CN105664932A - Boron-ruthenium and titanium dioxide nanotube composite photocatalyst and preparation method thereof - Google Patents
Boron-ruthenium and titanium dioxide nanotube composite photocatalyst and preparation method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 239000002071 nanotube Substances 0.000 title claims abstract description 86
- KFKXDXMQVFMFET-UHFFFAOYSA-N boron ruthenium Chemical compound [Ru].[B] KFKXDXMQVFMFET-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 19
- 229910052796 boron Inorganic materials 0.000 claims abstract description 31
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 30
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 239000012530 fluid Substances 0.000 claims description 16
- 238000005868 electrolysis reaction Methods 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008151 electrolyte solution Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 6
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 238000002048 anodisation reaction Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910020808 NaBF Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 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
- B01J23/002—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
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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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
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a boron-ruthenium and titanium dioxide nanotube composite photocatalyst. Titanium dioxide exists in a nanotube array mode, and a crystal structure adopts an anatase phase; the concentration of surface atoms of boron ranges from 0.5% to 1.5%, and the concentration of the surface atoms of ruthenium ranges from 0.1% to 0.2%. In addition, the invention further discloses a preparation method of the boron-ruthenium and titanium dioxide nanotube composite photocatalyst. The boron-ruthenium and titanium dioxide nanotube composite photocatalyst is high in photocatalytic activity and stable in performance, visible light can be effectively absorbed, the separation efficiency of photogenerated electrons-hole pairs of the titanium dioxide nanotube can be obviously improved, and the degradation rate of organic pollutants under visible light is greatly increased. The preparation method of the boron-ruthenium and titanium dioxide nanotube composite photocatalyst has the advantages that the technology is simple and easy to operate, influence factors are easy to control, and very high application value and an application prospect are achieved.
Description
Technical field
The present invention relates to nano-photocatalyst material technical field, particularly relate to a kind of boron-ruthenium/titania nanotube composite photo-catalyst and its preparation method.
Background technology
Titanium dioxide (the TiO of the high-sequential that electrochemistry anodic oxidation is obtained2) nano-tube array is except having conventional Ti O2Catalytic activity height, inexpensive, erosion resistance is strong and outside the series of advantages such as pollution-free, also has that specific surface area is big, charge transfer fast, an easy plurality of advantages such as recycling, thus utilizes TiO2Nano-tube array photocatalysis degradation organic contaminant is widely studied. But Nano tube array of titanium dioxide still also exists the problem of following two aspects: (1) spectral response scope is narrower, TiO2The energy gap of semi-conductor is 3.2eV, and this just determines it can only utilize the UV-light accounted in solar spectrum less than 5%, and the utilization ratio of sun power is lower; (2) TiO2Nano-tube array grows on conductive base metal titanium, and light induced electron and hole very easily compound, its recombination time is less than 10-9Second, thus quantum yield is lower, thus is difficult to meet actual needs.
Existing research finds, to TiO2Carry out suitable doping or surface modification and such as nonmetal C, N, S, F, B plasma doping, metal ion mixing and noble metal decorated etc. can strengthen TiO2To the absorption of visible ray, and can effectively suppress the compound in light induced electron and hole, thus improve its visible light photocatalysis active. But in production application, technique is comparatively complicated, control difficulty, equipment cost height, therefore still need to research and develop novel titania nanotube photocatalyst material, to meet practical application request. At present, there is not yet about the report preparing boron-ruthenium/titania nanotube composite photo-catalyst.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, boron-ruthenium/titania nanotube composite photo-catalyst that a kind of photocatalytic activity is high is provided, to significantly improve the separation efficiency in light induced electron-hole pair, widen the responding range of visible ray, thus photochemical catalysis, photoelectrocatalysis organic pollutant aspect under visible light obtains widespread use.Another object of the present invention is to provide the preparation method of above-mentioned boron-ruthenium/titania nanotube composite photo-catalyst, to obtain product by processing method simple and easy to control, that cost is low.
The object of the present invention is achieved by the following technical programs:
A kind of boron-ruthenium/titania nanotube composite photo-catalyst provided by the invention is that described titanium dioxide exists with nano-tube array form, and its crystalline structure is anatase octahedrite phase; The surface atom concentration of described boron is 0.5～1.5%, and the surface atom concentration of described ruthenium is 0.1～0.2%. Further, described boron is with interstitial boron and B2O3Form enter respectively titanium dioxide lattice and attached in titania nanotube surface, the surface atom concentration of described interstitial boron is 0.15～0.45%, B2O3Surface atom concentration be 0.35～1.05%; Described ruthenium is with RuO2Form be carried on titania nanotube surface.
Further, titania nanotube of the present invention is the double-pipe titanium dioxide nano-pipe array being grown on metal titanium paper tinsel matrix.
Another object of the present invention is achieved by the following technical programs:
The preparation method of above-mentioned boron-ruthenium/titania nanotube composite photo-catalyst provided by the invention is as follows: first carry out electrochemical anodization reaction using metal titanium paper tinsel as anode, containing the ethylene glycol solution in boron source as electrolytic solution, through dry, calcining after reaction, described metal titanium paper tinsel prepares boron doped titanic oxide nano tube array; Then by RuCl3Ethanolic soln electrolysis obtains ruthenium steeping fluid, adopts pickling process that ruthenium loads to described boron doped titanic oxide nano tube surface; Afterwards drying, calcining, i.e. obtained boron-ruthenium/titania nanotube composite photo-catalyst.
Preparation method of the present invention can take following measure further:
The preparation method of boron-ruthenium/titania nanotube composite photo-catalyst of the present invention, comprises the following steps:
(1) preparation of boron doped titanic oxide nano tube array
Using metal titanium paper tinsel as anode, with the addition of NaBF4、NH4F、NH4NO3And the ethylene glycol mixing solutions of water is as electrolytic solution, relative to ethylene glycol, the consumption of each additive is: NaBF40.2～1.0wt%, NH4F0.1～1wt%, NH4NO30.001～0.05mol/L, water 2～15vol%; Oxidation voltage is 30～90V, and oxidization time is 2～30h; Anodic oxidation reactions complete after with alcohol flushing, drying, calcining, i.e. obtained boron doped titanic oxide nano tube array;
(2) preparation of ruthenium steeping fluid
It is the RuCl of 0.001～0.005mol/L by ruthenium ion concentration3Ethanolic soln carries out electrolysis, and electrolysis bias voltage is 0.6～1.0V, and electrolysis time is 20～60min, obtains ruthenium steeping fluid;
(3) preparation of boron-ruthenium/titania nanotube
Described boron doped titanic oxide nano tube array is flooded in ruthenium steeping fluid 15～30h, then drying, calcining, i.e. obtained boron-ruthenium/titania nanotube composite photo-catalyst.
In such scheme, in step (1) described in preparation method of the present invention, calcining temperature is 450～550 DEG C, and temperature rise rate is 5 DEG C/min, insulation 1～3h. In described step (3), calcining temperature is 400～650 DEG C, and temperature rise rate is 5 DEG C/min, insulation 1～3h.
The present invention has following useful effect:
(1) boron-ruthenium/titania nanotube composite photo-catalyst of the present invention, Nano tube array of titanium dioxide oriented growth, high-sequential arranges, and nanotube has two-layer pipe, and specific surface area is big;By the doping of boron and RuO2Compound the separation efficiency in light induced electron-hole pair of titania nanotube is improved significantly, and can more effectively absorb visible ray, thus there is better photocatalytic activity, the degradation rate of organic pollutant under visible ray is significantly improved.
(2) active high, nontoxic, the good stability of boron-ruthenium of the present invention/titania nanotube composite photo-catalyst, is convenient to recycling, can be used for the fields such as sewage disposal, purification of air, energy and material, have very high practical value and application prospect.
(3) preparation method of the present invention is without the need to the equipment of costliness, and technique is simple to operation, and influence factor is easy to control, RuO2Recombination process adopt electrolysis pickling process, belong to the category of Green Chemistry compared with other method, contribute to promotion and application.
Accompanying drawing explanation
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail:
Fig. 1 is scanning electron microscope (SEM) photo (magnification is 30000 times, and illustration magnification wherein is 100000 times) of boron doped titanic oxide nano tube array in the embodiment of the present invention one;
Fig. 2 is uv-visible absorption spectra figure before and after the electrolysis of ruthenium steeping fluid in the embodiment of the present invention one;
Fig. 3 is the non-doped titanic oxide nano tube of comparative example and the XRD figure spectrum of the obtained boron-ruthenium/titania nanotube composite photo-catalyst of the embodiment of the present invention one;
Fig. 4 is scanning electron microscope (SEM) photo (magnification is 30000 times, and illustration magnification wherein is 100000 times) of the obtained boron-ruthenium/titania nanotube composite photo-catalyst of the embodiment of the present invention one;
Fig. 5 is the XPSB1s spectrum of B of adulterating in the obtained boron-ruthenium/titania nanotube composite photo-catalyst of the embodiment of the present invention one;
Fig. 6 is the XPSRu3d spectrum of Ru of adulterating in the obtained boron-ruthenium/titania nanotube composite photo-catalyst of the embodiment of the present invention one;
Fig. 7 is boron-ruthenium/titania nanotube composite photo-catalyst photocatalytic degradation methylene blue graphic representation that the embodiment of the present invention obtains.
Embodiment
The embodiment of the present invention taking commercially available purity as 99.5%, thickness be the metal titanium paper tinsel of 0.1～0.5mm for matrix, and it is carried out following pre-treatment:
Above-mentioned titanium paper tinsel is cut into the titanium sheet of some 4cm × 1cm sizes, first with sand papering polishing titanium plate surface to no marking, then carry out following step successively: (polishing fluid is 8wt%HF and 10mol/LHNO for acetone sonochemistry oil removing 15min, distilled water ultrasonic cleaning 15min, chemical rightenning 30s3Mixed solution), finally with distilled water flushing, it is immersed in distilled water for subsequent use.
Embodiment one:
The preparation method of a kind of boron-ruthenium/titania nanotube composite photo-catalyst of the present embodiment, its step is as follows:
(1) preparation of boron doped titanic oxide nano tube array
Being connected to DC voltage-stabilizing power supply on as anode, graphite rod or platinum sheet or platinum filament as negative electrode using above-mentioned pretreated titanium sheet, anodic oxidation area is 1cm2, interelectrode distance is 3cm; Electrolytic solution is for the addition of NaBF4、NH4F、NH4NO3And the ethylene glycol mixing solutions of water (relative to ethylene glycol, the consumption of each additive is: NaBF40.8wt%, NH4F0.5wt%, NH4NO30.003mol/L, water 5vol%); Electrolytic solution volume is 30ml, and oxidation voltage is 60V, and oxidization time is 20h; Anodic oxidation reactions complete after with alcohol flushing, dry at 80 DEG C of temperature, then calcine at 500 DEG C of temperature, temperature rise rate is 5 DEG C/min, and insulation 2h, namely obtains boron doped anatase-type Nano tube array of titanium dioxide (see Fig. 1).
Can clearly see the Nano tube array of titanium dioxide of high-sequential from Fig. 1, the diameter of titania nanotube is 80～100nm, thickness of pipe is 20～30nm.
(2) preparation of ruthenium steeping fluid
Two graphite rods or other conductive electrode are inserted ruthenium ion concentration is the RuCl of 0.003mol/L3In ethanolic soln, between the two poles of the earth, bestow the electrolysis bias voltage of 0.8V, electrolysis 30min, obtain ruthenium steeping fluid.
RuCl3It is dissociated into Ru in the solution3+And Cl-, during electrolysis, Ru3+Obtaining electron reduction is Ru2+, and only have Ru2+Just can deposit on titania nanotube. As can be seen from Figure 2, before and after electrolysis, steeping fluid abosrption spectrogram there occurs considerable change, and now ruthenium becomes divalence by trivalent.
(3) preparation of boron-ruthenium/titania nanotube
In ruthenium steeping fluid, boron doped titanic oxide nano tube array being flooded 20h, dries, then calcine at 450 DEG C of temperature at 80 DEG C of temperature, temperature rise rate is 5 DEG C/min, insulation 2h, i.e. obtained boron-ruthenium/titania nanotube composite photo-catalyst.
With non-doped titanium dioxide nanotube array, (its preparation condition does not add NaBF except in electrolytic solution as a comparison case4Outward, other condition is identical with the preparation of the present embodiment step (1) boron doped titanic oxide nano tube array). As seen from Figure 3, comparative example and the present embodiment are corresponding to titania nanotube before and after doping, and its crystalline structure is Detitanium-ore-type.
Fig. 4 and Fig. 1 contrasts visible, ruthenium has successfully loaded on boron doped titanic oxide nano tube, not destroying the surface topography of titania nanotube, ruthenium has been filled up the gap between nanotube and nanotube and has closely been stacked on the nanotube mouth of pipe, and be evenly distributed, particle diameter tiny.
As shown in Figure 5, B1s combines and can enter lattice for the B of 192.22eV, exists with the form of interstitial boron, and surface atom concentration is 0.25%; In conjunction with can be that the B of 192.89eV is with B2O3Form exist, surface atom concentration is 0.72%.
As shown in Figure 6, Ru3d combination can be about 280.9eV, Ru element is with Ru4+(RuO2) the form existence (Ru being deposited on titania nanotube2+RuO is become after burning till2), Ru element surface atom concentration is 0.15%.
Embodiment two:
The present embodiment and embodiment one difference are: NaBF in the electrolytic solution of the present embodiment preparation method's step (1)4Amount be 0.6wt%.
Embodiment three:
The present embodiment and embodiment one difference are: the steeping fluid RuCl of the present embodiment preparation method's step (2)3In ethanolic soln, ruthenium ion concentration is 0.004mol/L.
Embodiment four:
The present embodiment and embodiment one difference are: in the present embodiment preparation method's step (2), electrolysis bias voltage is 0.6V.
Embodiment five:
The present embodiment and embodiment one difference are: in the present embodiment preparation method's step (3), the dipping time of boron doped titanic oxide nano tube array in ruthenium steeping fluid is 25h.
Performance test:
Sheet boron-ruthenium/titania nanotube composite photo-catalyst (10mm × 10mm) that the embodiment of the present invention is obtained is put into the solution that 12ml simulating pollution thing is housed, carries out light-catalyzed reaction at ambient temperature. Using the 18W efficient energy-saving fluorescent lamp of wavelength 400～700nm as light source, simulating pollution thing is 8mg/L methylene blue, 15g/LNa2SO4, pH be the solution of 2.10, light application time is 2h, during DeR, with 721 type spectrophotometers detection solution change in concentration, obtain photocatalytic degradation methylene blue curve as shown in Figure 7.The performance test of comparative example is the same.
As seen from Figure 7, compared with doped titanic oxide nano tube non-with comparative example, sheet boron-ruthenium/titania nanotube composite photo-catalyst prepared by the embodiment of the present invention has good photocatalytic activity, effectively improves the degradation capability to pollutent. Active high, nontoxic, the good stability of boron-ruthenium of the present invention/titania nanotube composite photo-catalyst, is convenient to recycling, can be used for sewage disposal, purification of air, the fields such as energy and material.
Claims (7)
1. boron-ruthenium/titania nanotube composite photo-catalyst, it is characterised in that: described titanium dioxide exists with nano-tube array form, and its crystalline structure is anatase octahedrite phase; The surface atom concentration of described boron is 0.5～1.5%, and the surface atom concentration of described ruthenium is 0.1～0.2%.
2. boron-ruthenium/titania nanotube composite photo-catalyst according to claim 1, it is characterised in that: described boron is with interstitial boron and B2O3Form enter respectively titanium dioxide lattice and attached in titania nanotube surface, the surface atom concentration of described interstitial boron is 0.15～0.45%, B2O3Surface atom concentration be 0.35～1.05%; Described ruthenium is with RuO2Form be carried on titania nanotube surface.
3. boron-ruthenium/titania nanotube composite photo-catalyst according to claim 1 and 2, it is characterised in that: described titania nanotube is the double-pipe titanium dioxide nano-pipe array being grown on metal titanium paper tinsel matrix.
4. the preparation method of the described boron-ruthenium/titania nanotube composite photo-catalyst of one of claim 1-3, it is characterized in that: first carry out electrochemical anodization reaction using metal titanium paper tinsel as anode, containing the ethylene glycol solution in boron source as electrolytic solution, through dry, calcining after reaction, described metal titanium paper tinsel prepares boron doped titanic oxide nano tube array; Then by RuCl3Ethanolic soln electrolysis obtains ruthenium steeping fluid, adopts pickling process that ruthenium loads to described boron doped titanic oxide nano tube surface; Afterwards drying, calcining, i.e. obtained boron-ruthenium/titania nanotube composite photo-catalyst.
5. the preparation method of boron-ruthenium/titania nanotube composite photo-catalyst according to claim 4, it is characterised in that comprise the following steps:
(1) preparation of boron doped titanic oxide nano tube array
Using metal titanium paper tinsel as anode, with the addition of NaBF4、NH4F、NH4NO3And the ethylene glycol mixing solutions of water is as electrolytic solution, relative to ethylene glycol, the consumption of each additive is: NaBF40.2～1.0wt%, NH4F0.1～1wt%, NH4NO30.001～0.05mol/L, water 2～15vol%; Oxidation voltage is 30～90V, and oxidization time is 2～30h; Anodic oxidation reactions complete after with alcohol flushing, drying, calcining, i.e. obtained boron doped titanic oxide nano tube array;
(2) preparation of ruthenium steeping fluid
It is the RuCl of 0.001～0.005mol/L by ruthenium ion concentration3Ethanolic soln carries out electrolysis, and electrolysis bias voltage is 0.6～1.0V, and electrolysis time is 20～60min, obtains ruthenium steeping fluid;
(3) preparation of boron-ruthenium/titania nanotube
Described boron doped titanic oxide nano tube array is flooded in ruthenium steeping fluid 15～30h, then drying, calcining, i.e. obtained boron-ruthenium/titania nanotube composite photo-catalyst.
6. the preparation method of boron-ruthenium/titania nanotube composite photo-catalyst according to claim 5, it is characterised in that: in described step (1), calcining temperature is 450～550 DEG C, and temperature rise rate is 5 DEG C/min, insulation 1～3h.
7. the preparation method of boron-ruthenium/titania nanotube composite photo-catalyst according to claim 5, it is characterised in that: in described step (3), calcining temperature is 400～650 DEG C, and temperature rise rate is 5 DEG C/min, insulation 1～3h.
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