CN103240084A - Titanium dioxide-silver nano-composite material and synthetic method thereof - Google Patents
Titanium dioxide-silver nano-composite material and synthetic method thereof Download PDFInfo
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- CN103240084A CN103240084A CN2013101697761A CN201310169776A CN103240084A CN 103240084 A CN103240084 A CN 103240084A CN 2013101697761 A CN2013101697761 A CN 2013101697761A CN 201310169776 A CN201310169776 A CN 201310169776A CN 103240084 A CN103240084 A CN 103240084A
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Abstract
The invention discloses a titanium dioxide-silver nano-composite material and a synthetic method thereof. The method comprises the following steps of: mixing arginine solution with the precursor solution dihydroxybis(ammoniumlactato)titanium of titanium to have reaction for a while; mixing the obtained titanium dioxide nano-particles and tyrosine with silver nitrate solution to have reaction for a while, and then performing centrifugal separation, freeze-drying and calcining, thus obtaining the titanium dioxide-silver nano-composite material. The synthetic method provided by the invention is simple, convenient and easy to implement, and moderate in reaction condition, and thus is a novel method for synthesizing the composite material.
Description
Technical field
The present invention relates to a kind of titanic oxide nano compound material and preparation method thereof, belong to the synthetic field of inorganic composite materials, can be applicable to the photocatalytic degradation pollutant, decomposition water, selective field of catalytic reactions.
Background technology
Titanic oxide material has obtained studying widely and using in photocatalysis field, for example is applied to decomposition water, degraded water body or airborne pollutant etc.Yet, because its wideer band gap (3.2eV) and higher electron-hole recombinations rate limit it to the utilization of visible light and the efficient of photochemical catalyst.Titanium dioxide-metal composite is a kind of common method of modifying, titanium dioxide-Jin for example, titanium dioxide-Yin, titanium dioxide-platinum etc.Gold and nano particle such as silver have surface plasma bulk effect (SPR effect), can with sunshine in the photon of corresponding energy produce resonance, strengthen the absorption of light, thereby the efficient of increase catalyst.Usually, the synthetic of titanium dioxide is synthetic by sol-gel process, need use poisonous reagent such as alcohols; Load such as gold on titanium dioxide, silver, metals such as platinum are by ultraviolet irradiation, strong reductant reduction etc. is comparatively finished under the exacting terms, therefore, develops a kind of synthetic method green non-poisonous in the aqueous solution and has good research and using value.
In nature, organism can utilize big molecule such as the protein in the body to induce the synthetic inorganic matter that specific function is arranged of inorganic precursor, and this phenomenon is called biomineralization.For example, the silicon cell membrane in the frustule, the tri-iron tetroxide magnetic corpusculum in the iron bacteria, the calcium carbonate shell of shell, the tooth in the human body, bone etc.These inorganic structures have very fine structure and special function, and are synthetic under the environment of normal temperature and pressure neutrality.Therefore, utilize biomineralization and biomimetic mineralization to come the synthesizing inorganic thing, and inorganic composite materials, be a kind of novelty, green, easy method.By research, the protein in the discovery organism or polypeptide be template and the catalyst of synthetic inorganic material often.The R5 polypeptide in the diatom for example, and the analog of R5 polypeptide, lysozyme, big molecule such as bovine serum albumin has been used to synthetic silica, titanium dioxide, calcium carbonate, inorganic material such as calcium phosphate are by regulation and control synthesis condition such as time, temperature, factors such as pH value can be controlled size and the pattern of synthetic material.And little minute subclass such as amino acid have played crucial effect as the basic composition unit of protein in biomineralization.Arginine, lysine have been used to synthetic silica, and tryptophan, tyrosine, phenylalanine have been used to synthetic golden nanometer particle.Therefore, utilize amino acid synthesis of titanium dioxide and titanium dioxide-metallic composite to provide a kind of new method for preparing inorganic composite materials.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing the bionical synthesis of titanium dioxide-argentum nano composite material of amino acid, and by the synthetic titanium dioxide-argentum nano composite material of this method.This method has the preparation condition gentleness, the characteristics that process stability is good and controllability is good.
The present invention is realized that by the following technical programs a kind of method of utilizing the bionical synthesis of titanium dioxide-argentum nano composite material of amino acid is characterized in that may further comprise the steps:
1) at room temperature, precursor solution two (2 hydroxy propanoic acid) two hydroxides two ammoniums of configuration arginine solution and titanium close the titanium aqueous solution (Ti-BALDH), make its concentration respectively at 0.1-0.5mol/L and 0.2-0.5mol/L, and 1:0.1 ~ 1:1 mixes stirring by volume, the centrifugal titanium dioxide nano-particle that obtains.
2) nano particle that step 1 is made is put into 1 ~ 10 mmol/L tyrosine solution of 50-200mL, and adding final concentration is 1 ~ 10 mmol/L liquor argenti nitratis ophthalmicus, regulates pH to 6 ~ 10, mix and stirred 12-48 hour, centrifugal, washing obtains titanium dioxide-silver composite nano particles.
3) after the nano particle washing drying that step 2 is made, 400 ~ 600 degrees centigrade of calcinings 0.5 ~ 3 hour, obtain titanium dioxide-silver composite nano particles.
The preparation method's that the present invention proposes advantage is: the preparation method is easy, mild condition, titanium dioxide nano-particle is Detitanium-ore-type in prepared titanium dioxide-argentum nano composite material, size is 100 ~ 800nm, the brilliant size of silver nanoparticle is 10 ~ 60nm, in photocatalysis field application prospect is arranged.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) photo of the Nano silver grain of embodiment 1 preparation.
Fig. 2 is transmission electron microscope (TEM) photo of the titanium dioxide-argentum nano composite material of embodiment 1 preparation.
Fig. 3 is ESEM (SEM) photo of the titanium dioxide-argentum nano composite material of embodiment 1 preparation.
Fig. 4 is X-ray diffraction (XRD) curve after the titanium dioxide-argentum nano composite material of embodiment 1 preparation is calcined.
The specific embodiment
Embodiment 1
Accurately take by weighing the 5.226g arginine, be dissolved in the 100mL deionized water, obtain the 0.3mol/L arginine solution, regulate pH=7.0 with red fuming nitric acid (RFNA); Accurately take by weighing 0.03624g tyrosine, be dissolved in the 100mL deionized water, obtain the 2mmol/L tyrosine solution, regulate pH=9.0 with red fuming nitric acid (RFNA); Get the Ti-BALDH of 25mL 2mol/L, with the deionized water dilution, be settled to 100mL, obtain the Ti-BALDH solution of 0.25 mol/L.Get the 20mL arginine solution, add 2mL Ti-BALDH solution, vigorous stirring 5 minutes obtains titanium dioxide nano-particle after 5000r/min is centrifugal.The nano particle that obtains is added in the tyrosine solution of 10mLpH=9.0, add the liquor argenti nitratis ophthalmicus of 1mL 10mM simultaneously, stirred 48 hours, 5000r/min is centrifugal, obtains titanium dioxide-silver composite nano particles after the washing.500oC in Muffle furnace calcined 2 hours with above-mentioned nano material, obtained titanium dioxide-Yin composite Nano photochemical catalyst.
Embodiment 2
Step is identical with embodiment 1, and difference is that the concentration of liquor argenti nitratis ophthalmicus is 20mM.
Embodiment 3
Step is identical with embodiment 1, and difference is that the concentration of liquor argenti nitratis ophthalmicus is 40mM.
Fig. 1 is transmission electron microscope (TEM) picture of the Nano silver grain of tyrosine preparation, and as can be seen from the figure, Nano silver grain is about 35nm.Fig. 2 is transmission electron microscope (TEM) picture of the titanium dioxide-argentum nano composite material of preparation, Fig. 3 is ESEM (SEM) picture of titanium dioxide-argentum nano composite material, this shows, spheroid about the synthetic about 400nm of titanium dioxide, in load on the titanium dioxide surface Nano silver grain about 35nm, constitute titanium dioxide-silver nanoparticle compound.Fig. 4 is X-ray diffraction (XRD) curve after titanium dioxide-argentum nano composite material of preparation is calcined, and this shows that synthetic titanium dioxide is anatase crystal, is conducive to light-catalyzed reaction.The mechanism of arginine synthesis of titanium dioxide is under neutrallty condition, arginine with positive charge can induce titanium precursor body synthesis of titanium dioxide; Phenolic hydroxyl group in the tyrosine has reproducibility at alkali condition, and the reduction silver ion is to silver-colored simple substance.This method is simple, and mild condition can provide example for the titanium dioxide-metal composite that synthesizes other, and synthetic compound is expected to be applied to the photocatalytic degradation pollutant, decomposition water, fields such as selective catalytic reaction.
Claims (6)
1. a titanium dioxide-silver composite nano particles is characterized in that titanium dioxide nano-particle is Detitanium-ore-type, and size is 100 ~ 800nm.
2. a titanium dioxide-silver composite nano particles as claimed in claim 1 is characterized in that the brilliant size of silver nanoparticle is 10 ~ 60nm.
3. the synthetic method as each described titanium dioxide-silver composite nano particles in claim 1 or 2 is characterized in that utilizing different amino acid synthetic at normal temperatures and pressures as derivant and reducing agent respectively.
4. a method as claimed in claim 3 is characterized in that utilizing arginine as derivant, utilizes tyrosine as reducing agent.
5. method as claimed in claim 4 is characterized in that may further comprise the steps:
1) at room temperature, precursor solution two (2 hydroxy propanoic acid) two hydroxides two ammoniums of configuration arginine solution and titanium close the titanium aqueous solution, make its concentration respectively at 0.1-0.5mol/L and 0.2-0.5mol/L, and 1:0.1 ~ 1:1 mix stirring by volume, the centrifugal titanium dioxide nano-particle that obtains;
2) nano particle that step 1 is made is put into 1 ~ 10 mmol/L tyrosine solution of 50-200mL, and adding concentration is the liquor argenti nitratis ophthalmicus of 1 ~ 10mmol/L, regulates pH to 6 ~ 10, mix and stirred 12-48 hour, centrifugal, washing obtains titanium dioxide-silver composite nano particles;
3) after the nano particle freeze drying that step 2 is made, 400 ~ 600 degrees centigrade of calcinings 0.5 ~ 3 hour, obtain titanium dioxide-silver composite nano particles.
6. the purposes of a titanium dioxide-silver composite nano particles as claimed in claim 1 or 2 in photocatalysis.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103978201A (en) * | 2014-06-05 | 2014-08-13 | 黑龙江大学 | Method for conducting nano-silver modification on tin dioxide nanorods through microwave assisting |
| CN115477394A (en) * | 2022-10-13 | 2022-12-16 | 天津城建大学 | Coupling method of nano titanium dioxide and microalgae, biological system and application |
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| WO2009048186A1 (en) * | 2007-10-08 | 2009-04-16 | Industrial Cooperation Foundation Chonbuk National University | Tio2-capsulated metallic nanoparticles photocatalyst enable to be excited by uv or visible lights and its preparation method |
| CN101972653A (en) * | 2010-10-27 | 2011-02-16 | 陕西科技大学 | Method for preparing anatase nano Ag/TiO2 composite material |
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| WO2009048186A1 (en) * | 2007-10-08 | 2009-04-16 | Industrial Cooperation Foundation Chonbuk National University | Tio2-capsulated metallic nanoparticles photocatalyst enable to be excited by uv or visible lights and its preparation method |
| CN101406834A (en) * | 2008-11-04 | 2009-04-15 | 浙江大学 | Method for preparing silver and titanic oxide nano compound material at low temperature |
| CN101972653A (en) * | 2010-10-27 | 2011-02-16 | 陕西科技大学 | Method for preparing anatase nano Ag/TiO2 composite material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103978201A (en) * | 2014-06-05 | 2014-08-13 | 黑龙江大学 | Method for conducting nano-silver modification on tin dioxide nanorods through microwave assisting |
| CN115477394A (en) * | 2022-10-13 | 2022-12-16 | 天津城建大学 | Coupling method of nano titanium dioxide and microalgae, biological system and application |
| CN115477394B (en) * | 2022-10-13 | 2023-12-29 | 天津城建大学 | Coupling method of nano titanium dioxide and microalgae, biological system and application |
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Application publication date: 20130814 |