107051451 A CN107051451 A CN 107051451A CN 201710216201 A CN201710216201 A CN 201710216201A CN 107051451 A CN107051451 A CN 107051451A
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- butyl titanate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000001228 spectrum Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000010931 gold Substances 0.000 claims abstract description 83
- 239000002121 nanofiber Substances 0.000 claims abstract description 63
- 239000002131 composite material Substances 0.000 claims abstract description 39
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 26
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 claims abstract description 24
- 239000002070 nanowire Substances 0.000 claims abstract description 22
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 22
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 22
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 22
- 229960000583 acetic acid Drugs 0.000 claims abstract description 13
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 12
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 8
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 27
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 238000013019 agitation Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 238000001523 electrospinning Methods 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 238000009987 spinning Methods 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 3
- 150000004040 pyrrolidinones Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 22
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 229910000085 borane Inorganic materials 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 11
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 11
- 125000005909 ethyl alcohol group Chemical group 0.000 description 8
- 238000010531 catalytic reduction reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical class Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- PHXKQKZYWQUGLW-UHFFFAOYSA-N 1h-pyrrole;pyrrolidin-2-one Chemical compound C=1C=CNC=1.O=C1CCCN1 PHXKQKZYWQUGLW-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
-
- 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
-
- 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
- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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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- Chemical Kinetics & Catalysis (AREA)
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Abstract
A kind of dendritic heterojunction structure photochemical catalyst of wide spectrum driving, it is that Au nano-particles are assembled in into TiO2Inside nanofiber and surface, then by W18O49TiO of the nanowire growth in Au Nanoparticle Modifieds2Nanofiber surface, so as to be classified the W constructed18O49/TiO2The dendritic heterojunction structures of/Au；Its preparation method is mainly：Glacial acetic acid, butyl titanate, gold chloride and polyvinylpyrrolidone are added in absolute ethyl alcohol, recycle electrostatic spinning technique to prepare gold chloride/butyl titanate/polyvinylpyrrolidone composite nano fiber, high-temperature calcination obtains TiO2/ Au composite nano fibers；Tungsten carbonyl is dissolved in absolute ethyl alcohol, above-mentioned obtained TiO is added2/ Au composite nano fibers, carry out solvent thermal reaction, and W is made18O49/TiO2The dendritic heterojunction structure photochemical catalysts of/Au.The catalysis material of the present invention has the advantages that light absorbs, higher carrier separation efficiency and the relatively low production Hydrogen over potential of approximate full solar spectrum.
Description
Technical field
The present invention relates to a kind of photochemical catalyst and preparation method.
Background technology：
With petering out for the fossil fuels such as coal, oil, energy shortage problem is increasingly sharpened, as puzzlement people
The global problem of class existence.The birth of Photocatalitic Technique of Semiconductor is not only that environmental improvement provides a kind of green method, together
When also open a brand-new route full of hope for the conversion of solar energy and fuel energy.Urged by light of semiconductor nano material
The solar energy of low-density can be effectively converted into highdensity chemical energy by agent.For example, passing through photocatalytic water or photic load hydrogen
Organic molecule reduction reaction can obtain one of presently the most preferable energy-Hydrogen Energy, and it can not only discharge huge when burning
Energy, and the product generated is the water of no pollution.This aspect reduces environmental pollution, on the other hand again that solar energy is effective
Change into for fuel energy.In numerous conventional semiconductors catalysis materials, TiO2So that its activity is high, stability is good, nothing
Malicious the advantages of and by extensive concern.However, the catalysis material still has some significant drawbacks, its development is restricted：(1) light is inhaled
The threshold wave-length of receipts is less than 400nm, therefore can only limit it to the sun using the ultraviolet light for accounting for solar energy 4% or so
The utilization of the visible ray and infrared light of rich content in spectrum；(2) its photo-generated carrier is compound very fast, reduces the production of its quantum
Rate；(3) production Hydrogen over potential is higher, it is suppressed that light energy use efficiency.
The content of the invention：
It is an object of the invention to provide one kind there is approximate full solar spectrum to absorb, photo-generated carrier separation rate it is higher with
And the dendritic heterojunction structure photochemical catalyst and preparation method of the relatively low wide spectrum driving of production Hydrogen over potential, hereinafter referred to as W18O49/
TiO2The dendritic heterojunction structure photochemical catalysts of/Au and preparation method.
The present invention is mainly by a diameter of 5~60nm, the W that length is 200~900nm18O49Nano wire, particle diameter be 5~
15nm Au nano-particles and a diameter of 200~500nm, length is 5~30 μm of TiO2Three kinds of material classifications of nanofiber
The W of assembling18O49/TiO2The dendritic heterojunction structures of/Au.Utilize W18O49Nano wire is visible-infrared light surface plasmon resonance and Au
TiO is widened in the collaboration of nano-particle visible ray surface plasmon resonance2The spectral response range of nanofiber；Utilize electrospinning TiO2
The unique light scattering behavior of nanofiber improves its uv absorption rate；Utilize W18O49/TiO2Electric charge at/Au heterogeneous interfaces turns
Moving past journey reduces the recombination probability of photo-generated carrier；The overpotential that system produces hydrogen is reduced using Au nano-particles, final collaboration is carried
The photo-reduction ammonia borine hydrogen manufacturing performance of high photochemical catalyst.
1st, W of the invention18O49/TiO2The dendritic heterojunction structure photochemical catalysts of/Au, it is to receive particle diameter for 5~15nm Au
Rice corpuscles assemble in situ is in a diameter of 200~500nm, the TiO that length is 5~30 μm2Nanofiber internal matrix and surface, then
By a diameter of 5~60nm, the W that length is 200~900nm18O49TiO of the nanowire growth in Au Nanoparticle Modifieds2Nanowire
Dimension table face, is classified the W constructed18O49/TiO2The dendritic heterojunction structure photochemical catalysts of/Au.
2nd, above-mentioned W18O49/TiO2The preparation method of the dendritic heterojunction structure photochemical catalysts of/Au is as follows：
1) Au nano-particles are assembled in TiO2Nanofiber internal matrix and surface：
First, glacial acetic acid and butyl titanate are added in absolute ethyl alcohol, the volume ratio of three is, glacial acetic acid：Butyl titanate：
Absolute ethyl alcohol=1~3：1~3：3~8, best glacial acetic acid is equal with butyl titanate volume ratio, then, by high-molecular polythene pyrrole
Pyrrolidone is according to itself and butyl titanate mass ratio, i.e. polyvinylpyrrolidone：Butyl titanate=0.15~0.4:1 be dissolved in it is above-mentioned molten
In liquid；Then, then by gold chloride according to its mass ratio with butyl titanate, i.e. gold chloride：Butyl titanate=0.5~1.5:100
It is dissolved in the precursor solution that gold chloride/butyl titanate/polyvinylpyrrolidone is configured in the solution.Then, Static Spinning is utilized
Silk technology prepares gold chloride/butyl titanate/polyvinylpyrrolidone composite nano fiber, will precursor solution loading electrostatic
In spinning equipment, 8~16KV of spinning voltage is adjusted, 8~15cm of distance is received, electrostatic spinning is carried out, prepares gold chloride/metatitanic acid fourth
Ester/polyvinylpyrrolidone composite nano fiber.Finally, 500 DEG C of high temperature are risen to 2~8 DEG C/min speed in Muffle furnace
Gold chloride/butyl titanate/polyvinylpyrrolidone composite nano fiber is calcined, and is incubated 1~3 hour, so as to obtain TiO2/Au
Composite nano fiber.
2) by W18O49TiO of the nanowire growth in Au Nanoparticle Modifieds2Nanofiber surface：
Tungsten carbonyl is added in absolute ethyl alcohol, wherein tungsten carbonyl concentration is：2~5 μm of ol/ml, magnetic agitation 10~
50min is allowed to dissolve.Then, step 1 is added into the solution) in obtained TiO2/ Au composite nano fibers make itself and six
The mass ratio of tungsten carbonyl, i.e. Au/TiO2Nanofiber：Tungsten carbonyl=0.15~1.5：1, continue 10~30min of magnetic agitation.
Then, the mixed solution is placed in reactor, sealed, then sealed reactor is placed in electric dry oven carried out hydro-thermal reaction,
Hydrothermal temperature is 160~200 DEG C, and the time is 10~16 hours.Reaction terminates rear reactor and naturally cools to room temperature, drives kettle, takes
Go out the blue lumpy precipitate of natural sedimentation, washed with ethanol, finally by the product in vacuum drying 10~14 hours at 60 DEG C,
Obtain W18O49/TiO2The dendritic heterojunction structure photochemical catalysts of/Au.
W18O49With TiO2The conduction band positions (reduction potential) of semi-conducting material can meet photo catalytic reduction ammonia borine system
Hydrogen, and Au nano-particles can further reduce the production Hydrogen over potential of system, improve photocatalysis yield；W18O49Absorb visible
Light and infrared light, Au nano-particles absorb visible ray, TiO2Ultraviolet light is absorbed, three is compound, and there is approximate full solar spectrum light to inhale
Receive characteristic；W18O49/TiO2/ Au band structure matching, can make light induced electron from W18O49It is transferred to TiO2Conduction band, is finally arrived
The relatively low Au nanoparticle surfaces of Hydrogen over potential are produced, effectively suppress the recombination process of photo-generated carrier, photo-quantum efficiency is improved；Separately
Outside, the unique nano net felt structure of electro spinning nano fiber has light scattering effect, can improve TiO2The UV Absorption of material
Characteristic；Therefore, by being rationally classified assembling W18O49Nano wire, Au nano-particles and TiO2Electro spinning nano fiber, constructs dendritic knot
Structure composite photo-catalyst can not only realize that wide spectrum absorbs, and can also improve photo-generated carrier separation, reduction system production hydrogen mistake
Potential, so as to effectively improve the photo catalytic reduction ammonia borine hydrogen manufacturing performance of material.
The present invention has the following advantages that compared with prior art：
1)W18O49Nano wire has visible-infrared light surface plasmon resonance characteristic；Au nano-particles have visible ray
Surface plasmon resonance characteristic, by the two and TiO2Nanofiber is compound can to obtain the ultra-wide light from ultraviolet light to infrared light
Spectrum absorbs, and its scope is similar to whole solar spectrum.
2)W18O49Nano wire and Au nano-particles all have visible ray surface plasmon resonance characteristic, and the two is combined can
To realize the surface phasmon coupled resonance of visible region, so as to further improve the photoproduction thermoelectron quantity of system.
3)W18O49Nano wire, Au nano-particles and TiO2The compound of nanofiber can form three kinds of heterogeneous interfaces, i.e. W18O49
Nano wire/Au nano-particles interface, TiO2Nanofiber/Au nano-particles interface and W18O49Nano wire/TiO2Nanofiber circle
Face, the feature can be effectively facilitated being spatially separating for photo-generated carrier in system, improve photocatalytic activity.
4) Au nano-particles have relatively low production Hydrogen over potential, by itself and W18O49Nano wire and TiO2Nanofiber is compound can
Ammonia borine hydrogen production efficiency is reduced with light induced electron in raising system.
5) W is constructed18O49/TiO2The dendritic heterojunction structure photochemical catalysts of/Au can be total to using the surface phasmon of wide spectrum
The nanostructured characteristic collaboration raising photocatalysis for the relatively low production Hydrogen over potential of effect, noble metal and the electro spinning nano fiber uniqueness of shaking
The photon energy absorption of material and photo-generated carrier separation process, so as to strengthen photo catalytic reduction ammonia borine hydrogen manufacturing performance.
Brief description of the drawings
Fig. 1 is the TiO prepared by the embodiment of the present invention 12The electron scanning micrograph figure of/Au composite nano fibers；
Fig. 2 is the W prepared by the embodiment of the present invention 118O49/TiO2The scanning electron of the dendritic heterojunction structure photochemical catalysts of/Au
Microphotograph figure；
Fig. 3 is the W prepared by the embodiment of the present invention 118O49/TiO2The low power transmission of the dendritic heterojunction structure photochemical catalysts of/Au
Electron micrograph figure；
Fig. 4 is the W prepared by the embodiment of the present invention 118O49/TiO2The high power transmission of the dendritic heterojunction structure photochemical catalysts of/Au
Electron micrograph figure；
Fig. 5 is the W prepared by the embodiment of the present invention 118O49/TiO2The X-ray diffraction of the dendritic heterojunction structure photochemical catalysts of/Au
Spectrogram；
Fig. 6 is the W prepared by the embodiment of the present invention 118O49/TiO2The UV-Vis-IR of the dendritic heterojunction structure photochemical catalysts of/Au
Abosrption spectrogram；
Fig. 7 is the W prepared by the embodiment of the present invention 118O49/TiO2The dendritic heterojunction structure photochemical catalysts of/Au and comparative sample
TiO2Nanofiber, W18O49Nano wire, TiO2/ Au composite nano fibers, W18O49/TiO2Heterojunction structure is in UV-Vis-IR light sources
The lower photo catalytic reduction ammonia borine hydrogen manufacturing figure of irradiation.
Embodiment
The invention will be further described in the way of specific embodiment below：
Embodiment 1：
2ml glacial acetic acid and 2ml butyl titanates are added in 5ml absolute ethyl alcohols, then by 0.4g high-molecular polythene pyrroles
Alkanone is dissolved in above-mentioned solution, then 0.0217g gold chloride is dissolved in above-mentioned solution is configured to gold chloride/butyl titanate/poly-
The precursor solution of vinylpyrrolidone.Then, the precursor solution is loaded into the doctor with a diameter of 0.6mm spinnerette orfices
It is 12cm with distance of the nozzle with being grounded receiver board in syringe, is kept, imposes 10KV high pressure, carry out electrostatic spinning, prepare
Gold chloride/butyl titanate/polyvinylpyrrolidone composite nano fiber.Finally, risen in Muffle furnace with 3 DEG C/min speed
500 DEG C of high-temperature calcination gold chloride/butyl titanate/polyvinylpyrrolidone composite nano fibers are simultaneously incubated 2 hours, so as to obtain
TiO2/ Au composite nano fibers.Obtained TiO2The electron scanning micrograph of/Au composite nano fibers is as shown in Figure 1.From
High-visible obtained TiO in figure2A diameter of 200~350nm of/Au composite nano fibers, length is 5~10 μm, and
The nano-particle of the visible denier of its smooth surface is present.
0.069mmol tungsten carbonyls are added in 20ml absolute ethyl alcohols, magnetic agitation 20min is allowed to dissolve.Then, to
Step 1 is added in the solution) in obtained TiO2/ Au composite nano fiber 5mg, continue magnetic agitation 20min.Then, will
The mixed solution is placed in reactor, sealing, then sealed reactor is placed in electric dry oven carries out hydro-thermal reaction, hydrothermal temperature
For 180 DEG C, the time is 12 hours.Reaction terminates rear reactor and naturally cools to room temperature, drives kettle, takes out the blue block of natural sedimentation
Shape sediment, is washed with ethanol, and the product is finally obtained into W in being dried in vacuo 12 hours at 60 DEG C18O49/TiO2/ Au is dendritic
Heterojunction structure photochemical catalyst.
Prepared W18O49/TiO2Electron scanning micrograph such as Fig. 2 institutes of the dendritic heterojunction structure photochemical catalysts of/Au
Show.The high-visible obtained W from figure18O49Nanowire diameter is that 5~40nm, length are 300~700nm, and is grown in
TiO2/ Au composite nano fibers, form W18O49/TiO2The dendritic heterojunction structures of/Au；From prepared by the present embodiment shown in Fig. 3
W18O49/TiO2The low power transmission electron microscope photo of the dendritic heterojunction structure photochemical catalysts of/Au can be seen that W18O49/TiO2/Au
Dendritic heterojunction structure photochemical catalyst is by W18O49Nanowire growth is in TiO2/ Au composite nano fiber surface constructions are formed；From Fig. 4
W prepared by shown the present embodiment18O49/TiO2The high power transmission electron microscope of the dendritic heterojunction structure photochemical catalysts of/Au shines
Piece, which can be seen that, is grown in TiO2The W on/Au composite nano fibers surface18O49The diameter of nano wire is about 20nm.Au nano-particles
Particle diameter be about 5~10nm, and be evenly distributed on TiO2Nanofiber surface and inside；From the present embodiment institute shown in Fig. 5
The W of preparation18O49/TiO2The X-ray diffraction spectrogram of the dendritic heterojunction structure photochemical catalysts of/Au can see, W18O49/TiO2/ Au
Except Anatase TiO in the diffraction maximum of shape heterojunction structure2Outside diffraction maximum, also in the presence of other new diffraction maximums, they respectively with
W18O49It is consistent with Au diffraction maximum.From the W prepared by the present embodiment shown in Fig. 618O49/TiO2The dendritic heterojunction structure light of/Au
The UV-Vis-IR absorption spectrum it can be seen from the figure thats W of catalyst18O49/TiO2The dendritic heterojunction structure photochemical catalysts of/Au have from purple
Wide spectrum optical absorption characteristics of the outer light to infrared light region.It can prove to have prepared W based on the above results18O49/TiO2/ Au
Shape heterojunction structure photochemical catalyst.
Embodiment 2：
1.5ml glacial acetic acid and 1.5ml butyl titanates are added in 4ml absolute ethyl alcohols, then by 0.4g high-molecular polythenes
Pyrrolidones is dissolved in above-mentioned solution, then 0.01085g gold chlorides are dissolved in above-mentioned solution be configured to gold chloride/butyl titanate/
The precursor solution of polyvinylpyrrolidone.Then, the precursor solution is loaded with a diameter of 0.6mm spinnerette orfices
In injector for medical purpose, the distance for keeping nozzle and ground connection receiver board is 9cm, imposes 11KV high pressure, carries out electrostatic spinning, is prepared
Gold chloride/butyl titanate/polyvinylpyrrolidone composite nano fiber.Finally, risen in Muffle furnace with 5 DEG C/min speed
500 DEG C of high-temperature calcination gold chloride/butyl titanate/polyvinylpyrrolidone composite nano fibers, and 1.5 hours are incubated, so as to obtain
Obtain TiO2/ Au composite nano fibers.
0.069mmol tungsten carbonyls are added in 20ml absolute ethyl alcohols, magnetic agitation 20min is allowed to dissolve.Then, to
Step 1 is added in the solution) in obtained TiO2/ Au composite nano fiber 10mg, continue magnetic agitation 10min.Then, will
The mixed solution is placed in reactor, sealing, then sealed reactor is placed in electric dry oven carries out hydro-thermal reaction, hydrothermal temperature
For 180 DEG C, the time is 12 hours.Reaction terminates rear reactor and naturally cools to room temperature, drives kettle, takes out the blue block of natural sedimentation
Shape sediment, is washed with ethanol, and the product is finally obtained into W in being dried in vacuo 12 hours at 60 DEG C18O49/TiO2/ Au is dendritic
Heterojunction structure photochemical catalyst.
Embodiment 3：
2ml glacial acetic acid and 2ml butyl titanates are added in 4ml absolute ethyl alcohols, then by 0.4g high-molecular polythene pyrroles
Alkanone is dissolved in above-mentioned solution, then 0.0217g gold chlorides are dissolved in above-mentioned solution are configured to gold chloride/butyl titanate/poly- second
The precursor solution of alkene pyrrolidone.Then, the precursor solution is loaded medical with a diameter of 0.6mm spinnerette orfices
In syringe, the distance for keeping nozzle and ground connection receiver board is 14cm, imposes 10KV high pressure, carries out electrostatic spinning, prepares chlorine
Auric acid/butyl titanate/polyvinylpyrrolidone composite nano fiber.Finally, risen in Muffle furnace with 8 DEG C/min speed
500 DEG C of high-temperature calcination gold chloride/butyl titanate/polyvinylpyrrolidone composite nano fibers are simultaneously incubated 1 hour, so as to obtain
TiO2/ Au composite nano fibers.
0.069mmol tungsten carbonyls are added in 20ml absolute ethyl alcohols, magnetic agitation 30min is allowed to dissolve.Then, to
Step 1 is added in the solution) in obtained TiO2/ Au composite nano fiber 15mg, continue magnetic agitation 10min.Then, will
The mixed solution is placed in reactor, sealing, then sealed reactor is placed in electric dry oven carries out hydro-thermal reaction, hydrothermal temperature
For 190 DEG C, the time is 14 hours.Reaction terminates rear reactor and naturally cools to room temperature, drives kettle, takes out the blue block of natural sedimentation
Shape sediment, is washed with ethanol, and the product is finally obtained into W in being dried in vacuo 12 hours at 60 DEG C18O49/TiO2/ Au is dendritic
Heterojunction structure photochemical catalyst.
Embodiment 4：
1.9ml glacial acetic acid and 1.9ml butyl titanates are added in 6ml absolute ethyl alcohols, then by 0.5g high-molecular polythenes
Pyrrolidones is dissolved in above-mentioned solution, then 0.01736g gold chlorides are dissolved in above-mentioned solution be configured to gold chloride/butyl titanate/
The precursor solution of polyvinylpyrrolidone.Then, the precursor solution is loaded with a diameter of 0.6mm spinnerette orfices
In injector for medical purpose, the distance for keeping nozzle and ground connection receiver board is 12cm, imposes 10KV high pressure, carries out electrostatic spinning, system
Standby gold chloride/butyl titanate/polyvinylpyrrolidone composite nano fiber.Finally, with 3 DEG C/min speed liter in Muffle furnace
To 500 DEG C of high-temperature calcination gold chloride/butyl titanate/polyvinylpyrrolidone composite nano fibers, and 2 hours are incubated, so as to obtain
Obtain TiO2/ Au composite nano fibers.
0.07mmol tungsten carbonyls are added in 20ml absolute ethyl alcohols, magnetic agitation 30min is allowed to dissolve.Then, to this
Step 1 is added in solution) in obtained TiO2/ Au composite nano fiber 30mg, continue magnetic agitation 10min.Then, by this
Mixed solution is placed in reactor, sealing, then sealed reactor is placed in electric dry oven carries out hydro-thermal reaction, and hydrothermal temperature is
200 DEG C, the time is 14 hours.Reaction terminates rear reactor and naturally cools to room temperature, drives kettle, and the blueness for taking out natural sedimentation is block
Sediment, is washed with ethanol, and the product is finally obtained into W in being dried in vacuo 10 hours at 60 DEG C18O49/TiO2/ Au is dendritic different
Matter structure photochemical catalyst.
Embodiment 5：
W18O49/TiO2The dendritic heterojunction structure photochemical catalysts of/Au are in the application of photo catalytic reduction ammonia borine hydrogen preparation field, emphasis
Investigate the photochemical catalyst and ammonia borine hydrogen manufacturing performance is reduced under UV-Vis-IR light irradiations.The specific practice is as follows：In light-catalyzed reaction
The ammonia borine aqueous solution that 12ml concentration is 0.17mg/ml is added in device, 5mg W is placed into18O49/TiO2The dendritic heterojunction structures of/Au
Photochemical catalyst, with rubber stopper seal, will then seal air discharge remaining in reactor by carrier gas of argon gas, at room temperature in
Darkroom magnetic agitation 30 minutes.300W xenon lamps are then turned on, test light intensity is 100mW/cm2Carry out photo catalytic reduction ammonia borine system
Hydrogen reacts.Product gas is measured with the change of light application time with the gas chromatograph equipped with TCD detectors, as a result sees Fig. 7.From figure
W in the present embodiment shown in 718O49/TiO2The dendritic heterojunction structure photochemical catalysts of/Au and comparative sample TiO2Nanofiber, W18O49
Nano wire, TiO2/ Au composite nano fibers, W18O49/TiO2Heterojunction structure photo catalytic reduction ammonia under the irradiation of UV-Vis-IR light sources
Knowable to borine hydrogen manufacturing figure, the W obtained by embodiment 118O49/TiO2The dendritic heterojunction structure photochemical catalysts of/Au have higher H2Production
Amount, W after illumination in 1 hour18O49/TiO2It is 42.12 μm of ol that the dendritic heterojunction structure photochemical catalysts of/Au, which obtain hydrogen output,；And comparative sample
TiO2Nanofiber, W18O49Nano wire, TiO2/ Au composite nano fibers, W18O49/TiO2The hydrogen output of hetero-junctions is only 1.6362
μm ol, 17.6 μm of ol, 3.606 μm of ol, and 22.2 μm of ol.
Claims (3)
1. a kind of dendritic heterojunction structure photochemical catalyst of wide spectrum driving, it is characterised in that：It is the Au for 5~15nm by particle diameter
Nano-particle is distributed in the TiO that a diameter of 200~500nm, length are 5~30 μm2The surface and inside of nanofiber, then will be straight
Footpath is the W that 5~60nm, length are 200~900nm18O49TiO of the nanowire growth in Au Nanoparticle Modifieds2Nanowire dimension table
Face, the W that classification assembling is constructed18O49/TiO2The dendritic heterojunction structure photochemical catalysts of/Au.
2. a kind of preparation method of the dendritic heterojunction structure photochemical catalyst of wide spectrum driving of claim 1, it is characterised in that：
1) Au nano-particles are assembled in TiO2Nanofiber internal matrix and surface：
First, glacial acetic acid and butyl titanate are added in absolute ethyl alcohol, the volume ratio of three is, glacial acetic acid：Butyl titanate：It is anhydrous
Ethanol=1~3：1~3：3~8, then by high-molecular polythene pyrrolidones according to itself and butyl titanate mass ratio, i.e., poly- second
Alkene pyrrolidone：Butyl titanate=0.15~0.4:1 is dissolved in above-mentioned solution；Then, then by gold chloride according to itself and metatitanic acid fourth
The mass ratio of ester, i.e. gold chloride：Butyl titanate=0.5~1.5:100 are dissolved in equipped with butyl titanate and polyvinylpyrrolidone
In ethanol/glacial acetic acid mixed solution, the precursor solution of gold chloride/butyl titanate/polyvinylpyrrolidone is configured to；Then,
Prepare gold chloride/butyl titanate/polyvinylpyrrolidone composite nano fiber using electrostatic spinning technique, will the presoma it is molten
Liquid is fitted into electrospinning device, adjusts 8~16KV of spinning voltage, receives 8~15cm of distance, carries out electrostatic spinning, prepares chlorine
Auric acid/butyl titanate/polyvinylpyrrolidone composite nano fiber, finally, with 2~8 DEG C/min speed liter in Muffle furnace
To 500 DEG C of high-temperature calcination gold chloride/butyl titanate/polyvinylpyrrolidone composite nano fibers, and 1~3 hour is incubated, so that
Obtain TiO2/ Au composite nano fibers；
2) by W18O49TiO of the nanowire growth in Au Nanoparticle Modifieds2Nanofiber surface：
Tungsten carbonyl is added in absolute ethyl alcohol, wherein tungsten carbonyl concentration is：2~5 μm of ol/ml, 10~50min of magnetic agitation
Be allowed to dissolve, then, step 1 added into the solution) in obtained TiO2/ Au composite nano fibers, make itself and six carbonyls
The mass ratio of tungsten, i.e. Au/TiO2Nanofiber：Tungsten carbonyl=0.15~1.5：1, continue 10~30min of magnetic agitation, connect
, the mixed solution is placed in reactor, seal, then sealed reactor is placed in electric dry oven carries out hydro-thermal reaction, water
Hot temperature is 160~200 DEG C, and the time is 10~16 hours, and reaction terminates rear reactor and naturally cools to room temperature, drives kettle, is taken out
The blue lumpy precipitate of natural sedimentation, is washed with ethanol, finally by the product at 60 DEG C be dried in vacuo 10~14 hours, i.e.,
Obtain W18O49/TiO2The dendritic heterojunction structure photochemical catalysts of/Au.
3. a kind of preparation method of the dendritic heterojunction structure photochemical catalyst of wide spectrum driving according to claim 2, it is special
Levy and be：Glacial acetic acid is added in absolute ethyl alcohol with butyl titanate, and glacial acetic acid is equal with butyl titanate volume ratio.
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