CN109987633B - Oxygen vacancy-rich tungsten trioxide porous nanorod, catalytic system, preparation method and application thereof - Google Patents
Oxygen vacancy-rich tungsten trioxide porous nanorod, catalytic system, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a tungsten trioxide porous nanorod rich in oxygen vacancies, a catalytic system, a preparation method and application thereof. Black WO3‑xThe porous nanorod contains oxygen vacancies, has a smaller band gap and a stable structure, and the porous structure and a large number of oxygen vacancies can accelerate the transfer and transmission of photo-generated charge carriers and have better performance in the aspect of photo-thermal water evaporation.
Description
Technical Field
The invention relates to the technical field of transition metal oxide nano materials, in particular to a tungsten trioxide porous nanorod rich in oxygen vacancies and a preparation method and application thereof.
Background
Because the transition metal oxide has the characteristics of good stability, abundant reserves, easy preparation, environmental friendliness and the like, the transition metal oxide is widely applied to the aspects of hydrogen production by electrolyzing water, oxygen production, oxygen reduction, carbon dioxide reduction and the like. However, some potential applications of transition metal oxides are limited due to their insufficient conductive ability and their large band gap. In recent years, there has been much interest in transition metal oxide nanostructures containing oxygen vacancies because oxygen vacancies can effectively modulate the electronic structure, conductivity, bandgap size, and catalytic properties of materials. However, a simple and universal method for generating oxygen vacancies in transition metal oxide nanostructures has been rarely reported.
In recent years, solar energy is utilized under the action of a catalyst to carry out applications such as solar water evaporation and the like, so that the method is very suitable for seawater desalination in coastal remote areas with sufficient sunlight and lack of power and electric energy, and has very important research value and application prospect for relieving the problem that the demand for drinking water is greatly increased in the current society.
At present, the multi-stage flash lamp distillation and reverse osmosis process, as a general seawater desalination mode, have the disadvantages of consuming a large amount of electric energy and discharging a large amount of greenhouse gases, and in recent years, numerous photothermal materials such as gold nanoparticles, aluminum nanoparticles and carbon-based composite materials are layered, but the photothermal conversion efficiency and stability are often low, and for transition metal oxides, due to the large band gap of the transition metal oxides, the transition metal oxides are not suitable for being used as photothermal conversion materials, so that it is particularly important to develop a novel method for preparing transition metal oxides containing oxygen vacancies to reduce the band gap of the transition metal oxides.
The invention obtains the black tungsten trioxide porous nanorod rich in oxygen vacancy by simply calcining the yellow tungsten trioxide porous nanorod at low temperature in the ammonia gas atmosphere, and introduces a simple and universal method for reducing a transition metal oxide nanostructure under the assistance of ammonia gas to generate the oxygen vacancy.
Disclosure of Invention
The invention aims to provide a simple and universal method for generating oxygen vacancies in tungsten trioxide by ammonia-assisted reduction aiming at the technical defects in the prior art.
The technical scheme adopted for realizing the purpose of the invention is as follows:
the invention relates to a method for enriching oxygenThe wall of the nanorod is provided with a mesoporous structure, and the oxygen vacancy-rich tungsten trioxide porous nanorod contains W5+An amorphous structure exists.
Preferably, the length of the tungsten trioxide porous nanorod is 1-3 micrometers, and the aperture of a mesopore on the wall of the nanorod is 2-10 nm.
Preferably, under the action of the tungsten trioxide porous nanorod rich in oxygen vacancies, the water evaporation conversion efficiency is 70-80% in 8 hours.
In another aspect of the invention, a method for preparing a tungsten trioxide porous nanorod rich in oxygen vacancies comprises the following steps:
heating the tungsten trioxide porous nanorod to 400-500 ℃ at a heating rate of 1-5 ℃/min in an ammonia atmosphere, calcining for 1-3 h, and naturally cooling to obtain the tungsten trioxide porous nanorod rich in oxygen vacancies.
Preferably, the preparation method of the tungsten trioxide porous nanorod comprises the following steps:
uniformly dispersing tungsten trioxide into ethylenediamine, wherein the mass volume ratio of the tungsten trioxide to the ethylenediamine is (0.3-0.5): (10-15), wherein the mass unit of tungsten trioxide is g, the volume unit of ethylenediamine is ml, the tungsten trioxide reacts at 150-200 ℃ for 6-9 h, then the reaction product is cooled to room temperature, the product is centrifugally separated, then washed with water and ethanol respectively, dried at 30-60 ℃ for 10-15 h, the dried product is heated to 600-800 ℃ at the speed of 1-5 ℃/min, the temperature is kept for 4-6 h, then the product is naturally cooled to room temperature of 20-25 ℃, and the obtained yellow powder is a yellow tungsten trioxide porous nanorod.
In another aspect of the invention, the application of the tungsten trioxide porous nanorod rich in oxygen vacancies in photo-thermal water evaporation is also included.
In another aspect of the invention, a catalytic system based on the oxygen vacancy rich tungsten trioxide porous nanorods comprises a stainless steel net, wherein the stainless steel net is coated with a coating layer formed by the oxygen vacancy rich tungsten trioxide porous nanorods, and a hydrophobic layer is arranged outside the coating layer.
Preferably, the hydrophobic layer is trichloro (1H 1H 2H 2H perfluorooctyl) silane.
In another aspect of the invention, the application of the catalytic system based on the tungsten trioxide porous nanorods rich in oxygen vacancies in photo-thermal water evaporation is also included.
In another aspect of the invention, the method for preparing the catalytic system comprises the following steps:
step 1, coating tungsten trioxide porous nanorods rich in oxygen vacancies on a stainless steel net by using a dripping method;
and 2, performing hydrophobic treatment on the stainless steel net coated with the black oxygen vacancy-rich tungsten trioxide porous nanorod prepared in the step 1.
Preferably, the specific steps of step 1 are: uniformly dispersing the tungsten trioxide porous nanorod rich in the oxygen vacancy in absolute ethyl alcohol, wherein the mass-volume ratio of the tungsten trioxide porous nanorod rich in the oxygen vacancy to the absolute ethyl alcohol is (50-70): (1-2), wherein the mass unit of the tungsten trioxide porous nanorod rich in oxygen vacancies is mg, the volume unit of absolute ethyl alcohol is ml, and Nafion solution is added, wherein the volume ratio of the Nafion solution to the absolute ethyl alcohol is (0.01-0.02): 1, performing ultrasonic treatment for 10-40min, and then coating the stainless steel mesh on a stainless steel mesh subjected to ultrasonic treatment by acetone and absolute ethyl alcohol;
preferably, the specific steps of step 2 are: and (2) taking trichloro (1H 1H 2H 2H perfluorooctyl) silane, and heating the trichloro (1H 1H 2H 2H perfluorooctyl) silane and the stainless steel net treated in the step (1) in a sealed tank at the temperature of 50-90 ℃ for 0.5-1H, and forming a hydrophobic layer on the surface of the stainless steel net through a vapor deposition process.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a simple and universal method for generating oxygen vacancies in tungsten trioxide under the assistance of ammonia gas, which supplements the blank in the field, and the ammonia gas is used as reducing gas with strong pungent smell, is safer than hydrogen and carbon monoxide, so that the transition metal oxide which has good stability, abundant reserves and environmental friendliness can break the limitation caused by large band gap of the transition metal oxide, and can be better applied in more aspects.
2. Black tungsten trioxide porous nanorod rich in oxygen vacancies (marked as black WO)3-xThe porous nano rod, wherein x is more than 0 and less than 3) has the advantages of low cost, low synthesis temperature, high photo-thermal conversion efficiency, strong light absorption capacity and the like.
3. Black WO3-xThe porous nanorod contains oxygen vacancies, has a smaller band gap and a stable structure, and the porous structure and a large number of oxygen vacancies can accelerate the transfer and transmission of photo-generated charge carriers and have better performance in the aspect of photo-thermal water evaporation.
Drawings
FIG. 1 is a black WO prepared by the present invention3-xTransmission electron microscope (SEM) pictures of the porous nanorods.
FIG. 2 is a black WO prepared by the present invention3-xTransmission Electron Microscope (TEM) photographs of the porous nanorods.
FIG. 3 is a black WO prepared by the present invention3-xHigh Resolution Transmission Electron Microscopy (HRTEM) photographs of the porous nanorods.
FIG. 4 is a black WO3-xAnd yellow WO3Photoluminescence spectrum (PL).
FIG. 5 is a black WO prepared by the present invention3-xX-ray photoelectron spectroscopy (XPS) of porous nanorods.
FIG. 6 is a yellow WO prepared by the present invention3Porous nanorod and black WO3-xX-ray diffraction (XRD) pattern of porous nanorods.
FIG. 7 is a black WO prepared by the present invention3-xThe photo-thermal water evaporation performance of the porous nano rod, the yellow tungsten trioxide porous nano rod and the blank stainless steel mesh.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention is described in further detail below with reference to the figures and specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The chemical reagents used in the invention are analytically pure tungsten trioxide, ethylenediamine and trichloro (1H 1H 2H 2H perfluorooctyl) silane. The hydrothermal reaction kettle in step 1 is generally a stainless steel reaction kettle with polytetrafluoroethylene as a lining.
Specific example 1:
step 1: weighing 0.4g of commercial tungsten trioxide, dispersing the tungsten trioxide into 12ml of ethylenediamine under strong stirring, transferring the ethylene diamine into a 15ml of stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, then placing the reaction kettle into an oven at 180 ℃ for reaction for 8h, naturally cooling to room temperature, transferring a product from the reaction kettle to a centrifuge tube for centrifugal separation, washing the product with water and ethanol for 3 times respectively, then placing the product into a vacuum drying oven for drying at 40 ℃ for 12 hours, placing the dried product into a quartz tube, heating to 700 ℃ at the speed of 1 ℃/min, keeping the temperature for 5h, and naturally cooling to obtain yellow powder which is a yellow tungsten trioxide porous nanorod;
step 2: placing the yellow tungsten trioxide porous nanorod obtained in the step 1 in a quartz tube, cleaning the quartz tube with ammonia gas for 30min to obtain an inert environment, heating to 400 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h, and then naturally cooling, wherein the whole process is carried out in the atmosphere of ammonia gas, and the obtained black powder is the black tungsten trioxide porous nanorod rich in oxygen vacancies;
and step 3: respectively taking 60mg of the yellow and black products, dispersing in 1ml of absolute ethyl alcohol, respectively adding 10 microliters of Nafion solution, and dispersing in an ultrasonic machine for 30 min; respectively treating the stainless steel mesh with acetone and absolute ethyl alcohol by ultrasonic wave, and then coating the prepared sample on the stainless steel mesh by using a dripping method to respectively obtain yellow WO3And oxygen vacancy-rich black WO3-xA stainless steel mesh coated with the porous nanorods;
and 4, step 4: 50 microliter of trichloro (1H 1H 2H 2H perfluorooctyl) silane is taken respectively and then heated together with the stainless steel mesh coated with the yellow tungsten trioxide and the black tungsten trioxide porous nanorod rich in oxygen vacancy for 0.5 hour at the temperature of 80 ℃ in a sealed tank respectively. A hydrophobic layer (a layer of trichloro (1H 2H perfluorooctyl) silane) was formed on the surface of the stainless steel mesh by a vapor deposition process.
Example 2:
step 1: weighing 0.8g of commercial tungsten trioxide, dispersing the tungsten trioxide into 24ml of ethylenediamine under strong stirring, transferring the tungsten trioxide into a 30ml of stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, then placing the reaction kettle into an oven at 180 ℃ for reaction for 8h, naturally cooling to room temperature, transferring a product from the reaction kettle to a centrifuge tube for centrifugal separation, washing the product with water and ethanol for 3 times respectively, then placing the product into a vacuum drying oven for drying at 40 ℃ for 12 hours, placing the dried product into a quartz tube, heating to 700 ℃ at the speed of 1 ℃/min, keeping the temperature for 5h, and naturally cooling to obtain yellow powder which is a yellow tungsten trioxide porous nanorod;
step 2: placing the yellow tungsten trioxide porous nanorod obtained in the step 1 in a quartz tube, cleaning the quartz tube with ammonia gas for 30min to obtain an inert environment, heating to 400 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h, and then naturally cooling, wherein the whole process is carried out in the atmosphere of ammonia gas, and the obtained black powder is the black tungsten trioxide porous nanorod rich in oxygen vacancies;
and step 3: respectively taking 60mg of the yellow and black products, dispersing in 1ml of absolute ethyl alcohol, respectively adding 10 microliters of Nafion solution, and dispersing in an ultrasonic machine for 30 min; respectively treating the stainless steel mesh with acetone and absolute ethyl alcohol by ultrasonic wave, and then coating the prepared sample on the stainless steel mesh by using a dripping method to respectively obtain yellow WO3And oxygen vacancy-rich black WO3-xA stainless steel mesh coated with the porous nanorods;
and 4, step 4: 50 microliter of trichloro (1H 1H 2H 2H perfluorooctyl) silane is taken and then heated together with the stainless steel net coated with the yellow tungsten trioxide and the black tungsten trioxide porous nanorods containing oxygen vacancies respectively for 0.5 hour at the temperature of 80 ℃ in a sealed tank. A hydrophobic layer is formed on the surface of the stainless steel mesh by a vapor deposition process.
Example 3:
step 1: weighing 0.4g of commercial tungsten trioxide, dispersing the tungsten trioxide into 12ml of ethylenediamine under strong stirring, transferring the ethylene diamine into a 15ml of stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, then placing the reaction kettle into an oven at 180 ℃ for reaction for 8h, naturally cooling to room temperature, transferring a product from the reaction kettle to a centrifuge tube for centrifugal separation, washing the product with water and ethanol for 3 times respectively, then placing the product into a vacuum drying oven for drying at 40 ℃ for 12 hours, placing the dried product into a quartz tube, heating to 700 ℃ at the speed of 1 ℃/min, keeping the temperature for 5h, and naturally cooling to obtain yellow powder which is a yellow tungsten trioxide porous nanorod;
step 2: placing the yellow tungsten trioxide porous nanorod obtained in the step 1 in a quartz tube, cleaning the quartz tube with ammonia gas for 30min to obtain an inert environment, heating to 500 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h, and then naturally cooling, wherein the whole process is carried out in the atmosphere of ammonia gas, and the obtained black powder is the black tungsten trioxide porous nanorod rich in oxygen vacancies;
and step 3: respectively taking 60mg of the yellow and black products, dispersing in 1ml of absolute ethyl alcohol, respectively adding 10 microliters of Nafion solution, and dispersing in an ultrasonic machine for 30 min; respectively treating the stainless steel mesh with acetone and absolute ethyl alcohol by ultrasonic wave, and then coating the prepared sample on the stainless steel mesh by using a dripping method to respectively obtain yellow WO3And oxygen vacancy-rich black WO3-xStainless steel mesh coated by porous nanorods
And 4, step 4: 50 microliter of trichloro (1H 1H 2H 2H perfluorooctyl) silane is taken and then heated together with the stainless steel net coated with the yellow tungsten trioxide and the black tungsten trioxide porous nanorods containing oxygen vacancies respectively for 0.5 hour at the temperature of 80 ℃ in a sealed tank. A hydrophobic layer is formed on the surface of the stainless steel mesh by a vapor deposition process.
Example 4:
the procedure was as in example 1 except that the temperature increase rate in step 2 was increased from 2 ℃/min to 5 ℃/min.
Example 5:
the procedure was as in example 1 except that the temperature increase rate in step 2 was decreased from 2 ℃/min to 1 ℃/min.
And (4) analyzing results:
prepared black W using SEM and TEM pairsO3-xThe porous nanorods are subjected to morphology characterization, the length of the nanomaterial is about 2 micrometers (figure 1), and the black tungsten trioxide is in a porous structure (figure 2).
As shown in FIG. 3, in the black WO3-xThe lattice stripe with the width of 0.265 nm can be observed in the high-resolution transmission diagram of the porous nanorod, belongs to the tungsten trioxide 220 crystal plane, and meanwhile, the appearance of the amorphous part (circled part in the diagram) also proves that black WO is caused by the appearance of oxygen vacancy3-xReduction of crystallinity of the porous nanorods.
To demonstrate that the generation of oxygen vacancies reduced the band gap, as shown in FIG. 4, the material was characterized by photoluminescence spectroscopy, as shown in FIG. 7, after photoexcitation, in comparison with the yellow WO3Porous nanorods, black WO3-xThe emission peak of the porous nanorod at 440nm is much weaker, which indicates that all photo-generated electrons are excited into the conduction band due to the reduction of the band gap, thereby reducing the recombination rate of electron-hole. The generation of oxygen vacancies is more intuitively proved to be capable of effectively reducing the band gap of the material.
As shown in FIG. 5, by X-ray photoelectron spectroscopy (XPS), it was compared with a yellow tungsten trioxide porous nanorod except for two W35.8 (W2, W4 f5/2) and 37.9eV (W1, W4 f7/2)6+Outside the characteristic peak of (1), black WO3-xThe porous nanorod has an appearance of a W at 34.1eV5+The new peak of (a), the decrease in the valence of W, also confirms the presence of oxygen vacancies.
The prepared yellow tungsten trioxide porous nanorod (figure 6) and the black tungsten trioxide porous nanorod (figure 6) highly rich in oxygen vacancies were tested by XRD, and as shown in figure 6, the diffraction peaks obtained were one-to-one corresponding to tungsten trioxide with card number JCPDS NO.20-1324, while the black WO was3-xThe peak of the porous nanorods was substantially identical to that of yellow tungsten trioxide, but the intensity was slightly weak, which may be caused by the decrease in crystallinity after the generation of oxygen vacancies.
We investigated the water evaporation performance of tungsten trioxide before and after ammonia treatment. Black WO prepared by the invention3-xSpecific steps of photo-thermal water evaporation test of porous nanorod materialThe following were used: the black WO was passed in a test in a cylindrical container having an inner diameter of 5.5 cm and a depth of 8 cm3-xWater evaporation of the porous nanorod coated superhydrophobic stainless steel mesh. The cylindrical container was stored on an electronic balance to measure the weight of the evaporated water. Each run, the vessel was filled with 120mL of distilled water, and black WO3-xThe super-hydrophobic stainless steel net coated with the porous nanorods floats on the water surface. A 300W xenon lamp (CEL-HXUV300) and an AM1.5 filter were used to simulate solar irradiance and the hole diameter was adjusted to be the same as the mesh. The light intensity is about 0.1Wcm-2After a certain time interval, the weight of the water in the container is recorded.
As shown in fig. 7, the quality of water evaporation is shown as a function of illumination time. In the absence of photothermal substances, the water evaporation amount reaches 4.05kg/m in 8 hours2The conversion efficiency (eta) is 32.94 percent, the yellow tungsten trioxide porous nano rod is used as a photo-thermal material, and the water evaporation capacity is 5.83kg/m2And the time is 8h (eta is 46.59%). Interestingly, under the same conditions, black WO3-xThe water evaporation capacity of the porous nano rod can reach 9.28kg/m2The η value is higher (73.67%). This result indicates that black WO is compared with the yellow tungsten trioxide porous nanorod3-xThe porous nanorod has higher photo-thermal evaporation performance.
Wherein the photothermal conversion efficiency can be calculated by the following formula (1):
η＝Qe/Qs (1)
(1) the method comprises the following steps: qsRepresenting the power of the light (0.1 Wcm)-2),QeRepresents the power required for water evaporation and can be calculated from the following equation (2):
(2) the method comprises the following steps: m is the mass of water evaporation, t is the illumination time, He is the heat of water evaporation (approximatively 2260kJ kg)-1)。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The application of the oxygen vacancy rich tungsten trioxide porous nanorod in photo-thermal water evaporation is characterized in that the wall of the nanorod is provided with a mesoporous structure, and the oxygen vacancy rich tungsten trioxide porous nanorod contains W5+And the presence of an amorphous structure,
the oxygen vacancy-rich tungsten trioxide porous nanorod is prepared by the following method:
step S1, uniformly dispersing tungsten trioxide into ethylenediamine, wherein the mass-volume ratio of the tungsten trioxide to the ethylenediamine is (0.3-0.5): (10-15), reacting at 150-200 ℃ for 6-9 h, cooling to room temperature, centrifugally separating the product, washing with water and ethanol respectively, drying at 30-60 ℃ for 10-15 h, heating the dried product to 600-800 ℃ at a speed of 1-5 ℃/min, keeping the temperature for 4-6 h, naturally cooling to room temperature for 20-25 ℃, and obtaining yellow powder which is a yellow tungsten trioxide porous nanorod;
and step S2, heating the tungsten trioxide porous nanorod to 400-500 ℃ at a heating rate of 1-5 ℃/min in an ammonia atmosphere, calcining for 1-3 h, and naturally cooling to obtain the tungsten trioxide porous nanorod rich in oxygen vacancies.
2. The use of claim 1, wherein the tungsten trioxide porous nanorods have a length of 1-3 μm, and the pore size of the mesopores on the nanorod wall is 2-10 nm.
3. The application of the oxygen vacancy-rich tungsten trioxide porous nanorods, wherein the 8-hour water evaporation conversion efficiency is 70-80% under the action of the oxygen vacancy-rich tungsten trioxide porous nanorods.
4. A catalytic system based on oxygen vacancy-rich tungsten trioxide porous nanorods is characterized by comprising a stainless steel net, wherein the stainless steel net is coated with oxygen vacancy-rich tungsten trioxide porous nanorodsThe coating layer formed by the tungsten trioxide porous nano rod containing oxygen vacancies has a mesoporous structure on the wall of the nano rod, and the tungsten trioxide porous nano rod containing oxygen vacancies contains W5+And an amorphous structure exists, and a hydrophobic layer is arranged outside the coating layer.
5. Use of the catalytic system based on porous nanorods of tungsten trioxide rich in oxygen vacancies according to claim 4 in photo-thermal water evaporation.
6. The use according to claim 5, wherein the catalytic system is prepared by a process comprising the steps of:
step 1, coating tungsten trioxide porous nanorods rich in oxygen vacancies on a stainless steel net by using a dripping method;
and 2, performing hydrophobic treatment on the stainless steel net coated with the black oxygen vacancy-rich tungsten trioxide porous nanorod prepared in the step 1.
7. The application of claim 6, wherein the specific steps of the step 1 are as follows: uniformly dispersing the tungsten trioxide porous nanorod rich in the oxygen vacancy in absolute ethyl alcohol, wherein the mass-volume ratio of the tungsten trioxide porous nanorod rich in the oxygen vacancy to the absolute ethyl alcohol is (50-70): (1-2) adding a Nafion solution, wherein the volume ratio of the Nafion solution to the absolute ethyl alcohol is (0.01-0.02): 1, performing ultrasonic treatment for 10-40min, and then coating the stainless steel mesh on a stainless steel mesh subjected to ultrasonic treatment by acetone and absolute ethyl alcohol;
the specific steps of the step 2 are as follows: and (2) taking trichloro (1H 1H 2H 2H perfluorooctyl) silane, and heating the trichloro (1H 1H 2H 2H perfluorooctyl) silane and the stainless steel net treated in the step (1) in a sealed tank at the temperature of 50-90 ℃ for 0.5-1H, and forming a hydrophobic layer on the surface of the stainless steel net through a vapor deposition process.
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| CN114521581B (en) * | 2022-01-14 | 2022-11-08 | 中国水产科学研究院南海水产研究所 | Ozone slow-release carrier microsphere and application thereof in quality guarantee of seawater fish |
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