CN102677122B - Preparation method of superfine cadmium sulfide particles-sensitized titanium dioxide nanotube array - Google Patents
Preparation method of superfine cadmium sulfide particles-sensitized titanium dioxide nanotube array Download PDFInfo
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Abstract
The invention discloses a preparation method of a superfine cadmium sulfide particles-sensitized titanium dioxide nanotube array, comprising the following steps of: 1) pretreating the surface of a substrate material, carrying put anodic oxidation to obtain pure TiO2-NTs by taking mixed solution of NH4F and H3PO4 as electrolyte, taking a Ti slice as a working electrode Pt slice and a counter electrode,, and roasting an obtained sample, to obtain an anatase type TiO2-NTs thin film; and 2) ultrasonically treating the sample obtained in the step 1), carrying out electro-deposition by taking CdCl2 as electrolyte to obtain Cd/TiO2-NTs, carrying out roasting and thermal oxidation to obtain CdO, carrying out ion exchange in Na2S solution, and withdrawing to obtain CdS/TiO2-NTs. In combination with the electro-deposition and the ion exchange, the superfine CdS particles are evenly dispersed at the tube opening of the TiO2 nanotube array and in the tube, so that the effective contact area between the CdS particles and the TiO2 nanotube array can be increased, therefore, the charge transfer among interfaces can be increased, the photoelectric conversion efficiency is higher, and the activity of the photo-electrically and catalytically degraded organic pollutants can be improved.
Description
Technical field
The present invention is a kind of preparation method of Nano tube array of titanium dioxide, the preparation method of the Nano tube array of titanium dioxide of particularly a kind of superfine cadmium sulfide particle sensitization.
Technical background
In recent years, the applied research report of titanium dioxide in photocatalysis degradation organic contaminant constantly increases.Wherein by titania nanotube battle array (TiO prepared by anonizing
2-NTs) cause broad interest (Yang, L., Luo, the S. of people because of the new kink characteristics such as its bigger serface, strong photoabsorption and excellent electric charge seepage flow approach, Cai, Q., Yao, S., Chin.Sci.Bull.2010,55,331-338.Roy, P., Berger, S., Schmuki, P., Angew.Chem.Int.Ed.2011,50,2904-2939.).But TiO
2as photocatalyst, energy gap is 3.2eV, and photoabsorption is only limitted to ultraviolet region, can only absorb the UV-light of in sunlight 5%.Research emphasis is placed on TiO by many research workers
2modification on, it is desirable to utilize visible ray, wherein composite semiconductor technology (CdS) is considered to a kind of simple and efficient approach (Xie, Y., Ali, G., Yoo, S.H., Cho, S.O., ACS Appl.Mater.Interfaces.2010,2,2910-2914.).Current preparation CdS modifies TiO
2method mostly adopt chemical bath deposition method (CBD) (Medina-Gonzalez, Y., Xu, W.Z., Chen, B., Farhanghi, N., Charpentier, P.A., Nanotechnology.2011,22Bai, J., L i, J.H., Liu, Y.B., Zhou, B.X., Cai, W.M., Appl.Catal.B.2010,95,408-413).Although this method is very simply, poor repeatability, bonding force is weak, and the CdS particle obtained is usually comparatively large, easily reunites at titania nanotube mouth, thus the contact area between both reductions, cause visible absorption to weaken and be deteriorated with charge separation laser propagation effect.Nano tube array of titanium dioxide (the CdS/TiO of the ultra-fine CdS particle sensitization of high dispersing as can be seen here
2-NTs) be only a kind of desirable photocatalyst.
Summary of the invention
The object of this invention is to provide the preparation method of the Nano tube array of titanium dioxide of a kind of superfine cadmium sulfide particle sensitization, to solve the problems referred to above of prior art.
Object of the present invention can be achieved through the following technical solutions:
A preparation method for the Nano tube array of titanium dioxide of superfine cadmium sulfide particle sensitization, the steps include:
1) TiO
2the preparation of-NTs: substrate material surface is carried out pre-treatment is 1: 1,0.2M NH with volume ratio
4f and 0.1M H
3pO
4mixing solutions be electrolytic solution, Ti sheet is working electrode Pt sheet for electrode, and control voltage is that 20V carries out anodic oxidation, obtains pure TiO after 7h
2-NTs, by the sample of gained in retort furnace in 450 DEG C-500 DEG C roasting 2h-3h, obtain Detitanium-ore-type TiO
2-NTs film;
2) CdS/TiO
2the preparation of-NTs: step 1) gained sample is placed in CdCl
2ultrasonic in solution, then with 0.2M CdCl
2for electrolytic solution galvanic deposit obtains Cd/TiO
2-NTs, then in retort furnace, Cd thermooxidizing is CdO by 500 DEG C of roasting 1h, finally at 0.2M Na
2carry out ion-exchange in S solution, take out and be drying to obtain CdS/TiO
2-NTs.
In step 1), described base material purity is 99.7%.
Described pre-treatment is cleaned in acetone, ethanol or deionized water for ultrasonic.In step 2) in, described ultrasonic time is 5min-7min; Galvanic deposit Cd electromotive force is 0.9V vs.SCE, and depositing time is 2s-60s; Ion-exchange temperature is 100 DEG C-140 DEG C, and swap time is 10h-15h.
The method that the present invention adopts galvanic deposit coupled ion to exchange, prepares the Nano tube array of titanium dioxide of superfine cadmium sulfide particle sensitization, because ultra-fine CdS uniform particle is dispersed in TiO
2in the mouth of pipe of nano-tube array and pipe, add effective contact area therebetween, thus increase the charge transfer between interface, photoelectric transformation efficiency is higher, and photoelectric catalysis degrading organic pollutant activity improves.
Accompanying drawing explanation
Fig. 1 is pure TiO
2the CdS/TiO that-NTs and embodiment 1 obtain
2the SEM figure of-NTs sample.In FIG, (a) is pure TiO
2-NT s, (b) is CdS/TiO
2-NT s schemes; Scale is 100nm.
Fig. 2 is pure TiO
2the CdS/TiO that-NTs, embodiment 1 and embodiment 2 is obtained
2the XRD figure of-NTs sample.In fig. 2, (a) is pure TiO
2-NTs, (b) is 30s-CdS/TiO
2-NTs schemes; C () is 60s-CdS/TiO
2-NTs schemes; Diffraction peak A:Anatase, diffraction peak Ti:Titanium.
Fig. 3 is pure TiO
2the CdS/TiO that-NTs and embodiment 1 obtain
2the UV-Vis diffuse reflection spectroscopy figure of-NTs sample.
Fig. 4 is pure TiO
2the CdS/TiO that-NTs and embodiment 1 obtain
2the photoelectricity flow graph of-NTs sample.In figure, light source is the visible ray of λ >400nm.
Fig. 5 is pure TiO
2the CdS/TiO that-NT s and embodiment 1 obtain
2the alternating-current impedance figure of-NTs sample.In figure, light source is the visible ray of λ >400nm.
Fig. 6 is the CdS/TiO that embodiment 1 obtains
2-NTs sample photoelectrocatalysis, photochemical catalysis, electrocatalysis and light under visible ray (λ >400nm) are directly degraded tropeolin-D (10mg.L
-1) active figure.In figure 6, photoelectrocatalysis process and electrocatalysis process institute biasing are 0.5V vs.SCE.
Fig. 7 is the CdS/TiO that embodiment 1 obtains
2-NTs sample is at photoelectric catalysis degrading tropeolin-D (10mg.L under visible ray (λ >400nm)
-1) activity applies mechanically figure.In the figure 7, photoelectrocatalysis process institute biasing is 0.5Vvs.SCE.
Embodiment
Technical characterstic of the present invention is set forth further below in conjunction with accompanying drawing and specific embodiment.
Embodiment 1
(1) base material is the titanium sheet of thick 0.3mm, cleans up respectively in acetone, ethanol and deionized water for ultrasonic, dries stand-by.Preparation 0.2M NH
4f and 0.1M H
3pO
4solution, with Ti sheet for working electrode Pt sheet is to electrode, control voltage is that 20V carries out anodic oxidation 7h, ultrasonic cleaning 1min post-drying, and in retort furnace, 500 DEG C of roasting 2h, namely obtain Detitanium-ore-type TiO
2-NTs film.
(2) method adopting galvanic deposit coupled ion to exchange prepares the Nano tube array of titanium dioxide of superfine cadmium sulfide particle sensitization.The sample of step (1) gained is placed in CdCl
2ultrasonic 6min in solution, with 0.2M CdCl
2for electrolytic solution, TiO
2-NTs is working electrode, and Pt sheet is to electrode, and saturated calomel electrode (SCE) is reference electrode, utilizes control electromotive force (0.9V vs.SCE) method galvanic deposit 30s to obtain Cd/TiO
2-NTs, then 500 DEG C of roasting 1h in retort furnace, finally at 140 DEG C in 0.2M Na
2carry out ion-exchange 10h in S solution, obtain CdS/TiO
2-NTs.
Embodiment 2
(1) TiO
2the preparation of-NTs film is with embodiment 1.
(2) sample of step (1) gained is placed in CdCl
2ultrasonic 6min in solution, with 0.2M CdCl
2for electrolytic solution, TiO
2-NTs is working electrode, and Pt sheet is to electrode, and saturated calomel electrode (SCE) is reference electrode, utilizes control electromotive force (0.9V vs.SCE) method galvanic deposit 60s to obtain Cd/TiO
2-NTs, then 500 DEG C of roasting 1h in retort furnace, finally at 140 DEG C in 0.2M Na
2carry out ion-exchange 10h in S solution, obtain CdS/TiO
2-NTs.
Embodiment 3
(1) TiO
2the preparation of-NTs film is with embodiment 1.
(2) sample of step (1) gained is placed in CdCl
2ultrasonic 6min in solution, with 0.2M CdCl
2for electrolytic solution, TiO
2-NTs is working electrode, and Pt sheet is to electrode, and saturated calomel electrode (SCE) is reference electrode, utilizes control electromotive force (0.9V vs.SCE) method galvanic deposit 30s to obtain Cd/TiO
2-NTs, then 500 DEG C of roasting 1h in retort furnace, finally at 140 DEG C in 0.2M Na
2carry out ion-exchange 15h in S solution, obtain CdS/TiO
2-NTs.
As can be seen from Figure 1, the ultra-fine CdS particle obtained in experiment is not only highly dispersed at TiO
2the nano-tube array mouth of pipe, and be distributed in nanotube.
As shown in Figure 2, from TiO
2-NTs and 30s-CdS/TiO
2the XRD figure of-NTs sample all can only see only having Ti substrate and anatase octahedrite TiO
2diffraction peak, increase electrodeposition time and just occur the peak of CdS to 60s.Illustrate that this method can successfully obtain CdS particle, due to its high dispersion, only could observe CdS diffraction peak from XRD figure when depositing time is longer.
TiO in comparison diagram 3
2-NTs and 30s-CdS/TiO
2the UV-Vis diffuse reflection spectroscopy figure of-NTs, the TiO of CdS sensitization
2nano-tube array have stronger absorption at 380nm-500nm.
As shown in Figure 4 and Figure 5, under visible light illumination, compared to pure TiO
2-NTs, 30s-CdS/TiO
2the density of photocurrent of-NTs enlarges markedly, and the radius of ac impedance spectroscopy obviously reduces.
Photoelectrocatalysis process efficiency is the highest as can be seen from Figure 6, and in 180min, the degradation rate of tropeolin-D can reach 89.8%, embodies the synergy of light and electricity.
Apply mechanically figure from Fig. 7 photoelectric catalytically active can illustrate, the CdS/TiO of gained
2-NTs is more stable, can use continuously and still have good activity 10 times.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (3)
1. a preparation method for the Nano tube array of titanium dioxide of superfine cadmium sulfide particle sensitization, is characterized in that: the steps include:
1) TiO
2the preparation of-NTs: substrate material surface is carried out pre-treatment take volume ratio as 1:1,0.2M NH
4f and 0.1M H
3pO
4mixing solutions be electrolytic solution, Ti sheet is working electrode Pt sheet for electrode, and control voltage is that 20V carries out anodic oxidation, obtains pure TiO after 7h
2-NTs, by the sample of gained in retort furnace in 450 DEG C-500 DEG C roasting 2h-3h, obtain Detitanium-ore-type TiO
2-NTs film;
2) CdS/TiO
2the preparation of-NTs: by step 1) gained sample is placed in CdCl
2ultrasonic in solution, then with 0.2M CdCl
2for electrolytic solution galvanic deposit obtains Cd/TiO
2-NTs, then in retort furnace, Cd thermooxidizing is CdO by 500 DEG C of roasting 1h, finally at 0.2M Na
2carry out ion-exchange in S solution, take out and be drying to obtain CdS/TiO
2-NTs;
In step 2) in, described ultrasonic time is 5min-7min; Galvanic deposit Cd electromotive force is 0.9V vs.SCE, and depositing time is 2s-60s; Ion-exchange temperature is 100 DEG C-140 DEG C, and swap time is 10h-15h.
2. the preparation method of the Nano tube array of titanium dioxide of superfine cadmium sulfide particle according to claim 1 sensitization, is characterized in that: step 1) in, described base material purity is 99.7%.
3. the preparation method of the Nano tube array of titanium dioxide of superfine cadmium sulfide particle according to claim 1 sensitization, is characterized in that: described pre-treatment is cleaned in acetone, ethanol or deionized water for ultrasonic.
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| CN103173764A (en) * | 2013-03-22 | 2013-06-26 | 天津大学 | TiO2 through hole nanotube and CdS compound array film and preparation method thereof |
| CN103489651A (en) * | 2013-09-03 | 2014-01-01 | 上海师范大学 | Preparing method for embellish titanium dioxide nanotube array electrode material embellished by cadmium selenide nano-particles |
| CN104709961B (en) * | 2015-02-12 | 2016-06-08 | 浙江工商大学 | A kind of Fe2O3-Bi2O3/NF-TiO2Combination electrode and its preparation method and application |
| CN104999078A (en) * | 2015-07-16 | 2015-10-28 | 广州中国科学院先进技术研究所 | Method for preparing false tooth support through 3D printing laser stereo-lithography technology |
| RU2624620C1 (en) * | 2016-04-14 | 2017-07-04 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский государственный университет" (СПбГУ) | METHOD FOR PRODUCING PHOTOCATALYST BASED ON NANO-HETEROSTRUCTURAL SEMICONDUCTOR CdS-WO3-TiO2 |
| CN107740150B (en) * | 2017-08-25 | 2019-11-08 | 洛阳师范学院 | A kind of germanium-selenide film and preparation method thereof |
| CN107620103B (en) * | 2017-09-11 | 2019-12-24 | 洛阳师范学院 | Preparation method of germanium sulfide film |
| CN108579766B (en) * | 2018-04-17 | 2020-10-20 | 华东理工大学 | Preparation method of cadmium sulfide-based composite catalyst capable of treating industrial wastewater |
| CN114261956B (en) * | 2021-12-09 | 2022-12-27 | 陕西师范大学 | Photoanode water-splitting electrolyte solution based on amino acid carbon dots |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102205224A (en) * | 2011-04-20 | 2011-10-05 | 浙江理工大学 | Method for preparing CdS/TiO2 nanocomposite |
| CN102352494A (en) * | 2011-09-30 | 2012-02-15 | 厦门大学 | Preparation method of CdSe/CdS quantum dot sensitized TiO2 nanometer tube composite film |
-
2012
- 2012-05-11 CN CN201210148421.XA patent/CN102677122B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102205224A (en) * | 2011-04-20 | 2011-10-05 | 浙江理工大学 | Method for preparing CdS/TiO2 nanocomposite |
| CN102352494A (en) * | 2011-09-30 | 2012-02-15 | 厦门大学 | Preparation method of CdSe/CdS quantum dot sensitized TiO2 nanometer tube composite film |
Non-Patent Citations (4)
| Title |
|---|
| CdS/TiO2复合纳米管制备和光催化性能的研究;马骏等;《天津师范大学学报》;20110731;第31卷(第3期);参见50页实验过程，53页结论部分 * |
| CdS/TiO2纳米管阵列的制备及其光电催化活性研究;凌世盛;《功能材料》;20101130(第11期);参见1911页实验 * |
| Coaxial Heterogeneous Structure of TiO2 Nanotube Arrays with CdS as a Superthin Coating Synthesized via Modified Electrochemical Atomic Layer Deposition;WEN ZHU等;《American Chemical Society》;20101231;第132卷(第36期);第12619-12626页 * |
| TiO2基纳米管的构筑、表征及其光电化学性质研究;刘世凯;《中国博士学位论文全文数据库-工程科技I辑》;20090815;参见68页小结部分 * |
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