CN105032411A - High-purity TiO2 mesoporous nano fiber loaded with Ag - Google Patents
High-purity TiO2 mesoporous nano fiber loaded with Ag Download PDFInfo
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- CN105032411A CN105032411A CN201510386147.3A CN201510386147A CN105032411A CN 105032411 A CN105032411 A CN 105032411A CN 201510386147 A CN201510386147 A CN 201510386147A CN 105032411 A CN105032411 A CN 105032411A
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Abstract
The invention discloses a high-purity TiO2 mesoporous nano fiber loaded with Ag. Main composition elements of the high-purity TiO2 mesoporous nano fiber are Ti, O, and Ag, wherein Ti and O mainly exist in the high-purity TiO2 mesoporous nano fiber in the form of TiO2, and Ag is a doping element; the high-purity TiO2 mesoporous nano fiber possesses a porous structure; and the porous structure possesses mesoporous. A preparation method is simple; production is convenient; product quality stability is excellent; catalytic efficiency of the high-purity TiO2 mesoporous nano fiber in water photolysis is high; and performance is stable.
Description
Technical field
The present invention relates to a kind of inorganic semiconductor photoelectric material, particularly high-purity Ag load TiO
2full meso-porous nano fiber.
Background technology
TiO
2have stable chemical nature, nontoxic, the advantages such as abundant raw material source, are widely used in the various fields such as environmental protection, chemical industry, electrical equipment, solar cell, medicine.Wherein TiO
2the application of material in photocatalysis technology is one of focus of current research, as utilized TiO
2photocatalytic activity degradation water in organic pollution, sterilization, photolysis water hydrogen etc.But, pure phase TiO
2the photo-generate electron-hole that material produces in the process of light-catalyzed reaction is to very easily compound, and photocatalysis efficiency is lower.Given this, researchers have employed a lot of method to its modification, wherein pass through at TiO
2surface deposition Ag nano particle, both interfaces form Schottky barrier, and the metal A g nano particle of load, as electron trap, reduces the probability of photo-generate electron-hole to compound, thus reach the object improving its photocatalysis efficiency.At present, a large amount of research work has been had to modify TiO to Ag
2report, but existing synthetic method mostly concentrates on and makes Ag particle reduce and be carried on conventional Ti O by reducing agent and stabilizing agent
2the surface of nano-powder material, specific area is lower, and the size of loaded Ag nano particle can not finely regulating, and light absorpting ability is limited, Ag load TiO
2the superiority of composite can not get effective performance.And the TiO of full meso-hole structure
2the advantages such as nanofiber has high surface, and light absorpting ability is strong are a kind of desirable Ag load carriers structure candidates, at present about Ag load TiO
2the preparation of full meso-porous nano fiber have not been reported.
Meanwhile, TiO
2be study the most at present and the most promising photocatalyst material, can be applied under the exciting of efficient light sources and purify air, hydrogen production by water decomposition, sewage disposal, the light-catalyzed reaction fields such as sterilization.But, traditional TiO
2usually there is the shortcomings such as the low and poor stability of photocatalysis efficiency in photochemical catalyst, limits its practical application to a great extent.Therefore, TiO
2photocatalyst becomes the focal issue of current researchers' extensive concern, and main method concentrates on appearance structure and constituent optimization etc.The TiO of full meso-hole structure
2nanofiber photocatalyst has higher specific area and typical one dimension structure, and photocatalysis efficiency and stability obtain significantly to be improved, and becomes TiO
2the important research direction that photochemical catalyst appearance structure is optimized.But, pure phase TiO
2photochemical catalyst comprises TiO
2full meso-porous nano fiber photocatalyst has ultraviolet light response, and solar energy utilization ratio is very low, and photo-generate electron-hole is to very easily compound, still cannot be applied in actual production life.Research shows, Ag nano particle loads to TiO
2the surface of photochemical catalyst can its photoresponse scope of broadening and effectively suppress the compound in light induced electron and hole, at component modification TiO
2photochemical catalyst research field has been a great concern.Existing a large amount of research work modifies TiO to Ag
2report, but the Ag load TiO of existing preparation method synthesis
2photochemical catalyst is usually nano-powder structure, still there is the flaws such as the low and poor stability of specific area, makes Ag load TiO
2the superiority of composite can not get effective performance.Known if preparation Ag load TiO by analyzing above
2full meso-porous nano fiber photocatalyst will be overall to TiO from both direction
2photochemical catalyst is optimized and modification, its photocatalysis performance of cooperative reinforcing.Therefore, explore a kind of simple process means and prepare Ag load TiO
2full meso-porous nano fiber photocatalyst seems particularly always, for it provides scientific basis and technical support in the application of photocatalysis field.
Summary of the invention
For solving the problem, high-purity Ag load TiO disclosed by the invention
2full meso-porous nano fiber, technique is simple, and convenient for production, constant product quality is good, and nanofiber has the surface mesoporous structure of steady ordered, highly sensitive.
High-purity Ag load TiO disclosed by the invention
2full meso-porous nano fiber, the main component of nanofiber is Ti, O and Ag,
Described nanofiber has loose structure, and the hole of described loose structure comprises mesoporous;
Wherein the main forms of Ti, O element in nanofiber is TiO
2, Ag is that Payload element is formed in nanofiber surface or loose structure.
High-purity Ag load TiO disclosed by the invention
2the one of full meso-porous nano fiber is improved, and nanofiber has loose structure and the hole of loose structure is mesoporous.
High-purity Ag load TiO disclosed by the invention
2the one of full meso-porous nano fiber is improved, and the specific area with the nanofiber of meso-hole structure is 45-55m
2/ g, mesoporous aperture averaging is 3-20nm.
High-purity Ag load TiO disclosed by the invention
2the preparation method of full meso-porous nano fiber, comprises the steps,
1), the configuration of precursor spinning solution: polyvinylpyrrolidone, butyl titanate, diisopropyl azodiformate are dissolved in absolute ethyl alcohol and glacial acetic acid mixed solvent and form even precursor spinning solution;
2), precursor the fabricate of nanowires: by step 1) the precursor spinning solution that obtains obtains precursor nano wire through spinning;
3), the preparation of nano wire: by step 2) the precursor nano wire that obtains can obtain TiO through high-temperature calcination
2full meso-porous nano fiber;
4), light deposition loaded Ag nano particle: by step 3) TiO that obtains
2full meso-porous nano fiber is dispersed in solvent (deionized water or distilled water), containing soluble silver salt in solvent, after light deposition is carried out in illumination under stirring, obtains high-purity Ag load TiO through post processing
2full meso-porous nano fiber.
High-purity Ag load TiO disclosed by the invention
2the one of the preparation method of full meso-porous nano fiber is improved, step 2) in spinning liquid as precursor obtain precursor nano wire through electrostatic spinning, wherein the field intensity of electrostatic spinning is less than or equal to 1KV/cm.Electrostatic spinning is with the metal needle of syringe (injection needle) for anode, and reception wire netting is negative electrode, and injection speed (single tube injection speed, i.e. each injection needle) is 1mL/h.
High-purity Ag load TiO disclosed by the invention
2the one of the preparation method of full meso-porous nano fiber is improved, step 2) in the precursor nano wire that obtains also after super-dry process, carry out high-temperature calcination again, drying is treated to low temperature drying or room temperature is dried in the shade.
High-purity Ag load TiO disclosed by the invention
2the one of the preparation method of full meso-porous nano fiber is improved, and low temperature drying is that precursor nano wire carries out dry process in 8-14 hour at 50-80 DEG C.
High-purity Ag load TiO disclosed by the invention
2the one of the preparation method of full meso-porous nano fiber is improved, and room temperature is dried in the shade for precursor nano wire aeration-drying 16-24 hour at ambient temperature, and ventilation wind speed is 1-2m/s.
High-purity Ag load TiO disclosed by the invention
2the one of the preparation method of full meso-porous nano fiber is improved, step 3) in high-temperature calcination be that 1-3h is calcined in insulation at calcining heat 300-600 DEG C.Before reaching calcining heat during calcining, the programming rate of nano wire is 2-4 DEG C/min, to make the low-volatile produced in original or thermal histories fully volatilize, is conducive to nano wire and forms form compact and stable structure.
High-purity Ag load TiO disclosed by the invention
2the one of the preparation method of full meso-porous nano fiber is improved, step 3) in high-temperature calcination for carry out under air ambient.
High-purity Ag load TiO disclosed by the invention
2the one of the preparation method of full meso-porous nano fiber is improved, step 1) in spinning liquid as precursor configuration time with every 1gPVP for benchmark, PVP and 3-6g butyl titanate to be dissolved in jointly in absolute ethyl alcohol and glacial acetic acid mixed solvent uniformly (stirring after 6-8 hour) after solution, more same be that benchmark adds 0-2g diisopropyl azodiformate uniformly precursor spinning solution with PVP.
High-purity Ag load TiO disclosed by the invention
2the one of the preparation method of full meso-porous nano fiber is improved, step 4) in solvent silver soluble salinity with Ag
+count 0.05-0.5mol/L.
High-purity Ag load TiO disclosed by the invention
2the one of the preparation method of full meso-porous nano fiber is improved, step 4) in the light application time of light deposition be 1-5 hour (here radiation source can be natural daylight also can for other light source is as xenon lamp).
High-purity Ag load TiO
2the application of full meso-porous nano fiber in visible-light photocatalyst; Especially for photodissociation aquatic products hydrogen.
In the present invention program, PVP decomposes and volatilizees completely in the process of calcination processing; TBOT provides Ti source for TiO
2synthesis; DIPA is blowing agent, decomposes and discharge a large amount of object of gas realization to fibrous matrix pore-creating in the process of calcination processing; Soluble silver salt (silver nitrate as water-soluble) is silver-colored source (change silver salt addition, can realize the load capacity of Ag nano particle and the finely regulating of size), and the Nano silver grain produced after calcining and decomposing loads to TiO
2full meso-porous nano fiber surface.
High-purity Ag load TiO is achieved in the present invention
2the preparation of full meso-porous nano fiber, has operating procedure simply controlled, practical, be easy to realize suitability for industrialized production, Ag supporting nanofibres stay in grade, with low cost simultaneously, highly sensitive advantage, can realize the Effective Regulation of Ag nano particle load capacity and size; Ag load TiO
2full meso-porous nano fiber photocatalyst not only has the one-dimensional mesoporous structure of high-ratio surface, and metal A g load can expand TiO
2the compound of photoresponse scope and effectively suppression photo-generated carrier, cooperative reinforcing photocatalysis performance, has potential application prospect in photocatalysis field.
Accompanying drawing explanation
Low power ESEM (SEM) figure of the solid-state organic precursor nanofiber of Fig. 1 obtained by the embodiment of the present invention one;
High power ESEM (SEM) figure of the solid-state organic precursor nanofiber of Fig. 2 obtained by the embodiment of the present invention one; ;
The TiO of Fig. 3 obtained by the embodiment of the present invention one
2low power ESEM (SEM) figure of full meso-porous nano fiber;
The TiO of Fig. 4 obtained by the embodiment of the present invention one
2high power ESEM (SEM) figure of full meso-porous nano fiber;
The TiO of Fig. 5 obtained by the embodiment of the present invention one
2n2 adsorption-desorption curve the figure of full meso-porous nano fibrous material;
The TiO of Fig. 6 obtained by the embodiment of the present invention one
2the graph of pore diameter distribution of full meso-porous nano fibrous material;
The Ag load TiO of Fig. 7 obtained by the embodiment of the present invention one
2low power ESEM (SEM) figure of full meso-porous nano fibrous material, illustration is the grain size distribution of Ag nano particle;
The Ag load TiO of Fig. 8 obtained by the embodiment of the present invention one
2high power ESEM (SEM) figure of full meso-porous nano fibrous material;
The Ag load TiO of Fig. 9 obtained by the embodiment of the present invention one
2x-ray diffraction (XRD) figure of full meso-porous nano fibrous material;
The Ag load TiO of Figure 10 obtained by the embodiment of the present invention one
2(EDS schemes the element power spectrum of full meso-porous nano fibrous material;
The Ag load TiO of Figure 11 obtained by the embodiment of the present invention two
2low power ESEM (SEM) figure of full meso-porous nano fibrous material, illustration is the grain size distribution of Ag nano particle;
The Ag load TiO of Figure 12 obtained by the embodiment of the present invention two
2high power ESEM (SEM) figure of full meso-porous nano fibrous material;
The Ag load TiO of Figure 13 obtained by the embodiment of the present invention two
2(EDS schemes the element power spectrum of full meso-porous nano fibrous material;
The Ag load TiO of Figure 14 obtained by the embodiment of the present invention three
2low power ESEM (SEM) figure of full meso-porous nano fibrous material, illustration is the grain size distribution of Ag nano particle;
The Ag load TiO of Figure 15 obtained by the embodiment of the present invention three
2high power ESEM (SEM) figure of full meso-porous nano fibrous material;
The Ag load TiO of Figure 16 obtained by the embodiment of the present invention three
2(EDS schemes the element power spectrum of full meso-porous nano fibrous material;
The Ag load TiO of Figure 17 obtained by the embodiment of the present invention one
2high-resolution-ration transmission electric-lens (HRTEM) figure of full meso-porous nano nanofiber photocatalyst;
The Ag load TiO of Figure 18 obtained by the embodiment of the present invention one
2x-ray photoelectron power spectrum (XPS) figure of full meso-porous nano nanofiber photocatalyst;
The Ag load TiO of Figure 19 obtained by the embodiment of the present invention one
2x-ray photoelectron power spectrum (the high-resolution XPS of the Ag3d) figure of full meso-porous nano nanofiber photocatalyst;
The Ag load TiO of Figure 20 obtained by the embodiment of the present invention one
2the uv-visible absorption spectra figure of full meso-porous nano nanofiber photocatalyst;
The Ag load TiO of Figure 21 obtained by the embodiment of the present invention one
2the comparison diagram of the hydrogen yield of full meso-porous nano nanofiber photocatalyst.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, illustrate the present invention further, following detailed description of the invention should be understood and be only not used in for illustration of the present invention and limit the scope of the invention.
In following examples, with high-purity Ag load TiO
2when full meso-porous nano fiber is as photochemical catalyst, its test condition is: the xenon source of 300W is visible light source (simulated solar light source); Taking the photochemical catalyst 0.05g that the present invention program obtains is scattered in the distilled water of 40ml, and after ultrasonic disperse 15min, then the methyl alcohol adding 10ml is as sacrifice agent, the hydrogen manufacturing of photodissociation distilled water; Detect at interval of set time (15min) sampling in reaction, 5 as a child terminated test.
Embodiment one
Take polyvinylpyrrolidone (PVP) 0.7g and butyl titanate (TBOT) 4.0g is dissolved in the mixed liquor of 7ml absolute ethyl alcohol and 3ml glacial acetic acid, stirred at ambient temperature adds 0.4g diisopropyl azodiformate (blowing agent, DIPA) after mixing 10 hours continues stirring and obtains spinning liquid as precursor in 1 hour.Measure in 6ml injected plastic needle tubing after being left standstill by spinning solution liquid, and be placed on micro-injection pump, arranging injection speed is 1ml/h.Metal needle makes Electrospun anode, and the negative electrode receiving material made by wire netting, and the distance between anode and negative electrode is 20cm, under 15kV high pressure, carry out electrostatic spinning, prepares organic precursor fibrous material.Then organic precursor fibrous material is placed in 60 DEG C of constant temp. drying boxes, obtains solid-state organic precursor fiber (Fig. 1 and Fig. 2).Finally SOLID ORGANIC presoma is placed in quartz boat, within 2 hours, carries out calcination processing in 550 DEG C of insulations in air atmosphere, then cool with stove.The typical scan Electronic Speculum (SEM) of prepared nano-fiber material under different amplification as shown in Figure 3 and Figure 4, shows that prepared material is the nanofiber of the full meso-hole structure of high-purity; Fig. 5 is that the N of the nanofiber of prepared full meso-hole structure adsorbs adsorption desorption curve, and analyzing its specific surface area value is as calculated 61.7m
2/ g.Fig. 6 is the pore size distribution curve of its correspondence, shows that average pore size value is 12.5nm, confirms the mesoporous structure of synthesized material.By prepared TiO
2full meso-porous nano fiber dispersion is in the deionized water of 50ml, and subsequently, the silver nitrate of about 1.0g joins in above-mentioned suspension and makes Ag
+concentration 0.12mol/L, carries out illumination 2h under the condition of Keep agitation, after centrifugal, filtration, drying, obtain Ag load TiO
2eSEM (SEM) figure is as shown in Figure 7 and Figure 8 under difference is amplified in different amplification for meso-porous nano fiber, observe and have a large amount of particles to be attached to surface on the surface of fiber, synthesized composite nano fiber still has typical full meso-hole structure, and after load silver, the specific surface area value of nanofiber is 39.8m
2/ g, average pore size is 20.4nm, and specific area diminishes here is because nanofiber surface hole is blocked by Nano Silver, and average pore size increase is simultaneously because less hole is covered by Nano Silver, and average pore size increases thus.Illustration in Fig. 7 is the grain size distribution of Ag nano particle, and the known average grain diameter of computational analysis is 23.5nm.Fig. 9 is X-ray diffraction (XRD) collection of illustrative plates of composite, and the contrast standard PDF card crystal structure of analyzing known material is by the Ag of Emission in Cubic and Anatase TiO
2composition, the material synthesized by proving is Ag load TiO
2full meso-porous nano fiber.Figure 10 is Ag load TiO
2energy spectrogram (EDS) of full meso-porous nano fiber, primarily of Ti, O and Ag element composition, the atomic ratio of Ag element is 0.74at%.Figure 17 is high-resolution-ration transmission electric-lens (HRTEM) figure of photocatalyst material of preparation, shows two kinds of dissimilar lattice fringes, belongs to anatase TiO respectively by analysis
2with Emission in Cubic Ag, and Ag nano particle is carried on TiO firmly
2on matrix.The high-resolution XPS that Figure 18 and Figure 19 is respectively x-ray photoelectron power spectrum (XPS) figure and Ag3d of photocatalyst material schemes, and again illustrate material and be made up of Ti, O and Ag tri-kinds of elements, and the valence state of Ag is 0 valency, i.e. the existence of simple substance Ag.
Ag load TiO prepared by the present embodiment
2full meso-porous nano fiber photocatalyst is applied to photocatalysis hydrogen production, and with the TiO of non-load
2full meso-porous nano fiber photocatalyst contrast.Before detector photocatalytic activity, detailed characterizations is done to the light absorption situation of photochemical catalyst.Figure 20 is uv-visible absorption spectra figure, compares non-loaded optic catalyst, and the absworption peak of about 500nm is attributable to the plasma resonance effect absworption peak of ball-type Ag nano particle, and Ag load TiO is described
2full meso-porous nano fiber photocatalyst has the photoresponse scope widened.Subsequently, the photochemical catalyst 0.05g taking preparation is scattered 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 simulated solar light source, the hydrogen produced is detected by online gas chromatograph, detects once every 15min, terminates test after 5 hours.Figure 21 is the comparison diagram of hydrogen yield, compares non-load TiO
2full meso-porous nano fiber photocatalyst, Ag load TiO prepared by the present invention
2full meso-porous nano fiber have significantly strengthening photocatalysis performance, hydrogen generation efficiency can improve more than 4 times.
Embodiment two
TiO
2the preparation of full meso-porous nano fiber with embodiment one, by prepared TiO
2full meso-porous nano fiber dispersion in the deionized water of 50ml, subsequently, the AgNO of about 2.0g
3join in above-mentioned suspension and make Ag
+concentration 0.24mol/L, carries out illumination 2h under the condition of Keep agitation, after centrifugal, filtration, drying, obtain Ag load TiO
2eSEM (SEM) figure is as is illustrated by figs. 11 and 12 under difference is amplified in different amplification for meso-porous nano fiber.Illustration in Figure 11 is the grain size distribution of Ag nano particle, and analytical calculation is known, and average grain diameter is 42.8nm.Figure 13 is Ag load TiO
2energy spectrogram (EDS) of full meso-porous nano fiber, primarily of Ti, O and Ag element composition, and the atomic ratio of Ag element is 1.26at%; The result of comparative example one is known, at AgNO
3amount when being increased to 2.0g, the load capacity of Ag obviously increases, and nanoparticle size increases, and AgNO is described
3addition to the load capacity of final Ag nano particle and size most important.
Ag load TiO prepared by the present embodiment
2full meso-porous nano fiber photocatalyst is applied to photocatalysis hydrogen production, and with the TiO of non-load
2full meso-porous nano fiber photocatalyst contrast.Before detector photocatalytic activity, detailed characterizations is done to the light absorption situation of photochemical catalyst.Detect through uv-visible absorption spectra, compare non-loaded optic catalyst, the absworption peak of about 500nm is attributable to the plasma resonance effect absworption peak of ball-type Ag nano particle, and Ag load TiO is described
2full meso-porous nano fiber photocatalyst has the photoresponse scope widened.Subsequently, the photochemical catalyst 0.05g taking preparation is scattered in the distilled water of 40ml, and after ultrasonic disperse 15min, then the methyl alcohol adding 10ml is as sacrifice agent.Adopt 300W xenon lamp as simulated solar light source, the hydrogen of generation is detected by online gas chromatograph, detects once every 15min, terminates test after 5 hours.Both contrasts hydrogen yield, compares non-load TiO
2full meso-porous nano fiber photocatalyst, Ag load TiO prepared by the present invention
2full meso-porous nano fiber have significantly strengthening photocatalysis performance, hydrogen generation efficiency can improve more than 4 times.
Embodiment three
TiO
2the preparation of full meso-porous nano fiber with embodiment one, by prepared TiO
2full meso-porous nano fiber dispersion in the deionized water of 50ml, subsequently, the AgNO of about 3.0g
3join in above-mentioned suspension and make Ag
+concentration 0.36mol/L, carries out illumination 2h under the condition of Keep agitation, after centrifugal, filtration, drying, obtain Ag load TiO
2eSEM (SEM) figure is as shown in Figure 14 and Figure 15 under difference is amplified in different amplification for meso-porous nano fiber.Illustration in Figure 14 is the grain size distribution of Ag nano particle, and analytical calculation is known, and average grain diameter is 68.9nm.Figure 16 is Ag load TiO
2energy spectrogram (EDS) of full meso-porous nano fiber, primarily of Ti, O and Ag element composition, and the atomic ratio of Ag element is 2.14at%; The result of comparative example one and embodiment two is known, at AgNO
3concentration when being increased to 0.24mol/L and 0.36mol/L, the load capacity of Ag increases further, and the particle size of loaded Ag also increases again, illustrates by changing AgNO
3addition, can realize the load capacity of Ag nano particle and the Effective Regulation of size.
Ag load TiO prepared by the present embodiment
2full meso-porous nano fiber photocatalyst is applied to photocatalysis hydrogen production, and with the TiO of non-load
2full meso-porous nano fiber photocatalyst contrast.Before detector photocatalytic activity, detailed characterizations is done to the light absorption situation of photochemical catalyst.Detect through uv-visible absorption spectra, compare non-loaded optic catalyst, the absworption peak of about 500nm is attributable to the plasma resonance effect absworption peak of ball-type Ag nano particle, and Ag load TiO is described
2full meso-porous nano fiber photocatalyst has the photoresponse scope widened.Subsequently, the photochemical catalyst 0.05g taking preparation is scattered 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 simulated solar light source, the hydrogen produced is detected by online gas chromatograph, detects once every 15min, terminates test after 5 hours.Both contrasts hydrogen yield, compares non-load TiO
2full meso-porous nano fiber photocatalyst, Ag load TiO prepared by the present invention
2full meso-porous nano fiber have significantly strengthening photocatalysis performance, hydrogen generation efficiency can improve more than 4 times.
Embodiment four
Take polyvinylpyrrolidone (PVP) 1g 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 adds 1g diisopropyl azodiformate (blowing agent, DIPA) and continues stirring and obtains spinning liquid as precursor in 1 hour after mixing 7 hours.Measure in 6ml injected plastic needle tubing after being left standstill by spinning solution liquid, and be placed on micro-injection pump, arranging injection speed (single tube injection speed) is 0.87ml/h.Metal needle makes Electrospun anode, and the negative electrode receiving material made by wire netting, and the distance between anode and negative electrode is 20cm, carries out electrostatic spinning, prepare organic precursor fibrous material under 19kV high pressure (electrostatic field intensity 0.95KV/cm).Then be placed in by organic precursor fibrous material in 50 DEG C of constant temp. drying boxes, drying time 8 hours, obtains solid-state organic precursor fiber.Finally SOLID ORGANIC presoma is placed in quartz boat, (now can to control nanowire surface programming rate be 2,2.7,3,3.2,4 DEG C/min and 2-4 DEG C/min within the scope of other arbitrary value) within 2 hours, carry out calcination processing in 550 DEG C of insulations in air atmosphere, then cool with stove, obtain nano wire, its specific area and aperture value are distributed as 45m after testing
2/ g and 5.3nm.By prepared TiO
2full meso-porous nano fiber takes 0.5g and is scattered in the deionized water of 50ml, subsequently, and AgNO
3join in above-mentioned suspension and obtain Ag
+the reactant liquor of concentration 0.4mol/L, carries out illumination 2h under the condition of Keep agitation, after centrifugal, filtration, drying, obtain Ag load TiO
2meso-porous nano fiber, the load capacity of Nano Silver on nanofiber is 2.41at%.The present embodiment catalyst, detecting catalyst photolysis water hydrogen under equal conditions, with non-load TiO
2full meso-porous nano fiber photocatalyst, hydrogen generation efficiency can improve more than 4 times.
Embodiment five
Take polyvinylpyrrolidone (PVP) 1g and butyl titanate (TBOT) 3.5g is dissolved in the mixed liquor of 7ml absolute ethyl alcohol and 3ml glacial acetic acid, stirred at ambient temperature adds 2g diisopropyl azodiformate (blowing agent, DIPA) and continues stirring and obtains spinning liquid as precursor in 1.2 hours after mixing 6 hours.Measure in 6ml injected plastic needle tubing after being left standstill by spinning solution liquid, and be placed on micro-injection pump, arranging injection speed (single tube injection speed) is 0.93ml/h.Metal needle makes Electrospun anode, and the negative electrode receiving material made by wire netting, and the distance between anode and negative electrode is 20cm, carries out electrostatic spinning, prepare organic precursor fibrous material under 18kV high pressure (electrostatic field intensity 0.9KV/cm).Then be placed in by organic precursor fibrous material in 80 DEG C of constant temp. drying boxes, drying time 14 hours, obtains solid-state organic precursor fiber.Finally SOLID ORGANIC presoma is placed in quartz boat, within 2 hours, carries out calcination processing in air atmosphere in 550 DEG C of insulations, then with stove cooling, obtain nano wire, its specific area and aperture value are distributed as 55m after testing
2/ g and 3nm.By prepared TiO
2full meso-porous nano fiber takes 0.5g and is scattered in the deionized water of 50ml, subsequently, and AgNO
3join in above-mentioned suspension and obtain Ag
+the reactant liquor of concentration 0.1mol/L, carries out illumination 2.5h under the condition of Keep agitation, after centrifugal, filtration, drying, obtain Ag load TiO
2meso-porous nano fiber, the load capacity of Nano Silver on nanofiber is 0.52at%.The present embodiment catalyst, detecting catalyst photolysis water hydrogen under equal conditions, with non-load TiO
2full meso-porous nano fiber photocatalyst, hydrogen generation efficiency can improve more than 2 times.
Embodiment six
Take polyvinylpyrrolidone (PVP) 1g and butyl titanate (TBOT) 4.3g is dissolved in the mixed liquor of 7ml absolute ethyl alcohol and 3ml glacial acetic acid, stirred at ambient temperature adds 1.4g diisopropyl azodiformate (blowing agent, DIPA) and continues stirring and obtains spinning liquid as precursor in 1.5 hours after mixing 7.3 hours.Measure in 6ml injected plastic needle tubing after being left standstill by spinning solution liquid, and be placed on micro-injection pump, arranging injection speed (single tube injection speed) is 0.75ml/h.Metal needle makes Electrospun anode, and the negative electrode receiving material made by wire netting, and the distance between anode and negative electrode is 20cm, carries out electrostatic spinning, prepare organic precursor fibrous material under 17kV high pressure (electrostatic field intensity 0.85KV/cm).Then be placed in by organic precursor fibrous material in 70 DEG C of constant temp. drying boxes, drying time 10 hours, obtains solid-state organic precursor fiber.Finally SOLID ORGANIC presoma is placed in quartz boat, within 2 hours, carries out calcination processing in air atmosphere in 550 DEG C of insulations, then with stove cooling, obtain nano wire, its specific area and aperture value are distributed as 52.3m after testing
2/ g and 3nm.By prepared TiO
2full meso-porous nano fiber takes 0.5g and is scattered in the deionized water of 50ml, subsequently, and AgNO
3join in above-mentioned suspension and obtain Ag
+the reactant liquor of concentration 0.05mol/L, carries out illumination 5h under the condition of Keep agitation, after centrifugal, filtration, drying, obtain Ag load TiO
2meso-porous nano fiber, the load capacity of Nano Silver on nanofiber is 0.35at%.The present embodiment catalyst, detecting catalyst photolysis water hydrogen under equal conditions, with non-load TiO
2full meso-porous nano fiber photocatalyst, hydrogen generation efficiency can improve more than 1.5 times.
Embodiment seven
Take polyvinylpyrrolidone (PVP) 1g and butyl titanate (TBOT) 6.0g is dissolved in the mixed liquor of 7ml absolute ethyl alcohol and 3ml glacial acetic acid, stirred at ambient temperature adds 0.3g diisopropyl azodiformate (blowing agent, DIPA) and continues stirring and obtains spinning liquid as precursor in 1.7 hours after mixing 6.2 hours.Measure in 6ml injected plastic needle tubing after being left standstill by spinning solution liquid, and be placed on micro-injection pump, arranging injection speed (single tube injection speed) is 0.9ml/h.Metal needle makes Electrospun anode, and the negative electrode receiving material made by wire netting, and the distance between anode and negative electrode is 20cm, carries out electrostatic spinning, prepare organic precursor fibrous material under 16kV high pressure (electrostatic field intensity 0.8KV/cm).Then be placed in by organic precursor fibrous material in 70 DEG C of constant temp. drying boxes, drying time 9 hours, obtains solid-state organic precursor fiber.Finally SOLID ORGANIC presoma is placed in quartz boat, within 2 hours, carries out calcination processing in air atmosphere in 550 DEG C of insulations, then with stove cooling, obtain nano wire, its specific area and aperture value are distributed as 50.7m after testing
2/ g and 15.5nm.By prepared TiO
2full meso-porous nano fiber takes 0.5g and is scattered in the deionized water of 50ml, subsequently, and AgNO
3join in above-mentioned suspension and obtain Ag
+the reactant liquor of concentration 0.5mol/L, carries out illumination 1h under the condition of Keep agitation, after centrifugal, filtration, drying, obtain Ag load TiO
2meso-porous nano fiber, the load capacity of Nano Silver on nanofiber is 1.87at% after testing.The present embodiment catalyst, detecting catalyst photolysis water hydrogen under equal conditions, with non-load TiO
2full meso-porous nano fiber photocatalyst, hydrogen generation efficiency can improve more than 4 times.
Embodiment eight
Take polyvinylpyrrolidone (PVP) 1g and butyl titanate (TBOT) 5.2g is dissolved in the mixed liquor of 7ml absolute ethyl alcohol and 3ml glacial acetic acid, stirred at ambient temperature adds 0.8g diisopropyl azodiformate (blowing agent, DIPA) and continues stirring and obtains spinning liquid as precursor in 1.9 hours after mixing 5.9 hours.Measure in 6ml injected plastic needle tubing after being left standstill by spinning solution liquid, and be placed on micro-injection pump, arranging injection speed (single tube injection speed) is 0.8ml/h.Metal needle makes Electrospun anode, and the negative electrode receiving material made by wire netting, and the distance between anode and negative electrode is 20cm, carries out electrostatic spinning, prepare organic precursor fibrous material under 15kV high pressure (electrostatic field intensity 0.75KV/cm).Then by the aeration-drying 16 at ambient temperature of organic precursor fibrous material (the aeration-drying time can also be other arbitrary value in 17,17.5,18,18.3,19.6,19,20,20.2,21,21.7,22,22.4,23,23.9,24 hours and 16-24 hours window) hour, ventilation wind speed is 1m/s (is nanowire surface wind speed, excessive easily blowing flies, 1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9, other arbitrary value within the scope of 2m/s and 1-2m/s), obtain solid-state organic precursor fiber.Finally SOLID ORGANIC presoma is placed in quartz boat, in 550 DEG C (rutile-types), (calcining heat can also be 300 (Detitanium-ore-types) in air atmosphere, 350 (Detitanium-ore-types), 400 (Detitanium-ore-types), 450 (80v/v% Detitanium-ore-types), 500 (80v/v% Detitanium-ore-types), 600 (rutile-types), 340 (80v/v% Detitanium-ore-types), 370 (Detitanium-ore-types), 420 (23v/v% Detitanium-ore-types), 480 (30v/v% Detitanium-ore-types), 530 (80v/v% Detitanium-ore-types), other arbitrary value within the scope of 590 DEG C (90v/v% rutile-types) and 300-600 DEG C) be incubated 2 hours and carry out calcination processing, then cool with stove, obtain nano wire, its specific area and aperture value are distributed as 54.1m after testing
2/ g and 14.2nm.By prepared TiO
2full meso-porous nano fiber takes 0.5g and is scattered in the deionized water of 50ml, subsequently, and AgNO
3join in above-mentioned suspension and obtain Ag
+the reactant liquor of concentration 0.3mol/L, carries out illumination 4h under the condition of Keep agitation, after centrifugal, filtration, drying, obtain Ag load TiO
2meso-porous nano fiber, the load capacity of Nano Silver on nanofiber is 1.08at% after testing.The present embodiment catalyst, detecting catalyst photolysis water hydrogen under equal conditions, with non-load TiO
2full meso-porous nano fiber photocatalyst, hydrogen generation efficiency can improve more than 3 times.
There is important impression by the content of silver in the visible catalyst of embodiment 1-8 to catalysis above, making to improve on the basis of silver-colored load capacity, catalysis photolytic efficiency can improved comparatively significantly.
The high-purity Ag load TiO obtained after calcining in the embodiment that the present invention is not exhaustive
2full meso-porous nano fiber after testing its specific area and aperture value be distributed as 45.1,45.8,46.3,46.9,47.4,47.5,48.3,48.7,49.2,49.4,50.3,50.6,51.2,51.6,52.4,52.7,53.5,53.6,54.3,54.8m
2/ g and 45-55m
2other arbitrary value and 3.1 within the scope of/g, 3.5,4.2,4.4,5.1,5.7,6.4,6.9,7.3,7.8,8.3,8.9,9.5,9.6,10.2,10.3,11.4,11.8,12.1,12.7,13.2,13.9,14.7,14.8,15.5,15.6,16.4,16.5,17.1,17.7,18.3,18.9,19.2, other arbitrary value within the scope of 19.3nm and 3-20nm.The field intensity of electrostatic spinning can also be 0.7,0.65,0.6,0.55,0.5,0.45,0.4KV/cm and other arbitrary value field intensity electrostatic field that is less than 1KV/cm carries out spinning.The loading content of Ag in nanofiber can also be 0.41at%, 0.51at%, 0.571at%, 0.62at%, 0.68at%, 0.71at%, 0.79at%, 0.82at%, 0.86at%, 0.94at%, 0.99at%, 1.01at%, 1.07at%, 1.12at%, 1.16at%, 1.22at%, 1.27at%, 1.34at%, 1.35at%, 1.48at%, 1.52at%, 1.57at%, 1.6at%, 1.65at%, 1.75at%, 1.78at%, 1.82at%, 1.87at%, 1.91at%, 1.93at%, 2at%, 2.03at%, 2.07at%, 2.11at%, 2.12at%, 2.22at%, 2.29at%, 2.31at%, 2.36at%, other arbitrary value within the scope of 2.40at% and 0.35-2.41at%.When silver nano-grain load capacity is less, its effect as catalysis is poor, and catalytic efficiency obviously declines, and not only causes the increase of Catalyst Production cost when silver nano-grain load capacity is excessive, also can hinder the carrying out of catalytic action significantly, to high-quality catalyst realize unfavorable.
The technical scope midrange non-limit part that this place embodiment is protected application claims and in embodiment technical scheme to the new technical scheme that the equal replacement of single or multiple technical characteristic is formed; equally all in the scope of protection of present invention; and between all parameters related to of the present invention program if not otherwise specified, then there is not interchangeable unique combinations each other.
Technological means disclosed in the present invention program is not limited only to the technological means disclosed in above-mentioned technological means, also comprises the technical scheme be made up of above technical characteristic.The above is the specific embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (9)
1. high-purity Ag load TiO
2full meso-porous nano fiber, is characterized in that: the main component of described nanofiber is Ti, O and Ag,
Described nanofiber has loose structure, and the hole of described loose structure comprises mesoporous;
Wherein the main forms of Ti, O element in nanofiber is TiO
2, Ag is that Payload element is formed in nanofiber surface or loose structure.
2. high-purity Ag load TiO according to claim 1
2full meso-porous nano fiber, is characterized in that: described nanofiber has loose structure and the hole of described loose structure is mesoporous.
3. high-purity Ag load TiO according to claim 1 and 2
2full meso-porous nano fiber, is characterized in that: described in there is the nanofiber of meso-hole structure specific area be 45-55m
2/ g, mesoporous aperture averaging is 3-20nm.
4. high-purity Ag load TiO according to claim 1
2full meso-porous nano fiber, is characterized in that: described high-purity Ag load TiO
2the preparation method of full meso-porous nano fiber comprises the steps,
1), the configuration of precursor spinning solution: polyvinylpyrrolidone, butyl titanate, diisopropyl azodiformate are dissolved in absolute ethyl alcohol and glacial acetic acid mixed solvent and form even precursor spinning solution;
2), precursor the fabricate of nanowires: by step 1) the precursor spinning solution that obtains obtains precursor nano wire through spinning;
3), the preparation of nano wire: by step 2) the precursor nano wire that obtains can obtain TiO through high-temperature calcination
2full meso-porous nano fiber;
4), light deposition loaded Ag nano particle: by step 3) TiO that obtains
2full meso-porous nano fiber is dispersed in solvent, containing soluble silver salt in solvent, after light deposition is carried out in illumination under stirring, obtains high-purity Ag load TiO through post processing
2full meso-porous nano fiber.
5. high-purity Ag load TiO according to claim 4
2full meso-porous nano fiber, is characterized in that: described step 2) in spinning liquid as precursor obtain precursor nano wire through electrostatic spinning, wherein the field intensity of electrostatic spinning is less than or equal to 1KV/cm.
6. high-purity Ag load TiO according to claim 4
2full meso-porous nano fiber, is characterized in that: described step 2) in the precursor nano wire that obtains also after super-dry process, carry out high-temperature calcination again, drying is treated to low temperature drying or room temperature is dried in the shade.
7. high-purity Ag load TiO according to claim 4
2full meso-porous nano fiber, it is characterized in that: described step 1) in spinning liquid as precursor configuration time with every 1gPVP for benchmark, PVP and 3-6g butyl titanate to be dissolved in jointly in absolute ethyl alcohol and glacial acetic acid mixed solvent uniformly after solution, more same be that benchmark adds 0-2g diisopropyl azodiformate uniformly precursor spinning solution with PVP.
8. high-purity Ag load TiO according to claim 4
2full meso-porous nano fiber, is characterized in that: described step 4) in solvent silver soluble salinity with Ag
+count 0.05-0.13mol/L.
9. high-purity Ag load TiO according to claim 4
2full meso-porous nano fiber, is characterized in that: described step 4) in the light application time of light deposition be 1-4 hour.
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