CN114602486B - Method for preparing nickel ion doped tungsten trioxide photocatalyst, product and application thereof - Google Patents
Method for preparing nickel ion doped tungsten trioxide photocatalyst, product and application thereof Download PDFInfo
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title claims abstract description 189
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910001453 nickel ion Inorganic materials 0.000 title claims abstract description 65
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 230000001699 photocatalysis Effects 0.000 claims abstract description 21
- 230000007547 defect Effects 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002135 nanosheet Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- -1 nickel oxide ions Chemical class 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 16
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 13
- 238000000926 separation method Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 5
- 239000000370 acceptor Substances 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 229940078494 nickel acetate Drugs 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 5
- 244000025254 Cannabis sativa Species 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
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- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing 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
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a method for preparing a nickel ion doped tungsten trioxide photocatalyst, a product and application thereof, comprising the following steps: 1) Mixing tungstate and a strong acid solution, stirring for reaction, centrifuging, washing to obtain a precipitate, drying the precipitate, and calcining to obtain tungsten trioxide; 2) Adding tungsten trioxide into a weak base solution, and performing ultrasonic dispersion and stirring to obtain a dispersion liquid; and adding nickel salt into the dispersion liquid, continuing stirring reaction, and after the reaction is finished, performing centrifugal washing to obtain the nickel ion doped tungsten trioxide catalyst. The nickel ion doped tungsten trioxide photocatalyst is mainly prepared by doping nickel ions on the surface of tungsten trioxide containing abundant defects and amorphous structures, and by utilizing the synergistic effect of the defects and high-valence nickel ions, the active sites of the nickel ion doped tungsten trioxide photocatalyst are obviously increased, and meanwhile, the defects such as oxygen vacancies and the like are used as electron acceptors, so that the separation efficiency of photo-generated electrons and holes can be improved, and the photocatalytic performance of the photocatalyst is improved.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a method for preparing a nickel ion doped tungsten trioxide photocatalyst, and a product and application thereof.
Background
With the rise of industrial revolution, industrialization and the flourishing development of human society, fossil fuels are the main energy source for the development of human economy, and face the exhaustion crisis under the continuously growing energy demand worldwide. On the other hand, the combustion of fossil fuels and human activities raise a series of environmental problems, such as global warming, glacier melting, land desertification, etc. Therefore, the technology of high efficiency and environmental protection is converted into available resources, and the photocatalytic water splitting is a very promising means for solving the energy and environmental problems, and is a challenging research direction in the energy field.
The photocatalysis technology refers to that a catalyst converts light energy into chemical under the illumination conditionThe energy required by the reaction, which further generates the catalysis, is a novel high-efficiency energy-saving environment-friendly technology. Among them, the photocatalytic decomposition of water by solar energy is the most interesting. Since the original work of Inoue et al, much research has been devoted to the photocatalytic decomposition of water by semiconductors, such as TiO 2 . But due to TiO 2 The forbidden bandwidth is about 3.2eV, and only about 4% of ultraviolet energy in sunlight can be utilized, so that the application of the ultraviolet energy in the field of photocatalysis is limited.
Tungsten trioxide is used as a visible light semiconductor catalyst, and has been attracting wide attention in the field of photocatalysis due to its advantages of no toxicity, low cost, high stability, etc. Although tungsten trioxide has good visible light absorption characteristics, the actual quantum efficiency is low and the photocatalytic activity is low due to the defects of small specific surface area, narrow energy band structure, easiness in recombination of photo-generated holes and electrons and the like. Thus, many studies are currently conducted to modify tungsten trioxide by a number of methods including noble metal deposition, semiconductor recombination, metal ion and nonmetal ion doping, etc., but the effect is still not ideal. Therefore, the development and preparation of the visible light catalyst with simple preparation, low price and high catalytic activity are still important research directions.
Disclosure of Invention
The invention aims to provide a method for preparing a nickel ion doped tungsten trioxide photocatalyst with wide light absorption range, high photo-generated electron-hole separation efficiency and high photocatalytic activity, and a product and application thereof.
The method for preparing the nickel ion doped tungsten trioxide photocatalyst comprises the following steps:
1) Mixing tungstate and a strong acid solution, stirring for reaction, centrifuging and washing to obtain precipitate, drying the precipitate, and further calcining to obtain tungsten trioxide;
2) Adding the tungsten trioxide in the step 1) into a weak base solution, performing ultrasonic dispersion, and stirring to obtain a dispersion liquid; and adding nickel salt into the dispersion liquid, continuing stirring reaction, and after the reaction is finished, performing centrifugal washing to obtain the nickel ion doped tungsten trioxide catalyst.
In the step 1), tungstate is Na 2 WO 4 ·2H 2 O, the strong acid is nitric acid, the concentration of the strong acid is 4-5M, and the concentration of tungstate in the strong acid solution is 2-3 mg/mL.
In the step 1), stirring and reacting for 24-48 hours; the washing is to adopt deionized water to wash to neutrality; the drying temperature is 50-70 ℃ and the drying time is 10-14 h; the calcination temperature is 400-600 ℃, the calcination temperature rising rate is 4-6 ℃/min, and the calcination time is 1-3 h.
In the step 2), the weak base solution is ammonia water solution, and the concentration of the weak base solution is 0.005-0.05 mmol/L; the concentration of tungsten trioxide in the weak base solution is 3-4 mg/mL; stirring time is 1-3 h, and stirring temperature is 40-60 ℃.
In the step 2), the nickel salt is nickel nitrate, the concentration of the nickel salt in the dispersion liquid is 0.005-0.08 mol/L, the continuous stirring reaction time is 6-12 h, and the continuous stirring reaction temperature is 40-60 ℃.
The nickel ion doped tungsten trioxide catalyst is prepared according to the preparation method.
The nickel ion doped tungsten trioxide catalyst has a micro-morphology of nano sheets and a nano size of 200-500 nm.
The mass percentage of the nickel ion doping in the nickel ion doped tungsten trioxide catalyst is 1-4%.
The surface of tungsten trioxide in the nickel ion doped tungsten trioxide catalyst is rich in defects and an amorphous structure.
The nickel ion doped tungsten trioxide catalyst is applied to photocatalytic water production oxygen.
The principle of the invention is as follows: according to the invention, part of tungsten trioxide is slowly dissolved in a weak alkaline solution, so that abundant defects and an amorphous structure are generated on the surface of tungsten trioxide, then the product is dispersed in a solution containing nickel ions and stirred, and high-valence nickel ions are generated by utilizing nickel ion autoxidation, so that the high-valence nickel ion doped tungsten trioxide photocatalyst with abundant defects is prepared. The surface defect of tungsten trioxide can be used as an electron acceptor, so that the separation efficiency of electrons and holes is improved, and meanwhile, after the catalyst is doped with nickel ions, active sites are increased, so that the catalytic reaction efficiency is improved. The catalyst of the invention increases the photoresponse range and improves the separation efficiency of photo-generated electron-hole pairs by utilizing the synergistic effect of high-valence nickel ions and abundant defects, thereby improving the photocatalytic activity of photocatalytic oxygen production.
The invention has the beneficial effects that:
(1) The nickel ion doped tungsten trioxide photocatalyst is mainly prepared by doping nickel ions on the surface of tungsten trioxide containing abundant defects and amorphous structures, and by utilizing the synergistic effect of the defects and high-valence nickel ions, the active sites of the nickel ion doped tungsten trioxide photocatalyst are obviously increased, and meanwhile, the defects such as oxygen vacancies and the like are used as electron acceptors, so that the separation efficiency of photo-generated electrons and holes can be improved, and the photocatalytic performance of the photocatalyst is improved. The synthesized photocatalyst has important practical application value in the aspect of photoelectric catalytic reaction.
(2) According to the preparation method, tungsten trioxide with a large number of defects on the surface is obtained through simple and mild solution treatment, and then high-valence nickel ion doped tungsten trioxide is formed by utilizing vacancy nickel oxide ions. The defect concentration and the nickel ion doping amount are controllable, and the defect concentration and the nickel ion doping amount can be regulated and controlled by regulating and controlling the conditions of reaction time, temperature, nickel source dosage and the like.
(3) The nickel ion doped tungsten trioxide photocatalyst has higher photocatalytic activity and high sunlight utilization rate compared with the original tungsten trioxide photocatalyst when photocatalytic water decomposition produces oxygen, and has better application prospect in the aspect of photocatalytic water decomposition to produce oxygen.
(4) The preparation method of the nickel ion doped tungsten trioxide photocatalyst is simple and easy to operate, and does not need complex instruments and equipment. And nickel ions are adopted as doping agents, so that the catalyst has low price compared with a catalyst material containing noble metals, and is suitable for industrial production.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the nickel ion-doped tungsten trioxide photocatalyst prepared in example 1 and example 2; (a) example 1; (b) example 2;
fig. 2 high resolution diagram of Ni element of X-ray photoelectron (XPS) spectrum of the nickel ion doped tungsten trioxide catalyst prepared in example 2 and comparative example 1: (a) comparative example 1; (b) example 2.
FIG. 3 is a Transmission Electron Microscope (TEM) image of the nickel ion doped tungsten trioxide photocatalyst prepared in example 1 and example 2; (a) and (c) example 1, (b) and (d) example 2;
FIG. 4 shows graphs of water oxygen evolution performance of decomposed tungsten trioxide prepared in example 1, the nickel ion-doped tungsten trioxide photocatalyst prepared in example 2, and the nickel ion-doped tungsten trioxide prepared in comparative example 1; (a) example 1; (b) example 2; (c) comparative example 1.
Detailed Description
The technical scheme of the present invention will be further described by specific examples, but the scope of the present invention is not limited to the following examples.
Example 1
Preparation of tungsten trioxide nano-sheet structure: 500mg of Na 2 WO 4 ·2H 2 O is dissolved in 200mL HNO 3 (4.8M) in solution, stirred for 36h, and collected by centrifugation as a yellow precipitate (WO 3 ·2H 2 O) washing with water to neutral pH, collecting WO 3 ·2H 2 Drying O in a vacuum drying oven at 60deg.C for 12 hr, and drying to obtain WO 3 ·2H 2 The O powder is heated to 500 ℃ at a heating rate of 5 ℃/min for calcination for 2 hours, and a light yellow tungsten trioxide sample is obtained.
Example 2
Preparation of a nickel ion doped tungsten trioxide photocatalyst: dispersing 0.1g of tungsten trioxide prepared in the embodiment 1 in 30mL of 0.01mmol/L ammonia water solution, performing ultrasonic dispersion, stirring for 2h at a constant temperature of 50 ℃, adding nickel acetate until the concentration of the nickel acetate in the solution is 0.01mol/L, stirring for 10h at 50 ℃, filtering, alternately washing with ethanol and water after filtering, and then drying in a vacuum drying oven at 60 ℃ for 12h to obtain a light grass green sample, namely the nickel ion doped tungsten trioxide photocatalyst.
Comparative example 1
Preparation of a nickel ion doped tungsten trioxide photocatalyst: taking 0.1g of tungsten trioxide prepared in the example 1, dispersing in 30mL of 0.01mol/L nickel acetate solution, performing ultrasonic dispersion, and stirring for 10 hours at a constant temperature of 50 ℃; and filtering, alternately washing with ethanol and water, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain a synthesized light grass green sample, namely the nickel ion doped tungsten trioxide photocatalyst.
Results and analysis:
as shown in an X-ray diffraction (XRD) spectrum of fig. 1, the tungsten trioxide sample prepared in example 1 has characteristic peaks at diffraction angles of 23.112 °, 23.58 °, 24.38 ° and the like, which are characteristic peaks of tungsten trioxide, and no other impurity peaks appear, indicating that the synthesized tungsten trioxide is monoclinic phase tungsten trioxide of a single phase and has good crystallinity. The nickel ion doped tungsten trioxide photocatalyst prepared in example 2 also has characteristic peaks of monoclinic tungsten trioxide, and no other impurity peaks appear, indicating that nickel ions are present in doped form in tungsten trioxide and do not create new phases.
FIG. 2 is a Ni 2p spectrum of XPS spectra of comparative example 1 (a) and example 2 (b), showing two main peaks at 856.1 and 873.8eV, and two satellite peaks at 862.0 and 880.3eV, which is Ni 2+ Is a typical characteristic peak of (a). At 856.1eV, the spectrum fits into two pairs of peaks, corresponding to Ni respectively 2+ And Ni 3+ ，Ni 3+ /Ni 2+ The ratio was 0.3, and the Ni peak position was shifted by 0.2eV in the direction of lower energy than a in the sample b treated with the weakly alkaline solution in example 2, and Ni could be obtained after the peak separation 3+ /Ni 2+ The ratio is 0.61, the ratio is obviously improved, indicating Ni in sample b 3+ The content is increased.
As shown in the Transmission Electron Microscope (TEM) image of fig. 3, the morphology (fig. 3 b) of the nickel ion doped tungsten trioxide photocatalyst prepared in example 2 did not change significantly in morphology size compared to the original tungsten trioxide material (fig. 3 a) in example 1, but showed significant jagged edges after etching.HRTEM FIGS. 3c and 3d clearly show the interplanar spacings corresponding to the planes of the nickel ion doped tungsten trioxide photocatalyst (020) of example 2, as
Compared with the (020) plane in unmodified tungsten trioxide of example 1 +.>
Slightly increased due to lattice expansion caused by doping and defects.
The experimental procedure for simulating catalytic water production of oxygen is as follows: the method for water oxidation under simulated sunlight by adopting the tungsten trioxide photocatalyst comprises the following steps: the experimental conditions for water oxidation were: a 500W xenon lamp is used as a light source; weighing 10mg of the prepared sample, dispersing in 100mL of distilled water, uniformly dispersing by ultrasonic, and adding 0.025mol/L silver nitrate as a capturing agent; the light source was then turned on and the reactor was automatically sampled and analyzed at 30 minute intervals to detect the gas composition and content for 180 minutes.
The results are shown as O in FIG. 4 2 The yield performance diagram shows: tungsten trioxide O prepared in example 1 under simulated sunlight 2 Yield was 0.85 mmolge -1 h -1 Nickel ion doped tungsten trioxide photocatalyst O prepared in example 2 2 Yield was 2.04 mmolgs -1 h -1 Catalyst O of comparative example 1, which was doped with only nickel ions and was not alkali-treated 2 Yield was 1.24 mmolge -1 h -1 And the result proves that the photocatalytic activity of the tungsten trioxide photocatalyst doped with nickel ions and having defects is far higher than that of the original tungsten trioxide and the tungsten trioxide doped with independent nickel ions, because the defects such as oxygen vacancies and the like can be used as electron acceptors, the separation of electron-hole pairs is effectively promoted, and the improvement of the photocatalytic activity is facilitated.
Example 3
Preparation of tungsten trioxide nano-sheet structure: 400mg of Na 2 WO 4 ·2H 2 O is dissolved in 200mL HNO 3 (4.0M) solution, stirring for 24h, centrifuging to collect yellow precipitateStarch (WO) 3 ·2H 2 O) washing with water to neutral pH, collecting WO 3 ·2H 2 Drying O in a vacuum drying oven at 50deg.C for 14 hr, and drying to obtain WO 3 ·2H 2 The O powder is heated to 600 ℃ at the heating rate of 6 ℃/min for calcination for 1 hour, and a light yellow tungsten trioxide sample is obtained.
Preparation of a nickel ion doped tungsten trioxide photocatalyst: dispersing 0.12g of prepared tungsten trioxide in 30mL of 0.02mmol/L ammonia water solution, performing ultrasonic dispersion, stirring for 3h at a constant temperature of 40 ℃, adding nickel acetate until the concentration of the nickel acetate in the solution is 0.02mol/L, stirring for 8h at 60 ℃, filtering, alternately washing with ethanol and water after filtering, and drying in a vacuum drying oven at 70 ℃ for 10h to obtain a light grass green sample, namely the nickel ion doped tungsten trioxide photocatalyst.
Example 4
Preparation of tungsten trioxide nano-sheet structure: 600mg Na 2 WO 4 ·2H 2 O is dissolved in 200mL HNO 3 (5.0M) in solution, stirred for 48h, and collected by centrifugation as a yellow precipitate (WO 3 ·2H 2 O) washing with water to neutral pH, collecting WO 3 ·2H 2 Drying O in a vacuum drying oven at 70deg.C for 10 hr, and drying to obtain WO 3 ·2H 2 The O powder is heated to 400 ℃ at a heating rate of 4 ℃/min for calcination for 3 hours, and a light yellow tungsten trioxide sample is obtained.
Preparation of a nickel ion doped tungsten trioxide photocatalyst: dispersing 0.09g of prepared tungsten trioxide in 30mL of 0.005mmol/L ammonia water solution, performing ultrasonic dispersion, stirring for 1h at a constant temperature of 60 ℃, adding nickel acetate until the concentration of the nickel acetate in the solution is 0.05mol/L, stirring for 12h at 40 ℃, filtering, alternately washing with ethanol and water after filtering, and drying in a vacuum drying oven at 50 ℃ for 14h to obtain a light grass green sample, namely the nickel ion doped tungsten trioxide photocatalyst.
By way of example, the applicant demonstrates the preparation of high-valence nickel ion doped tungsten trioxide photocatalysts and the effect of photocatalytic decomposition on the oxygen production performance of water by way of example. The above-mentioned embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all equivalent changes and modifications made by the claims of the present invention shall fall within the scope of the present invention, and the protection scope of the present invention is as shown in the claims of the present application.
Claims (7)
1. The method for preparing the nickel ion doped tungsten trioxide photocatalyst is characterized in that partial tungsten trioxide is slowly dissolved in a weak alkaline solution, so that abundant defects and an amorphous structure are generated on the surface of the tungsten trioxide, and high-valence nickel ion doped tungsten trioxide with abundant defects is formed by utilizing vacancy nickel oxide ions, and the method specifically comprises the following steps of:
1) Mixing tungstate and a strong acid solution, stirring for reaction, centrifuging and washing after the reaction is finished to obtain a precipitate, drying the precipitate, and further calcining to obtain tungsten trioxide;
2) Adding the tungsten trioxide in the step 1) into a weak base solution, performing ultrasonic dispersion, and stirring to obtain a dispersion liquid; adding nickel salt into the dispersion liquid, continuing stirring reaction, and after the reaction is finished, performing centrifugal washing to obtain the nickel ion doped tungsten trioxide photocatalyst;
in the step 2), the weak base solution is ammonia water solution, and the concentration of the weak base solution is 0.005-0.05 mmol/L; the concentration of tungsten trioxide in the weak base solution is 3-4 mg/mL; stirring for 1-3 h at 40-60 ℃;
in the step 2), the nickel salt is nickel nitrate, the concentration of the nickel salt in the dispersion liquid is 0.005-0.08 mol/L, the continuous stirring reaction time is 6-12 h, and the continuous stirring reaction temperature is 40-60 ℃.
2. The method for preparing a nickel ion doped tungsten trioxide photocatalyst according to claim 1, characterized in that in step 1), the tungstate is Na 2 WO 4 ·2H 2 And the strong acid is nitric acid, the concentration of the strong acid is 4-5M, and the concentration of tungstate in the strong acid solution is 2-3 mg/mL.
3. The method for preparing a nickel ion doped tungsten trioxide photocatalyst according to claim 1, characterized in that in the step 1), the stirring reaction time is 24-48 hours; the washing is to adopt deionized water to wash to neutrality; the drying temperature is 50-70 ℃, and the drying time is 10-14 h; the calcination temperature is 400-600 ℃, the calcination temperature rising rate is 4-6 ℃/min, and the calcination time is 1-3 h.
4. The nickel ion doped tungsten trioxide photocatalyst prepared by the method according to any one of claims 1-3.
5. The nickel ion doped tungsten trioxide photocatalyst according to claim 4, characterized in that the nickel ion doped tungsten trioxide photocatalyst has a micro morphology of nanosheets with a nano size of 200-500 nm.
6. The nickel ion doped tungsten trioxide photocatalyst according to claim 5, characterized in that the mass percentage of the nickel ion doping in the nickel ion doped tungsten trioxide photocatalyst is 1-4%.
7. The use of the nickel ion doped tungsten trioxide photocatalyst according to claim 4 for photocatalytic water production of oxygen.
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