CN106582888A - TiO2-Pd-PPy compound photocatalyst and preparation method and application thereof - Google Patents
TiO2-Pd-PPy compound photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 title abstract 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 229910002666 PdCl2 Inorganic materials 0.000 claims abstract description 9
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 41
- 239000002131 composite material Substances 0.000 claims description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 101150003085 Pdcl gene Proteins 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(II) nitrate Inorganic materials [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000364 palladium(II) sulfate Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 20
- 230000001699 photocatalysis Effects 0.000 abstract description 19
- 238000007146 photocatalysis Methods 0.000 abstract description 14
- 238000000354 decomposition reaction Methods 0.000 abstract description 12
- 238000000151 deposition Methods 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000007539 photo-oxidation reaction Methods 0.000 abstract 2
- 239000000969 carrier Substances 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 230000001706 oxygenating effect Effects 0.000 abstract 1
- 238000013032 photocatalytic reaction Methods 0.000 abstract 1
- 229920000128 polypyrrole Polymers 0.000 description 43
- 239000004408 titanium dioxide Substances 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 150000003233 pyrroles Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
-
- 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
- B01J37/16—Reducing
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
-
- 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
-
- 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
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- 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
Abstract
The invention discloses a TiO2-Pd-PPy compound photocatalyst and a preparation method and application thereof. The TiO2-Pd-PPy compound photocatalyst is prepared by the steps: ultrasonically dispersing TiO2 in water, adding PdCl2 and a pyrrole monomer into the water, removing dissolved oxygen, and irradiating with a xenon lamp for photooxidation reduction. A one-step simultaneous photooxidation reduction deposition method adopted in the invention can realize precise positioning and loading of the Pd and PPy. In the compound photocatalyst prepared according to the preparation method, the deposition positions of the Pd and PPy are just the photocatalytic reaction active spots of photo-generated electrons and holes, and can effectively promote separation of photon-generated carriers. The prepared TiO2-Pd-PPy compound photocatalyst shows preferable photocatalysis activity, wherein under full gloss, the hydrogen production efficiency of a TiO2-0.5Pd-0.6PPy photocatalyst through photocatalystic decomposition of water can reach 602mumol/h.
Description
Technical field
The present invention relates to a kind of novel photocatalysis material, more particularly to a kind of TiO2- Pd-PPy composite photo-catalysts and its
Preparation method and application.
Background technology
Hydrogen Energy as a kind of carbon-free fuel, Fossil fuel can be replaced because of which to reduce the discharge of carbon be considered as a kind of
The preferable energy.Since 1972, Fijishima and Honda was reported in n-type semiconductor TiO2Photic decomposition on Single Crystalline Electrodes
Water produces H2And O2, photocatalysis technology just becomes solar energy is converted into one of available strategy of Hydrogen Energy directly.So far, it is several
In terms of photocatalyst in the thousands is applied to photocatalytic hydrogen production by water decomposition.Wherein, titanium dioxide (TiO2) be research earliest and
Most photocatalyst, however, its wider band gap (- 3.2eV) and relatively low quantum efficiency seriously limit titanium dioxide
Practical application.Therefore, titanium dioxide is modified will be with very important strategy to improve its photochemical catalyzing efficiency
And realistic meaning.
Precious metal palladium (Pd) and conductive polymer polypyrrole (PPy) are that two kinds of conventional modified semiconductor light-catalyst light are urged
Change the material of performance.Wherein, the Pd for being carried on semiconductor light-catalyst surface can effectively capture light induced electron, so as to reduce
The combined efficiency of photo-generated carrier.And conducting polymer PPy is urged semiconductor light is expanded as a kind of conventional photosensitive materials
While agent light abstraction width, the also migration for photohole provides more fast and effectively passage.
By precious metal palladium (Pd) and polypyrrole (PPy) while being carried on TiO2Surface forms TiO2- Pd-PPy composite photocatalysts
After agent, on the one hand, expanded TiO2Light abstraction width；On the other hand, the separation of photo-generated carrier is promoted, so as to improve
TiO2Photochemical catalyzing efficiency.
And in prior art, TiO2The preparation method of-Pd-PPy composite photo-catalysts is except time-consuming longer.Synthesis condition is complicated
Outward, the precise positioning load of Pd and PPy cannot be also realized, the photocatalysis performance of the photocatalyst for preparing is also poor.
The content of the invention
For technical problem present in above-mentioned prior art, it is an object of the present invention to provide a kind of novel photocatalysis
Agent TiO2The preparation method of-Pd-PPy, the method can realize the precise positioning load of Pd and PPy, with stronger photocatalysis
Decomposition water hydrogen generation efficiency.
Second object of the present invention is to provide the TiO that above-mentioned preparation method is prepared2- Pd-PPy composite photocatalysts
Agent.
Third object of the present invention is to provide above-mentioned TiO2The application of-Pd-PPy composite photo-catalysts.
In order to solve above technical problem, the technical scheme is that：
A kind of TiO2The preparation method of-Pd-PPy composite photo-catalysts, including step is as follows：
By TiO2Ultrasonic disperse is added thereto to palladium source and pyrrole monomer in water, after removing dissolved oxygen, is shone with xenon lamp
Penetrate, photoredox reaction obtains TiO2- Pd-PPy composite photo-catalysts.
Preferably, the palladium source is PdCl2、(Pd(NO3)2、PdSO4Or Pd (CH3COO)2。
Preferably, TiO2、PdCl2It is 30000 with the mass ratio that pyrrole monomer is added:200-250:1-3.
It is further preferred that the PdCl for adding2Concentration be 0.03-0.08mol/L.First, the load capacity of Pd is very low, its
It is secondary, the PdCl of low concentration2The load effect of Pd can be made more uniform.Therefore, from the PdCl of low concentration2。
Preferably, the power of the xenon lamp is 300-500W, and full exposure penetrates 20-40min.
Full exposure is penetrated：Any optical filter is not added with, the wave-length coverage of irradiation light contains ultraviolet light and visible light wave range.
Preferably, the method for removing dissolved oxygen is to be passed through nitrogen thereto.
Preferably, the TiO for preparing2In-Pd-PPy composite photo-catalysts, the load capacity of Pd is 0.5wt%, and PPy's is negative
Carrying capacity is 0.4-1.0wt%.
It is further preferred that the load capacity of the PPy is 0.6wt%.
Work as TiO2When being penetrated by full exposure, a photon can be absorbed, produce light induced electron and hole pair.The photoproduction electricity of generation
Son can be by PdCl2Pd nano-particle is reduced in palladium source；At the same time, the photohole of generation can be by pyrroles's Py free oxygens
Turn to PPy nano-particle.By this method, the deposition position for realizing the positioning load of Pd and PPy, i.e. Pd and PPy is just
The light-catalyzed reaction avtive spot in light induced electron and hole.And the TiO that prior art is prepared2- Pd-PPy composite photocatalysts
Agent, the deposition position for using general chemistry sedimentation, Pd and PPy are random, it is impossible to rationally play Pd and PPy and efficiently separate light
The effect of raw carrier.
The TiO that above-mentioned preparation method is prepared2- Pd-PPy composite photo-catalysts.
Above-mentioned TiO2Application of-Pd-PPy the composite photo-catalysts in photochemical catalyzing.
The excellent results of the present invention are as follows：
1st, the step for adopting in the present invention is while photoredox reaction sedimentation can realize that the precise positioning of Pd and PPy is born
Carry.
2nd, the TiO obtained by the present invention2In-Pd-PPy composite photo-catalysts, the deposition position of Pd and PPy is just photoproduction
The light-catalyzed reaction avtive spot in electronics and hole, can effectively facilitate the separation of photo-generated carrier.
3rd, the TiO obtained by the present invention2- Pd-PPy composite photo-catalysts, show preferable photocatalytic activity, wherein,
Under full light, TiO2The photochemical catalyzing hydrogen generation efficiency of -0.5Pd-0.6PPy photocatalysts is up to 602 μm of ol/h.
4th, the synthetic method simple and fast adopted in the present invention, reaction condition are gentle, without the need for template molecule and sacrifice agent, tool
There is higher commercial applications prospect.
Description of the drawings
Fig. 1 is the X-ray diffractogram of obtained sample in the present invention；
Fig. 2 is obtained sample TiO in the present invention2The SEM figures of -0.5Pd；
Fig. 3 is the ultraviolet-visible diffuse-reflectance absorption figure of obtained sample in the present invention；
Fig. 4 is the full light photocatalysis Decomposition Aquatic product hydrogen yield comparison figure of obtained sample in the present invention；
Fig. 5 is the visible ray (λ of obtained sample in the present invention>400nm) photocatalysis Decomposition Aquatic product hydrogen yield comparison figure；
Fig. 6 is the TiO of distinct methods synthesis in the present invention2The full light photocatalysis Decomposition Aquatic product of -0.5Pd-0.6PPy samples
Hydrogen yield comparison figure；
Fig. 7 is the TiO of distinct methods synthesis in the present invention2Visible ray (the λ of -0.5Pd-0.6PPy samples>400nm) light is urged
Change and decompose Aquatic product hydrogen yield comparison figure.
Specific embodiment：
The present invention will be further described below in conjunction with the accompanying drawings, but not limited to this.
The method that photocatalytic activity test is carried out to prepared material in embodiment is as follows：
The test of photocatalysis Decomposition Aquatic product hydrogen is carried out being connected with the glass container system that recirculated cooling water (20 DEG C) closes, very
Empty condition is -97KPa.At top, the light source of irradiation selects 300W xenon lamps.Before the test of photocatalysis Decomposition Aquatic product hydrogen, lucifuge magnetic force is stirred
1h is mixed, the interference of residual gas is excluded.Tested every 20 minutes after thang-kng, turned by the peak area value that gas chromatograph is measured
Turn to the yield of hydrogen.When can see below photochemical catalyzing product hydrogen test, the optical filter for being more than 400nm using wavelength is provided can
See light.
Embodiment 1
Weigh TiO2(P25) during 300mg adds 100mL deionized waters, ultrasound 5 minutes so as to form uniform suspension.
Under constant agitation, to TiO2250 μ L Palladous chloride. (PdCl are added in suspension2, 0.0564mol/L) and 1.2 × 10-2-
3.0×10-2Mg pyrroles (Py) monomer.Wherein, relative to TiO2, the mass fraction of Pd and PPy is 0.5wt% and 0.2wt%,
0.4wt%, 0.6wt%, 0.8wt%, 1.0wt%.Then, high pure nitrogen is passed through thereto 30 minutes to remove dissolving therein
Oxygen.Finally, 300W xenon lamps, full exposure is used to penetrate 30 minutes, by gained sample sucking filtration, and deionized water and absolute ethanol washing number
Secondary, the drying in 60 DEG C of air atmospheres is obtained TiO in 12 hours2- Pd-PPy composite photo-catalysts.
Pyrrole monomer being substituted with methanol, and the pH of reactant liquor being adjusted to 3.0 with 1.0mol/L sodium hydroxide, remaining step is same
On, you can obtain comparative sample TiO2-0.5Pd。
X-ray diffractogram of the accompanying drawing 1 for 1 gained sample of the present embodiment, as seen from the figure, due to Pd and PPy in composite sample
Content less than X-ray diffractometer test limit, therefore, in the XRD figure of sample, the feature for not being found Pd and PPy is spread out
Penetrate peak.The XRD diffraction maximums of all products all with pure TiO2Peak position it is corresponding, and diffraction maximum is stronger, has no impurity peaks and detects,
Illustrate that the crystallinity of sample is good and free from admixture is generated.Accompanying drawing 2 is 1 gained TiO of the present embodiment2The HRTEM figures of -0.5Pd samples,
As seen from the figure, nano-particle uniform depositions of the Pd with average diameter as 5nm is in TiO2Surface.Accompanying drawing 3 is 1 gained sample of the present embodiment
The UV-vis DRS of product absorbs figure.As seen from the figure, compared to TiO2, TiO2The light absorbs of-Pd-PPy composite photo-catalysts are obtained
Effective expansion is arrived.Accompanying drawing 4 is the full light photocatalysis Decomposition Aquatic product hydrogen yield comparison figure of 1 gained sample of the present embodiment, and accompanying drawing 5 is
1 gained sample visible ray (λ of the present embodiment>400nm) photocatalysis Decomposition Aquatic product hydrogen yield comparison figure.From Fig. 4 and Fig. 5, nothing
By under full light or visible light conditions, TiO2The photochemical catalyzing hydrogen generation efficiency of-Pd-PPy composite photo-catalysts is all much
Higher than TiO2- Pd and TiO2, when the load capacity of PPy reaches 0.6%, TiO2The photocatalytic water hydrogen generation efficiency of -0.5Pd-0.6PPy is most
It is high.
Comparative example
In order to further illustrate the advantage of synthetic method used in the present invention, we are prepared according to the method reported
Three kinds of TiO below2- 0.5Pd-0.6PPy photocatalysts：
(1) one-step method chemical deposition.250uL 0.0564mol/L PdCl2With 1.8 × 10-2Mg pyrrole monomers are added to
100mL TiO2(3mg/mL) aqueous solution, stirring under room temperature are obtained required sample in 12 hours, and the sample is labeled as TiO2-
0.5Pd-0.6PPy-RT。
(2) two step sedimentations (first deposit Pd, redeposited PPy).Weigh obtained TiO in embodiment 12- 0.5Pd samples
300mg ultrasonic disperses are added thereto to 1.8 × 10 in 100mL deionized waters, then-2Mg pyrrole monomers and 0.44mg tri-chlorinations
Ferrum (FeCl3), stir 12 hours in ice-water bath, gained sample is labeled as into TiO2-0.5Pd-0.6PPy-T1。
(3) two step sedimentations (first deposit PPy, redeposited Pd).By 300mg TiO2, 1.8 × 10-2Mg pyrrole monomers and
0.44mg ferric chloride (FeCl3) while being added in 100mL deionized waters, the stirring in ice-water bath obtains TiO in 12 hours2-
0.6PPy.Then, by dried TiO2- 0.6PPy is scattered in 100mL deionized waters again, and is added thereto to 250uL
0.0564mol/L PdCl2With 10mL methanol, it is passed through nitrogen and removes dissolved oxygen and after adjusting pH to 3.0, with 300W xenon lamps are used, entirely
Light irradiation 30 minutes, gained sample is labeled as TiO2-0.5Pd-0.6PPy-T2。
Accompanying drawing 6 is the TiO of distinct methods synthesis in the present embodiment2The full light photocatalysis Decomposition of -0.5Pd-0.6PPy samples
Aquatic product hydrogen yield comparison figure；
Accompanying drawing 7 is the TiO of distinct methods synthesis in comparative example2Visible ray (the λ of -0.5Pd-0.6PPy samples>400nm) light
Catalytic decomposition Aquatic product hydrogen yield comparison figure.Compared with traditional two-step method, in the present invention, used method can be accurately positioned
Synthesis Pd and PPy, the wherein outlet of the load situation of Pd exactly electric transmission, the outlet of PPy exactly hole transports, therefore its work
Property the sample for preparing far above the two-step method in comparative example.
From Fig. 6 and Fig. 7, no matter under full light or visible light conditions, in the present invention, synthetic method used is obtained
TiO2The photocatalytic water hydrogen generation efficiency of -0.5Pd-0.6PPy samples is above other three kinds of methods.Illustrate conjunction of the present invention
More efficiently TiO can be obtained into method2- Pd-PPy composite photo-catalysts.
Although the above-mentioned accompanying drawing that combines is described to the specific embodiment of the present invention, not to invention protection domain
Restriction, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not required to
The various modifications or deformation made by creative work is paid are still within the scope of the present invention.
Claims (10)
1. a kind of TiO2The preparation method of-Pd-PPy composite photo-catalysts, it is characterised in that：It is as follows including step：
By TiO2Ultrasonic disperse is added thereto to palladium source and pyrrole monomer in water, after removing dissolved oxygen, is irradiated with xenon lamp, photic
Oxidoreduction obtains TiO2- Pd-PPy composite photo-catalysts.
2. preparation method according to claim 1, it is characterised in that：The palladium source is PdCl2、(Pd(NO3)2、PdSO4Or
Pd(CH3COO)2, preferably PdCl2。
3. preparation method according to claim 2, it is characterised in that：TiO2、PdCl2The mass ratio added with pyrrole monomer
For 30000:200-250:1-3.
4. preparation method according to claim 3, it is characterised in that：The PdCl of addition2Concentration be 0.03-0.08mol/
L。
5. preparation method according to claim 1, it is characterised in that：The power of the xenon lamp be 300-500W, full exposure
Penetrate 20-40min.
6. preparation method according to claim 1, it is characterised in that：The method for removing dissolved oxygen is to be passed through nitrogen thereto
Gas.
7. preparation method according to claim 1, it is characterised in that：The TiO for preparing2- Pd-PPy composite photo-catalysts
The load capacity of middle Pd is 0.5wt%, and the load capacity of PPy is 0.4-1.0wt%.
8. preparation method according to claim 7, it is characterised in that：The load capacity of the PPy is 0.6wt%.
9. the TiO that the arbitrary preparation method of claim 1-8 is prepared2- Pd-PPy composite photo-catalysts.
10. TiO described in claim 82Application of-Pd-PPy the composite photo-catalysts in photochemical catalyzing.
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