CN103243336B - A kind of preparation method of nano platinum/titanium dioxide nanotube array composite material - Google Patents
A kind of preparation method of nano platinum/titanium dioxide nanotube array composite material Download PDFInfo
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- CN103243336B CN103243336B CN201310179538.9A CN201310179538A CN103243336B CN 103243336 B CN103243336 B CN 103243336B CN 201310179538 A CN201310179538 A CN 201310179538A CN 103243336 B CN103243336 B CN 103243336B
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Abstract
The invention discloses a kind of preparation method of nano platinum/titanium dioxide nanotube array composite material, the method prepares Nano tube array of titanium dioxide by anonizing at titanium plate surface; First by the titanium sheet aqueous slkali soaking of the surface of gained containing Nano tube array of titanium dioxide, then soak in acid solution, obtain the titanium sheet of Nano tube array of titanium dioxide surface active; The titanium sheet of above-mentioned Nano tube array of titanium dioxide surface active is placed in Pt (NH
3)
4cl
2soak in solution, obtained nano platinum/titanium dioxide nanotube array composite material presoma; The nano platinum/titanium dioxide nanotube array composite material presoma NaBH of gained
4after solution reduction reaction, to obtain final product; The Pt nanoparticle particle diameter of the nano platinum/titanium dioxide nanotube array composite material load that the method obtains is little, and charge capacity is large and be evenly distributed; This preparation method is simple, reaction conditions is gentle, cost is low, can industrial applications.
Description
Technical field
The present invention relates to a kind of preparation method of nano platinum/titanium dioxide nanotube array composite material; Belong to field of nanometer material technology.
Background technology
Titanium dioxide is a kind of important multifunctional semiconductor material, and stable chemical nature is nontoxic, inexpensive.The optics of Nano tube array of titanium dioxide uniqueness and electrology characteristic, and be convenient to the advantage such as geometric properties and high-specific surface area of electric transmission, make it have excellent photoelectric transformation efficiency and photocatalytic activity, and become a kind of catalyst support material of excellence, have broad application prospects in solar cell, photocatalysis degradation organic contaminant, photocatalysis hydrogen production, sensor, Kaolinite Preparation of Catalyst etc.Particularly metal or metal oxide nanoparticles, quantum dot, dyestuff etc. on titania nanotube area load, after being prepared into composite nano materials, its application performance can be greatly improved, and becomes study hotspot in recent years.Wherein studying more is noble metal nano particles on titania nanotube area load, and as platinum, gold nano grain, conventional method is electrochemical deposition method.Electrochemical deposition method is larger at the noble metal nano particles particle diameter of titania nanotube area load, and the limited (J.Solid.State.Electrochem. of charge capacity, 2010,14:1109-1115), what have only deposits at the mouth of pipe of Nano tube array of titanium dioxide, cannot form nano particle, even be connected, the mouth of pipe is hidden completely (J.Phys.Chem.C., 2010,114:4408-4413).So the matrix material adopting electrochemical deposition method to prepare, noble metal nano particles and Nano tube array of titanium dioxide advantage separately cannot be given full play to, and synergistic effect each other.
Summary of the invention
The noble metal nano particles particle diameter that the present invention is directed to the titania nanotube area load prepared in prior art is larger, and charge capacity is limited, what have only deposits at the mouth of pipe of Nano tube array of titanium dioxide, nano particle cannot be formed, even be connected, the defect that the mouth of pipe is hidden completely, object is to provide a kind of Pt nanoparticle particle diameter preparing load little, the large and method of the nano platinum/titanium dioxide nanotube array composite material be evenly distributed of charge capacity; This preparation method is simple, reaction conditions is gentle, cost is low, can industrial applications.
The invention provides a kind of preparation method of nano platinum/titanium dioxide nanotube array composite material, this preparation method prepares Nano tube array of titanium dioxide by anonizing at titanium plate surface; The titanium sheet the concentration first surface of gained being contained Nano tube array of titanium dioxide is the alkaline solution of 1mol/L ~ 10mol/L, soak at 25 ~ 100 DEG C, be soak at 0 ~ 45 DEG C in the acid solution of 0.01 ~ 1mol/L again in concentration, obtain the titanium sheet of Nano tube array of titanium dioxide surface active; The titanium sheet of above-mentioned Nano tube array of titanium dioxide surface active being placed in concentration is 10 ~ 100mmol/L Pt (NH
3)
4cl
2soak in solution, obtained nano platinum/titanium dioxide nanotube array composite material presoma; The nano platinum/titanium dioxide nanotube array composite material presoma concentration of gained is the NaBH of 0.05 ~ 0.5mol/L
4after solution reduction reaction, to obtain final product.
Described alkaline concentration is preferably 3 ~ 8mol/L; Be particularly preferably 5mol/L.
Described alkaline solution be in sodium hydroxide solution, potassium hydroxide solution one or both, be preferably sodium hydroxide solution.
The concentration of described acid solution is preferably 0.05 ~ 0.5mol/L, is particularly preferably 0.1mol/L.
Described acid solution is one or more in hydrochloric acid, nitric acid, sulfuric acid; Be preferably hydrochloric acid.
Described Pt (NH
3)
4cl
2strength of solution is preferably 25 ~ 50mmol/L, is particularly preferably 25mmol/L.
Described NaBH
4strength of solution is preferably 0.08 ~ 0.3mol/L; Be particularly preferably 0.1mol/L.
The time of described Nano tube array of titanium dioxide aqueous slkali soaking is 1 ~ 10h; Be preferably 5 ~ 8h.
The time that described Nano tube array of titanium dioxide soaks in acid solution is 1 ~ 24h; Be preferably 8 ~ 16h.
The Nano tube array of titanium dioxide that described surface active is crossed is at Pt (NH
3)
4cl
2in solution, soak time is 12 ~ 24h; Be preferably 14 ~ 18h.
The described reduction reaction time is 3 ~ 10h; Be preferably 6 ~ 8h.
60 ~ 100 DEG C are preferably by the temperature that alkali soaks in aforesaid method.
10 ~ 38 DEG C are preferably by the temperature of acid soak in aforesaid method.
In above-mentioned preparation method, after having soaked each time, after all clean with distilled water wash, then carry out next step operation.
The present invention is by the titanium sheet of anonizing preparation surface containing Nano tube array of titanium dioxide: in anodic oxidation device, with clean titanium sheet for anode, copper sheet or platinized platinum are negative electrode, containing 0.3 ~ 0.7wt% Neutral ammonium fluoride, the ethylene glycol of 10wt% water and 0.9wt% sulfuric acid is electrolytic solution, magnetic agitation is continuously applied to electrolytic solution, voltage 100 ~ 150V, 10 ~ 30 minutes time, it is 25 DEG C by temperature controlled water baths, anodic oxidation terminates, take out, be placed in high temperature process furnances 450 DEG C of calcining at constant temperature 3h, temperature rise rate 10 DEG C/min, room temperature is naturally cooled to stove, obtained surface growth has the titanium sheet of the Nano tube array of titanium dioxide of Detitanium-ore-type.
The preparation method of nano platinum/titanium dioxide nanotube array composite material of the present invention:
The surface activation process of step 1) Nano tube array of titanium dioxide: the surface of anonizing being prepared is placed in the basic solution of 1 ~ 10mol/L containing the titanium sheet of Nano tube array of titanium dioxide, at 25 ~ 100 DEG C, 1 ~ 10 hour is processed under solution Keep agitation condition, distilled water flushing is clean, then at 0 ~ 45 DEG C, be soak 1 ~ 24 hour in the acidic solution of 0.01 ~ 1mol/L in concentration, solution Keep agitation, distilled water flushing is clean, obtains the titanium sheet of Nano tube array of titanium dioxide surface active;
Step 2) nano platinum/titanium dioxide nanotube array composite material precursor power: the titanium sheet of the Nano tube array of titanium dioxide surface active of step 1) gained is placed in 10 ~ 100mmol/L Pt (NH
3)
4cl
2soak 12 ~ 24 hours in solution, solution Keep agitation, with distilled water flushing, obtains nano platinum/titanium dioxide nanotube array composite material presoma;
Step 3) nano platinum/titanium dioxide nanotube array composite material presoma reduces: by step 2) the nano platinum/titanium dioxide nanotube array composite material presoma of gained is placed in 0.05 ~ 0.5mol/L NaBH
4reduce 3 ~ 10 hours in solution, solution Keep agitation, obtained metal nanoparticle/Nano tube array of titanium dioxide matrix material.
Nano platinum/titanium dioxide nanotube array composite material prepared by the present invention can be applicable to multiple fields such as fuel cell, solar cell, pollutant control, sensor and catalyzer.
Beneficial effect of the present invention:
(1) the present invention adopts alkali and acid to activate the surface of Nano tube array of titanium dioxide first, active group is on the surface increased greatly, significantly improve the ability of loaded with nano platinum and the distributing homogeneity of nano-platinum particle, reduce the particle diameter of nano-platinum particle simultaneously; The surface active of Nano tube array of titanium dioxide can be found out relative to the quantity showed increased of the nano-platinum particle not activating Nano tube array of titanium dioxide load from transmission electron microscope picture (Fig. 3 and Fig. 4), and nano-platinum particle is evenly distributed on the inwall of titania nanotube, median size is about 5nm;
(2) technique is simple, and reaction conditions is gentle, and preparation cost is low, and equipment is common anodic oxidation device, High Temperature Furnaces Heating Apparatus and whipping appts, without the need to other Special Equipments, both can be used for experimental implementation, again can industrial scale operation;
(3) the present invention propose the method for activating surface of Nano tube array of titanium dioxide and the carrying method of Platinum Nanoparticles, for the preparation of other kind composite titanium dioxide nano materials provides brand-new thinking.
Accompanying drawing explanation
[Fig. 1] is the scanning electron microscope (SEM) photograph of Nano tube array of titanium dioxide surface loaded with nano platinum when not activating.
[Fig. 2] is the scanning electron microscope (SEM) photograph of Nano tube array of titanium dioxide surface active back loading Platinum Nanoparticles.
[Fig. 3] is the transmission electron microscope picture of Nano tube array of titanium dioxide surface loaded with nano platinum when not activating.
[Fig. 4] is the transmission electron microscope picture of Nano tube array of titanium dioxide surface active back loading Platinum Nanoparticles.
Embodiment
Below in conjunction with example, the invention will be further described, and these embodiments, just for illustration of the present invention, do not limit the present invention.
Embodiment 1
Titanium sheet carries out mechanical polishing with silicon carbide paper, abrasive paper for metallograph successively, then respectively at 1mol/L sulfuric acid, and acetone, ethanol, each ultrasonic 5min in distilled water, nitrogen gas stream dries up; With clean titanium sheet for anode, copper sheet is negative electrode, be placed in the ethylene glycol electrolytic solution containing 0.5% Neutral ammonium fluoride, 10% water and 0.9% sulfuric acid, electrode distance 2 centimetres, constant temperature 25 DEG C, 150V voltage anodic oxygen 10min, in whole process, magnetic agitation is carried out to electrolytic solution, take out the titanium sheet being coated with Nano tube array of titanium dioxide, be placed in high temperature process furnances 450 DEG C of calcining at constant temperature 3h, temperature rise rate 10 DEG C/min, naturally cools to room temperature with stove, obtains anatase type titanium dioxide nano tube array at titanium plate surface; By the obtained titanium sheet being coated with anatase type titanium dioxide nano tube array, being placed in 100 DEG C of concentration is 5mol/L sodium hydroxide solution, 6 hours are processed under solution Keep agitation condition, with distilled water flushing to weakly acidic pH, be immersed in 0.1mol/L hydrochloric acid soln, 12 hours are processed under solution Keep agitation condition, with distilled water flushing to weakly acidic pH at 25 DEG C; Immerse 25mmol/L Pt (NH again
3)
4cl
2in the aqueous solution, at room temperature, load process 24 hours under solution Keep agitation condition; With distilled water flushing 3 times, be placed in 0.1mol/L NaBH
4in the aqueous solution, solution at room temperature reduction 8 hours under Keep agitation condition, obtain the anatase type titanium dioxide nano tube array that the load grown on platinized platinum has Platinum Nanoparticles, Fig. 2 and Fig. 4 is respectively its scanning electron microscope and transmission electron microscope photo;
Fig. 1 and Fig. 2 is the Nano tube array of titanium dioxide before activation treatment and after activation treatment respectively, and according to the scanning electron microscope (SEM) photograph after the inventive method loaded with nano platinum grain, visible activation treatment does not have an impact to the pattern of Nano tube array of titanium dioxide; Fig. 3 and Fig. 4 is the Nano tube array of titanium dioxide before activation treatment and after activation treatment respectively, and according to the transmission electron microscope picture after the inventive method loaded with nano platinum grain, after obviously can seeing activation treatment, the Platinum Nanoparticles of load increases greatly; In addition, the median size that directly can estimate Platinum Nanoparticles according to the ratio scale of transmission electron microscope picture Fig. 4 is about 5nm.
Claims (10)
1. a preparation method for Platinum Nanoparticles/anatase type titanium dioxide nano tube array composite material, is characterized in that, prepares anatase type titanium dioxide nano tube array by anonizing at titanium plate surface; The titanium sheet the concentration first surface of gained being contained anatase type titanium dioxide nano tube array is the alkaline solution of 1mol/L ~ 10mol/L, soak at 25 ~ 100 DEG C, be soak at 0 ~ 45 DEG C in the acid solution of 0.01 ~ 1mol/L again in concentration, obtain the titanium sheet of anatase type titanium dioxide nano tube array surface activation; It is 10 ~ 100mmol/L Pt (NH that the titanium sheet of above-mentioned anatase type titanium dioxide nano tube array surface activation is placed in concentration
3)
4cl
2soak in solution, obtained Platinum Nanoparticles/anatase type titanium dioxide nano tube array composite material presoma; Platinum Nanoparticles/anatase type titanium dioxide nano tube array composite material presoma the concentration of gained is the NaBH of 0.05 ~ 0.5mol/L
4after solution reduction reaction, to obtain final product.
2. preparation method as claimed in claim 1, it is characterized in that, described alkaline concentration is 3 ~ 8mol/L.
3. preparation method as claimed in claim 1 or 2, is characterized in that, described alkaline solution be in sodium hydroxide solution, potassium hydroxide solution one or both.
4. preparation method as claimed in claim 1, it is characterized in that, the concentration of described acid solution is 0.05 ~ 0.5mol/L.
5. the preparation method as described in claim 1 or 4, is characterized in that, described acid solution is one or more in hydrochloric acid, nitric acid, sulfuric acid.
6. preparation method as claimed in claim 1, is characterized in that, Pt (NH
3)
4cl
2strength of solution is 25 ~ 50mmol/L.
7. preparation method as claimed in claim 1, is characterized in that, described NaBH
4strength of solution is 0.08 ~ 0.3mol/L.
8. preparation method as claimed in claim 1, it is characterized in that, the time of described anatase type titanium dioxide nano tube array aqueous slkali soaking is 1 ~ 10h; The time that described anatase type titanium dioxide nano tube array soaks in acid solution is 1 ~ 24h.
9. preparation method as claimed in claim 1, it is characterized in that, the anatase type titanium dioxide nano tube array that described surface active is crossed is at Pt (NH
3)
4cl
2in solution, soak time is 12 ~ 24h.
10. preparation method as claimed in claim 1, it is characterized in that, the described reduction reaction time is 3 ~ 10h.
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| CN108380205B (en) * | 2018-02-11 | 2019-09-20 | 杭州电子科技大学 | A kind of preparation method of platinum filling titania nanotube |
| CN110404571B (en) * | 2019-05-17 | 2023-08-04 | 中南大学 | High-activity visible light response TiO 2 Preparation method and application of powder |
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| CN102383164A (en) * | 2011-11-08 | 2012-03-21 | 天津大学 | Titanium dioxide nano-honeycomb nested nanowire array film and preparation method thereof |
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| CN102383164A (en) * | 2011-11-08 | 2012-03-21 | 天津大学 | Titanium dioxide nano-honeycomb nested nanowire array film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Highly uniform Pt nanoparticle decoration on TiO2 nanotube arrays: A refreshable platform for methanol electrooxidation;Yan-Yan Song, et al.;《Electrochemistry Communications》;20110114;第13卷;290-293 * |
| Pt 负载型二氧化钛纳米管/纳米晶复合光催化剂的制备及其光催化性能;余威威等;《无机材料学报》;20110731;第26卷(第7期);747-752 * |
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