CN108554435A - A kind of PdO load N, B codope titanium dioxide nanotube photochemical catalyst and preparation method thereof - Google Patents
A kind of PdO load N, B codope titanium dioxide nanotube photochemical catalyst 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 178
- 239000002071 nanotube Substances 0.000 title claims abstract description 84
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 69
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 65
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 235000010215 titanium dioxide Nutrition 0.000 claims description 75
- 239000010936 titanium Substances 0.000 claims description 28
- 229910001199 N alloy Inorganic materials 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 125000004429 atom Chemical group 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 5
- 229910011208 Ti—N Inorganic materials 0.000 claims description 4
- 238000002048 anodisation reaction Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 101150003085 Pdcl gene Proteins 0.000 claims description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000003595 spectral effect Effects 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910020808 NaBF Inorganic materials 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 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 1
- -1 Ethyl alcohol Chemical compound 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 210000002659 acromion Anatomy 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention discloses a kind of PdO to load N, B codope titanium dioxide nanotube photochemical catalyst, and the titanium dioxide exists with anatase-phase nano pipe array format；The palladium is carried on titania nanotube surface in the form of PdO, and the surface atom concentration of the palladium is 0.1~0.2%；The surface atom concentration of the nitrogen is 1.0~2.0%, and the surface atom concentration of the boron is 0.3~0.5%.In addition the preparation method of above-mentioned PdO loads N, B codope titanium dioxide nanotube photochemical catalyst is also disclosed.The present invention by nonmetallic and nonmetallic codope and with PdO loads by being combined to TiO2Nanotube is modified, solve the problems, such as that spectral response range is relatively narrow and quantum efficiency is low simultaneously, to significantly improve visible light utilization efficiency and quantum efficiency, contribute under using sunlight photocatalysis and the organic Recalcitrant chemicals of photoelectric catalysis degrading in terms of obtain extensive use.
Description
Technical field
The present invention relates to nanometer titanium dioxide photocatalysis material technical fields more particularly to a kind of PdO to load N, B codope
Titanic oxide nano pipe light catalyst and preparation method thereof.
Background technology
Titanium dioxide (TiO as catalysis material2) film of Nano tube array, because it is passed with large specific surface area, charge
Pass it is fast, be easy recycling many advantages, such as and become research hotspot.But the photocatalysis of titania nanotube is imitated at present
Rate is still too low, the problem of also reaching the requirement of practical application far away, essentially consist in following two aspects：First, spectral response
Range is relatively narrow, TiO2The energy gap of semiconductor is 3.2eV, can only generate response in 390nm ultraviolet lights below to wavelength, because
And it is relatively low to the utilization rate of sunlight；Second is that quantum efficiency is relatively low, TiO2The light induced electron generated under light excitation and hole
Recombination probability is relatively high, to reduce TiO2Photocatalytic activity.
In view of the above-mentioned problems, research hotspot in recent years be titanium dioxide is doped or surface be modified, with enhancing
TiO2Absorption to visible light, and inhibit the compound of light induced electron and hole, to improve its visible light photocatalysis active.Mesh
Before, although the prior art achieves certain effect in achievement in research, still it is difficult to meet reality in production application
Therefore border demand still needs to research and develop novel titania nanotube catalysis material, to effectively improve the same of photocatalysis efficiency
When, be conducive to promote and apply and develop.Currently, there is not yet loading N, B codope titanium dioxide nanotube photocatalysis about PdO
The report of agent.
Invention content
The PdO loads with highlight catalytic active that it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of
N, B codope titanium dioxide nanotubes photochemical catalyst, by mutually being tied by nonmetallic and nonmetallic codope and with PdO loads
It closes to TiO2Nanotube is modified, while solving the problems, such as that spectral response range is relatively narrow and quantum efficiency is low, to obviously carry
High visible utilization rate and quantum efficiency, contribute to using under sunlight photocatalysis and photoelectric catalysis degrading it is organic difficult to degrade
Extensive use is obtained in terms of pollutant.Another object of the present invention is to provide above-mentioned PdO load N, B codope titanium dioxides to receive
The preparation method of mitron photochemical catalyst.
The purpose of the present invention is achieved by the following technical programs：
A kind of PdO provided by the invention loads N, B codope titanium dioxide nanotube photochemical catalyst, the titanium dioxide with
Anatase-phase nano pipe array format exists；The palladium is carried on titania nanotube surface in the form of PdO, the palladium
Surface atom concentration is 0.1~0.2%；The surface atom concentration of the nitrogen is 1.0~2.0%, and the surface atom of the boron is dense
Degree is 0.3~0.5%.
Further, nitrogen-atoms of the present invention enters titanium dioxide lattice instead of oxygen atom formation O-Ti-N keys；It is described
Boron atom is adulterated in two forms, is respectively：B-O-Ti keys, surface atom concentration 0.2 are formed into titanium dioxide lattice
~0.3%, with B2O3Form be carried on titania nanotube surface, surface atom concentration is 0.1~0.2%.
Further, titania nanotube of the present invention is the nanotube battle array being grown on Ti -- N alloy sheet matrix
Row.
Another object of the present invention is achieved by the following technical programs：
The preparation method of above-mentioned PdO loads N, B codope titanium dioxide nanotube photochemical catalyst provided by the invention, first
Organic solution using Ti -- N alloy piece as anode, containing boron source carries out electrochemical anodization reaction, the Ti-N as electrolyte
Alloy sheet reaction generates N and adulterates TiO2While nano-tube array, B doping enters TiO2Nanotube, to which N, B codope be made
Nano tube array of titanium dioxide；Then N, B codope titanium dioxide nanotube is impregnated in PdCl2In solution, make PdCl2
It is adsorbed in nanotube surface；After through drying, calcining, obtain PdO load N, B codope titanium dioxide nanotube photocatalysis
Agent.
Preparation method of the present invention can take measure further below：
The preparation method of PdO loads N, B codope titanium dioxide nanotube photochemical catalyst of the present invention, including it is following
Step：
(1) preparation of Ti -- N alloy piece
It is prepared using the method for arc-melting-rapid cooling, titanium sponge is mixed with TiN powder first, is suppressed through hydraulic press
At electrode block, it is placed in cold-mo(u)ld furnace and carries out melting as anode, obtain blocky Ti -- N alloy；Then by institute
It states blocky Ti -- N alloy to be cut, polished, pre-processed, obtains Ti -- N alloy piece；
(2) preparation of N, B codope titanium dioxide nanotube
Using the Ti -- N alloy piece as anode, with dissolved with NaBF4、NH4The ethylene glycol of F and the mixed solution of water are as electricity
It solves liquid and carries out electrochemical anodization reaction, relative to ethylene glycol, the NaBF4、NH4F, the dosage of water be respectively 0.4~
0.8wt%, 0.2~0.5wt%, 5~15vol%；The anodic oxidation reactions time is 10~30h；Through washing after reaction completion
It washs, dry, calcine, obtain N, B codope titanium dioxide nanotube；
(3) PdO loads the preparation of N, B codope titanium dioxide nanotube
It is 0.001~0.005mol/L's that N, B codope titanium dioxide nanotube, which is impregnated in palladium ion concentration,
PdCl215~30h is impregnated in the mixed solution of ethyl alcohol and water, then through drying, calcining, obtains PdO load N, B codope two
Titanium oxide nanotubes.
In said program, the dosage of TiN powder is 2~4mol% of titanium sponge in step (1) described in preparation method of the present invention.
Calcination temperature is 450~550 DEG C in the step (2), and heating rate is 4 DEG C/min, and soaking time is 1~2h.The step
(3) calcination temperature is 400~500 DEG C in, and heating rate is 4 DEG C/min, and soaking time is 1~2h.
The invention has the advantages that：
(1) PdO of the present invention loads N, B codope titanium dioxide nanotube photochemical catalyst, and titania nanotube height has
Sequence is grown, large specific surface area.By the binary synergistic effect of the codoping modified generation of N, B, spectral response model is efficiently solved
This narrow critical issue is enclosed, titania nanotube is enable more effectively to absorb visible light；The load of PdO makes nanometer simultaneously
The separative efficiency of the photo-generate electron-hole pair of pipe is improved significantly, and PdO can not only capture photohole, and PdO itself is still very
Good catalyst, so that TiO2With stronger photocatalytic activity.
(2) under PdO of the present invention load N, B codope titanium dioxide nanotube visible light catalytic activity it is high, it is safe and non-toxic, time
It receives using convenient, recycling performance is good, can be used for the fields such as organic matter sewage disposal, air purification, energy and material, have very
High practical value and application prospect.
(3) preparation process of the present invention is simple, and influence factor is easy to control, contributes to promotion and application.
Description of the drawings
Below in conjunction with embodiment and attached drawing, the present invention is described in further detail：
Fig. 1 is scanning electron microscope (SEM) photo (amplification of N, B codope titanium dioxide nanotube in the embodiment of the present invention one
Multiple is 30000 times, and illustration amplification factor therein is 100000 times)；
Fig. 2 is that PdO obtained load N, B codope titanium dioxide nanotube photochemical catalyst is swept in the embodiment of the present invention one
Retouch Electronic Speculum (SEM) photo (amplification factor is 100000 times)；
Fig. 3 is that comparative example is received undoped with N, B codope titanium dioxide in titania nanotube, the embodiment of the present invention one
The XRD spectrum of mitron and PdO obtained load N, B codope titanium dioxide nanotube photochemical catalysts；
Fig. 4 is adulterated in PdO loads N, B codope titanium dioxide nanotube photochemical catalyst made from the embodiment of the present invention one
The XPS N1s spectrums of N；
Fig. 5 is adulterated in PdO loads N, B codope titanium dioxide nanotube photochemical catalyst made from the embodiment of the present invention one
The XPS B1s spectrums of B；
Fig. 6 is adulterated in PdO loads N, B codope titanium dioxide nanotube photochemical catalyst made from the embodiment of the present invention one
The XPS Pd3d spectrums of Pd；
Fig. 7 is that PdO made from the embodiment of the present invention one to five loads N, B codope titanium dioxide nanotube photochemical catalyst light
Catalytic degradation methylene blue curve graph.
Specific implementation mode
The embodiment of the present invention is with commercially available purity Ti >=99.7%, the titanium sponge that granularity is 3~10mm and granularity for 200
Mesh, purity TiN >=99.9% TiN powder be raw material prepare Ti -- N alloy piece.
Embodiment one：
A kind of preparation method of PdO loads N, B codope titanium dioxide nanotube photochemical catalyst of the present embodiment, step is such as
Under：
(1) preparation of Ti -- N alloy piece
It is prepared using the method for arc-melting-rapid cooling, is first the titanium sponge and TiN powder (TiN powder of 500g by total amount
Dosage be titanium sponge 3mol%) mixing, be pressed into electrode block through hydraulic press, be placed in conduct in cold-mo(u)ld furnace
Anode carries out melting, and smelting parameter is：Vacuum degree 2 × 10-2Pa, voltage 35V, electric current 250A, obtain blocky Ti -- N alloy；So
Above-mentioned blocky Ti -- N alloy is cut afterwards, is polished, the Ti -- N alloy piece that size is 4cm × 1cm × 0.1cm is made；
Above-mentioned Ti -- N alloy piece is pre-processed：First use sand paper sanding and polishing to surface no marking, then successively into
Row acetone sonochemistry oil removing and distilled water are cleaned by ultrasonic each 10min, (polishing fluid is in molar ratio HF: HNO to chemical polishing 10s3
=1: 1 mixed liquor), it is finally totally spare with distilled water flushing；
(2) preparation of N, B codope titanium dioxide nanotube
Electrochemical anodization reaction is carried out using D.C. regulated power supply, is sun with above-mentioned pretreated Ti -- N alloy piece
Pole, platinized platinum are connected to as cathode in equipment, electrode spacing 2cm；With 30mL dissolved with NaBF4、NH4The ethylene glycol of F and mixing for water
Solution is closed as electrolyte, relative to ethylene glycol, NaBF4、NH4F, the dosage of water is respectively 0.6wt%, 0.4wt%, 6vol%；
Ti -- N alloy piece is inserted into 1cm, oxidation voltage 60V, oxidation time 20h under electrolyte；Reaction is washed after completing through ethyl alcohol
It washs, after drying, calcined for 4 DEG C/min to 450 DEG C with heating rate at a temperature of 80 DEG C, keep the temperature 2h, obtain N, B codope
Anatase type titanium dioxide nano tube, microscopic appearance are shown in that Fig. 1, crystalline structure are shown in Fig. 3；
(3) PdO loads the preparation of N, B codope titanium dioxide nanotube
Above-mentioned N, B codope titanium dioxide nanotube is impregnated in the PdCl that palladium ion concentration is 0.003mol/L2Ethyl alcohol
With the mixed solution (PdCl of water2Pure for commercially available analysis, the volume ratio of ethyl alcohol and water is 1: 1) in, 20h is impregnated, in 80 DEG C of temperature
Then lower drying is warming up to 400 DEG C with 4 DEG C/min of heating rate and is calcined, keep the temperature 2h, obtains PdO load N, B codopes
Titanic oxide nano pipe light catalyst, microscopic appearance are shown in that Fig. 2, crystalline structure are shown in Fig. 3.
Comparative example：
Using unmodified titania nanotube as comparative example, preparation method is as follows：Embodiment one the step of in (1),
Ti -- N alloy piece is replaced by the metal titanium foil of 0.5mm by 99.5%, thickness with commercially available purity；Embodiment one the step of in (2),
Electrolyte is free of NaBF4；Without one step of embodiment (3).Obtained unmodified titania nanotube, crystalline structure
See Fig. 3.
Fig. 1 shows that N, B codope titanium dioxide nanotube made from the present embodiment step (2) display high-sequential, nanometer
Gap length of the bore between 70~110nm, thickness of pipe wall 15~50nm, Guan Yuguan is 0~100nm.
Fig. 2 and Fig. 1 comparisons are as it can be seen that PdO has successfully been loaded on N, B codope titanium dioxide nanotube, PdO deposits
Particle is equably attached to nanotube nozzle while gap between having filled up Guan Yuguan, and part PdO deposits enter nanotube
Interior, PdO sediment distributions are uniform, and grain size is tiny.
As seen from Figure 3, the crystalline structure of titania nanotube is rutile titania before and after N, B codope and before and after PdO loads
Mine type.
As shown in figure 4, N1s combinations can be 401.78eV, N element enters TiO2Lattice forms O-Ti-N keys, surface atom
A concentration of 1.21%.
As shown in figure 5, B1s combinations can enter TiO for the B of 192.26eV2Lattice, forms B-O-Ti keys, and surface atom is dense
Degree is 0.22%；Existence form in conjunction with the B that can be 193.01eV is B2O3, surface atom concentration 0.13%.
As shown in fig. 6, Pd 3d5/2Photoelectron peak is made of 2 different acromions of intensity, in conjunction with can be respectively 336.34
And 341.72eV, it is 5.38eV that two peaks, which combine energy difference, and Pd elements are with Pd2+(PdO) form exists, Pd element surface atom concentrations
It is 0.12%.
Embodiment two：
A kind of preparation method of PdO loads N, B codope titanium dioxide nanotube photochemical catalyst of the present embodiment, with embodiment
One the difference is that：
In step (1), the dosage of TiN powder is the 3.5mol% of titanium sponge.
In step (2), the NaBF in electrolyte4Its dosage is 0.4wt%, oxidation time 30h.
Embodiment three：
A kind of preparation method of PdO loads N, B codope titanium dioxide nanotube photochemical catalyst of the present embodiment, with embodiment
One the difference is that：
In step (2), the NaBF in electrolyte4Its dosage is 0.4wt%.
In step (3), palladium ion concentration is 0.004mol/L in the mixed solution of dipping.
Example IV：
A kind of preparation method of PdO loads N, B codope titanium dioxide nanotube photochemical catalyst of the present embodiment, with embodiment
One the difference is that：
In step (1), the dosage of TiN powder is the 2.5mol% of titanium sponge.
In step (3), palladium ion concentration is 0.002mol/L, dip time 30h in the mixed solution of dipping.
Embodiment five：
A kind of preparation method of PdO loads N, B codope titanium dioxide nanotube photochemical catalyst of the present embodiment, with embodiment
One the difference is that：
In step (2), the NaBF in electrolyte4Its dosage is 0.8wt%.
In step (3), dip time 30h.
Performance test：
Sheet made from the embodiment of the present invention (10mm × 10mm) PdO is loaded into N, B codope titanium dioxide nanotube light
Catalyst is placed in equipped with 15mL simulating pollution object solution (10mg/L methylene blues, 10g/LNa2SO4, pH=2.00) container in,
At room temperature, it uses and is mounted with that ultraviolet light ends the 200W xenon lamps of filter plate (λ >=400nm) as visible light source, light application time is
2h during degradation reaction, takes appropriate pollutant solution to detect its concentration with 721 type spectrophotometers every 20min.Comparative example
Performance test methods and step are same as above.Acquired results are as shown in Figure 7.
As seen from Figure 7, compared with the unmodified titania nanotube of comparative example, PdO prepared by the embodiment of the present invention is loaded
N, B codope titanium dioxide nanotubes photochemical catalyst has good visible light photocatalysis active.PdO loads N, B of the present invention are total
Activity is high under doped titanic oxide nano tube photochemical catalyst visible light, safe and non-toxic, recycling facility, recycling performance
It is good, it can be used for the fields such as organic matter sewage disposal, air purification, energy and material.
Claims (8)
1. a kind of PdO loads N, B codope titanium dioxide nanotube photochemical catalyst, it is characterised in that：The titanium dioxide is with sharp
Titanium ore phase nano-tube array form exists；The palladium is carried on titania nanotube surface, the table of the palladium in the form of PdO
Face atomic concentration is 0.1~0.2%；The surface atom concentration of the nitrogen is 1.0~2.0%, the surface atom concentration of the boron
It is 0.3~0.5%.
2. PdO according to claim 1 loads N, B codope titanium dioxide nanotube photochemical catalyst, it is characterised in that：Institute
It states nitrogen-atoms and enters titanium dioxide lattice instead of oxygen atom formation O-Ti-N keys；The boron atom is adulterated in two forms, respectively
It is：B-O-Ti keys are formed into titanium dioxide lattice, surface atom concentration is 0.2~0.3%, with B2O3Form be carried on
Titania nanotube surface, surface atom concentration are 0.1~0.2%.
3. PdO according to claim 1 or 2 loads N, B codope titanium dioxide nanotube photochemical catalyst, feature exists
In：The titania nanotube is the nano-tube array being grown on Ti -- N alloy sheet matrix.
4. the preparation method of one of claim 1-3 PdO loads N, B codope titanium dioxide nanotube photochemical catalysts,
It is characterized in that：Organic solution first using Ti -- N alloy piece as anode, containing boron source carries out electrochemical anodic oxidation as electrolyte
Reaction, the Ti -- N alloy piece reaction generate N and adulterate TiO2While nano-tube array, B doping enters TiO2Nanotube, to
N, B codope titanium dioxide nanotube array is made；Then N, B codope titanium dioxide nanotube is impregnated in PdCl2
In solution, make PdCl2It is adsorbed in nanotube surface；After through drying, calcining, obtain PdO load N, B codope titanium dioxide
Nano pipe light catalyst.
5. the preparation method of PdO loads N, B codope titanium dioxide nanotube photochemical catalyst according to claim 4,
It is characterized in that including the following steps：
(1) preparation of Ti -- N alloy piece
It is prepared using the method for arc-melting-rapid cooling, titanium sponge is mixed with TiN powder first, electricity is pressed into through hydraulic press
Pole block is placed in cold-mo(u)ld furnace and carries out melting as anode, obtains blocky Ti -- N alloy；Then by described piece
Shape Ti -- N alloy is cut, is polished, is pre-processed, and Ti -- N alloy piece is obtained；
(2) preparation of N, B codope titanium dioxide nanotube
Using the Ti -- N alloy piece as anode, with dissolved with NaBF4、NH4The ethylene glycol of F and the mixed solution of water are as electrolyte
Carry out electrochemical anodization reaction, relative to ethylene glycol, the NaBF4、NH4F, the dosage of water be respectively 0.4~0.8wt%,
0.2~0.5wt%, 5~15vol%；The anodic oxidation reactions time is 10~30h；Washed, dry after the completion of reaction,
Calcining, obtains N, B codope titanium dioxide nanotube；
(3) PdO loads the preparation of N, B codope titanium dioxide nanotube
N, B codope titanium dioxide nanotube is impregnated in the PdCl that palladium ion concentration is 0.001~0.005mol/L2Second
15~30h is impregnated in the mixed solution of alcohol and water, then through drying, calcining, obtains PdO load N, B codope titanium dioxides
Nanotube.
6. the preparation method of PdO loads N, B codope titanium dioxide nanotube photochemical catalyst according to claim 5,
It is characterized in that：The dosage of TiN powder is 2~4mol% of titanium sponge in the step (1).
7. the preparation method of PdO loads N, B codope titanium dioxide nanotube photochemical catalyst according to claim 5,
It is characterized in that：Calcination temperature is 450~550 DEG C in the step (2), and heating rate is 4 DEG C/min, and soaking time is 1~2h.
8. the preparation method of PdO loads N, B codope titanium dioxide nanotube photochemical catalyst according to claim 5,
It is characterized in that：Calcination temperature is 400~500 DEG C in the step (3), and heating rate is 4 DEG C/min, and soaking time is 1~2h.
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