CN111495401A - Preparation method of tungsten trioxide monohydrate/titanium carbide nano composite material with oxygen defect - Google Patents
Preparation method of tungsten trioxide monohydrate/titanium carbide nano composite material with oxygen defect Download PDFInfo
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- YGIGBRKGWYIGPA-UHFFFAOYSA-N trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O YGIGBRKGWYIGPA-UHFFFAOYSA-N 0.000 title claims abstract description 77
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 67
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000001301 oxygen Substances 0.000 title claims abstract description 48
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 42
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 33
- 230000007547 defect Effects 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 229910001868 water Inorganic materials 0.000 claims abstract description 45
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 33
- 239000008367 deionised water Substances 0.000 claims abstract description 31
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 31
- 230000002950 deficient Effects 0.000 claims abstract description 29
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000010936 titanium Substances 0.000 claims abstract description 27
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 8
- 239000008103 glucose Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000002135 nanosheet Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910009819 Ti3C2 Inorganic materials 0.000 abstract description 22
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 239000000706 filtrate Substances 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 206010021143 Hypoxia Diseases 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- HCMUXIHYOADWLV-UHFFFAOYSA-N O=[W].O=[Ti]=O Chemical compound O=[W].O=[Ti]=O HCMUXIHYOADWLV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/39—
-
- B01J35/40—
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
Abstract
The invention discloses a preparation method of an oxygen-deficient tungsten trioxide monohydrate/titanium carbide nano composite material. The method comprises the following steps: (1) dissolving sodium tungstate and citric acid, adding glucose and acid, and stirring to obtain a mixed solution; (2) cooling, centrifuging, washing and drying the mixed solution after reaction to obtain WO3·H2O; (3) adding Ti to hydrofluoric acid solution3AlC2Stirring, filtering, adding deionized water into the filtrate, centrifuging, and adjusting pH to obtain precipitate; (4) drying the precipitate, adding an organic solvent, performing ultrasonic treatment, centrifuging, washing and drying to obtain titanium carbide; (5) dissolving titanium carbide and WO3·H2O reaction, cooling, introducing nitrogen, centrifuging and washing to obtain WO3·H2O/Ti3C2. The preparation method is simple, the reaction condition is mild, the prepared composite material has good photoelectrochemical activity, low impedance and high electron transfer efficiency, andthe method has wide application prospect in the fields of photocatalysis, photochemistry and electrochemical sensing.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method of a tungsten trioxide monohydrate/titanium carbide nano composite material with oxygen defects.
Background
MXene is a novel carbon/nitride two-dimensional nano-layered material, and most typically titanium carbide (Ti)3C2) The nano material has a unique graphene-like laminated structure, a large specific surface area and a stable structure, can be used as a sensitivity enhancing material of an electrode, is used for manufacturing an electrochemical modified electrode with good performance, analyzes and detects biological micromolecules, and opens up a new way for the development of the field of electrochemical sensing. Further, Ti3C2The graphene oxide is also an ideal doped material, and has good selectivity on the premise of not introducing a functional group due to accurate and controllable interlayer spacing, so that the selectivity can exceed that of doped graphene after the functional group is introduced theoretically, and the material also becomes one of hot spots behind the graphene.
Tungsten trioxide (WO)3) Is an n-type indirect band gap semiconductor material and has an energy band structure (E) which is matched with sunlightg2.5-2.8eV), appropriate hole diffusion distance (-150 nm), and faster electron mobility (about 12 cm)2V-1s-1). Meanwhile, WO3Has higher valence band energy of 3.0eV (vs. NHE) and is more than O2/H2O (1.23V vs. NHE) redox potential, so that photogenerated holes have strong oxidizing capability and are excellent photoelectrode materials. However, WO is a material having a forbidden band width comparable to that of a semiconductor material such as silicon at ordinary temperature3The forbidden band width of the semiconductor device is slightly larger, which brings some troubles to the semiconductor device. In order to improve the electrochemical performance, the method needs to be further applied to WO3Modification is carried out, with compounding with other materials being one of the most effective modification strategies.
Therefore, we will substitute Ti3C2Materials and WO3Coupled to form tungsten trioxide monohydrate/titanium carbide (WO)3·H2O/Ti3C2) The nano composite material is used for improving the photoelectrochemical property of the nano composite material. However, WO is considered in the preparation process3The material has multiple crystal phases and hydrates, and does not containThe same structure will have different effects on the whole composite material, affecting the overall performance. Swapnil B.Ambade et al experimentally produced a monoclinic phase/hexagonal phase tungsten trioxide-titanium carbide composite material (Mono/Hexa WO)3-Ti3C2) WO which is prepared by adding hydrochloric acid or nitric acid into a mixed solution of sodium tungstate and thioacetamide to control pH 2 or pH 5 to respectively prepare monoclinic phase and hexagonal phase3Then continuously stirring the suspension of sodium tungstate and thioacetamide by adopting high-speed constant magnetic stirring, transferring the obtained solution into a stainless steel Teflon-lined water autoclave (50m L), reacting for 18 hours at 160 ℃, and finally dropwise adding pre-synthesized Ti into the suspension3C2MXene (7% by mass of tungsten precursor) was dispersed in deionized water (sonication), stirred for 20 minutes and transferred to a hydrothermal autoclave, and all the reaction precipitates were washed repeatedly with deionized water and ethanol and dried in an oven at 80 ℃ for 6 hours. The final product is verified to have greatly improved performance compared with the product before doping (Swapnil B.Ambade, Rohan B.Ambade, Wonnik Eom, Sung Hyun Noh, Seung Hun Kim, and Tae Hee Han, 2D Ti3C2MXene/WO3Hybrid Architectures for high-Rate Supercapacitors, 2018,5, 1801361). However, the monoclinic phase/hexagonal phase tungsten trioxide-titanium carbide composite material manufactured by the method has a high requirement on controlling the pH in terms of the manufacturing process, the ratio of the reactant amount is required to be more carefully controlled when the two crystal phases are synthesized, and the doping step is complicated, so that the method is not suitable for large-scale production. Disclosure of Invention
The invention aims to provide a preparation method of a tungsten trioxide monohydrate/titanium carbide nano composite material with simple synthesis method and mild conditions and oxygen deficiency.
The invention is realized by the following technical scheme:
a preparation method of an oxygen-deficient tungsten trioxide monohydrate/titanium carbide nanocomposite material comprises the following steps:
(1) adding water to dissolve sodium tungstate and citric acid, adding glucose and stirring, and continuously adding acid and stirring to form a mixed solution;
(2) transferring the mixed solution into a reaction kettle for heating reaction, cooling to room temperature after the reaction, centrifuging, washing and drying the product to obtain the tungsten trioxide monohydrate nanosheets with oxygen defects;
(3) adding Ti to hydrofluoric acid solution3AlC2Stirring the powder, filtering, adding deionized water into the filtered powder, centrifuging, and adjusting the pH value to obtain a precipitate;
(4) drying the precipitate, adding an organic solvent, stirring, performing ultrasonic treatment, introducing nitrogen, centrifuging, washing and drying to obtain titanium carbide;
(5) adding water to dissolve titanium carbide to obtain a titanium carbide solution, mixing the titanium carbide solution with the tungsten trioxide monohydrate nanosheets with oxygen defects in a reaction kettle, heating for reaction, cooling to room temperature after the reaction is finished, centrifuging and washing a product to obtain the tungsten trioxide monohydrate/titanium carbide nanocomposite with oxygen defects.
Further, in the step (1), the amount ratio of the sodium tungstate to the citric acid substance is 1: (1-5), the volume ratio of the sodium tungstate and the water is 1 mol:
(10-30) m L, wherein the mass ratio of the glucose to the sodium tungstate is 10: 1, the volume ratio of the mass of the sodium tungstate to the acid is 1mol, (3-5) m L, the water is deionized water, and the acid is hydrochloric acid.
Further, in the step (2), the reaction kettle is a polytetrafluoroethylene insulation reaction kettle.
Further, in the step (2), the heating temperature is 100-120 ℃, the reaction time is 20-24 hours, the washing adopts deionized water or ethanol as a solvent, the washing times are 3-5 times, the drying is vacuum drying, the drying temperature is 60-80 ℃, and the drying time is 8-12 hours.
Further, in the step (3), the mass fraction of hydrofluoric acid in the hydrofluoric acid solution is 49%, the stirring time is 12-24 hours, the pH value is adjusted within a range of 6-7, and the volume of the hydrofluoric acid solution and the Ti are mixed3AlC2The mass ratio of the powder is (10-25) m L (1-2) g.
Further, in the step (4), the drying temperature is 60-80 ℃, the drying time is 8-12 hours, the organic solvent is any one or a mixture of several of ethanol, dimethylformamide and dimethyl sulfoxide, the stirring time is 6-12 hours, and the volume ratio of the organic solvent to the hydrofluoric acid solution is (10-50): (1-2.5).
Further, the power of a machine used for ultrasonic treatment is 250-400W, the ultrasonic treatment time is 1-3 hours, the washing is respectively carried out for 3-5 times by using deionized water and ethanol, the drying is vacuum drying, the drying temperature is 60-80 ℃, and the drying time is 8-12 hours.
Further, the concentration of the titanium carbide solution in the step (5) is 1mg/m L, and the volume ratio of the mass of the oxygen-deficient tungsten trioxide monohydrate nanosheets to the titanium carbide solution is (50-150) mg: 10m L.
Further, the heating temperature in the step (5) is 110-.
The invention has the beneficial effects that:
(1) the preparation method is simple, the reaction condition is mild and easy to control; tungsten trioxide monohydrate with oxygen deficiency introduced in the present invention (WO)3·H2O) the surface of the nanosheet has oxygen vacancies,
The acid site can provide a coordination unsaturated site, activates oxygen molecules to form a superoxide radical and triggers a reaction, and the acid site can greatly improve the catalytic performance and is greatly helpful for improving the photocatalytic performance of the whole material.
(2) Titanium carbide (Ti) introduced in the present invention3C2) The surface rich functional groups (such as-OH and the like) can be combined with the action of a semiconductor, and are beneficial to the effective migration of photo-generated electrons and holes, so that the utilization efficiency and the photoelectric conversion performance of light are improved; further, titanium carbide (Ti)3C2) The conductive material also has good conductivity, and can effectively promote the electron transfer process of semiconductor photo-induced reaction, thereby improving the photoelectric conversion efficiency; titanium carbide (Ti)3C2) The Ti sites on the surface make the catalyst have stronger redox activity and thus stronger catalytic activity than other carbon materials (such as carbon nitride, graphene and the like).
(3) The oxygen deficient tungsten trioxide monohydrate/titanium carbide (WO) prepared by the present invention3·H2O/Ti3C2) The nano composite material has better photoelectrochemical activity, lower impedance and higher electron transfer efficiency, and has wide application prospect in the fields of photocatalysis, photochemistry and electrochemical sensing.
Drawings
FIG. 1 shows Ti of example 2 of the present invention3AlC2Titanium carbide (Ti)3C2) And oxygen deficient tungsten trioxide monohydrate/titanium carbide (WO)3·H2O/Ti3C2) XRD patterns of three materials of the nano composite material;
FIG. 2 is an oxygen deficient tungsten trioxide monohydrate (WO) of example 2 of the present invention3·H2O), titanium carbide (Ti)3C2) And oxygen deficient tungsten trioxide monohydrate/titanium carbide (WO)3·H2O/Ti3C2) A photo-amperometric pattern of the nanocomposite;
FIG. 3 is an oxygen deficient tungsten trioxide monohydrate (WO) of example 2 of the present invention3·H2O), titanium carbide (Ti)3C2) And oxygen deficient tungsten trioxide monohydrate/titanium carbide (WO)3·H2O/Ti3C2) EIS diagram of nanocomposite.
Detailed Description
The invention is illustrated in detail below with reference to specific examples:
example 1
(1) Weighing 1.0mol of sodium tungstate and 1.0mol of citric acid samples, placing the sodium tungstate and the citric acid samples in a beaker, then weighing 10.0m L of deionized water, adding the deionized water into the beaker to dissolve the sodium tungstate and the citric acid samples to form a uniform and transparent solution, then adding 10.0mol of glucose, stirring the solution for 10 minutes, and continuously adding 3.0m L of hydrochloric acid, stirring the solution for 30 minutes to form a mixed solution;
(2) the mixed solution is transferred to a 50m L polytetrafluoroethylene insulated reaction kettle at 120 DEG CHeating for 24 hours for reaction, cooling to room temperature after the reaction is finished, centrifugally separating the product, washing for 3 times by deionized water until the organic matter is removed, and then drying in vacuum at 60 ℃ for 12 hours to obtain the tungsten trioxide monohydrate with oxygen deficiency (WO)3·H2O) a nanosheet;
(3) 1.0g of Ti was added to a hydrofluoric acid solution of 10.0m L mass% at 49%3AlC2Stirring the powder for 24 hours at room temperature to remove aluminum elements in the powder, then filtering, adding deionized water into the filtered powder, and centrifuging for 3-5 times until the pH value is 6.5 to obtain a precipitate;
(4) drying the precipitate at 70 deg.C for 12 hr, adding 100.0m L ethanol and stirring for 9 hr, ultrasonic treating with 250W ultrasonic cleaner for 2 hr, introducing nitrogen gas into the dispersion for half an hour, centrifuging, washing with deionized water and ethanol for 4 times, and drying in 60 deg.C vacuum drying oven for 12 hr to obtain titanium carbide (Ti)3C2)；
(5) 10.0mg of the prepared titanium carbide was weighed out and dissolved in 10.0m L m deionized water to obtain a titanium carbide solution of 1mg/m L, and 50.0mg of the prepared oxygen-deficient tungsten trioxide monohydrate (WO)3·H2O) nanosheets prepared by mixing a titanium carbide solution with oxygen deficient tungsten trioxide monohydrate (WO)3·H2O) nano sheets are mixed in a reaction kettle, the reaction kettle is placed in an oven with the temperature of 110 ℃ for reaction for 6 hours, the reaction kettle is cooled to room temperature after the reaction is finished, the product is centrifuged, and then the product is washed by deionized water to obtain tungsten trioxide monohydrate/titanium carbide (WO) with oxygen defects3·H2O/Ti3C2) A nanocomposite material.
Example 2
(1) Weighing 1.0mol of sodium tungstate and 2.5mol of citric acid samples, placing the sodium tungstate and citric acid samples in a beaker, then weighing 20.0m of L deionized water, adding the deionized water into the beaker to dissolve the sodium tungstate and the citric acid samples to form a uniform and transparent solution, then adding 10.0mol of glucose, stirring the solution for 15 minutes, and continuously adding 4.0m of L hydrochloric acid, and stirring the solution for 40 minutes to form a mixed solution;
(2) the mixed solution is transferred to a 50m L polytetrafluoroethylene insulation reaction kettle at 100 DEG CHeating for reaction for 22 hours, cooling to room temperature after the reaction is finished, centrifugally separating the product, washing for 5 times by deionized water until the organic matter is removed, and then drying in vacuum for 10 hours at 70 ℃ to obtain the tungsten trioxide monohydrate with oxygen defects (WO)3·H2O) a nanosheet;
(3) 1.5g of Ti was added to a 49% hydrofluoric acid solution of 15.0m L mass fraction3AlC2Stirring the powder for 18 hours at room temperature to remove aluminum elements in the powder, then filtering, adding deionized water into the filtered powder, and centrifuging for 3-5 times until the pH value is 6 to obtain a precipitate;
(4) drying the precipitate at 80 deg.C for 10 hr, adding 300.0m L dimethylformamide and stirring for 6 hr, then ultrasonic treating with 350W ultrasonic cleaning machine for 3 hr, introducing nitrogen gas into the dispersion for half an hour, centrifuging, respectively cleaning with deionized water and ethanol for 3 times, and finally drying in 70 deg.C vacuum drying oven for 10 hr to obtain titanium carbide (Ti)3C2)；
(5) 10.0mg of the prepared titanium carbide was weighed out and dissolved in 10.0m L of deionized water to obtain a titanium carbide solution of 1mg/m L, and 150.0mg of the prepared oxygen-deficient tungsten trioxide monohydrate (WO)3·H2O) nanosheets prepared by mixing a titanium carbide solution with oxygen deficient tungsten trioxide monohydrate (WO)3·H2O) nano sheets are mixed in a reaction kettle, the reaction kettle is placed in an oven with the temperature of 120 ℃ for reaction for 8 hours, the reaction kettle is cooled to room temperature after the reaction is finished, the product is centrifuged, and then the product is washed by deionized water to obtain tungsten trioxide monohydrate/titanium carbide (WO) with oxygen defects3·H2O/Ti3C2) A nanocomposite material.
Example 3
(1) Weighing 1.0mol of sodium tungstate and 5.0mol of citric acid samples, placing the sodium tungstate and 5.0mol of citric acid samples in a beaker, then weighing 30.0m L of deionized water, adding the deionized water into the beaker to dissolve the sodium tungstate and the citric acid samples to form a uniform and transparent solution, then adding 10.0mol of glucose solution, stirring the solution for 20 minutes, and continuously adding 5.0m L of hydrochloric acid, stirring the solution for 30 minutes to form a mixed solution;
(2) the mixed solution was transferred to a 50m L Teflon insulatorHeating at 110 deg.C in a kettle for 20 hr, cooling to room temperature after reaction, centrifuging, washing with ethanol for 4 times until organic matter is removed, and vacuum drying at 80 deg.C for 8 hr to obtain tungsten trioxide monohydrate with oxygen deficiency (WO)3·H2O) a nanosheet;
(3) 2.0g of Ti was added to a 49% hydrofluoric acid solution of 25.0m L mass fraction3AlC2Stirring the powder for 12 hours at room temperature to remove aluminum elements in the powder, then filtering, adding deionized water into the filtered powder, and centrifuging for 3-5 times until the pH value is 7 to obtain a precipitate;
(4) drying the precipitate at 60 deg.C for 8 hr, adding 500.0m L dimethyl sulfoxide, stirring for 12 hr, ultrasonic treating with 400W ultrasonic cleaner for 1 hr, introducing nitrogen gas into the dispersion for half an hour, centrifuging, washing with deionized water and ethanol for 5 times, and drying in 80 deg.C vacuum drying oven for 8 hr to obtain titanium carbide (Ti)3C2)；
(5) 10.0mg of the prepared titanium carbide was weighed out and dissolved in 10m L of deionized water to obtain a titanium carbide solution of 1mg/m L, and then 100.0mg of the prepared oxygen-deficient tungsten trioxide monohydrate (WO)3·H2O) nanosheets prepared by mixing a titanium carbide solution with oxygen deficient tungsten trioxide monohydrate (WO)3·H2O) nano sheets are mixed in a reaction kettle, the reaction kettle is placed in an oven with the temperature of 130 ℃ for reaction for 10 hours, the reaction kettle is cooled to room temperature after the reaction is finished, the product is centrifuged, and then the product is washed by deionized water to obtain tungsten trioxide monohydrate/titanium carbide (WO) with oxygen defects3·H2O/Ti3C2) A nanocomposite material.
Example 4
Taking Ti used in example3AlC2And titanium carbide (Ti) obtained in example 23C2) And oxygen deficient tungsten trioxide monohydrate/titanium carbide (WO)3·H2O/Ti3C2) The X-ray diffraction of the three materials is carried out on the nano composite material, the XRD pattern of the nano composite material is tested, as shown in figure 1, the degrees of diffraction peaks of the three materials in the figure can be comparedTungsten trioxide monohydrate/titanium carbide (WO) illustrating oxygen deficiency3·H2O/Ti3C2) Nanocomposites were successfully prepared and significantly more, higher spikes also indicate doping improves lattice quality; the oxygen-deficient tungsten trioxide monohydrate prepared in example 2 (WO)3·H2O) nanosheet, titanium carbide (Ti)3C2) And oxygen deficient tungsten trioxide monohydrate/titanium carbide (WO)3·H2O/Ti3C2) The nano composite material is measured by a working station of CHI-660B model Chen Hua Shanghai to obtain a photoelectromogram, and as shown in figure 2, tungsten trioxide monohydrate/titanium carbide (WO) doped with oxygen defects can be found through observation3·H2O/Ti3C2) The photocurrent intensity of the nano composite material is greatly higher than that of the two materials before doping, and the tungsten trioxide monohydrate/titanium carbide (WO) with oxygen defects is illustrated3·H2O/Ti3C2) The nano composite material has excellent photocatalytic performance; tungsten trioxide monohydrate continuing with the oxygen deficiency prepared in example 2 (WO)3·H2O) nanosheet, titanium carbide (Ti)3C2) And oxygen deficient tungsten trioxide monohydrate/titanium carbide (WO)3·H2O/Ti3C2) The EIS diagram of the nanocomposite material measured by CHI-660B model Chen Hua Shanghai as shown in FIG. 3 shows that titanium carbide (Ti) is one of the three materials3C2) The radius of the incomplete circle of (A) is the largest, oxygen deficient tungsten trioxide monohydrate (WO)3·H2O) radius of nanoplatelets second, oxygen deficient tungsten trioxide monohydrate/titanium carbide (WO)3·H2O/Ti3C2) Tungsten trioxide monohydrate/titanium carbide with minimal radius of nanocomposite material illustrating oxygen defects (WO)3·H2O/Ti3C2) The nanocomposite material has a lower electrical resistance than the other two materials, and thus oxygen deficient tungsten trioxide monohydrate/titanium carbide (WO)3·H2O/Ti3C2) The nanocomposite has higher charge transfer efficiency.
The above-mentioned preferred embodiments of the present invention are provided for illustration only and not for the purpose of limiting the invention. Obvious variations or modifications of the present invention are within the scope of the present invention.
Claims (9)
1. A method for preparing an oxygen-deficient tungsten trioxide monohydrate/titanium carbide nanocomposite, comprising the steps of:
(1) adding water to dissolve sodium tungstate and citric acid, adding glucose and stirring, and continuously adding acid and stirring to form a mixed solution;
(2) transferring the mixed solution into a reaction kettle for heating reaction, cooling to room temperature after the reaction, centrifuging, washing and drying the product to obtain tungsten trioxide monohydrate nano sheets with oxygen defects;
(3) adding Ti to hydrofluoric acid solution3AlC2Stirring the powder, filtering, adding deionized water into the filtered powder, centrifuging, and adjusting the pH value to obtain a precipitate;
(4) drying the precipitate, adding an organic solvent, stirring, performing ultrasonic treatment, introducing nitrogen, centrifuging, washing and drying to obtain titanium carbide;
(5) adding water to dissolve titanium carbide to obtain a titanium carbide solution, mixing the titanium carbide solution with the tungsten trioxide monohydrate nanosheets with oxygen defects in a reaction kettle, heating for reaction, cooling to room temperature after the reaction is finished, centrifuging and washing a product to obtain the tungsten trioxide monohydrate/titanium carbide nanocomposite with oxygen defects.
2. The method for preparing oxygen-deficient tungsten trioxide monohydrate/titanium carbide nanocomposite material according to claim 1, wherein the amount ratio of sodium tungstate to citric acid in step (1) is 1: (1-5), the volume ratio of the sodium tungstate and the water is 1 mol: (10-30) ml, wherein the quantity ratio of the glucose to the sodium tungstate substance is 10: 1, the volume ratio of the sodium tungstate and the acid is 1 mol: (3-5) ml, wherein the water is deionized water, and the acid is hydrochloric acid.
3. The method for preparing oxygen-deficient tungsten trioxide monohydrate/titanium carbide nanocomposite as claimed in claim 1, wherein the reaction vessel in the step (2) is a polytetrafluoroethylene insulated reaction vessel.
4. The method as claimed in claim 1, wherein the heating temperature in step (2) is 100-120 ℃, the reaction time is 20-24 hours, the solvent used for washing is deionized water or ethanol, the number of washing times is 3-5, the drying is vacuum drying, the drying temperature is 60-80 ℃, and the drying time is 8-12 hours.
5. The method for preparing oxygen-deficient tungsten trioxide monohydrate/titanium carbide nanocomposite as claimed in claim 1, wherein the hydrofluoric acid solution in the step (3) has a mass fraction of 49% hydrofluoric acid, the stirring time is 20-24 hours, the pH is adjusted to 6-7, the volume of the hydrofluoric acid solution and the Ti are mixed together3AlC2The mass ratio of the powder is (10-25) ml: (1-2) g.
6. The method for preparing oxygen-deficient tungsten trioxide monohydrate/titanium carbide nanocomposite material according to claim 1, wherein the drying temperature in step (4) is 60-80 ℃, the drying time is 8-12 hours, the organic solvent is one or a mixture of ethanol, dimethylformamide and dimethyl sulfoxide, the stirring time is 6-12 hours, and the volume ratio of the organic solvent to the hydrofluoric acid solution is (10-50): (1-2.5).
7. The method as claimed in claim 1, wherein the power of the ultrasonic treatment machine in step (4) is 250-400W, the ultrasonic treatment time is 1-3 hours, the washing is respectively carried out 3-5 times by using deionized water and ethanol, the drying is vacuum drying, the drying temperature is 60-80 ℃, and the drying time is 8-12 hours.
8. The method for preparing oxygen-deficient tungsten trioxide monohydrate/titanium carbide nanocomposite material according to claim 1, wherein the concentration of the titanium carbide solution in step (5) is 1mg/ml, and the volume ratio of the mass of the oxygen-deficient tungsten trioxide monohydrate nanosheets to the titanium carbide solution is (50-150) mg: 10 ml.
9. The method as claimed in claim 1, wherein the heating temperature in step (5) is 110-130 ℃, and the reaction time is 6-10 hours.
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| CN113791124A (en) * | 2021-05-20 | 2021-12-14 | 中国石油大学(华东) | NO driven by wind power friction nano generator2Gas monitoring system and preparation method and application thereof |
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