CN109926063B - Preparation method of copper tungstate nanofiber photocatalyst - Google Patents
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Abstract
The invention relates to a preparation method of a copper tungstate nanofiber photocatalyst, and belongs to the technical field of photocatalysis. The one-dimensional copper tungstate nano-fiber is prepared by an electrostatic spinning technology, has uniform diameter, large specific surface area and short transmission distance of photon-generated carriers, and can effectively improve the catalytic activity of visible light degradation organic matters. The preparation method of the photocatalyst mainly comprises the following steps: dissolving inorganic tungsten salt and inorganic copper salt in ethanol or DMF solution, adding PAN or PVP to obtain spinning solution, obtaining composite fiber through an electrostatic spinning device, and calcining at high temperature to obtain the porous copper tungstate nanofiber. The preparation process is simple to operate and low in cost, is expected to realize large-scale preparation of the copper tungstate nanofiber, and has wide application prospects in the fields of environment and energy.
Description
Technical Field
The invention relates to a preparation method of a copper tungstate nanofiber photocatalyst, belongs to the technical field of photocatalysis, and particularly provides a preparation method of a copper tungstate nanofiber photocatalyst with high photocatalytic activity, large surface area and high stability.
Background
With the high-speed growth of economy in China and the development of global industrialization, the problem of environmental pollution is increasingly serious. Find an itemThe low-cost green common technology has important significance for environmental pollutant treatment. The semiconductor photocatalysis technology can directly utilize the oxygen in the solar energy and the air to mineralize the organic pollutants in the solution into nontoxic CO at normal temperature and normal pressure2The technology has the advantages of low treatment cost, simple operation, no secondary pollution and wide application prospect. Among the numerous semiconductor photocatalysts, TiO2Most widely used, but TiO2The band gap is large, and only the ultraviolet part of a solar spectrum can be absorbed, so that the solar utilization rate is low, and the practical application of the solar spectrum is limited.
CuWO4The semiconductor is an n-type semiconductor, has a band gap of 2.25eV, can absorb sunlight with the wavelength of less than 550nm in a solar spectrum, and absorbs more and more attention of researchers in recent years. However, copper tungstate has the problems of small specific surface area, low conductivity, high carrier recombination speed, short charge transmission distance and the like, so that the copper tungstate has low solar energy conversion efficiency and cannot meet the requirements of practical application. The development of the one-dimensional copper tungstate nanofiber is expected to eliminate some defects of copper tungstate, increase the surface area of the copper tungstate, improve the number of surface active sites of the copper tungstate, reduce the transmission distance of photo-generated charges and further improve the activity of copper tungstate for degrading environmental pollutants through photocatalysis. The electrostatic spinning technology is a strong and powerful means for synthesizing nanofiber materials, but copper tungstate nanofiber materials have not been reported, mainly because the preparation of copper tungstate nanofiber materials is not facilitated due to the lack of a copper tungstate spinning solution formula and a technical scheme related to copper tungstate spinning process parameters. In the invention, a spinning solution formula of the copper tungstate nanofiber is successfully prepared, the copper tungstate nanofiber with uniform diameter is synthesized by an electrostatic spinning device, and the fiber has good degradation effect on dye molecules in the solution under the irradiation of visible light. In a word, the preparation method is simple to operate and low in cost, is expected to realize large-scale production of copper tungstate, and promotes wide application of the copper tungstate in the field of environmental management.
Disclosure of Invention
The invention aims to provide a preparation method of a copper tungstate nanofiber photocatalyst, and the aim of the invention is realized by the following operation steps:
1) weighing a certain amount of inorganic tungsten salt, dissolving the inorganic tungsten salt in ethanol or N, N-Dimethylformamide (DMF), then adding a certain amount of inorganic copper salt, controlling the molar ratio of copper to tungsten to be 1:1, and stirring for dissolving; adding a certain amount of polyvinylpyrrolidone (PVP) or Polyacrylonitrile (PAN) into the solution, and stirring for 2-72h to obtain a homogeneous spinning solution;
2) adding the spinning solution into an electrostatic spinning device, adjusting the propelling speed of an injector to be 0.5-15mm/h, the spinning voltage to be 10-30kV, the receiving distance between a needle head and a roller to be 5-20cm, and the rotating speed of the roller to be 300-;
3) and (3) placing the dried composite fiber into a muffle furnace, calcining for 0.5-5h at the temperature of 400-800 ℃, controlling the heating rate to be 0.5-10 ℃/min, and cooling to obtain the inorganic copper tungstate nanofiber with the porous structure.
The technical scheme has simple operation and low cost, and is suitable for large-scale preparation of the copper tungstate nano porous fiber material; the obtained copper tungstate nano-fibers have uniform diameter and wider pore size distribution, and the specific surface area of the copper tungstate photocatalyst is effectively improved. Under the irradiation of visible light, compared with copper tungstate powder synthesized by a hydrothermal method, the nano fiber improves the removal efficiency of dye molecules. More importantly, the prepared copper tungstate nano-fibers are convenient to recycle and can be recycled for many times. The advantages enable the copper tungstate nano-fiber to have wide application prospect in the fields of future energy and environment.
Drawings
Fig. 1 is an X-ray diffraction pattern of the copper tungstate nanofiber prepared in example one.
FIG. 2 is a UV-visible diffuse reflectance spectrum of copper tungstate nanofibers prepared in example two;
FIG. 3 is a graph showing the pore size distribution of the copper tungstate nanofibers prepared in example III;
FIG. 4 is a scanning electron micrograph of copper tungstate nanofibers prepared in example four;
FIG. 5 is a scanning electron micrograph of copper tungstate nanofibers prepared in example V;
fig. 6 is a scanning electron microscope image of the copper tungstate nanofibers prepared in example six.
Fig. 7 is a time curve diagram of degradation of methyl orange by copper tungstate nano fibers and copper tungstate powder prepared in example seven under irradiation of visible light.
Detailed Description
For a better understanding of the present invention, the following examples and drawings are included to further illustrate the present invention, but the present invention is not limited to the following examples.
Example one
A preparation method of a copper tungstate nanofiber photocatalyst comprises the following specific steps:
1g of WCl6Dissolving in 10mL of DMF, stirring for dissolving, then adding 0.5g of copper acetate, stirring for dissolving, supplementing 1g of PAN, and stirring overnight to obtain a precursor spinning solution; pouring the spinning solution into a 10ml injector, and adjusting the spinning process parameters as follows: spinning voltage is 15kV, the advancing speed of the injector is 2mm/h, the receiving distance between the needle head and the roller is 10cm, the rotating speed of the roller is 300r/min, and the indoor temperature is controlled to be 25 ℃; and (3) putting the dried composite fiber into a muffle furnace, calcining for 1h at 600 ℃, controlling the heating rate to be 1 ℃/min, and cooling to obtain the porous copper tungstate nanofiber.
Fig. 1 shows an X-ray diffraction pattern of copper tungstate nanofibers, which shows that the crystal form of copper tungstate is well matched with a triclinic system, and no crystal phase of other substances appears in an XRD pattern, indicating that the synthesized copper tungstate is pure phase.
Example two
A preparation method of a copper tungstate nanofiber photocatalyst comprises the following specific steps:
1g of WCl6Dissolving in 10mL of DMF, stirring for twenty minutes, then adding 0.5g of copper acetate, stirring for dissolving, supplementing 1g of PVP, and stirring overnight to obtain a spinning solution; pouring the spinning solution into a 10ml injector, and adjusting the spinning process parameters as follows: spinning voltage is 16kV, the advancing speed of an injector is 3mm/h, the receiving distance between a needle head and a roller is 10cm, the rotating speed of the roller is 350r/min, the composite nanofiber is obtained, and the constant temperature of 120 ℃ is 6 h; putting the dried composite fiber into a muffle furnace,calcining for 1h at 650 ℃, controlling the heating rate to be 1 ℃/min, and cooling to obtain the porous copper tungstate nanofiber.
Fig. 2 is an ultraviolet-visible diffuse reflectance spectrum of the prepared copper tungstate nanofiber, below 550nm, the absorption of copper tungstate is sharply increased, indicating that copper tungstate is a visible light photocatalyst with a band gap of about 2.25eV.
EXAMPLE III
A preparation method of a copper tungstate nanofiber photocatalyst comprises the following specific steps:
dissolving 0.61g of ammonium tungstate in 12mL of DMF, ultrasonically dissolving, then adding 0.44g of copper acetate, stirring for dissolving, supplementing 1.5g of PVP, heating for dissolving, and stirring overnight to obtain a spinning solution; pouring the spinning solution into a 10ml injector, and adjusting the spinning process parameters as follows: spinning voltage is 17kV, the advancing speed of the injector is 6mm/h, the receiving distance between the needle head and the roller is 10cm, the rotating speed of the roller is 380r/min, and the porous nanofiber is obtained and is kept at the constant temperature of 150 ℃ for 10 h; and (3) putting the dried composite fiber into a muffle furnace, calcining for 1h at 550 ℃, controlling the heating rate to be 5 ℃/min, and cooling to obtain the yellow copper tungstate nano-particles.
FIG. 3 is a graph showing the pore size distribution of copper tungstate measured by a specific surface area and pore analyzer, wherein the pore size distribution of copper tungstate is wide (2.4-106nm), but mainly includes pores. And its specific surface area (A)sp) Calculated to 13.58m using the Brunauer-Emmett-Teller (BET) adsorption isotherm equation2/g。
Example four
A preparation method of a copper tungstate nanofiber photocatalyst comprises the following specific steps:
dissolving 0.08g of sodium tungstate in 12mL of DMF, ultrasonically dissolving, then adding 0.6g of copper nitrate, stirring for dissolving, supplementing 1g of PVP, heating for dissolving, and stirring overnight to obtain a spinning solution; pouring the spinning solution into a 10ml injector, and adjusting the spinning process parameters as follows: spinning voltage is 18kV, the advancing speed of an injector is 6mm/h, the receiving distance between a needle head and a roller is 10cm, the rotating speed of the roller is 400r/min, the composite nanofiber is obtained, and the temperature is kept at 150 ℃ for 10 h; and (3) putting the dried composite fiber into a muffle furnace, calcining for 2h at 550 ℃, and controlling the heating rate to be 2 ℃/min to obtain the yellow copper tungstate nano particles.
Fig. 4 is a scanning electron microscope image of copper tungstate nanofibers before calcination, and it can be seen that the surface of copper tungstate before calcination is very smooth, the diameter of the fibers is about 200nm, the length of the fibers can reach dozens of micrometers, and the fibers are overlapped with each other to form a network structure.
EXAMPLE five
A preparation method of a copper tungstate nanofiber photocatalyst comprises the following specific steps:
1.2g of WCl6Dissolving in 10mL of ethanol, stirring for half an hour, then adding 0.6g of copper acetate, stirring for dissolving, supplementing 0.5g of PVP, and stirring overnight to obtain a spinning solution; pouring the spinning solution into a 10ml injector, and adjusting the spinning process parameters as follows: spinning voltage is 15kV, the advancing speed of an injector is 4mm/h, the receiving distance between a needle head and a roller is 12cm, the rotating speed of the roller is 450r/min, the composite nanofiber is obtained, and the constant temperature of 150 ℃ is 8 h; and (3) putting the dried composite fiber into a muffle furnace, calcining for 2h at 550 ℃, controlling the heating rate to be 1 ℃/min, and cooling to obtain the copper tungstate nanofiber.
FIG. 5 is a scanning electron microscope image of calcined copper tungstate nanofibers, showing that the diameter of the fibers is about 250 nm. At high temperature, organic matters are heated and decomposed, the surface of the nanofiber is not smooth any more, but the nanofiber consists of a plurality of fine nano particles, and the small particles can effectively increase the specific surface area of the copper tungstate.
EXAMPLE six
A preparation method of a copper tungstate nanofiber photocatalyst comprises the following specific steps:
0.5g WCl6Dissolving in 5mL of DMF, stirring for half an hour, then adding 0.3g of copper acetate, stirring for dissolving, supplementing 0.5g of PAN, and stirring overnight to obtain a spinning solution; pouring the spinning solution into a 10ml injector, and adjusting the spinning process parameters as follows: spinning voltage is 14kV, the advancing speed of an injector is 2mm/h, the receiving distance between a needle head and a roller is 15cm, the rotating speed of the roller is 500r/min, the composite nanofiber is obtained, then the composite nanofiber is transferred to a muffle furnace and calcined at 550 ℃ for 1h, the heating rate is controlled to be 2 ℃/min, and the composite nanofiber is cooled, so that the copper tungstate nanofiber is obtained.
Fig. 6 is a scanning electron microscope image of the calcined copper tungstate nano-fibers prepared by the method, and it can be seen that the copper tungstate nano-fibers prepared by the method are skeleton-shaped and have a diameter of about 120 nm. Because the organic matter is heated and decomposed, a large number of holes are generated in the fiber, and fine particles are generated on the surface of the fiber, so that the specific surface area of the copper tungstate is effectively increased.
EXAMPLE seven
Fig. 7 is a graph of visible light photocatalytic degradation of methylene blue dye by using the copper tungstate nanofibers prepared in example three and copper tungstate powder synthesized by a hydrothermal method, wherein the degradation rate of the copper tungstate nanofibers on the dye reaches about 90% after 4 hours, and the degradation rate of the copper tungstate powder synthesized by the hydrothermal method on the dye is only about 50%, which shows that the photocatalytic activity of the copper tungstate nanofibers is better than that of the copper tungstate powder synthesized by the hydrothermal method.
The visible light degradation methylene blue experiment is simulated, and the specific operation is as follows:
(1) preparing a methylene blue solution with the concentration of 10 mg/L;
(2) respectively adding 25mg of copper tungstate nano-fibers and hydrothermally synthesized copper tungstate powder into a quartz tube, and then respectively adding 50mL of methylene blue solution;
(3) transferring the reaction liquid into a photocatalytic reactor, taking a 500W xenon lamp as a light source, and removing light with the wavelength below 420nm by using an optical filter so as to simulate visible light catalysis conditions;
(4) ventilating and stirring in a dark room for 1h, starting a xenon lamp, performing photocatalytic degradation, sampling from the quartz tube every 1h, centrifuging, and taking supernatant; and (3) measuring the absorbance of the methylene blue solution at 664nm by using a spectrophotometer, and calculating the degradation rate.
Claims (4)
1. A preparation method of a copper tungstate nanofiber photocatalyst is characterized by comprising the following steps:
1) dissolving inorganic tungsten salt and inorganic copper salt serving as raw materials in ethanol or N, N-dimethylformamide, adding a certain amount of organic high molecular polymer, and stirring for 2-72 hours to obtain a spinning solution;
2) adding the spinning solution into a 10mL injector, setting certain spinning process parameters through an electrostatic spinning device, receiving the solidified composite fiber on a roller covered with aluminum foil paper, and drying at 100-150 ℃;
3) transferring the composite fiber into a muffle furnace, and controlling a certain heating rate to calcine to obtain copper tungstate nano-fiber;
the organic high molecular polymer in the step 1 is polyvinylpyrrolidone or polyacrylonitrile;
the electrostatic spinning process parameters in the step 2 are as follows: the advancing speed of the injector is 0.5-15mm/h, the spinning voltage is 10-30kV, the receiving distance is 5-20cm, and the rotating speed of the roller is 300-;
in the step 3, the calcination temperature is 400-800 ℃, the heating rate is 0.5-10 ℃/min, and the calcination time is 0.5-2 h.
2. The method for preparing the copper tungstate nanofiber photocatalyst as claimed in claim 1, wherein the inorganic tungsten salt used in the step 1 is one or more of sodium tungstate, ammonium tungstate and tungsten hexachloride.
3. The method as claimed in claim 1, wherein the inorganic copper salt used in step 1 is one or more selected from copper nitrate, copper acetate, copper chloride, and copper sulfate.
4. The method for preparing the copper tungstate nanofiber photocatalyst as claimed in claim 1, wherein the ratio of inorganic copper salt to inorganic tungsten salt Cu: the molar ratio of W is 1: 1.
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| CN113293391B (en) * | 2020-10-23 | 2022-08-09 | 台州学院 | Preparation method of stannic tungstate nanofiber photoanode material |
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