CN110013824B - Mulching film-shaped two-dimensional nano thin layer sodium titanate covered silver oxide/titanium oxide heterojunction photocatalytic film material and preparation method thereof - Google Patents
Mulching film-shaped two-dimensional nano thin layer sodium titanate covered silver oxide/titanium oxide heterojunction photocatalytic film material 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 87
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 43
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001923 silver oxide Inorganic materials 0.000 title claims abstract description 11
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 38
- 239000010410 layer Substances 0.000 claims description 132
- 239000010408 film Substances 0.000 claims description 95
- 239000000243 solution Substances 0.000 claims description 81
- 229910052719 titanium Inorganic materials 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 23
- 238000005342 ion exchange Methods 0.000 claims description 23
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 17
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 16
- 235000011092 calcium acetate Nutrition 0.000 claims description 16
- 239000001639 calcium acetate Substances 0.000 claims description 16
- 229960005147 calcium acetate Drugs 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 11
- 239000002105 nanoparticle Substances 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 3
- 239000010409 thin film Substances 0.000 claims 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 1
- 239000004317 sodium nitrate Substances 0.000 claims 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 abstract description 19
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 230000006798 recombination Effects 0.000 abstract description 6
- 238000005215 recombination Methods 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 238000006303 photolysis reaction Methods 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 5
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 4
- 235000019799 monosodium phosphate Nutrition 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000002457 bidirectional effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000002186 photoelectron spectrum Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 229910020293 Na2Ti3O7 Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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Abstract
The invention discloses a ground film type two-dimensional nano thin layer sodium titanate covered silver oxide/titanium oxide heterojunction photocatalytic film material and a preparation method thereof, belongs to the technical field of preparation of nano photocatalytic materials, and solves the problem that the combination of a titanium oxide heterojunction and a narrow forbidden band or a semiconductor with long-wavelength light absorption capacity and the combination of a cocatalyst to increase active sites are difficult to realize simultaneously2An O-modified layer with TiO as the inner layer2And the layer presents the porous appearance of the micro-arc oxidation film layer. Nano Ag2O and TiO2The formed heterojunction structure can reduce the recombination probability of photo-generated electron-hole pairs and broaden TiO2The photoresponse range of the material improves the absorption of the material to light in a visible light range, and the outer-layer NTO has good adsorption effect while protecting silver oxide from photolysis corrosion, thereby improving the photocatalytic degradation efficiency.
Description
Technical Field
The invention belongs to the technical field of preparation of nano photocatalytic materials, and particularly relates to continuous 'mulching film-shaped' two-dimensional nano thin-layer sodium titanate (Na)(2n-4m)TimOnNTO for short), silver oxide (Ag)2O) nanoparticles, titanium dioxide (TiO)2) A porous film heterojunction photocatalytic film layer material and a preparation method thereof.
Background
TiO2The traditional photocatalytic material has the characteristics of high stability, good safety, strong catalytic activity, no toxicity, wide raw material preparation range, low price and the likeIs being used up to now. But due to TiO2The structural reasons of the material itself are numerous disadvantages. First, TiO2The forbidden band width of the titanium dioxide is larger (3.2ev), the response range to light is narrow, and the titanium dioxide can only absorb ultraviolet light, and the ultraviolet light only accounts for about 4% of sunlight, so that the utilization rate of the titanium dioxide to the sunlight is low; II, TiO2The photo-generated electron-hole pairs have high recombination efficiency and low quantum utilization rate, and seriously affect the photocatalytic activity of the titanium dioxide. Thirdly, from the aspect of catalytic kinetics, TiO2Like most catalysts, the surface has weak adsorption capacity to pollutants and few active sites. To solve the above problems, researchers have tried a variety of strategies in succession. For example, on TiO2The crystal grain structure is regulated and controlled, and the TiO is improved by nano-crystallization, lamella formation or preparation into a porous structure2The specific surface area of the crystal shortens the path of the photo-generated electrons or holes to the surface of the crystal grains so as to reduce the recombination loss of the electron-hole pairs. Or to TiO2Doping to control TiO2The band structure reduces the band width and improves the light utilization rate and the charge mobility. However, the most effective solution to date is to form a heterojunction structure by combining it with other materials. The principle of the heterojunction structure is generally considered in two aspects, one of which is to mix TiO2The material is combined with a narrow forbidden band or a semiconductor or other materials with long-wavelength light absorption capacity to improve the light absorption capacity and charge mobility and improve the overall light utilization rate; secondly, adding TiO2Combined with a cocatalyst to increase the active sites (including adsorption active sites and catalytic reaction active sites) and improve the photocatalytic reaction rate from a kinetic perspective. The two factors are all passed through the whole process of converting light energy into electric energy and then into chemical energy in the photocatalytic reaction. A good photocatalyst must combine these two factors, but it is a difficult point to organically combine the two factors. To date, there has been no effective solution and suitable catalyst material. Therefore, the research of photocatalyst, especially TiO, has become2The hot point and difficulty in the research of heterojunction photocatalyst modification.
Aiming at the problems, the invention provides Ag covered by a continuous 'plastic film-shaped' two-dimensional nano NTO thin layer2O/TiO2Heterojunction photocatalyst material (NTO/Ag for short)2O/TiO2) And a preparation method thereof to solve the problem of TiO2The problem of low photocatalytic efficiency makes it meet the urgent need of high-efficiency, low-cost and high-stability photocatalysts in the field of photocatalytic degradation of organic pollutants.
NTO/Ag2O/TiO2The composition and microstructure of the heterojunction photocatalyst make it have excellent photocatalytic performance. The Ag2O component is a typical p-type semiconductor, the band gap is 1.46eV, and the Ag2O component is used as a light absorption sensitizer in the structure, so that the absorption of the catalyst in a visible light region can be remarkably enhanced, and the utilization rate of the catalyst to sunlight is improved. Ag2O and TiO2When a heterostructure is formed by compounding to carry out photocatalysis, photoproduction electrons can move to n-type TiO2The photogenerated holes can move to the p-type Ag2And on the valence band of O, the interface electron transfer process is promoted, and the recombination of photo-generated electron-hole pairs is inhibited. The NTO layer has an ultrathin two-dimensional nano thin layer structure and is a reaction active layer in the catalyst. The fold structure of the NTO layer and the super strong pollutant adsorption capacity of the fold structure can provide a large number of adsorption active sites, and in addition, the ultra-thin structure of the NTO layer can easily realize the transmission and transfer of charges, thereby providing a large number of catalytic reaction active sites for the catalyst. In addition, the NTO two-dimensional nano thin layer is aligned with Ag2The O nano-particles form compact packaging protection and can effectively prevent Ag2Photolysis, corrosion and pollution of O, and increase of Ag2Stability and durability of O nanoparticles. NTO two-dimensional nano thin layer and Ag2TiO to which O nanoparticles are attached2The base layer is a ceramic layer prepared by micro-arc oxidation technology. The material has high bonding strength and mechanical property. And due to the process characteristics of the micro-arc oxidation technology, the prepared film layer naturally has a micro-nano porous structure, the rough porous surface structure can greatly improve the specific surface area and provide more reaction active point sites, and the micro-arc oxidation film is an ideal structure of a catalytic material. More importantly, the technology for preparing the film layer is simple in process and low in costAnd can rapidly prepare large-area films. Then, simple ion exchange and hydrothermal treatment are carried out, so that NTO/Ag related in the patent can be prepared2O/TiO2The heterojunction photocatalyst can also be used for preparing a micro-nano composite material with a more complex structure. Therefore, the patent not only provides an excellent heterojunction photocatalyst material based on sunlight as an excitation light source, but also provides a technical approach for preparing a complex micro-nano structure composite film layer.
Disclosure of Invention
The invention discloses a continuous 'mulching film-shaped' two-dimensional nano thin layer NTO (nitrilotriacetic acid) and nano Ag (silver) prepared based on a micro-arc oxidation technology2O particles, TiO2A porous film ternary heterojunction photocatalytic film material and a related preparation process. The catalyst material and the preparation method thereof provide an effective way for the design and preparation of high-performance photocatalysts and related nano composite membrane materials, and the heterojunction photocatalytic membrane material prepared by the method has wide application prospects in the fields of sewage treatment, environmental protection and the like.
The preparation method of the geomembrane-shaped sodium titanate two-dimensional nano thin layer covered silver oxide/titanium oxide heterojunction photocatalytic film material comprises the following specific steps:
1) preparing Ca-containing TiO on a titanium sheet substrate by using a micro-arc oxidation technology by taking a titanium sheet substrate material as an anode, a stainless steel electrolytic tank as a cathode and a mixed solution containing calcium ions, phosphate ions and EDTA disodium salt as an electrolyte2And (5) film layer. The titanium sheet base material may use pure titanium or a titanium alloy.
2) Forming Ca-rich TiO on the surface2The titanium sheet substrate of the film layer is placed in a silver-containing solution for ion exchange, and Ag is formed on the surface of the film layer2And an O nanoparticle modification layer.
3) Mixing Ag with water2O nanoparticle modified TiO2The film layer is hydrothermally treated in a sodium salt-containing aqueous solution with the concentration of 10g-50 g/L to finally form a continuous 'mulching film-shaped' two-dimensional nano NTO thin layer and nano Ag2O particles, TiO2Porous film ternary heterogeneousAnd a photocatalytic film layer.
The preparation method of the electrolyte containing silver ions and phosphate ions used in the micro-arc oxidation process in the step 1) comprises the following steps:
a. respectively preparing a solution A and a solution B:
solution A8-16 g/L NaH2PO4、
2-6g/L EDTA-2Na
Solution B is 2-4 g/L calcium acetate;
b. adding solution B to solution A to obtain a clear solution, and ensuring that the quantity ratio of the substances of calcium acetate and EDTA-2Na in solution A and solution B is less than 1, namely EDTA-2Na is excessive relative to calcium acetate.
The micro-arc oxidation treatment power supply setting parameters in the step 1) are as follows:
the power supply adopts a biphase pulse mode, the frequency is 50-1200 Hz, and the electrical parameters of the power supply input mode under the constant voltage mode and the constant current mode are set as follows:
under a constant voltage mode, forward voltage of 350-450V is applied to micro-arc oxidation treatment, and the treatment time is kept for 10-30 min; under the constant current mode, the micro-arc oxidation treatment is carried out to apply forward voltage to ensure that the current density is 0.01A/cm2-1A/cm2Keeping the treatment time for 10-30 min.
The preparation method of the ion exchange solution in the step 2) comprises the following steps:
a. respectively preparing a solution A and a solution B:
the solution A is 2.5-4 g/L EDTA-2Na,
1-2g/LKOH；
Solution B0.3-0.6 g/L AgNO3
b. Gradually adding the solution B dropwise into the solution A until the last drop of solution generates yellow insoluble precipitate, centrifuging, and retaining the solution.
The ion exchange conditions in step 2) were as follows: ion exchange is carried out in the air atmosphere in a dark place at room temperature, and the exchange time is 4-8 h.
The solution used in the hydrothermal reaction in the step 3) is sodium salt, such as various sodium phosphates, sodium sulfates, sodium nitrates and the like
The hydrothermal reaction conditions in step 3) are as follows: the hydrothermal reaction temperature is 160-180 ℃, the retention time is 4-24h, and the temperature is cooled to room temperature.
The continuous ground film-shaped two-dimensional nano thin layer NTO and nano Ag obtained by the method2O particles, TiO2The porous film ternary heterojunction photocatalytic film layer is composed of an inner layer, a middle layer and an outer layer, wherein the outer layer is a 'ground film shaped' continuous nano NTO protective layer with the thickness of 5nm-30nm, and the middle layer is Ag2The O modification layer has particle diameter of 50-200nm and TiO as inner layer2And the layer presents the porous appearance of the micro-arc oxidation film layer, and the thickness of the film layer is 5-100 mu m.
The invention has the beneficial effects that:
1. the equipment is micro arc oxidation equipment and an oven, is simple and easy to operate, has low cost, and can realize the continuous preparation of large-area film materials.
2. Nano Ag2O and TiO2The formed heterojunction structure can reduce the recombination probability of photo-generated electron-hole pairs and broaden TiO2The light response range of the light-emitting diode further improves the absorption of the light-emitting diode to light in a visible light range. The outer-layer 'mulching film-shaped' NTO has good adsorption effect while protecting the silver oxide from photolysis corrosion, so that the photocatalytic degradation efficiency of the film layer on organic pollutants is effectively improved, and the film-shaped NTO has high practical value and application prospect.
Drawings
FIG. 1 shows NTO/Ag formed in example 1 of the present invention2O/TiO2Scanning electron microscope photo of the ternary heterojunction photocatalytic film layer;
FIG. 2 shows NTO/Ag formed in example 1 of the present invention2O/TiO2An element energy spectrogram of the ternary heterojunction photocatalytic film layer;
FIG. 3 shows NTO/Ag formed in example 1 of the present invention2O/TiO2An X-ray diffraction spectrogram of the ternary heterojunction photocatalytic film layer;
FIG. 4 is NTO/Ag prepared in example 2 of the present invention2O/TiO2An X-ray surface photoelectron spectrum of the ternary heterojunction film layer; wherein FIG. 4a is a full spectrum and FIG. 4b is a fine sweep of Ag 3dThe scanning spectrum is shown as Na 1s in FIG. 4c and Ti 2p in FIG. 4 d.
FIG. 5 shows NTO/Ag formed in example 1 of the present invention2O/TiO2The ternary heterojunction photocatalytic film layer has the degradation effect on methyl blue under different illumination time;
FIG. 6 shows NTO/Ag prepared in example 2 of the present invention2O/TiO2Ternary heterojunction photocatalytic film layer, Ag2O-TiO2Film layer and pure TiO prepared by micro-arc oxidation2Ultraviolet-visible absorption spectrum of the film layer;
FIG. 7 shows NTO/Ag prepared in example 2 of the present invention2O/TiO2Ternary heterojunction photocatalytic film layer, Ag2O-TiO2Film layer and pure TiO prepared by micro-arc oxidation2The degradation effect of the film layer on the methyl blue under different illumination time.
Detailed Description
The technical solution of the present invention is further explained and illustrated below with reference to the examples and the accompanying drawings.
Example 1
In this embodiment, a continuous "ground film-like" two-dimensional nano thin layer NTO, nano Ag2O particles, TiO2The preparation method of the porous film ternary heterojunction photocatalytic film material comprises the following steps:
s1, mixing 2cm2The pure titanium sample is treated by degreasing and descaling with acid liquor, and then is cleaned with ethanol and deionized water by ultrasonic waves for 5 minutes respectively;
s2, performing micro-arc oxidation treatment under the stirring condition by using a bidirectional pulse power supply, taking a pure titanium sample as an anode, a stainless steel electrolytic tank as a cathode and a solution containing sodium dihydrogen phosphate, disodium ethylene diamine tetraacetate and calcium acetate as an electrolyte; the electrolyte solution is prepared by dissolving 8g of sodium dihydrogen phosphate and 2g of disodium ethylene diamine tetraacetate in 500ml of deionized water to prepare solution A, and dissolving 2g of calcium acetate in 500ml of deionized water to prepare solution B. And adding the B into the solution A to obtain a clear electrolyte. The power supply mode adopts constant voltage mode, the treatment time is 30min under the constant forward voltage of 370V, the reaction is finished, the titanium sheet is taken out and usedWashing with deionized water, and naturally drying to obtain Ca-containing TiO precursor2And (5) film layer.
Carrying Ca-containing precursor TiO2The titanium sheet of the film layer is put into silver-containing ion exchange liquid for ion exchange at room temperature in a dark place, and the nano Ag can be obtained after keeping for 4 hours2O modified TiO2Then placing the heterojunction photocatalytic film layer material in 0.1 g/L trisodium phosphate solution for hydrothermal reaction, and keeping the temperature at 160 ℃ for 24h to obtain NTO/Ag2O/TiO2Ternary heterojunction photocatalytic film layer material.
FIG. 1 shows NTO/Ag2O/TiO2Scanning electron microscope photo of the ternary heterojunction photocatalytic film layer. It can be seen from the figure that a layer of nano Ag is uniformly distributed on the surface of the film layer2O particles of Ag in this layer2The surface of the O particles is covered with a continuous two-dimensional nano thin layer substance in a 'ground film shape'. As can be seen from the energy spectrum result of FIG. 2, the surface contains a large amount of Ti, O and Na elements besides Ag, which indicates that the two-dimensional nano-thin layer substance is formed by NTO (Na)(2n-4m)TimOn) And (4) forming. FIG. 3 is NTO/Ag2O/TiO2And (3) an X-ray diffraction spectrum of the ternary heterojunction photocatalytic film layer. Only TiO is found in the map2Due to Ag2The O-particle layer and NTO are thin and cannot be detected by X-ray diffraction methods. To further confirm the existence of surface elements, X-ray surface photoelectron spectroscopy was performed, and NTO/Ag is shown in FIG. 42O/TiO2And an X-ray surface photoelectron spectrum of the ternary heterojunction photocatalytic film layer. It can be seen from the figure that the binding energy of Ag element and Ag2O corresponds to, the binding energy of Na and Ti elements is combined with Na(2n-4m)TimOnAnd (7) corresponding. As can be seen from the results of FIG. 1, FIG. 2, FIG. 3 and FIG. 4, NTO/Ag is formed after the three steps of micro-arc oxidation, ion exchange and hydrothermal treatment2O/TiO2The ternary heterojunction photocatalytic film layer is successfully prepared.
FIG. 4 shows NTO/Ag under simulated sunlight irradiation2O/TiO2The experimental result of the ternary heterojunction photocatalytic film layer on the degradation of the methyl blue dye can be seen from the figureThe methyl blue is gradually degraded along with the prolonging of the illumination time, which shows that NTO/Ag2O/TiO2The ternary heterojunction photocatalytic film layer has good capability of degrading pollutants through photocatalysis.
Example 2
S1, mixing 2cm2The pure titanium sample is treated by degreasing and descaling with acid liquor, and then is cleaned with ethanol and deionized water by ultrasonic waves for 5 minutes respectively;
s2, performing micro-arc oxidation treatment under the stirring condition by using a bidirectional pulse power supply, taking a pure titanium sample as an anode, a stainless steel electrolytic tank as a cathode and a solution containing sodium dihydrogen phosphate, disodium ethylene diamine tetraacetate and calcium acetate as an electrolyte; the electrolyte solution is prepared by dissolving 8g of sodium dihydrogen phosphate and 2g of disodium ethylene diamine tetraacetate in 500ml of deionized water to prepare solution A, and dissolving 2g of calcium acetate in 500ml of deionized water to prepare solution B. And adding the B into the solution A to obtain a clear electrolyte. The power supply mode adopts a constant voltage mode, the treatment time is 20min under the constant forward voltage of 420V, the reaction is finished, the titanium sheet is taken out, washed by deionized water and naturally dried to obtain the Ca-containing precursor TiO2And (5) film layer.
Carrying Ca-containing precursor TiO2The titanium sheet of the film layer is put into the Ag-containing ion exchange liquid at room temperature in a dark place for ion exchange, and the nano Ag can be obtained after keeping for 4 hours2O modified TiO2Then placing the heterojunction photocatalytic film layer material in 0.1 g/L trisodium phosphate solution for hydrothermal reaction, and keeping the temperature at 160 ℃ for 24h to obtain NTO/Ag2O/TiO2Ternary heterojunction photocatalytic film layer material.
To show NTO/Ag2O/TiO2The ternary heterojunction photocatalytic film layer has the advantage of degrading organic pollutants in sunlight, and is mixed with pure TiO prepared by micro-arc oxidation2Film layer and Ag2O nanoparticle modified TiO2Film layer (Ag)2O-TiO2) And (6) carrying out comparison. The UV-Vis Spectroscopy results of FIG. 6 show that NTO/Ag2O/TiO2The absorption of the ternary heterojunction photocatalytic film layer in a visible light region is obviously enhanced, and the absorption edge is red-shifted. This indicates NTO/Ag2O/TiO2The ternary heterojunction photocatalytic film layer has higher light utilization rate compared with other two catalysts. The three photocatalyst film layers are simultaneously used for carrying out the degradation experiment of the methyl blue dye, and the methyl blue degradation experiment of figure 7 shows that NTO/Ag is carried out in the dark reaction stage2O/TiO2The adsorption capacity of the ternary heterojunction photocatalytic film layer to methyl blue is obviously higher than that of the other two film layers, which shows that Na(2n-4m)TimOnThe layer provides more organic contaminant surface adsorption active sites for the catalyst. This will kinetically facilitate subsequent solar degradation. From the overall degradation results of FIG. 7, it can be seen that NTO/Ag2O/TiO2The performance of the ternary heterojunction photocatalytic film layer is obviously higher than that of pure TiO2Film layer and Ag2O-TiO2And (5) film layer.
In the micro-arc oxidation process of step S1, the prepared Ca-rich TiO can be controlled by adjusting the micro-arc oxidation process conditions2The quality of the film layer.
Therefore, in other embodiments, the micro-arc oxidation treatment process conditions are as follows: the power supply adopts a biphase pulse power supply, the frequency is 50-1200 Hz, and the power supply output mode adopts a constant voltage mode.
The method comprises the following steps: applying forward voltage of 350-450V, and maintaining the treatment time for 10-30 min.
In another embodiment, the micro-arc oxidation treatment process conditions are as follows: the power supply adopts a double-phase pulse power supply, the frequency is 50-1200 Hz, and the power supply output mode adopts a constant current mode.
The method comprises the following steps: after applying a forward voltage, the current density was adjusted to 0.01A/cm2-1A/cm2Keeping the treatment time for 10-30 min.
Thus, the current or voltage in the micro-arc oxidation process or the micro-arc oxidation time in each step can be controlled effectively to control TiO2The thickness, the composition, the internal microcrystalline structure and the surface appearance of the film layer are optimized, so that the mechanical properties (including hardness, bonding strength and the like), the surface characteristics (including porosity, pore size distribution, specific surface area and the like) and the like of the film layer are optimized, and the TiO is ensured2The quality of the film layer is obviously improved.
In the step S2, the Ca-rich TiO formed by micro-arc oxidation2The membrane layer is subjected to ion exchange treatment for the purpose of making the TiO rich in Ca component2Conversion of the film layer into Ag-rich TiO2Film layer, thereby forming Ag2O-modified TiO2Film layer, finally forming NTO/Ag by hydrothermal treatment2O/TiO2Ternary heterojunction photocatalytic film layer material.
Thus, in other embodiments, the ion exchange process is: ion exchange was carried out at room temperature under air atmosphere, in the dark. The concentration of the ion exchange solution and the ion exchange time are controlled, so that the nano Ag can be controlled2Distribution state of O particles on the surface, particle size and the like. Nano Ag2The formation of the O particles enables the film layer to utilize an expanded visible region for light, thereby improving the light utilization rate of the film layer material. Regulating nano Ag2The particle size and distribution of the O particles can more effectively inhibit the recombination of photo-generated electron-hole pairs and provide more reactive active sites. In the hydrothermal process, the shape and the covering thickness of the sodium titanate can be controlled by adjusting the hydrothermal time and temperature, so that the adsorption capacity of the film layer on the organic dye is improved, and the capacity of the film layer for degrading pollutants through photocatalysis is integrally improved.
The nano Ag obtained by the methods of S1 and S22O、Na2Ti3O7Modified TiO2The structure of the triple heterojunction photocatalysis film layer consists of an inner layer, a middle layer and an outer layer, wherein the outer layer is nano Na(2n-4m)TimOnA middle layer of Ag2The O modification layer has particle diameter of 10-100nm and TiO as inner layer2And the layer presents the porous appearance of the micro-arc oxidation film layer, and the thickness of the film layer is 5-100 mu m.
Claims (5)
1. The structure of the material is composed of an inner layer, a middle layer and an outer layer, wherein the outer layer is a 'ground film-shaped' continuous nano NTO protective layer with the thickness of 5nm-30nm, and the middle layer is Ag2An O modification layer with the particle diameter of 50-200nm,the inner layer is TiO2The layer presents the porous appearance of the micro-arc oxidation film layer, the thickness of the film layer is 5-100 μm, and the preparation method is characterized by comprising the following specific steps:
1) preparing Ca-containing TiO on a titanium sheet substrate by using a micro-arc oxidation technology by taking a titanium sheet substrate material as an anode, a stainless steel electrolytic tank as a cathode and a mixed solution containing calcium ions, phosphate ions and EDTA disodium salt as an electrolyte2A film layer; the titanium sheet base material is pure titanium or titanium alloy;
2) forming Ca-containing TiO on the surface2The titanium sheet substrate of the film layer is placed in a silver-containing solution for ion exchange, and Ag is formed on the surface of the film layer2An O nanoparticle modification layer; the conditions of ion exchange were: ion exchange is carried out in the air atmosphere in a dark place at room temperature for 4-8 h;
3) mixing Ag with water2O nanoparticle modified TiO2The film layer is hydrothermally treated in sodium-containing saline solution with the concentration of 10g-50 g/L, the hydrothermal reaction temperature is 160-2O particles, TiO2A porous thin film ternary heterojunction photocatalytic film layer;
the preparation method of the electrolyte used in the micro-arc oxidation process in the step 1) comprises the following steps:
a. respectively preparing a solution A and a solution B:
solution A8-16 g/L NaH2PO4、
2-6 g/L EDTA-2Na
Solution B is 2-4 g/L calcium acetate;
b. adding the solution B into the solution A to obtain a clear solution, and ensuring that the quantity ratio of calcium acetate to EDTA-2Na substances in the solution A and the solution B is less than 1, namely the EDTA-2Na is excessive relative to the calcium acetate;
the micro-arc oxidation treatment power supply setting parameters in the step 1) are as follows:
the power supply adopts a biphase pulse mode, the frequency is 50-1200 Hz, and the electrical parameters of the power supply input mode under the constant voltage mode and the constant current mode are set as follows:
under a constant voltage mode, forward voltage of 350-450V is applied to micro-arc oxidation treatment, and the treatment time is kept for 10-30 min; under the constant current mode, the micro-arc oxidation treatment is carried out to apply forward voltage to ensure that the current density is 0.01A/cm2-1A/cm2Keeping the treatment time for 10-30 min;
the preparation method of the ion exchange solution in the step 2) comprises the following steps:
a. respectively preparing a solution A and a solution B:
the solution A is 2.5-4 g/L EDTA-2Na,
1-2g/LKOH;
Solution B0.3-0.6 g/L AgNO3
b. Gradually adding the solution B dropwise into the solution A until the last drop of solution generates yellow insoluble precipitate, centrifuging, and retaining the solution.
2. The preparation method of the plastic film-shaped two-dimensional nano thin layer sodium titanate covered silver oxide/titanium oxide heterojunction photocatalytic film material as claimed in claim 1, comprises the following steps:
1) preparing Ca-containing TiO on a titanium sheet substrate by using a micro-arc oxidation technology by taking a titanium sheet substrate material as an anode, a stainless steel electrolytic tank as a cathode and a mixed solution containing calcium ions, phosphate ions and EDTA disodium salt as an electrolyte2A film layer; the titanium sheet base material is pure titanium or titanium alloy;
2) forming Ca-containing TiO on the surface2The titanium sheet substrate of the film layer is placed in a silver-containing solution for ion exchange, and Ag is formed on the surface of the film layer2An O nanoparticle modification layer; the conditions of ion exchange were: ion exchange is carried out in the air atmosphere in a dark place at room temperature for 4-8 h;
3) mixing Ag with water2O nanoparticle modified TiO2The film layer is hydrothermally treated in sodium-containing saline solution with the concentration of 10g-50 g/L, the hydrothermal reaction temperature is 160-2O particles, TiO2A porous thin film ternary heterojunction photocatalytic film layer;
the preparation method of the electrolyte used in the micro-arc oxidation process in the step 1) comprises the following steps:
a. respectively preparing a solution A and a solution B:
solution A8-16 g/L NaH2PO4、
2-6 g/L EDTA-2Na
Solution B is 2-4 g/L calcium acetate;
b. adding the solution B into the solution A to obtain a clear solution, and ensuring that the quantity ratio of calcium acetate to EDTA-2Na substances in the solution A and the solution B is less than 1, namely the EDTA-2Na is excessive relative to the calcium acetate;
the micro-arc oxidation treatment power supply setting parameters in the step 1) are as follows:
the power supply adopts a biphase pulse mode, the frequency is 50-1200 Hz, and the electrical parameters of the power supply input mode under the constant voltage mode and the constant current mode are set as follows:
under a constant voltage mode, forward voltage of 350-450V is applied to micro-arc oxidation treatment, and the treatment time is kept for 10-30 min; under the constant current mode, the micro-arc oxidation treatment is carried out to apply forward voltage to ensure that the current density is 0.01A/cm2-1A/cm2Keeping the treatment time for 10-30 min;
the preparation method of the ion exchange solution in the step 2) comprises the following steps:
a. respectively preparing a solution A and a solution B:
the solution A is 2.5-4 g/L EDTA-2Na,
1-2g/LKOH;
Solution B0.3-0.6 g/L AgNO3
b. Gradually adding the solution B dropwise into the solution A until the last drop of solution generates yellow insoluble precipitate, centrifuging, and retaining the solution.
3. The method for preparing the mulch-like two-dimensional nano thin layer sodium titanate covered silver oxide/titanium oxide heterojunction photocatalytic film material as claimed in claim 2, wherein the sodium-containing salt is sodium phosphate, sodium sulfate or sodium nitrate.
4. The preparation method of the plastic film-shaped two-dimensional nano thin layer sodium titanate covered silver oxide/titanium oxide heterojunction photocatalytic film material according to claim 2, wherein the preparation method of the electrolyte used in the micro-arc oxidation process in the step 1) comprises the following steps:
a. respectively preparing a solution A and a solution B:
solution A16 g/L NaH2PO4、
4 g/L EDTA-2Na
Solution B, 4 g/L calcium acetate;
b. adding solution B to solution A to obtain a clear solution, and ensuring that the quantity ratio of the substances of calcium acetate and EDTA-2Na in solution A and solution B is less than 1, namely EDTA-2Na is excessive relative to calcium acetate.
5. The method for preparing the photocatalytic film material covered by the two-dimensional nano thin film sodium titanate covered silver oxide/titanium oxide heterojunction as claimed in claim 2, wherein the hydrothermal reaction temperature is 160 ℃ and the retention time is 24 h.
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