CN105013485A - Application of high-purity TiO2/CuO/Cu total mesoporous nanofiber in photocatalyst - Google Patents
Application of high-purity TiO2/CuO/Cu total mesoporous nanofiber in photocatalyst Download PDFInfo
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Abstract
The invention relates to application of high-purity TiO2/CuO/Cu total mesoporous nanofiber in a photocatalyst and belongs to the technical field of nanofiber and photocatalysts. The main composition elements of the nanofiber are Ti, O and Cu in a main form of expression of TiO2, CuO and Cu. The nanofiber has porous structures, pores of which comprise mesopores, and the pores in the porous structures are total mesopores. The specific surface area of the nanofiber is 19.6 m2/g and the bore diameter value is 34.8 nm. The nanofiber can be prepared by the preparation method in the following steps: carrying out electrostatic spinning on an organic precursor spinning solution at a high voltage of 18-22kV to obtain organic precursor nanofiber; and calcining the organic precusor nanofiber at 540-560 DEG C for 1-3 hours to obtain the TiO2/CuO/Cu total mesoporous nanofiber. The TiO2/CuO/Cu total mesoporous nanofiber provided by the invention can be effectively applied to a photocatalyst for photocatalytically splitting of water into hydrogen, and has high efficiency and stability. By regulating the components of the raw materials, the structure of the TiO2/CuO/Cu total mesoporous nanofiber is effectively regulated, and the preparation method is simple and controllable.
Description
Technical field
The present invention relates to a kind of high purity Ti O
2the application of the full meso-porous nano fiber of/CuO/Cu in photochemical catalyst, belongs to nanofiber technology field and photocatalyst technology field.
Background technology
Increasingly sharpening of environmental pollution and energy crisis, has seriously constrained the sustainable development of human economy and society, and development and utilization regenerative resource becomes one of common hot issue paid close attention in the whole world.Solar energy is that the mankind can utilize the abundantest energy resource supply, effective exploitation and the research theme utilizing solar energy to become current researchers to pay close attention to the most.Photocatalysis technology utilizes semiconductor light-catalyst to absorb decomposing water with solar energy hydrogen manufacturing or degrade poisonous pollutant, has reaction condition gentleness, non-secondary pollution and the advantage such as with low cost, become an important technical of solar energy development and utilization.The core of photocatalysis technology is the development of photochemical catalyst, wherein TiO
2nano-powder is photochemical catalyst the most conventional at present as P25, receives the favor of researchers because of advantages such as it are nontoxic, cheap.But, in actual applications, there is two problems still to govern TiO
2the extensive use of nano powder photocatalyst: 1) photo-generate electron-hole commute compound in light-catalyzed reaction, photocatalysis efficiency is lower; 2) traditional TiO
2it is on the low side to there is specific area in nano powder photocatalyst, and under liquid phase photocatalysis system, nano particle is easily reunited, and cannot ensure the photocatalytic activity of stability and high efficiency.
The representative CuO of Cu oxide belongs to p-type semiconductor, and its band gap is narrower, with the TiO of N-shaped
2the TiO of p-n junction is formed after compound
2-CuO photochemical catalyst, during ultraviolet excitation, from TiO
2the excited electron of the upper transition of valence band (VB), the hole of easily close with its conduction band (CB) CuO is combined, and the hole with strong reducing property excitation electron and strong oxidizing property remains on conduction band (CB) and the TiO of CuO respectively
2valence band (VB) on, achieve light induced electron and be separated with the effective of hole.In addition, simple substance Cu modifies TiO
2also effectively can extend the life-span of photo-generated carrier, strengthen its photocatalysis performance.The nanofiber photocatalyst of full meso-hole structure has typical mesopore structure and one-dimentional structure, gives its high-ratio surface and stable geometry, can keep the photocatalytic activity of efficient stable in light-catalyzed reaction.Therefore, based on above discussion, if explore a kind of effective method to prepare TiO
2/ CuO/Cu photochemical catalyst, will be expected to solve current conventional Ti O
2the subject matter that nano powder photocatalyst exists, strong promotion photocatalysis technology is in the application of field of solar energy conversion.
Summary of the invention
The object of the invention is to there are the problems referred to above for existing technology, propose a kind of TiO of the full meso-hole structure of high-purity that can effectively be applied in photochemical catalyst
2/ CuO/Cu nanofiber, and its catalytic activity is efficient, stable.
Object of the present invention realizes by following technical proposal: high purity Ti O
2the application of the full meso-porous nano fiber of/CuO/Cu in photochemical catalyst, the main component of described nanofiber is Ti, O, Cu, and main forms is TiO
2, CuO, Cu, described nanofiber has loose structure, and the hole of described loose structure comprises mesoporous.
As preferably, described nanofiber has loose structure and the hole of described loose structure is entirely mesoporous.
As preferably, the specific area of described nanofiber is 15-40m
2/ g, aperture value is 30-45nm.
High purity Ti O
2the full meso-porous nano fiber of/CuO/Cu being applied as high purity Ti O in photochemical catalyst
2/ CuO/Cu is complete there is catalytic reaction under light illumination in meso-porous nano fiber dispersion in decomposed substance, and wherein decomposed substance is moisture and material that is degradation material.
As preferably, the volume ratio of described water and degradation material is 2-5:1.
Further preferably, described degradation material is organic.
Again further preferably, described organic matter is methyl alcohol.
Above-mentioned high purity Ti O
2/ CuO/Cu full meso-porous nano fiber obtains by following preparation method:
Preparation spinning liquid as precursor;
Spinning liquid as precursor is carried out electrostatic spinning and obtains organic precursor nanofiber;
By organic precursor nanofiber through high-temperature calcination, TiO
2the full meso-porous nano fiber of/CuO/Cu.
At above-mentioned high purity Ti O
2in the preparation method of the full meso-porous nano fiber of/CuO/Cu, the method of described preparation spinning liquid as precursor is: be dissolved in solvent by polyvinylpyrrolidone (PVP) and butyl titanate (TBOT), stir, then add blowing agent and copper acetate and continue to stir to obtain spinning liquid as precursor.
The concentration of spinning liquid as precursor is mainly by affecting pattern and the diameter that solution viscosity affects fiber.If the concentration of spinning liquid as precursor is too low, in electrostatic spinning, solution viscosity is extremely low, is difficult to the continuity maintaining spray silk thread, can not forms stable fluid, and define liquid droplets, therefore obtains, in irregular blocks nanofiber, not having fiber to occur.If the excessive concentration of spinning liquid as precursor, fiber has slightly to be had carefully, skewness, even occur bonding phenomenon, its reason is, the interphase interaction of polymer molecule starts the motion affecting polymer chain, polymer molecular chain tangles mutually, if concentration continues to increase, polymer is mutually handed over and is worn, and forms frozen glue.The fluid of high concentration syringe needle rapidly dry and polymer form the instability that fluid that frozen glue causes flow at syringe needle, be difficult to maintain and spray silk thread, cause shower nozzle adhesion simultaneously, electrostatic spinning cannot be carried out.Therefore, in preparation spinning liquid as precursor, need the relationship between quality controlled well between each raw material, thus make the concentration that spinning liquid as precursor reaches suitable, and then form fine fiber morphology, the nanofiber that diameter is evenly distributed.In the preparation of above-mentioned spinning liquid as precursor, TBOT provides Ti source for TiO
2synthesis, PVP regulates and controls the viscosity of spinning solution, decomposes volatilization completely in follow-up calcination processing, and blowing agent decomposes and discharges a large amount of gas and carry out pore-creating to fibrous matrix in calcination processing process.
As preferably, the solvent described in method of preparation spinning liquid as precursor is the mixed liquor of absolute ethyl alcohol and glacial acetic acid.
Further preferably, the preparation absolute ethyl alcohol described in method of spinning liquid as precursor and the volume ratio of glacial acetic acid are 2-3:1.
As preferably, the blowing agent described in method of preparation spinning liquid as precursor is diisopropyl azodiformate (DIPA).Nanofiber of the present invention adopts foaming auxiliary electrostatic spin processes to make full meso-hole structure, and wherein DIPA adds the object that can realize fibrous matrix pore-creating as blowing agent.
At above-mentioned high purity Ti O
2in the preparation method of the full meso-porous nano fiber of/CuO/Cu, the method of described electrostatic spinning is: injected by spinning liquid as precursor in needle tubing, and be placed in electrostatic spinning machine, metal needle makes Electrospun anode, the negative electrode receiving material made by tinfoil paper or wire netting, under high pressure carry out electrostatic spinning, then obtain organic precursor nanofiber from iron wire online collection.
Electrostatic spinning is one and simply, flexibly prepares fibre technology, and its general principle is: under the effect of high voltage electric field, and the spinning liquid as precursor droplet deformation being suspended from capillary outlet is taylor cone.Along with the further raising of electric-field intensity, when drop surface due to the electrostatic repulsion forces of electrically charged formation exceed the surface tension of itself time, liquid stream is formed on the top of taylor cone, liquid stream with electric charge flows in the electric field, be subject to stretching action further, solvent evaporation (or melt cooling) simultaneously, becomes fiber and deposits on the reception device, forming organic precursor fibre material.In electrostatic spinning process, the electrospinning parameter affecting fibre property mainly contains: the concentration of spinning liquid as precursor, spinning voltage, Distance geometry solution flow rate etc. between anode and negative electrode.
As preferably, in electrostatic spinning, spinning liquid as precursor injects the injection speed in needle tubing is 0.8-1.2ml/h.
As preferably, condition during electrostatic spinning is: the distance between described anode and negative electrode is 18cm-22cm, and described high pressure is 18kV-22kV.Along with the change of receiving range between anode and negative electrode, the form of nanofiber also there occurs change, and when not considering other factors, too small " beads shape " fiber that can produce of receiving range is close to negative electrode, and then affects the character of nanofiber.When voltage is less than 18kV, most of spinning liquid as precursor is dropped on the wire netting of collection, and electrostatic spinning can not carry out; When voltage is higher than 22kV, strong corona discharge occurs, electrostatic spinning then can not proceed.Spinning liquid as precursor is in the electrostatic spinning of 18kV-22kV high pressure, and average fibre diameter increases along with the increase of spinning voltage.
As preferably, obtaining organic precursor nanofiber from tinfoil paper or iron wire online collection described in electrostatic spinning also needs to carry out drying process.Further preferably, the temperature of described drying is 50-70 DEG C.
At above-mentioned high purity Ti O
2in the preparation method of the full meso-porous nano fiber of/CuO/Cu, the temperature of described high-temperature calcination is 540-560 DEG C, and temperature retention time is 1-3h.
As preferably, in order to improve the degree of crystallinity of nanofiber, the calcination processing in step (2) is carried out in air atmosphere.
Compared with prior art, tool of the present invention has the following advantages:
1, TiO of the present invention
2the full meso-porous nano fiber of/CuO/Cu can be applied in photochemical catalyst effectively, makes photolysis water hydrogen, has high efficiency and stability.
2, nanofiber of the present invention is the composite nano fiber of the ternary system with full meso-hole structure, i.e. TiO
2/ CuO/Cu nanofiber.
3, preparing by regulation and control raw material composition in nanofiber, Effective Regulation TiO
2the structure of the full meso-porous nano fiber of/CuO/Cu.
4, TiO of the present invention
2the preparation method of/CuO/Cu full meso-porous nano fiber is simply controlled.
Accompanying drawing explanation
Fig. 1 is low power ESEM (SEM) figure of the organic precursor nanofiber that the embodiment of the present invention 1 obtains.
Fig. 2 is low power ESEM (SEM) figure of the nanofiber that the embodiment of the present invention 1 obtains.
Fig. 3 is high power ESEM (SEM) figure of the nanofiber that the embodiment of the present invention 1 obtains.
Fig. 4 is X-ray diffraction (XRD) figure of the nanofiber that the embodiment of the present invention 1 obtains.
Fig. 5 is X-ray diffraction (XRD) regional enlarged drawing of the nanofiber that the embodiment of the present invention 1 obtains.
Fig. 6 is transmission electron microscope (TEM) figure of the single nanofiber of the nanofiber that the embodiment of the present invention 1 obtains.
Fig. 7 is the elemental line scan figure that the obtained nanofiber of the embodiment of the present invention 1 is corresponding.
Fig. 8 is the corresponding high-resolution-ration transmission electric-lens of nanofiber (HRTEM) figure that the embodiment of the present invention 1 obtains.
Fig. 9 is x-ray photoelectron power spectrum (XPS) collection of illustrative plates of the nanofiber that the embodiment of the present invention 1 obtains.
Figure 10 is the high-resolution XPS collection of illustrative plates of Cu2p.
Figure 11 is specific surface and the pore analysis figure of the nanofiber that the embodiment of the present invention 1 obtains.
Figure 12 is organic precursor nanofiber ESEM (SEM) figure that comparative example 1 of the present invention obtains.
Figure 13 is ESEM (SEM) figure of the nanofiber that comparative example 1 of the present invention obtains.
Figure 14 is X-ray diffraction (XRD) figure of the nanofiber that comparative example 1 of the present invention obtains.
Figure 15 is specific surface and the pore analysis figure of the nanofiber that comparative example 1 of the present invention obtains.
Figure 16 is solid-state organic precursor nanofiber ESEM (SEM) figure that comparative example 2 of the present invention obtains.
Figure 17 is ESEM (SEM) figure of the nanofiber that comparative example 2 of the present invention obtains.
Figure 18 is the TiO that comparative example 2 of the present invention obtains
2x-ray diffraction (XRD) figure of the full meso-porous nano fiber of/CuO.
Figure 19 is specific surface and the pore analysis figure of the nanofiber that comparative example 2 of the present invention obtains.
Figure 20 is solid-state organic precursor nanofiber ESEM (SEM) figure that comparative example 3 of the present invention obtains.
Figure 21 is ESEM (SEM) figure of the nanofiber that comparative example 3 of the present invention obtains.
Figure 22 is X-ray diffraction (XRD) figure of the nanofiber that comparative example 3 of the present invention obtains.
Figure 23 is specific surface and the pore analysis figure of the nanofiber that comparative example 3 of the present invention obtains.
Figure 24 is TiO in Application Example 1 of the present invention
2the full meso-porous nano fiber of/CuO/Cu is as the active comparison diagram of Photocatalyzed Hydrogen Production of photochemical catalyst and P25.
Figure 25 is TiO in Application Example 1 of the present invention
2the full meso-porous nano fiber of/CuO/Cu is as the Photocatalyzed Hydrogen Production stability comparison diagram of photochemical catalyst and P25.
Detailed description of the invention
Be below specific embodiments of the invention and by reference to the accompanying drawings, technical scheme of the present invention is further described, but the present invention be not limited to these embodiments.
Embodiment 1
Take polyvinylpyrrolidone (PVP) 0.6g and butyl titanate (TBOT) 3.0g is dissolved in the mixed liquor of 7ml absolute ethyl alcohol and 3ml glacial acetic acid, stirred at ambient temperature add 1.0g diisopropyl azodiformate (blowing agent, DIPA) and 0.5g copper acetate after mixing 8 hours and continue stirring 2 hours spinning liquid as precursor.
Measure in 6ml injected plastic needle tubing after being left standstill by spinning liquid as precursor, and be placed on micro-injection pump, arranging injection speed is 1ml/h.Metal needle makes Electrospun anode, the negative electrode receiving material made by wire netting, distance between anode and negative electrode is 20cm, electrostatic spinning is carried out under 20kV high pressure, obtain SOLID ORGANIC precursor fibre material from iron wire online collection and be placed in the constant temp. drying box of 60 DEG C, obtained organic precursor nanofiber.
Finally organic precursor nanofiber is placed in quartz boat, in air atmosphere, is warming up to 550 DEG C of calcination processing 2 hours, then with stove cooling, obtained TiO
2the full meso-porous nano fiber of/CuO/Cu.
Embodiment 2
Take polyvinylpyrrolidone (PVP) 0.6g and butyl titanate (TBOT) 3.0g is dissolved in the mixed liquor of 7ml absolute ethyl alcohol and 3ml glacial acetic acid, stirred at ambient temperature add 0.5g diisopropyl azodiformate (blowing agent, DIPA) and 0.6g copper acetate after mixing 7 hours and continue stirring 1.5 hours spinning liquid as precursor.
Measure in 6ml injected plastic needle tubing after being left standstill by spinning liquid as precursor, and be placed on micro-injection pump, arranging injection speed is 1.1ml/h.Metal needle makes Electrospun anode, the negative electrode receiving material made by wire netting, distance between anode and negative electrode is 19cm, electrostatic spinning is carried out under 19kV high pressure, obtain SOLID ORGANIC precursor fibre material from iron wire online collection and be placed in the constant temp. drying box of 65 DEG C, obtained organic precursor nanofiber.
Finally organic precursor nanofiber is placed in quartz boat, in air atmosphere, is warming up to 545 DEG C of calcination processing 1.5 hours, then with stove cooling, obtained TiO
2the full meso-porous nano fiber of/CuO/Cu.
Embodiment 3
Take polyvinylpyrrolidone (PVP) 0.6g and butyl titanate (TBOT) 3.0g is dissolved in the mixed liquor of 8ml absolute ethyl alcohol and 3ml glacial acetic acid, stirred at ambient temperature add 0.5g diisopropyl azodiformate (blowing agent, DIPA) and 0.4g copper acetate after mixing 8 hours and continue stirring 2.5 hours spinning liquid as precursor.
Measure in 6ml injected plastic needle tubing after being left standstill by spinning liquid as precursor, and be placed on micro-injection pump, arranging injection speed is 0.9ml/h.Metal needle makes Electrospun anode, the negative electrode receiving material made by wire netting, distance between anode and negative electrode is 21cm, electrostatic spinning is carried out under 21kV high pressure, obtain SOLID ORGANIC precursor fibre material from iron wire online collection and be placed in the constant temp. drying box of 68 DEG C, obtained organic precursor nanofiber.
Finally organic precursor nanofiber is placed in quartz boat, in air atmosphere, is warming up to 555 DEG C of calcination processing 2.5 hours, then with stove cooling, obtained TiO
2the full meso-porous nano fiber of/CuO/Cu.
Embodiment 4
Take polyvinylpyrrolidone (PVP) 0.6g and butyl titanate (TBOT) 3.0g is dissolved in the mixed liquor of 8ml absolute ethyl alcohol and 3ml glacial acetic acid, stirred at ambient temperature add 0.5g diisopropyl azodiformate (blowing agent, DIPA) and 0.5g copper acetate after mixing 9 hours and continue stirring 3 hours spinning liquid as precursor.
Measure in 6ml injected plastic needle tubing after being left standstill by spinning liquid as precursor, and be placed on micro-injection pump, arranging injection speed is 0.8ml/h.Metal needle makes Electrospun anode, the negative electrode receiving material made by wire netting, distance between anode and negative electrode is 22cm, electrostatic spinning is carried out under 18kV high pressure, obtain SOLID ORGANIC precursor fibre material from iron wire online collection and be placed in the constant temp. drying box of 70 DEG C, obtained organic precursor nanofiber.
Finally organic precursor nanofiber is placed in quartz boat, in air atmosphere, is warming up to 540 DEG C of calcination processing 1 hour, then with stove cooling, obtained TiO
2the full meso-porous nano fiber of/CuO/Cu.
Embodiment 5
Take polyvinylpyrrolidone (PVP) 0.6g and butyl titanate (TBOT) 3.0g is dissolved in the mixed liquor of 7.5ml absolute ethyl alcohol and 2.5ml glacial acetic acid, stirred at ambient temperature add 0.5g diisopropyl azodiformate (blowing agent, DIPA) and 0.6g copper acetate after mixing 7 hours and continue stirring 1 hour spinning liquid as precursor.
Measure in 6ml injected plastic needle tubing after being left standstill by spinning liquid as precursor, and be placed on micro-injection pump, arranging injection speed is 1.2ml/h.Metal needle makes Electrospun anode, the negative electrode receiving material made by wire netting, distance between anode and negative electrode is 18cm, electrostatic spinning is carried out under 22kV high pressure, obtain SOLID ORGANIC precursor fibre material from iron wire online collection and be placed in the constant temp. drying box of 62 DEG C, obtained organic precursor nanofiber.
Finally organic precursor nanofiber is placed in quartz boat, in air atmosphere, is warming up to 560 DEG C of calcination processing 3 hours, then with stove cooling, obtained TiO
2the full meso-porous nano fiber of/CuO/Cu.
Comparative example 1
Take polyvinylpyrrolidone (PVP) 0.6g and butyl titanate (TBOT) 3.0g is dissolved in the mixed liquor of 7ml absolute ethyl alcohol and 3ml glacial acetic acid, stirred at ambient temperature add 0.5g copper acetate after mixing 8 hours and continue stirring 2 hours spinning liquid as precursor.
Measure in 6ml injected plastic needle tubing after being left standstill by spinning liquid as precursor, and be placed on micro-injection pump, arranging injection speed is 1ml/h.Metal needle makes Electrospun anode, the negative electrode receiving material made by wire netting, distance between anode and negative electrode is 20cm, electrostatic spinning is carried out under 20kV high pressure, obtain SOLID ORGANIC precursor fibre material from iron wire online collection and be placed in the constant temp. drying box of 60 DEG C, obtained organic precursor nanofiber.
Finally organic precursor nanofiber is placed in quartz boat, in air atmosphere, is warming up to 550 DEG C of calcination processing 2 hours, then with stove cooling, obtained TiO
2the full meso-porous nano fiber of/CuO/Cu.
Comparative example 2
Only distinguish with embodiment 1 and adding 0.2g copper acetate, other techniques are identical with embodiment 1, are not repeated herein.
Comparative example 3
Only distinguish with embodiment 1 and adding 0.8g copper acetate, other techniques are identical with embodiment 1, are not repeated herein.
Fig. 1 is ESEM (SEM) figure of organic precursor nanofiber obtained in embodiment 1; Fig. 2 and Fig. 3 is respectively low power and high power ESEM (SEM) figure of nanofiber obtained in embodiment 1, and as can be seen from Figure, the nanofiber obtained is the full meso-hole structure of high-purity; Fig. 4, Fig. 5 are X-ray diffractogram (XRD) and the regional enlarged drawing of nanofiber obtained in embodiment 1, show that prepared full meso-porous nano fiber is TiO from figure
2/ CuO/Cu composite nano fiber; Fig. 6 is transmission electron microscope (TEM) figure of the single nanofiber of the nanofiber that embodiment 1 obtains, and again illustrates prepared nanofiber and has full meso-hole structure; Fig. 7 is the elemental line scan picture that the obtained nanofiber of embodiment 1 is corresponding, shows that the full meso-porous nano fiber prepared is made up of Ti, O and Cu tri-kinds of elements; Fig. 8 is the corresponding high-resolution-ration transmission electric-lens of nanofiber (HRTEM) figure that embodiment 1 obtains, and shows the lattice fringe of three kinds of different spacing, corresponds respectively to TiO
2, CuO and Cu crystal structure, confirm that prepared full meso-porous nano fiber is TiO
2/ CuO/Cu composite nano fiber; Fig. 9 is x-ray photoelectron power spectrum (XPS) collection of illustrative plates of the obtained nanofiber of embodiment 1, again illustrates prepared material and is made up of Ti, O and Cu tri-kinds of elements; Figure 10 is the high-resolution XPS collection of illustrative plates of Cu2p, and show that Cu coexists with CuO and Cu two kinds of forms, the photocatalyst material namely prepared is TiO
2/ CuO/Cu composite nano fiber; Figure 11 is the N of nanofiber obtained in embodiment 1
2adsorption desorption curve and pore size distribution curve (illustration), further demonstrate that the nanofiber prepared exists mesoporous, and its specific area and aperture averaging value are respectively 19.6m
2/ g and 34.8nm.
Figure 12 is ESEM (SEM) figure of organic precursor nanofiber obtained in comparative example 1; Figure 13 is ESEM (SEM) figure of the nanofiber that comparative example 1 obtains, and shows that the nanofiber prepared is not for having obvious pore structure from figure; Figure 14 is X-ray diffraction (XRD) figure of the nanofiber that comparative example 1 obtains, and shows that the nanofiber obtained is TiO from figure
2/ Cu composite; Figure 15 is the TiO that comparative example 1 of the present invention obtains
2/ Cu nanofiber N
2adsorption desorption curve and pore size distribution curve, further demonstrate that obtained nanofiber specific area is lower, its specific area and aperture averaging value are respectively 13.3m
2/ g and 6.1nm.
Comparing embodiment 1 and comparative example 1, comparison diagram 1-11 and Figure 12-15, known: when not adding blowing agent DIPA in initial feed, be the common atresia TiO that specific area is lower finally by the nanofiber prepared by calcining
2/ CuO nanofiber, what blowing agent was described adds the structure and its constituent that affect final fiber, has the full meso-hole structure TiO of high-purity for preparation
2/ CuO/Cu nano-fiber material is most important.
Figure 16 is ESEM (SEM) figure of organic precursor nanofiber obtained in comparative example 2; Figure 17 is ESEM (SEM) figure of the nanofiber that comparative example 2 obtains, and shows that the nanofiber prepared is not for having obvious pore structure from figure; Figure 18 is X-ray diffraction (XRD) figure of the nanofiber that comparative example 2 obtains, and shows that the nanofiber prepared is TiO from figure
2/ CuO composite; Figure 19 is the TiO that comparative example 2 obtains
2/ CuO nanofiber N
2adsorption desorption curve and pore size distribution curve, further demonstrate that obtained nanofiber exists mesoporous, and its specific area and aperture averaging value are respectively 24.8m
2/ g and 24.4nm.
Comparing embodiment 1 and comparative example 2, comparison diagram 1-11 and Figure 16-19, known: when adding a small amount of copper acetate in initial feed, be TiO finally by the nanofiber prepared by calcining
2the full meso-porous nano fiber of/CuO, the final fibrous composition of introduction volume impact of copper acetate is described, the introduction volume of regulation and control copper acetate has the full meso-hole structure TiO of high-purity for preparation
2/ CuO/Cu nano-fiber material is most important.
Figure 20 is ESEM (SEM) figure of organic precursor nanofiber obtained in comparative example 3; Figure 21 is ESEM (SEM) figure of the nanofiber that comparative example 3 obtains, and shows that the nanofiber prepared is not for having obvious pore structure from figure; Figure 22 is X-ray diffraction (XRD) figure of the nanofiber that comparative example 3 obtains, and shows that the nanofiber prepared is TiO from figure
2/ CuO/Cu composite; Figure 23 be the obtained nanofiber of comparative example 3 N
2adsorption desorption curve and pore size distribution curve, further demonstrate that obtained nanofiber exists mesoporous, and its specific area and aperture averaging value are respectively 13.6m
2/ g and 35.7nm.
Comparing embodiment 1 and comparative example 3, comparison diagram 1-11 and Figure 20-23, known: when adding more copper acetate in initial feed, be TiO finally by the nanofiber prepared by calcining
2the full meso-porous nano fiber of/CuO, its specific area decreases, and the final fibrous composition of introduction volume impact of copper acetate is described, the introduction volume of regulation and control copper acetate has the full meso-hole structure TiO of high-purity for preparation
2/ CuO/Cu nano-fiber material is most important.
Application Example 1
Take 0.05gTiO obtained in embodiment 1
2the full meso-porous nano fiber dispersion of/CuO/Cu is in the distilled water of 40ml, after ultrasonic disperse 15min, add the methyl alcohol of 10ml again as sacrifice agent, adopt 300W xenon lamp as analog light source, the hydrogen produced is detected by online gas chromatograph, detect once every 15min, after 5 hours, terminate test.
Contrast Application Example 1
In prior art, the P25 nano powder photocatalyst of business produces hydrogen at 300W xenon lamp as under analog light source, and the hydrogen of generation is detected by online gas chromatograph, detects once every 15min, terminates test after 5 hours.
Figure 24 is TiO of the present invention
2the full meso-porous nano fiber of/CuO/Cu, as the active comparison diagram of Photocatalyzed Hydrogen Production of photochemical catalyst and P25, illustrates TiO prepared by the present invention
2/ CuO/Cu full meso-porous nano fiber photocatalyst has more efficient hydrogen generation efficiency than P25 photochemical catalyst, and its hydrogen generation efficiency can improve more than 4 times.After a catalysis terminates, catalyst is leached, repeatedly recycles after washes clean.
Figure 25 is TiO of the present invention
2the full meso-porous nano fiber of/CuO/Cu circulates as the photochemical catalyst of photochemical catalyst and P25 and produces hydrogen Comparative result figure afterwards 3 times, and P25 obviously reduces its Photocatalyzed Hydrogen Production after three times recycle is active, and TiO
2the hydrogen output of/CuO/Cu full meso-porous nano fiber photocatalyst maintains a more constant value substantially, and TiO of the present invention is described
2/ CuO/Cu full meso-porous nano fiber has more stable photocatalysis performance as photochemical catalyst.
Specific embodiment described herein is only to the explanation for example of the present invention's spirit.Those skilled in the art can make various amendment or supplement or adopt similar mode to substitute to described specific embodiment, but can't depart from spirit of the present invention or surmount the scope that appended claims defines.
Claims (10)
1. high purity Ti O
2the application of the full meso-porous nano fiber of/CuO/Cu in photochemical catalyst, wherein the main component of nanofiber is Ti, O, Cu, and main forms is TiO
2, CuO, Cu, described nanofiber has loose structure, and the hole of described loose structure comprises mesoporous.
2. high purity Ti O according to claim 1
2the application of the full meso-porous nano fiber of/CuO/Cu in photochemical catalyst, is characterized in that, described nanofiber has loose structure and the hole of described loose structure is entirely mesoporous.
3. high purity Ti O according to claim 1
2the application of the full meso-porous nano fiber of/CuO/Cu in photochemical catalyst, is characterized in that, the specific area of described nanofiber is 15-40m
2/ g, aperture value is 30-45nm.
4. high purity Ti O according to claim 1
2the application of the full meso-porous nano fiber of/CuO/Cu in photochemical catalyst, it is characterized in that, described is applied as high purity Ti O
2/ CuO/Cu is complete there is catalytic reaction under light illumination in meso-porous nano fiber dispersion in decomposed substance, and wherein decomposed substance is moisture and material that is degradation material.
5. high purity Ti O according to claim 4
2the application of the full meso-porous nano fiber of/CuO/Cu in photochemical catalyst, is characterized in that, the volume ratio of described water and degradation material is 2-5:1.
6. high purity Ti O according to claim 4 or 5
2the application of the full meso-porous nano fiber of/CuO/Cu in photochemical catalyst, is characterized in that, described degradation material is organic.
7. high purity Ti O according to claim 6
2the application of the full meso-porous nano fiber of/CuO/Cu in photochemical catalyst, it is characterized in that, described organic matter is methyl alcohol.
8. the high purity Ti O according to claim arbitrary in claim 1-7
2the application of the full meso-porous nano fiber of/CuO/Cu in photochemical catalyst, is characterized in that, described TiO
2the preparation method of the full meso-porous nano fiber of/CuO/Cu comprises the steps:
Preparation spinning liquid as precursor;
Spinning liquid as precursor is carried out electrostatic spinning and obtains organic precursor nanofiber;
By organic precursor nanofiber through high-temperature calcination, TiO
2the full meso-porous nano fiber of/CuO/Cu.
9. high purity Ti O according to claim 8
2the application of the full meso-porous nano fiber of/CuO/Cu in photochemical catalyst, is characterized in that, TiO
2distance in the preparation method of the full meso-porous nano fiber of/CuO/Cu during electrostatic spinning between anode and negative electrode is 18cm-22cm, and high pressure is 18kV-22kV.
10. high purity Ti O according to claim 8
2the application of the full meso-porous nano fiber of/CuO/Cu in photochemical catalyst, is characterized in that, TiO
2described in the preparation method of the full meso-porous nano fiber of/CuO/Cu, the temperature of high-temperature calcination is 540-560 DEG C, and temperature retention time is 1-3h.
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