CN102534726A - Titanium dioxide (TiO2) nanotube composite material and method for depositing SnSe/Ag nanoparticles - Google Patents
Titanium dioxide (TiO2) nanotube composite material and method for depositing SnSe/Ag nanoparticles Download PDFInfo
- Publication number
- CN102534726A CN102534726A CN2012100089603A CN201210008960A CN102534726A CN 102534726 A CN102534726 A CN 102534726A CN 2012100089603 A CN2012100089603 A CN 2012100089603A CN 201210008960 A CN201210008960 A CN 201210008960A CN 102534726 A CN102534726 A CN 102534726A
- Authority
- CN
- China
- Prior art keywords
- concentration
- nanotube
- snse
- preferred
- tio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a titanium dioxide (TiO2) nanotube composite material and a method for depositing SnSe/Ag nanoparticles. The method comprises the following steps of: firstly, preparing TiO2 nanotubes by using a two-electrode system; secondly, electrochemically depositing SnSe nanoparticles on the prepared titanium alloy or pure titanium with the TiO2 nanotubes; and finally, putting a nanotube array deposited with the SnSe nanoparticles into a silver nitrate solution, and chemically depositing nano-silver. The defect of the prior art is overcome, the obtained material is high in electrocatalysis efficiency, uniform nanoparticles with controllable sizes are distributed on the surface of the material, and the whole process has the characteristics of low cost and simple preparation process.
Description
Technical field
The present invention relates to a kind of field of nanometer material technology, more particularly, relate to a kind of method of modifying of titanium dioxide nano material and the method for deposit nanometric particles thereof.
Background technology
Because the energy is shortage relatively, people begin to seek environmentally friendly new energy materials and replace traditional.At present, people concentrate one's energy to study and have the high specific surface area and the material of high catalytic activity more.Nano-TiO
2As a kind of green functional material, have some special nature, such as: N-type semiconductor, chemistry and mechanical stability, photocatalytic activity, biological activity, low preparation cost etc. have become one of this hot research fields.With nano-TiO
2Powder is compared, TiO
2Nanotube has low, the big specific surface area of preparation cost, the surface topography of rule, advantageous property such as light stability and unreactiveness preferably; And have higher adsorptive power and an active site position; Have high photocatalysis efficiency, can be applicable to aspects such as vessel senser element, catalyzer, solar cell and biomaterial.But the energy gap broad of titanium oxide; Can only utilize the UV-light part in the sunshine; And UV-light only accounts for 4% of sunshine total energy; How reducing its energy gap, make it to utilize the part of visible light in the sunshine (account for sun power total energy 43%), is the key that improves its photochemical catalysis and optoelectronic transformation efficiency.At present, for further improving TiO
2The catalytic efficiency (of nanotube, investigators adopt the auto-doping method at TiO
2The nanotube surface all kinds of precious metals that mix, such as: Pd, Pt, Au, Rt etc., however these metal prices are expensive, are difficult in the industrial scale to promote.Also there is the scholar to take at TiO
2Two kinds of nano particles of nanotube surface doping carry out TiO
2The ternary of nanotube is compound, such as Pt/Au/TiO
2-NTs, Pt/Ru/TiO
2-NTs, CdS/PtTiO
2-NTs, CdS/CdSe/TiO
2-NTs etc., however deposit to that nanoparticle on the nanotube is not of uniform size, skewness, tackiness be bad.
Summary of the invention
The present invention is intended to overcome the deficiency of prior art; The method of a kind of titania nanotube matrix material and deposition SnSe/Ag nano particle is provided; To obtain electrocatalysis efficient preferably; Obtain surface arrangement evenly and the nano particle of controlled amount, whole technology has that cost is low, preparation process characteristic of simple.
The object of the invention is achieved through following technical proposals:
At first (be that step 1) utilizes two electrode systems to prepare titania nanotube: titanium alloy that will use as anode or pure titanium are packed in the anodic oxidation device; Negative electrode is platinized platinum or graphite; Electrolytic solution is the mixing solutions of water and glycerine, and wherein the volume ratio of glycerine and water is 0.4-3, NH
4The concentration of F is 0.1-0.5mol/L, and the constant voltage of feeding is 10-60V, and the time that feeds voltage is 10min-4h, can make self-assembly TiO
2Nanotube.
The titanium alloy that uses in the wherein said step (1) is the Ti-Zr alloy, and wherein the atomic molar of Ti and Zr is than being (7-9): (3-1), the atomic molar ratio of preferred Ti and Zr is 7: 3,8: 2 or 9: 1.
The titanium alloy that uses in the said step (1) is the Ti-Zr-Nb alloy, and wherein the atomic molar of Ti, Zr and Nb is than being (73-74): (2-4): (22-25), the atomic molar ratio of preferred Ti, Zr and Nb is 74: 4: 22 or 73: 2: 25.
The titanium alloy that said step (1) is used is the Ti-Zr-Nb-Sn alloy, and wherein the atomic molar of Ti, Zr, Nb and Sn ratio is 72: 4: 22: 2.
In the said step (1), the volume ratio of glycerine and water is preferably 1, NH
4The concentration of F is preferably 0.27-0.3mol/L.
In the said step (1), the constant voltage of feeding is preferably 30V, and the time that feeds voltage is preferably 3h.
Secondly (being step 2) will prepare has TiO
2The titanium alloy of nanotube or pure titanium carry out electrochemical deposition SnSe nano particle: what will prepare has a TiO
2The titanium alloy of nanotube or pure titanium place electrochemical deposition solution, in the wherein said electrochemistry precipitation solution, and SnCl
22H
2The concentration of O is 0.045-0.06mol/L, SeO
2Concentration be 0.0015-0.0025mol/L, Na
2CO
3Concentration be 0.0015-0.0025mol/L; The concentration of trisodium citrate is 0.015-0.03mol/L, and the volume ratio of USP Kosher and water is (3-2): (2-3), regulating the pH value is 0.5-1.5; Solution temperature is 20 ℃-30 ℃; Pulsed voltage in the deposition reaction process is-0.5V～-1V, dutycycle is 0.02mV-0.08mV, the reaction times is 1000s-3600s.(wherein preparation has a TiO
2The titanium alloy of nanotube or pure titanium are that mercurous chloride electrode, counter electrode are platinum electrode as working electrode, reference electrode)
In the wherein said step (2), solution temperature is 20 ℃-25 ℃, the pulsed voltage in the deposition reaction process is-and 0.5V～-1V, dutycycle is 0.04-0.08, the reaction times is 1500s-3000s.
In the said step (2), in the electrochemistry precipitation solution, SnCl
22H
2The concentration of O is 0.046-0.058mol/L, preferred 0.05-0.055mol/L; SeO
2Concentration be 0.0018-0.0025mol/L, preferred 0.002-0.0025mol/L; Na
2CO
3Concentration be 0.0018-0.0025mol/L, preferred 0.002-0.0025mol/L; The concentration of trisodium citrate is 0.018-0.026mol/L, preferred 0.02-0.025mol/L; The volume ratio of USP Kosher and water is preferably 2: 3, regulates the pH value and is preferably 1-1.5.
(be that the nano-tube array that step 3) will deposit the SnSe nano particle places silver nitrate solution at 40 ℃ of-50 ℃ of deposit 3-11h at last; In the said silver nitrate solution; The volume ratio of terepthaloyl moietie and water is (3-2): (2-3); The concentration of Vinylpyrrolidone polymer is 0.00002-0.0026mol/L, NaBH
4Concentration be 0.026-0.068mol/L, AgNO
3Concentration be 0.035-0.060mol/L.
Depositing temperature in the wherein said step (3) is 40-45 ℃, and depositing time is 3-7h.
In the said step (3), the volume ratio of terepthaloyl moietie and water is (3-2) in the silver nitrate solution: (2-3), be preferably both equal-volume ratios; The concentration of Vinylpyrrolidone polymer is 0.00002-0.0026mol/L, preferred 0.0016-0.0026mol/L, more preferably 0.0016mol/L; NaBH
4Concentration be 0.026-0.068mol/L, preferred 0.048-0.068mol/L, more preferably 0.048mol/L; AgNO
3Concentration be 0.035-0.060mol/L, preferred 0.035-0.045mol/L, more preferably 0.045mol/L.
Method cost of the present invention is low, easy and simple to handle, and is consuming time shorter, compares with the traditional preparation process method, and mainly contain following advantage: (1) has solved the characteristics of particle agglomeration, makes it be evenly distributed on (as attaching shown in Fig. 1 and 2) on the nanotube; (2) reaction times shortens greatly, and simple to operate; (3) can effectively control the particle grain size size; (4) can be securely attached to TiO
2On the nanotube matrix.At first obtain titania nanotube and (after 450 ℃ of annealing, obtained Detitanium-ore-type TiO through self-assembly
2, therefore before the self-assembly after annealing, successfully prepared the titanium oxide of unformed shape), then successively through electrochemical deposition and electroless plating at TiO
2Nanotube surface prepares the nanometer SnSe/Ag particle (through RIGAKU/DMAX2500, the XRD analysis of Japan can be known, on metal substrate, has deposited the SnSe/Ag particle) that is evenly distributed; Through sem S4800; Hitachi, Japan, the power spectrum probe of EDAX company carries out the EDS test; Shown in accompanying drawing 3 and 4, the ratio of each element is as shown in the table.(solvent is a water in alkaline ethanol solution, to carry out the electrocatalysis test; Concentration sodium hydroxide is 0.15mol/L; Concentration of ethanol is 0.5mol/L), the oxidation peak and the current density of reduction peak that obtain depositing the titania nanotube of SnSe/Ag nano-Ag particles can reach 3.75mA/cm
2And 0.45mA/cm
2, have higher electrocatalysis efficient.
EDS analytical data shown in table 1 accompanying drawing 4
| Element | Weight percentage Wt% | Atomic percent At% |
| OK | 26.28 | 59.74 |
| SeL | 03.31 | 01.53 |
| ZrL | 03.99 | 01.59 |
| AgL | 26.95 | 09.09 |
| SnL | 04.22 | 01.29 |
| TiK | 35.25 | 26.76 |
| Matrix | Correction | ZAF |
EDS analytical data shown in table 2 accompanying drawing 3
| Element | Weight percentage Wt% | Atomic percent At% |
| OK | 20.15 | 50.71 |
| SeL | 03.34 | 01.70 |
| ZrL | 05.13 | 02.26 |
| AgL | 26.96 | 10.07 |
| SnL | 04.18 | 01.42 |
| TiK | 40.25 | 33.84 |
| Matrix | Correction | ZAF |
Description of drawings
Fig. 1 is at TiO
2The SnSe nano particle pattern photo that nanotube surface obtains (Japan), form: the mixed solution of USP Kosher/water (volume ratio is 2: 3), 0.05mol/L SnCl for sem S4800, Hitachi by electrolytic solution
2.2H
2O, 0.002mol/L SeO
2, 0.002mol/L Na
2CO
3, the 0.02mol/L trisodium citrate, pH=1, pulsed voltage is-0.5V, and dutycycle is 0.05mV, and depositing time is 3600s, and temperature of reaction is 25 ℃.
Fig. 2 is at TiO
2Two kinds of nano particle patterns of SnSe/Ag photo (sem S4800 that nanotube surface obtains; Hitachi; Japan); Behind the condition deposit SnSe of Fig. 1 nano particle, carry out the electroless plating nanometer Ag, electrolytic solution is formed: the mixing solutions of glycol/water (volume ratio is 1: 1) adds 0.035mol/L AgNO
3, 0.026mol/L NaBH4,0.001mol/L PVP, depositing time 7h, 40 ℃ of hydrothermal temperatures.
Fig. 3 is at TiO
2The EDS of two kinds of nano particles of SnSe/Ag that nanotube surface obtains (sem S4800, Hitachi, Japan, the power spectrum probe is EDAX)
Fig. 4 is at TiO
2The EDS of two kinds of nano particles of SnSe/Ag that nanotube surface obtains (sem S4800, Hitachi, Japan, the power spectrum probe is EDAX)
Fig. 5 is at TiO
2The XRD spectra of two kinds of nano particles of SnSe/Ag that nanotube surface obtains (RIGAKU/DMAX2500, Japan)
Two kinds of nano-particle doped TiO of Fig. 6 SnSe/Ag
2The cyclic voltammetry curve of nanotube.
Embodiment
Further specify technical scheme of the present invention below in conjunction with specific embodiment, wherein preparation has a TiO
2The titanium alloy of nanotube or pure titanium are that mercurous chloride electrode, counter electrode are platinum electrode as working electrode, reference electrode; The electrochemical workstation model of utilizing is Gamry Reference 600.
800# is used on pure Ti sheet surface respectively, 1000#, 2000#, the 2500# sand papering is to smooth, and the back cleans up with deionized water, and the ultrasonic 5min after drying of absolute ethyl alcohol is subsequent use
Adopt two electrode systems to prepare titania nanotube: anode is that pure titanium sheet, negative electrode are platinized platinum; In the electrolytic solution, the volume ratio of G & W is 1, NH
4F concentration is 0.3mol/L, and constant voltage is 30V, and feeding voltage time is 3 hours, promptly utilizes anonizing to prepare self-assembly TiO
2Nanotube
Preparation there is self-assembly TiO
2The pure titanium of nanotube carries out electrochemical deposition SnSe nano particle: will treat adulterated TiO
2Nanotube places electrochemical deposition solution, wherein SnCl
2.2H
2O concentration is 0.05mol/L, SeO
2Concentration 0.002mol/L, Na
2CO
3Concentration is 0.002mol/L, and the concentration of trisodium citrate is 0.02mol/L, and the volume ratio of USP Kosher and water is 2: 3, and using hydrochloric acid conditioning solution pH is 1; Solution temperature is 25 ℃ in the deposition process, and pulsed voltage is-0.5V, and dutycycle is 0.05mV, and the reaction times is 3600s; Sample is taken out, clean with the absolute ethyl alcohol excusing from death, promptly at TiO
2Nanotube surface obtains equally distributed SnSe nano particle
With the TiO that deposits the SnSe nano particle
2The pure titanium sheet of the metal of nanotube carries out electroless plating nanometer Ag particle: the TiO that will deposit the SnSe nano particle
2The pure titanium sheet of the metal of nanotube places electroless plating solution, and wherein the volume ratio of terepthaloyl moietie and water is 1: 1, AgNO
3Concentration is 0.035mol/L, NaBH
4Concentration 0.026mol/L, Vinylpyrrolidone polymer (PVP) concentration is 0.001mol/L, and depositing temperature (being hydrothermal temperature) is 40 ℃, and depositing time is 7h, and sample is taken out, and uses the absolute ethyl alcohol ultrasonic cleaning, promptly at TiO
2Nanotube surface obtains two kinds of nano particles of equally distributed SnSe/Ag
800# is used on Ti-Zr alloy slice (the atomic molar ratio of Ti and Zr is 7: 3) surface respectively, 1000#, 2000#, the 2500# sand papering is to smooth, and the back cleans up with deionized water, and the ultrasonic 10min after drying of absolute ethyl alcohol is subsequent use
Adopt two electrode systems to prepare titania nanotube: anode is that titanium alloy sheet, negative electrode are graphite; In the electrolytic solution, the volume ratio of G & W is 3, NH
4F concentration is 0.5mol/L, and constant voltage is 60V, and the feeding voltage time is 10min, promptly utilizes anonizing to prepare self-assembly TiO
2Nanotube
Preparation there is self-assembly TiO
2The titanium alloy sheet of nanotube carries out electrochemical deposition SnSe nano particle: will treat adulterated TiO
2Nanotube places electrochemical deposition solution, wherein SnCl
2.2H
2O concentration is 0.06mol/L, SeO
2Concentration 0.0025mol/L, Na
2CO
3Concentration is 0.0015mol/L, and the concentration of trisodium citrate is 0.015mol/L, and the volume ratio of USP Kosher and water is 3: 2, and using hydrochloric acid conditioning solution pH is 0.5; Solution temperature is 20 ℃ in the deposition process, and pulsed voltage is-1V, and dutycycle is 0.02mV, and the reaction times is 3000s; Sample is taken out, clean with the absolute ethyl alcohol excusing from death, promptly at TiO
2Nanotube surface obtains equally distributed SnSe nano particle
With the TiO that deposits the SnSe nano particle
2The titanium alloy sheet of nanotube carries out electroless plating nanometer Ag particle: the TiO that will deposit the SnSe nano particle
2The titanium alloy sheet of nanotube places electroless plating solution, and wherein the volume ratio of terepthaloyl moietie and water is 2: 3, AgNO
3Concentration is 0.045mol/L, NaBH
4Concentration 0.068mol/L, Vinylpyrrolidone polymer (PVP) concentration is 0.0016mol/L, and depositing temperature (being hydrothermal temperature) is 50 ℃, and depositing time is 11h, and sample is taken out, and uses the absolute ethyl alcohol ultrasonic cleaning, promptly at TiO
2Nanotube surface obtains two kinds of nano particles of equally distributed SnSe/Ag
Embodiment 3
800# is used on Ti-Zr alloy slice (the atomic molar ratio of Ti and Zr is 8: 2) surface respectively, 1000#, 2000#, the 2500# sand papering is to smooth, and the back cleans up with deionized water, and the ultrasonic 10min after drying of absolute ethyl alcohol is subsequent use
Adopt two electrode systems to prepare titania nanotube: anode is that titanium alloy sheet, negative electrode are graphite; In the electrolytic solution, the volume ratio of G & W is 0.4, NH
4F concentration is 0.1mol/L, and constant voltage is 10V, and feeding voltage time is 4 hours, promptly utilizes anonizing to prepare self-assembly TiO
2Nanotube
Preparation there is self-assembly TiO
2The titanium alloy sheet of nanotube carries out electrochemical deposition SnSe nano particle: will treat adulterated TiO
2Nanotube places electrochemical deposition solution, wherein SnCl
2.2H
2O concentration is 0.045mol/L, SeO
2Concentration 0.0015mol/L, Na
2CO
3Concentration is 0.0025mol/L, and the concentration of trisodium citrate is 0.03mol/L, and the volume ratio of USP Kosher and water is 1: 1, and using hydrochloric acid conditioning solution pH is 1.5; Solution temperature is 30 ℃ in the deposition process, and pulsed voltage is-1V, and dutycycle is 0.08mV, and the reaction times is 1000s; Sample is taken out, clean with the absolute ethyl alcohol excusing from death, promptly at TiO
2Nanotube surface obtains equally distributed SnSe nano particle
With the TiO that deposits the SnSe nano particle
2The titanium alloy sheet of nanotube carries out electroless plating nanometer Ag particle: the TiO that will deposit the SnSe nano particle
2The titanium alloy sheet of nanotube places electroless plating solution, and wherein the volume ratio of terepthaloyl moietie and water is 3: 2, AgNO
3Concentration is 0.06mol/L, NaBH
4Concentration 0.048mol/L, Vinylpyrrolidone polymer (PVP) concentration is 0.0026mol/L, and depositing temperature (being hydrothermal temperature) is 45 ℃, and depositing time is 3h, and sample is taken out, and uses the absolute ethyl alcohol ultrasonic cleaning, promptly at TiO
2Nanotube surface obtains two kinds of nano particles of equally distributed SnSe/Ag
800# is used on Ti-Zr alloy slice (the atomic molar ratio of Ti and Zr is 9: 1) surface respectively, 1000#, 2000#, the 2500# sand papering is to smooth, and the back cleans up with deionized water, and the ultrasonic 10min after drying of absolute ethyl alcohol is subsequent use
Adopt two electrode systems to prepare titania nanotube: anode is that titanium alloy sheet, negative electrode are platinized platinum; In the electrolytic solution, the volume ratio of G & W is 2: 1, NH
4F concentration is 0.27mol/L, and constant voltage is 50V, and feeding voltage time is 1 hour, promptly utilizes anonizing to prepare self-assembly TiO
2Nanotube
Preparation there is self-assembly TiO
2The titanium alloy sheet of nanotube carries out electrochemical deposition SnSe nano particle: will treat adulterated TiO
2Nanotube places electrochemical deposition solution, wherein SnCl
2.2H
2O concentration is 0.055mol/L, SeO
2Concentration 0.0018mol/L, Na
2CO
3Concentration is 0.0018mol/L, and the concentration of trisodium citrate is 0.026mol/L, and the volume ratio of USP Kosher and water is 2: 3, and using hydrochloric acid conditioning solution pH is 1; Solution temperature is 25 ℃ in the deposition process, and pulsed voltage is-0.5V, and dutycycle is 0.06mV, and the reaction times is 1500s; Sample is taken out, clean with the absolute ethyl alcohol excusing from death, promptly at TiO
2Nanotube surface obtains equally distributed SnSe nano particle
With the TiO that deposits the SnSe nano particle
2The titanium alloy sheet of nanotube carries out electroless plating nanometer Ag particle: the TiO that will deposit the SnSe nano particle
2The titanium alloy sheet of nanotube places electroless plating solution, and wherein the volume ratio of terepthaloyl moietie and water is 2: 3, AgNO
3Concentration is 0.045mol/L, NaBH
4Concentration 0.048mol/L, Vinylpyrrolidone polymer (PVP) concentration is 0.00002mol/L, and depositing temperature (being hydrothermal temperature) is 50 ℃, and depositing time is 11h, and sample is taken out, and uses the absolute ethyl alcohol ultrasonic cleaning, promptly at TiO
2Nanotube surface obtains two kinds of nano particles of equally distributed SnSe/Ag
Embodiment 5
800# is used on Ti-Zr-Nb alloy slice (the atomic molar ratio of Ti, Zr and Nb is 74: 4: 22) surface respectively, 1000#, 2000#, the 2500# sand papering is to smooth, and the back cleans up with deionized water, and the ultrasonic 10min after drying of absolute ethyl alcohol is subsequent use
Adopt two electrode systems to prepare titania nanotube: anode is that titanium alloy sheet, negative electrode are platinized platinum; In the electrolytic solution, the volume ratio of G & W is 1: 1, NH
4F concentration is 0.27mol/L, and constant voltage is 20V, and the feeding voltage time is 2.5h, promptly utilizes anonizing to prepare self-assembly TiO
2Nanotube
Preparation there is self-assembly TiO
2The titanium alloy sheet of nanotube carries out electrochemical deposition SnSe nano particle: will treat adulterated TiO
2Nanotube places electrochemical deposition solution, wherein SnCl
2.2H
2O concentration is 0.045mol/L, SeO
2Concentration 0.0025mol/L, Na
2CO
3Concentration is 0.0015mol/L, and the concentration of trisodium citrate is 0.018mol/L, and the volume ratio of USP Kosher and water is 3: 2, and using hydrochloric acid conditioning solution pH is 0.5; Solution temperature is 20 ℃ in the deposition process, and pulsed voltage is-1V, and dutycycle is 0.03mV, and the reaction times is 2500s; Sample is taken out, clean with the absolute ethyl alcohol excusing from death, promptly at TiO
2Nanotube surface obtains equally distributed SnSe nano particle
With the TiO that deposits the SnSe nano particle
2The titanium alloy sheet of nanotube carries out electroless plating nanometer Ag particle: the TiO that will deposit the SnSe nano particle
2The titanium alloy sheet of nanotube places electroless plating solution, and wherein the volume ratio of terepthaloyl moietie and water is 2: 3, AgNO
3Concentration is 0.035mol/L, NaBH
4Concentration 0.03mol/L, Vinylpyrrolidone polymer (PVP) concentration is 0.002mol/L, and depositing temperature (being hydrothermal temperature) is 50 ℃, and depositing time is 4h, and sample is taken out, and uses the absolute ethyl alcohol ultrasonic cleaning, promptly at TiO
2Nanotube surface obtains two kinds of nano particles of equally distributed SnSe/Ag
800# is used on Ti-Zr-Nb alloy slice (the atomic molar ratio of Ti, Zr and Nb is 73: 2: 25) surface respectively, 1000#, 2000#, the 2500# sand papering is to smooth, and the back cleans up with deionized water, and the ultrasonic 10min after drying of absolute ethyl alcohol is subsequent use
Adopt two electrode systems to prepare titania nanotube: anode is that titanium alloy sheet, negative electrode are platinized platinum; In the electrolytic solution, the volume ratio of G & W is 2: 1, NH
4F concentration is 0.27mol/L, and constant voltage is 50V, and feeding voltage time is 1 hour, promptly utilizes anonizing to prepare self-assembly TiO
2Nanotube
Preparation there is self-assembly TiO
2The titanium alloy sheet of nanotube carries out electrochemical deposition SnSe nano particle: will treat adulterated TiO
2Nanotube places electrochemical deposition solution, wherein SnCl
2.2H
2O concentration is 0.055mol/L, SeO
2Concentration 0.0018mol/L, Na
2CO
3Concentration is 0.0018mol/L, and the concentration of trisodium citrate is 0.026mol/L, and the volume ratio of USP Kosher and water is 2: 3, and using hydrochloric acid conditioning solution pH is 1; Solution temperature is 25 ℃ in the deposition process, and pulsed voltage is-0.5V, and dutycycle is 0.06mV, and the reaction times is 1500s; Sample is taken out, clean with the absolute ethyl alcohol excusing from death, promptly at TiO
2Nanotube surface obtains equally distributed SnSe nano particle
With the TiO that deposits the SnSe nano particle
2The titanium alloy sheet of nanotube carries out electroless plating nanometer Ag particle: the TiO that will deposit the SnSe nano particle
2The titanium alloy sheet of nanotube places electroless plating solution, and wherein the volume ratio of terepthaloyl moietie and water is 2: 3, AgNO
3Concentration is 0.045mol/L, NaBH
4Concentration 0.048mol/L, Vinylpyrrolidone polymer (PVP) concentration is 0.00002mol/L, and depositing temperature (being hydrothermal temperature) is 50 ℃, and depositing time is 11h, and sample is taken out, and uses the absolute ethyl alcohol ultrasonic cleaning, promptly at TiO
2Nanotube surface obtains two kinds of nano particles of equally distributed SnSe/Ag
Embodiment 7
With the Ti-Zr-Nb-Sn alloy slice (the atomic molar ratio of Ti, Zr, Nb and Sn is 72: 4: 22: 2) 800# is used on the surface respectively, 1000#, 2000#, the 2500# sand papering is to smooth, the back cleans up with deionized water, the ultrasonic 10min after drying of absolute ethyl alcohol is subsequent use
Adopt two electrode systems to prepare titania nanotube: anode is that titanium alloy sheet, negative electrode are graphite; In the electrolytic solution, the volume ratio of G & W is 1.5: 1, NH
4F concentration is 0.35mol/L, and constant voltage is 35V, and the feeding voltage time is 2h, promptly utilizes anonizing to prepare self-assembly TiO
2Nanotube
Preparation there is self-assembly TiO
2The titanium alloy sheet of nanotube carries out electrochemical deposition SnSe nano particle: will treat adulterated TiO
2Nanotube places electrochemical deposition solution, wherein SnCl
2.2H
2O concentration is 0.046mol/L, SeO
2Concentration 0.002mol/L, Na
2CO
3Concentration is 0.0025mol/L, and the concentration of trisodium citrate is 0.02mol/L, and the volume ratio of USP Kosher and water is 2: 3, and using hydrochloric acid conditioning solution pH is 1; Solution temperature is 30 ℃ in the deposition process, and pulsed voltage is-0.5V, and dutycycle is 0.04mV, and the reaction times is 2000s; Sample is taken out, clean with the absolute ethyl alcohol excusing from death, promptly at TiO
2Nanotube surface obtains equally distributed SnSe nano particle
With the TiO that deposits the SnSe nano particle
2The titanium alloy sheet of nanotube carries out electroless plating nanometer Ag particle: the TiO that will deposit the SnSe nano particle
2The titanium alloy sheet of nanotube places electroless plating solution, and wherein the volume ratio of terepthaloyl moietie and water is 1: 1, AgNO
3Concentration is 0.055mol/L, NaBH
4Concentration 0.065mol/L, Vinylpyrrolidone polymer (PVP) concentration is 0.0008mol/L, and depositing temperature (being hydrothermal temperature) is 50 ℃, and depositing time is 3h, and sample is taken out, and uses the absolute ethyl alcohol ultrasonic cleaning, promptly at TiO
2Nanotube surface obtains two kinds of nano particles of equally distributed SnSe/Ag
Embodiment 8
800# is used on Ti-Zr-Nb alloy slice (the atomic molar ratio of Ti, Zr and Nb is 74: 4: 22) surface respectively, 1000#, 2000#, the 2500# sand papering is to smooth, and the back cleans up with deionized water, and the ultrasonic 10min after drying of absolute ethyl alcohol is subsequent use
Adopt two electrode systems to prepare titania nanotube: anode is that titanium alloy sheet, negative electrode are platinized platinum; In the electrolytic solution, the volume ratio of G & W is 1: 1, NH
4F concentration is 0.27mol/L, and constant voltage is 20V, and the feeding voltage time is 2.5h, promptly utilizes anonizing to prepare self-assembly TiO
2Nanotube
Preparation there is self-assembly TiO
2The titanium alloy sheet of nanotube carries out electrochemical deposition SnSe nano particle: will treat adulterated TiO
2Nanotube places electrochemical deposition solution, wherein SnCl
2.2H
2O concentration is 0.058mol/L, SeO
2Concentration 0.0018mol/L, Na
2CO
3Concentration is 0.0015mol/L, and the concentration of trisodium citrate is 0.018mol/L, and the volume ratio of USP Kosher and water is 3: 2, and using hydrochloric acid conditioning solution pH is 0.5; Solution temperature is 20 ℃ in the deposition process, and pulsed voltage is-1V, and dutycycle is 0.05mV, and the reaction times is 2000s; Sample is taken out, clean with the absolute ethyl alcohol excusing from death, promptly at TiO
2Nanotube surface obtains equally distributed SnSe nano particle
With the TiO that deposits the SnSe nano particle
2The titanium alloy sheet of nanotube carries out electroless plating nanometer Ag particle: the TiO that will deposit the SnSe nano particle
2The titanium alloy sheet of nanotube places electroless plating solution, and wherein the volume ratio of terepthaloyl moietie and water is 2: 3, AgNO
3Concentration is 0.045mol/L, NaBH
4Concentration 0.048mol/L, Vinylpyrrolidone polymer (PVP) concentration is 0.005mol/L, and depositing temperature (being hydrothermal temperature) is 50 ℃, and depositing time is 4h, and sample is taken out, and uses the absolute ethyl alcohol ultrasonic cleaning, promptly at TiO
2Nanotube surface obtains two kinds of nano particles of equally distributed SnSe/Ag
More than the present invention has been done exemplary description; Should be noted that; Under the situation that does not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (10)
1. a titania nanotube matrix material is characterized in that, the nanoparticle deposition of SnSe and Ag is realized the compound of nanostructure in titania nanotube, prepares according to following step:
At first (be that step 1) utilizes two electrode systems to prepare titania nanotube: titanium alloy that will use as anode or pure titanium are packed in the anodic oxidation device; Negative electrode is platinized platinum or graphite; Electrolytic solution is the mixing solutions of water and glycerine, and wherein the volume ratio of glycerine and water is 0.4-3, NH
4The concentration of F is 0.1-0.5mol/L, and the constant voltage of feeding is 10-60V, and the time that feeds voltage is 10min-4h, can make self-assembly TiO
2Nanotube;
Secondly (being step 2) will prepare has TiO
2The titanium alloy of nanotube or pure titanium carry out electrochemical deposition SnSe nano particle: what will prepare has a TiO
2The titanium alloy of nanotube or pure titanium place electrochemical deposition solution, in the wherein said electrochemistry precipitation solution, and SnCl
22H
2The concentration of O is 0.045-0.06mol/L, SeO
2Concentration be 0.0015-0.0025mol/L, Na
2CO
3Concentration be 0.0015-0.0025mol/L; The concentration of trisodium citrate is 0.015-0.03mol/L; The volume ratio of USP Kosher and water is (3-2): (2-3), solution temperature is 20 ℃-30 ℃, the pulsed voltage in the deposition reaction process is-and 0.5V～-1V; Dutycycle is 0.02mV-0.08mV, and the reaction times is 1000s-3600s;
(be that the nano-tube array that step 3) will deposit the SnSe nano particle places silver nitrate solution at 40 ℃ of-50 ℃ of deposit 3-11h at last; In the said silver nitrate solution; The volume ratio of terepthaloyl moietie and water is (3-2): (2-3); The concentration of Vinylpyrrolidone polymer is 0.00002-0.0026mol/L, NaBH
4Concentration be 0.026-0.068mol/L, AgNO
3Concentration be 0.035-0.060mol/L.
2. a kind of titania nanotube matrix material according to claim 1; It is characterized in that; The titanium alloy that uses in the said step (1) is the Ti-Zr alloy, and wherein the atomic molar of Ti and Zr is than being (7-9): (3-1), the atomic molar ratio of preferred Ti and Zr is 7: 3,8: 2 or 9: 1; The titanium alloy that uses in the said step (1) is the Ti-Zr-Nb alloy, and wherein the atomic molar of Ti, Zr and Nb is than being (73-74): (2-4): (22-25), the atomic molar ratio of preferred Ti, Zr and Nb is 74: 4: 22 or 73: 2: 25; The titanium alloy that said step (1) is used is the Ti-Zr-Nb-Sn alloy, and wherein the atomic molar of Ti, Zr, Nb and Sn ratio is 72: 4: 22: 2.
3. a kind of titania nanotube matrix material according to claim 1 is characterized in that in the said step (1), the volume ratio of glycerine and water is preferably 1, NH
4The concentration of F is preferably 0.27-0.3mol/L, and the constant voltage of feeding is preferably 30V, and the time that feeds voltage is preferably 3h.
4. a kind of titania nanotube matrix material according to claim 1 is characterized in that, in the said step (2); Solution temperature is 20 ℃-25 ℃; Pulsed voltage in the deposition reaction process is-0.5V～-1V, dutycycle is 0.04mV-0.08mV, the reaction times is 1500s-3000s; In the electrochemistry precipitation solution, SnCl
22H
2The concentration of O is 0.046-0.058mol/L, preferred 0.05-0.055mol/L; SeO
2Concentration be 0.0018-0.0025mol/L, preferred 0.002-0.0025mol/L; Na
2CO
3Concentration be 0.0018-0.0025mol/L, preferred 0.002-0.0025mol/L; The concentration of trisodium citrate is 0.018-0.026mol/L, preferred 0.02-0.025mol/L; The volume ratio of USP Kosher and water is preferably 2: 3.
5. a kind of titania nanotube matrix material according to claim 1 is characterized in that the depositing temperature in the said step (3) is 40-45 ℃, and depositing time is 3-7h; The volume ratio of terepthaloyl moietie and water is (3-2) in the silver nitrate solution: (2-3), be preferably both equal-volume ratios; The concentration of Vinylpyrrolidone polymer is 0.00002-0.0026mol/L, preferred 0.0016-0.0026mol/L, more preferably 0.0016mol/L; NaBH
4Concentration be 0.026-0.068mol/L, preferred 0.048-0.068mol/L, more preferably 0.048mol/L; AgNO
3Concentration be 0.035-0.060mol/L, preferred 0.035-0.045mol/L, more preferably 0.045mol/L.
6. the method for a deposition SnSe/Ag nano particle in titania nanotube is characterized in that, carries out according to following step:
At first (be that step 1) utilizes two electrode systems to prepare titania nanotube: titanium alloy that will use as anode or pure titanium are packed in the anodic oxidation device; Negative electrode is platinized platinum or graphite; Electrolytic solution is the mixing solutions of water and glycerine, and wherein the volume ratio of glycerine and water is 0.4-3, NH
4The concentration of F is 0.1-0.5mol/L, and the constant voltage of feeding is 10-60V, and the time that feeds voltage is 10min-4h, can make self-assembly TiO
2Nanotube;
Secondly (being step 2) will prepare has TiO
2The titanium alloy of nanotube or pure titanium carry out electrochemical deposition SnSe nano particle: what will prepare has a TiO
2The titanium alloy of nanotube or pure titanium place electrochemical deposition solution, in the wherein said electrochemistry precipitation solution, and SnCl
22H
2The concentration of O is 0.045-0.06mol/L, SeO
2Concentration be 0.0015-0.0025mol/L, Na
2CO
3Concentration be 0.0015-0.0025mol/L; The concentration of trisodium citrate is 0.015-0.03mol/L; The volume ratio of USP Kosher and water is (3-2): (2-3), solution temperature is 20 ℃-30 ℃, the pulsed voltage in the deposition reaction process is-and 0.5V～-1V; Dutycycle is 0.02mV-0.08mV, and the reaction times is 1000s-3600s;
(be that the nano-tube array that step 3) will deposit the SnSe nano particle places silver nitrate solution at 40 ℃ of-50 ℃ of deposit 3-11h at last; In the said silver nitrate solution; The volume ratio of terepthaloyl moietie and water is (3-2): (2-3); The concentration of Vinylpyrrolidone polymer is 0.00002-0.0026mol/L, NaBH
4Concentration be 0.026-0.068mol/L, AgNO
3Concentration be 0.035-0.060mol/L.
7. a kind of method that in titania nanotube, deposits the SnSe/Ag nano particle according to claim 6; It is characterized in that; The titanium alloy that uses in the said step (1) is the Ti-Zr alloy; Wherein the atomic molar of Ti and Zr is than being (7-9): (3-1), the atomic molar ratio of preferred Ti and Zr is 7: 3,8: 2 or 9: 1; The titanium alloy that uses in the said step (1) is the Ti-Zr-Nb alloy, and wherein the atomic molar of Ti, Zr and Nb is than being (73-74): (2-4): (22-25), the atomic molar ratio of preferred Ti, Zr and Nb is 74: 4: 22 or 73: 2: 25; The titanium alloy that said step (1) is used is the Ti-Zr-Nb-Sn alloy, and wherein the atomic molar of Ti, Zr, Nb and Sn ratio is 72: 4: 22: 2.
8. a kind of method that in titania nanotube, deposits the SnSe/Ag nano particle according to claim 6 is characterized in that in the said step (1), the volume ratio of glycerine and water is preferably 1, NH
4The concentration of F is preferably 0.27-0.3mol/L, and the constant voltage of feeding is preferably 30V, and the time that feeds voltage is preferably 3h.
9. a kind of method that in titania nanotube, deposits the SnSe/Ag nano particle according to claim 6; It is characterized in that; In the said step (2), solution temperature is 20 ℃-25 ℃, the pulsed voltage in the deposition reaction process is-and 0.5V～-1V; Dutycycle is 0.04mV-0.08mV, and the reaction times is 1500s-3000s; In the electrochemistry precipitation solution, SnCl
22H
2The concentration of O is 0.046-0.058mol/L, preferred 0.05-0.055mol/L; SeO
2Concentration be 0.0018-0.0025mol/L, preferred 0.002-0.0025mol/L; Na
2CO
3Concentration be 0.0018-0.0025mol/L, preferred 0.002-0.0025mol/L; The concentration of trisodium citrate is 0.018-0.026mol/L, preferred 0.02-0.025mol/L; The volume ratio of USP Kosher and water is preferably 2: 3.
10. a kind of method that in titania nanotube, deposits the SnSe/Ag nano particle according to claim 6 is characterized in that the depositing temperature in the said step (3) is 40-45 ℃, and depositing time is 3-7h; The volume ratio of terepthaloyl moietie and water is (3-2) in the silver nitrate solution: (2-3), be preferably both equal-volume ratios; The concentration of Vinylpyrrolidone polymer is 0.00002-0.0026mol/L, preferred 0.0016-0.0026mol/L, more preferably 0.0016mol/L; NaBH
4Concentration be 0.026-0.068mol/L, preferred 0.048-0.068mol/L, more preferably 0.048mol/L; AgNO
3Concentration be 0.035-0.060mol/L, preferred 0.035-0.045mol/L, more preferably 0.045mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100089603A CN102534726A (en) | 2012-01-12 | 2012-01-12 | Titanium dioxide (TiO2) nanotube composite material and method for depositing SnSe/Ag nanoparticles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100089603A CN102534726A (en) | 2012-01-12 | 2012-01-12 | Titanium dioxide (TiO2) nanotube composite material and method for depositing SnSe/Ag nanoparticles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102534726A true CN102534726A (en) | 2012-07-04 |
Family
ID=46342710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100089603A Pending CN102534726A (en) | 2012-01-12 | 2012-01-12 | Titanium dioxide (TiO2) nanotube composite material and method for depositing SnSe/Ag nanoparticles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102534726A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965710A (en) * | 2012-11-13 | 2013-03-13 | 同济大学 | Preparation of silver/cadmium sulfide-nanoparticle-comodified titanium dioxide nanotube array |
| CN103110981A (en) * | 2013-01-10 | 2013-05-22 | 内蒙金属材料研究所 | Method for preparing antibacterial active titanium oxide nanotube array composite coating material |
| CN104078244A (en) * | 2013-03-26 | 2014-10-01 | 中国科学院大连化学物理研究所 | Metallic-niobium-doping titanium dioxide nanometer sheet, and preparing method and application of metallic-niobium-doping titanium dioxide nanometer sheet |
| CN110504438A (en) * | 2019-08-31 | 2019-11-26 | 河南师范大学 | A kind of preparation method and applications of exotic atom doping carbon coating two-dimensional metallic selenides nanosheet composite material |
| CN110732303A (en) * | 2019-12-05 | 2020-01-31 | 中南大学 | transition metal selenide modified molding demercuration material and preparation method thereof |
| CN111632602A (en) * | 2019-03-01 | 2020-09-08 | 南京理工大学 | Preparation method of nanoparticle/nanotube composite material |
| CN113456896A (en) * | 2021-05-20 | 2021-10-01 | 宁波市医疗中心李惠利医院 | Selenium-doped titanium dioxide nanotube array orthopedic anti-tumor implant |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080078962A (en) * | 2007-02-26 | 2008-08-29 | 요업기술원 | Processing of 3-dimensional photocatalytic parts |
| CN101591001A (en) * | 2009-06-29 | 2009-12-02 | 西北有色金属研究院 | A kind of Pd doped Ti O 2The preparation method of nanotube array composite material |
| CN101613080A (en) * | 2009-07-23 | 2009-12-30 | 重庆大学 | A kind of method for preparing composite material for nanometer nickel/titanium dioxide nanotube array |
| CN101899701A (en) * | 2010-07-19 | 2010-12-01 | 西南交通大学 | Method for preparing composite material of copper sulfide and titanium dioxide nano-tube |
| CN101922044A (en) * | 2010-09-11 | 2010-12-22 | 天津大学 | Method for doping nano-Ag particles in TiO2 nanotubes |
| CN101922036A (en) * | 2010-09-11 | 2010-12-22 | 天津大学 | Method for doping magnetic particles of ferroferric oxide in titanium dioxide nanotube |
-
2012
- 2012-01-12 CN CN2012100089603A patent/CN102534726A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080078962A (en) * | 2007-02-26 | 2008-08-29 | 요업기술원 | Processing of 3-dimensional photocatalytic parts |
| CN101591001A (en) * | 2009-06-29 | 2009-12-02 | 西北有色金属研究院 | A kind of Pd doped Ti O 2The preparation method of nanotube array composite material |
| CN101613080A (en) * | 2009-07-23 | 2009-12-30 | 重庆大学 | A kind of method for preparing composite material for nanometer nickel/titanium dioxide nanotube array |
| CN101899701A (en) * | 2010-07-19 | 2010-12-01 | 西南交通大学 | Method for preparing composite material of copper sulfide and titanium dioxide nano-tube |
| CN101922044A (en) * | 2010-09-11 | 2010-12-22 | 天津大学 | Method for doping nano-Ag particles in TiO2 nanotubes |
| CN101922036A (en) * | 2010-09-11 | 2010-12-22 | 天津大学 | Method for doping magnetic particles of ferroferric oxide in titanium dioxide nanotube |
Non-Patent Citations (3)
| Title |
|---|
| KUNPENG XIE ET AL.: "Electrochemical construction of Z-scheme type CdS–Ag–TiO 2 nanotube arrays with enhanced photocatalytic activity", 《ELECTROCHEMISTRY COMMUNICATIONS》, vol. 13, 1 October 2011 (2011-10-01) * |
| Y. Q. LIANG ET AL.: "SnSe Nanoparticles Anchored on TiO 2 Nanotube Arrays by Pulsed Electrochemical Deposition", 《ELECTROCHEMICAL AND SOLID-STATE LETTERS》, vol. 15, no. 1, 21 November 2011 (2011-11-21) * |
| Y.Q. LIANG ET AL.: "Silver nanoparticles supported on TiO 2 nanotubes as active catalysts for ethanol oxidation", 《JOURNAL OF CATALYSIS》, vol. 278, 3 February 2011 (2011-02-03) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965710A (en) * | 2012-11-13 | 2013-03-13 | 同济大学 | Preparation of silver/cadmium sulfide-nanoparticle-comodified titanium dioxide nanotube array |
| CN103110981A (en) * | 2013-01-10 | 2013-05-22 | 内蒙金属材料研究所 | Method for preparing antibacterial active titanium oxide nanotube array composite coating material |
| CN103110981B (en) * | 2013-01-10 | 2014-06-04 | 内蒙金属材料研究所 | Method for preparing antibacterial active titanium oxide nanotube array composite coating material |
| CN104078244A (en) * | 2013-03-26 | 2014-10-01 | 中国科学院大连化学物理研究所 | Metallic-niobium-doping titanium dioxide nanometer sheet, and preparing method and application of metallic-niobium-doping titanium dioxide nanometer sheet |
| CN111632602A (en) * | 2019-03-01 | 2020-09-08 | 南京理工大学 | Preparation method of nanoparticle/nanotube composite material |
| CN110504438A (en) * | 2019-08-31 | 2019-11-26 | 河南师范大学 | A kind of preparation method and applications of exotic atom doping carbon coating two-dimensional metallic selenides nanosheet composite material |
| CN110732303A (en) * | 2019-12-05 | 2020-01-31 | 中南大学 | transition metal selenide modified molding demercuration material and preparation method thereof |
| CN113456896A (en) * | 2021-05-20 | 2021-10-01 | 宁波市医疗中心李惠利医院 | Selenium-doped titanium dioxide nanotube array orthopedic anti-tumor implant |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101922044B (en) | Method for doping nano-Ag particles in TiO2 nanotubes | |
| Saraswat et al. | Recent advancements in semiconductor materials for photoelectrochemical water splitting for hydrogen production using visible light | |
| Wang et al. | Crystal facet engineering of photoelectrodes for photoelectrochemical water splitting | |
| Qin et al. | Intergrowth of cocatalysts with host photocatalysts for improved solar-to-hydrogen conversion | |
| Sun et al. | Phase Effect of Ni x P y Hybridized with g-C3N4 for Photocatalytic Hydrogen Generation | |
| Wang et al. | Monoclinic β-AgVO3 coupled with CdS formed a 1D/1D p–n heterojunction for efficient photocatalytic hydrogen evolution | |
| CN102534726A (en) | Titanium dioxide (TiO2) nanotube composite material and method for depositing SnSe/Ag nanoparticles | |
| CN102352524B (en) | Metal oxide modified TiO2 nanometer tube array electrode and preparation method thereof | |
| CN102251266B (en) | Method for preparing nano platinum/titanium dioxide nanotube electrode by pulse electrodeposition | |
| Xiong et al. | Silicon nanowire array/Cu2O crystalline core–shell nanosystem for solar-driven photocatalytic water splitting | |
| Koteeswara Reddy et al. | Electrochemical water oxidation of ultrathin cobalt oxide-based catalyst supported onto aligned ZnO nanorods | |
| Wu et al. | Enhanced photoelectrocatalytic hydrogen production activity of SrTiO3–TiO2 hetero-nanoparticle modified TiO2 nanotube arrays | |
| CN102240550A (en) | Low-concentration copper-doped titanium dioxide nanotube photocatalyst and preparation method thereof | |
| CN110592614B (en) | Three-dimensional self-supporting electrocatalyst for preparing hydrogen by water decomposition and preparation method thereof | |
| CN105297107A (en) | Method for preparing nanometer platinum nickel/titanium dioxide nanotube electrode by cyclic voltammeter electrodeposition | |
| Wang et al. | Electrochemical deposition of p-type β-Ni (OH) 2 nanosheets onto CdS nanorod array photoanode for enhanced photoelectrochemical water splitting | |
| Chen et al. | Boosting visible-light hydrogen evolution on CdS hollow nanospheres with CoN as cocatalyst | |
| CN102703953B (en) | Method for preparing nanometer platinum/titanium dioxide nanotube electrode through cyclic voltammetry electrodeposition | |
| Jia et al. | Improvement of photocatalytic hydrogen generation of leaves-like CdS microcrystals with a surface decorated by dealloyed Pt-Cox nanoparticles | |
| Wang et al. | Well-dispersed Pd–Sn nanocatalyst anchored on TiO2 nanosheets with enhanced activity and durability for ethanol electarooxidation | |
| Ma et al. | A highly efficient (Mo, N) codoped ZnIn2S4/g-C3N4 Z-scheme photocatalyst for the degradation of methylene blue | |
| CN108866563A (en) | A kind of pucherite film photo cathode, preparation method and the purposes of the modification of boronation cobalt | |
| CN108232207B (en) | Preparation method of nano platinum catalyst | |
| CN113789535B (en) | Rod-shaped ruthenium particle/selenide composite catalyst and preparation method and application thereof | |
| CN113235125A (en) | Nickel-based NiCo2O4Electrocatalyst and its use in electrocatalytic oxidation of glycerol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120704 |