CN109055919A - The TiO of the activity improvement of semiconductor2Nanotube array composite material and preparation method thereof - Google Patents

The TiO of the activity improvement of semiconductor2Nanotube array composite material and preparation method thereof Download PDF

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CN109055919A
CN109055919A CN201810821799.9A CN201810821799A CN109055919A CN 109055919 A CN109055919 A CN 109055919A CN 201810821799 A CN201810821799 A CN 201810821799A CN 109055919 A CN109055919 A CN 109055919A
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tio
nano
wall
precursor solution
tube array
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CN109055919B (en
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顾艳红
郑新华
罗彦
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Beijing Institute of Petrochemical Technology
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Beijing Institute of Petrochemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1287—Process of deposition of the inorganic material with flow inducing means, e.g. ultrasonic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides

Abstract

The present invention relates to a kind of TiO of the activity improvement of semiconductor2Nanotube array composite material and preparation method thereof, wherein method includes the following steps: Step 1: preparing TiO using anodizing2Nano-tube array；Cadmium source precursor solution, lead source precursor solution and sulphur source precursor solution are obtained Step 2: cadmium source, lead source and sulphur source are dissolved in respectively in alcohols solvent；Step 3: carrying out continuous ionic layer using ultrasonic wave added is deposited in TiO2The inner and outer wall of nano-tube array is formed simultaneously uniform CdS particle and PbS particle, then after heat treatment obtains the TiO of the activity improvement of semiconductor2Nanotube array composite material.CdS/PbS/TiO produced by the present invention2The uniform CdS and PbS particle of large area is capable of forming in nanotube array composite material on the inside and outside wall of nanotube, greatly strengthens the composite material to the utilization rate of sunlight.Method is simple simultaneously, process is easily manipulated and Material cladding is uniform.

Description

The TiO of the activity improvement of semiconductor2Nanotube array composite material and preparation method thereof
Technical field
The invention belongs to semiconductor composite technical fields, are related to a kind of TiO of the activity improvement of semiconductor2Nano-tube array is multiple Condensation material and preparation method thereof.
Background technique
TiO2Nano-tube array has biggish specific surface area, so there is the capture of large area to sunlight, therefore embodies Preferable photoelectric properties, are concerned.Again due to effects such as its preferable stability and small sizes, so in solar battery, Photocatalysis, hydrogen production by water decomposition gas aspect are concerned.Existing middle preparation TiO2The method of nano-tube array has hydro-thermal method, template Method, sol-gal process and anodizing, using TiO made from hydro-thermal method and sol-gal process2Nanotube both ends are opening, But more chaotic, irregular is arranged, performance is poor；Template although available more regular array structure, still Preparation process is complicated, and process is difficult to.And use TiO made from anodizing2Nano-tube array high-sequential rule, tool Become the most common method of current researcher for superior performance.
TiO2Forbidden bandwidth be 3.2eV, can only utilize λ < 387nm ultraviolet portion, so cause to light utilize Significant ASIC limitation.But it is based on TiO2The excellent properties of itself can effectively go to make up this using certain means and lack It falls into.In TiO2The middle a certain amount of metal or nonmetalloid of mixing can effectively cause some lattice defects, and be formed Impurity band can widen light abstraction width.In contrast, the most obvious using metal semiconductor modified effect, metal is partly led Body and TiO2Between be capable of forming heterojunction structure, can effectively realize the transfer of the electrons and holes between valence band conduction band, have Effect inhibits the compound of light induced electron and hole, improves the utilization rate of electronics.Simultaneously because the band gap of some metal semiconductors compared with It is narrow, it can use visible light, this greatly enhances composite Ti O again2Afterwards to the utilization of sunlight.
In existing generally using electrochemical deposition method, electrophoretic deposition, chemical vapour deposition technique, atomic layer deposition method or Continuous ionic sedimentation etc. is by above-mentioned semiconductor deposition in TiO2On nanotube.Although having been obtained to its light abstraction width different It improves, but using nanotube bottom end made from anodic oxidation is closed state, is found in research: due to the pipe of nanotube Diameter is very thin (about in 100 rans), its internal air is difficult to be discharged when this has resulted in nanotube in the solution, together When titanium dioxide hydrophily it is poor, when causing in existing no matter to carry out composite semiconductor using which kind of above-mentioned method, can only It is compounded in the surface (i.e. at nozzle) of nanotube, can not or seldom be doped into the inside of nanotube, and simultaneously uneven.And then it can not Utilize TiO2The advantages of nanotube large specific surface area, can not effectively reduce the compound of electrons and holes, to raising hetero-junctions Photoelectric properties cause very big influence.
Therefore, how to solve semiconductor grain and be difficult to enter TiO2It the inside of nanotube simultaneously can not be in the inside and outside wall of nanotube The problem of upper formation large area hetero-junctions, is as the hot spot studied at present.
Summary of the invention
(1) technical problems to be solved
In order to solve the above problem of the prior art, the present invention provides a kind of TiO of the activity improvement of semiconductor2Nano-tube array is multiple Condensation material and preparation method thereof solves semiconductor grain in the prior art and is difficult to enter TiO2It the inside of nanotube simultaneously can not be The problem of large area hetero-junctions is formed on the inside and outside wall of nanotube.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
One aspect of the present invention provides a kind of TiO of the activity improvement of semiconductor2The preparation method of nanotube array composite material, including Following steps: Step 1: preparing TiO using anodizing2Nano-tube array；Step 2: cadmium source, lead source and sulphur source are distinguished It is dissolved in alcohols solvent and obtains cadmium source precursor solution, lead source precursor solution and sulphur source precursor solution；Wherein, cadmium source forerunner Concentration, the concentration of lead source precursor solution and the concentration of sulphur source precursor solution of liquid solution are 0.005~0.2mol/L；Step Rapid three, continuous ionic layer is carried out using ultrasonic wave added be deposited in TiO2The inner and outer wall of nano-tube array is formed simultaneously uniformly CdS particle and PbS particle, then after heat treatment obtain the TiO of the activity improvement of semiconductor2Nanotube array composite material；Wherein, in step In rapid three, the temperature of heat treatment is 280~400 DEG C, and heating rate when heat treatment is 1~4 DEG C/min, and the time of heat treatment is 0.5~3h.
Wherein, the concentration of precursor solution can have an impact to the size for the CdS and PbS particle that deposition generates, when concentration is big When 0.2mol/L, CdS the and PbS particle of formation is larger, easily there is a phenomenon where reuniting, therefore, to the concentration of precursor solution It is strict controlled in 0.005~0.2mol/L.Further preferably 0.01mol/L, under this parameter, the particle of formation is small and equal It is even.
Further, in step 3, due to CdS and PbS and TiO2Expansibility and contractibility it is different, when the temperature of heat treatment When degree is greater than 400 DEG C, CdS and PbS particle and TiO are easily caused2The place of combining easily causes removing and crystals to generate defect, And the temperature being heat-treated less than 280 DEG C when, CdS and PbS particle can not be fully crystallized, therefore, tight to the temperature of heat treatment Lattice are controlled at 280~400 DEG C, to be fully crystallized and the preferable CdS and PbS particle of performance.Further preferably, it is heat-treated Temperature be 300 DEG C, heating rate is 2 DEG C/min, and time of heat treatment is 2h, and the performance of obtained CdS and PbS particle is most It is good.
According to the present invention, in step 2: alcohols solvent is that second alcohol and water is what 3.5~8:1 was prepared by volume Mixed solution；Cadmium source is Cd (NO3)2Or CdCl2, lead source is Pb (NO3)2Or PbCl2, sulphur source Na2S or thiocarbamide；Prepare cadmium source It is all made of ultrasonic wave added when precursor solution, lead source precursor solution and sulphur source precursor solution and dissolves 6~20min.
Wherein, the volume ratio of second alcohol and water is more preferably 4:1, and under this parameter, the precursor solution of formation more holds Easily enter the inside of nanotube.
According to the present invention, step 3 includes following sub-step: c1, by TiO2Nano-tube array immerses lead source precursor solution In, and ultrasonic assistant soakage is utilized in the precursor solution of lead source, in TiO2Nano-tube array outer wall and inner wall attachment lead from Then son is rinsed and rinses；C2, the outer wall obtained after rinsing in step c1 and inner wall are attached with the TiO of lead ion2It receives Mitron array immerses in sulphur source precursor solution, and ultrasonic assistant soakage is utilized in sulphur source precursor solution, in TiO2Nanometer The outer wall and inner wall of pipe array deposit to form PbS particle, are then rinsed and rinse；C3, it is obtained after being rinsed in step c2 Outer wall and inner wall be deposited with the TiO of PbS particle2Nano-tube array immerses in the precursor solution of cadmium source, and in cadmium source presoma Ultrasonic assistant soakage is utilized in solution, in TiO2The outer wall and inner wall of nano-tube array adhere to cadmium ion, be then rinsed and It rinses；C4, the outer wall obtained after rinsing in step c3 and inner wall are attached with the TiO of cadmium ion2Nano-tube array immerses sulphur source In precursor solution, and ultrasonic assistant soakage is utilized in sulphur source precursor solution, in TiO2The outer wall of nano-tube array and interior Wall deposits to form CdS particle, is then rinsed and rinses；C5, CdS is formed simultaneously with to the obtained outer wall of step c4 and inner wall The TiO of particle and PbS particle2Nano-tube array is dried and is heat-treated, and obtains CdS/PbS/TiO2Nano-tube array composite wood Material.
Wherein, it should be noted that considered critical is not done for the sequencing of c1 and c2 and c3 and c4, it both can be first It carries out step c1 and c2 and deposits PbS, then carry out step c3 and c4 deposition CdS, can also first carry out step c3 and c4 deposition CdS, Step c1 and c2 deposition PbS are carried out again.Further preferably first cyclic deposition PbS, rear cyclic deposition CdS, by largely trying Test studies have shown that due to PbS and CdS self structure difference, using first depositing the obtained composite material of deposition CdS after PbS Performance is best.
According to the present invention, before step c3, first repetitive cycling step c1 and c2 totally 5~12 times, then carry out step c3 and Then c4 repeats step c3 and c4 8~16 times, finally enter back into step c5 totally；Or carry out step c1, c2, c3 and c4 it Afterwards, it first carries out repetitive cycling step c1, c2, c3 and c4 totally 8~12 times, then enters back into step c5.
Wherein, it is emphasized that, during above-mentioned circulation, for using the phosphoric acid and ammonium fluoride body in the present invention The characteristics of nanotube made of the electrolyte of system, finds by a large amount of experimental study, as cyclic deposition cycle P bS respectively and follows When ring deposits CdS, repetitive cycling deposits the number of PbS less than 5 times and when the number of repetitive cycling deposition CdS is less than 8 times, especially It is cycle P bS less than 3 times and when circulation CdS is less than 6 times, it is relatively fewer in the semiconductor grain that the inside and outside wall of nanotube is formed, Performance is simultaneously bad, and repetitive cycling deposition PbS number be greater than 12 times and repetitive cycling deposition CdS number be greater than 16 times when, It easily causes the agglomeration of semiconductor grain and influences the performance of material.
Therefore, when difference cyclic deposition cycle P bS and cyclic deposition CdS, the number of repetitive cycling will be strict controlled in weight Multiple cyclic deposition PbS totally 5~12 times, repetitive cycling deposits CdS 8~16 times totally.It is total to be further preferably repeatedly cycling deposition PbS 9 times, repetitive cycling deposits CdS 15 times totally, and the material property of acquisition is best.Wherein, precipitating is more readily formed in PbS, is easier to grow It forms sediment, and CdS is there is no this characteristic, grows slower compared to PbS, therefore, the number of cycle P bS is than circulation CdS's Number is relatively less.
And when recycling using one time PbS and one time CdS of deposition as one and constantly repeating, using a small amount of multiple layer by layer deposition When, when the number of repetitive cycling is less than 8 times, relatively fewer in the semiconductor grain that the inside and outside wall of nanotube is formed, performance is not It is good, and when the number of repetitive cycling is greater than 12 times, it easily causes the agglomeration of semiconductor grain and influences the performance of material.Cause This, when using a small amount of multiple layer by layer deposition, the number of repetitive cycling will be strict controlled in 8~12 times.Further preferably repeat Circulation 9 times, the material property of acquisition is best.
According to the present invention, in step c1, c2, c3 and c4, the power of ultrasonic wave added is 80~150W, auxiliary using ultrasound The time for helping dipping is 8~25s, and the solvent or ethyl alcohol for being all made of the formation of second alcohol and water carry out repeated flushing and rinse repeatedly It washes.
Wherein, in step c1, c2, c3 and c4, when the power of ultrasonic wave added is less than 80W, precursor solution is difficult to enter The inside of nanotube, and power be greater than 150W when, easily cause the destruction of nanotube, therefore, the power of ultrasonic wave added should control 80~150W.
Further, the time of ultrasonic assistant soakage is longer, then the CdS or PbS particle growth for depositing formation is bigger, when super The phenomenon that when time of sound assistant soakage is greater than 25s, particle is larger, easily causes reunion.And short grained CdS or PbS is on the one hand It is easy to immerse the inside of nanotube, another aspect little particle will not keep off TiO2The daylighting of itself, and little particle is more sensitive, more Acceptant sunlight, and then greatly increase the utilization rate to sunlight.Furthermore, it is necessary to, it is emphasized that since the present invention is benefit With the mode for repeating ultrasound, a large amount of experimental study discovery of process, under the power bracket of above-mentioned ultrasonic wave added, when each When the time of ultrasonic assistant soakage is greater than 25s, the established semiconductor in nanotube will lead to after ultrasound is repeated several times There may be exceeded from pipe particle by ultrasonic energy damages.
Therefore, the time of ultrasonic assistant soakage will be strict controlled in 8~25s, can either form more CdS or PbS Grain, while it is excessive and cause to reunite not will cause CdS or PbS particle again, and not will cause and cause shape because ultrasound is repeated At semiconductor grain damage.
According to the present invention, in step c1, c2, c3 and c4: being rinsed and rinse using the solvent of the formation of second alcohol and water When washing, the volume ratio of second alcohol and water is 3.5~8:1；It repeated flushing and repeatedly rinses equal 8~25 times；And/or after being rinsed, Again to the TiO after rinsing2Nano-tube array is dried up.
According to the present invention, in step c4, dry temperature is 65~90 DEG C, and the dry time is 60~180min.
According to the present invention, TiO is prepared using anodizing2Nano-tube array includes following sub-step: a1, to titanium sheet into Row pretreatment；A2, phosphoric acid solution and ammonium fluoride solution are mixed, the electrolyte as anodic oxidation；A3, with pretreatment after Titanium sheet as anode, graphite carries out anodic oxidation certain time as cathode, using D.C. regulated power supply, obtains TiO2Nanometer Pipe array presoma；A4, to TiO2Nano-tube array presoma is heat-treated, and TiO is obtained2Nano-tube array.
According to the present invention, in step a1, pretreatment include first by titanium sheet respectively successively deionized water, acetone, go from 6~20min of cleaning is carried out using ultrasonic wave added in sub- water, isopropanol, deionized water and dehydrated alcohol, is then dried again； In step a2, the concentration of phosphoric acid solution is 0.05~0.3mol/L, the mass percentage concentration of ammonium fluoride solution is 0.2~ 0.8%；In step a3, voltage is 15~25V, and the time of anodic oxidation is 1~3h；In step a4, the temperature of heat treatment It is 450~600 DEG C, heating rate when heat treatment is 2~5 DEG C/min, and the time of heat treatment is 2~5h.
Wherein, in step a2, the concentration of phosphoric acid solution and ammonium fluoride solution mainly will affect the speed of growth of nanotube And regular degree, the concentration of phosphoric acid solution is more preferably 0.1mol/L, and the mass percentage concentration of ammonium fluoride solution is further Preferably 0.5%, under this parameter, the speed of growth is best, obtains the more uniform rule of nanotube.
Further, in step a3, the pattern for the nanotube that different voltage will affect, by largely testing The study found that voltage is excessive, can drive ion-transfer, easily causes the destruction of nanotube, causes nanometer when voltage is greater than 25V Pipe it is imperfect；And when being less than 15V, nanotube grows and is not thorough, and desired value can be not achieved in pipe range, caliber etc., and performance is not It is good.Therefore voltage will be controlled in 15~25V.And the time of anodic oxidation will affect the pipe range of nanotube, by largely testing Studies have shown that can make nanotube growth more abundant when 1~3h of anodic oxidation, specific oxidization time is according to the constant pressure of selection The difference of voltage and be specifically chosen.
Further preferably voltage is 20V, and the time of anodic oxidation is 1h, and nanotube growth can be made under this parameter more Add sufficiently, while performance is best, it is finally obtained be along titanium sheet same direction growth, arrangement it is relatively closer and height has The nanotube of sequence, rule.
Further, in step a4, the temperature of heat treatment will cause very the crystal grain composition of finally obtained nanotube It is big to influence.If temperature is greater than 600 DEG C, obtained titanium oxide can be changed into the crystal form of another rutile, but the light of this crystal form Electrical property is poor, to solar energy use less efficient.If temperature, less than 450 DEG C, finally formed crystallization is not thorough enough, can also deposit In part amorphous state, and amorphous titanium dioxide is to solar energy use less efficient.Therefore, the temperature of heat treatment will be controlled strictly System is at 450~600 DEG C.The temperature being further preferably heat-treated is 500 DEG C, and heating rate is 2 DEG C/min, the time of heat treatment For 3h, under this parameter, the crystal form of obtained nanotube is best, performance is best.
Another aspect of the present invention provides a kind of TiO of the activity improvement of semiconductor2Nanotube array composite material is appointed using above-mentioned One method is prepared.
(3) beneficial effect
The beneficial effects of the present invention are:
Ultrasonic wave added and continuous ionic sedimentation are combined carry out preparation CdS/PbS/TiO for the first time by the present invention2Nanotube The TiO of arrangement high-sequential is first made using anodizing for array composite material2Nano-tube array recycles ultrasonic wave Energy can make solution more uniform, while the energy can be such that the air retained in nanotube is effectively discharged, and then cadmium source Precursor solution, lead source precursor solution and sulphur source precursor solution bring the inside of nanotube into, and solution drives the ion of the inside Into after the inside of nanotube, it is compound that one is formed in internal and external walls, and then form the multi-element heterogeneous knot of equably large area.
Carried out when continuous ionic sedimentation simultaneously the repeatedly mode that deposits repeatedly and by ultrasonic wave added by CdS and PbS with TiO2Nano-tube array carries out compound, can prevent the formation bulky grain of large area, avoid that there is a phenomenon where reunite.And ultrasound Auxiliary can make solution be easier to enter the inside of nanotube and more uniform, therefore be easier the shape on the inside and outside wall of nanotube At CdS the and PbS particle more evenly of large area.And CdS compares TiO with PbS2Not only there is relatively narrow band-gap energy, simultaneously Band-gap degree between short grained CdS and PbS is preferable.Therefore, final compound obtained CdS/PbS/TiO2Nanotube Array composite material can successfully realize the transfer between electrons and holes, effective to inhibit the compound of hole and electronics, together When can also improve utilization rate to sunlight.In addition, preparation method of the invention is easy to operate, process is easily manipulated and material is multiple It closes uniform.
Detailed description of the invention
Fig. 1 is TiO made from following examples 12The infiltration shape test chart of nano-tube array in deionized water；
Fig. 2 is TiO made from following examples 12Infiltration shape of the nano-tube array in the second alcohol and water that volume ratio is 4:1 Test chart；
Fig. 3 is TiO made from following examples 12The SEM on the surface of nano-tube array schemes；
Fig. 4 is TiO made from following examples 12The SEM in the section of nano-tube array schemes；
Fig. 5 is CdS/PbS/TiO made from following examples 12The SEM on the surface of nanotube array composite material schemes；
Fig. 6 is CdS/PbS/TiO made from following examples 12The SEM in the section of nanotube array composite material schemes；
Fig. 7 is CdS/PbS/TiO made from following examples 12The EDS energy spectrum diagram of nanotube array composite material；
Fig. 8 is TiO made from following examples 12Nano-tube array and CdS/PbS/TiO2Nanotube array composite material XRD diagram；
Fig. 9 is TiO made from following examples 12Nano-tube array and CdS/PbS/TiO2Nanotube array composite material Ultraviolet-visible absorption spectroscopy figure.
Specific embodiment
In order to preferably explain the present invention, in order to understand, with reference to the accompanying drawing, by specific embodiment, to this hair It is bright to be described in detail.
Embodiment 1
The present embodiment provides a kind of TiO of the activity improvement of semiconductor2The preparation method of nanotube array composite material, and in particular to A kind of CdS/PbS/TiO2The preparation method of nanotube array composite material, includes the following steps:
Step 1: preparing TiO using anodizing2Nano-tube array.
Step 2: by Cd (NO3)2(i.e. cadmium source), which is dissolved in the mixed solution of second alcohol and water formation, to be obtained concentration and is The cadmium source precursor solution of 0.01mol/L, Pb (NO3)2(i.e. lead source), which is dissolved in the mixed solution of second alcohol and water formation, obtains concentration For the lead source precursor solution of 0.01mol/L, by Na2S (i.e. sulphur source) be dissolved in second alcohol and water formation mixed solution in obtain it is dense Degree is the sulphur source precursor solution of 0.01mol/L.Ultrasonic wave added dissolution 10min is all made of during being prepared simultaneously, It is dissolved in reagent preferably in the mixed solution that water and ethyl alcohol are formed, to guarantee that reagent can be completely dissolved.
Wherein, when preparing, the volume ratio of the second alcohol and water in mixed solution used is 4:1, due to deionized water TiO can not be directly entered2The inside of nanotube, and organic solvent can easily enter, and therefore, herein carry out second alcohol and water Mixed solution is mixed to get to carry out preparing cadmium source precursor solution, lead source precursor solution and sulphur source precursor solution, a side again Face water energy enough makes cadmium source, lead source and the sufficiently dissolution of sulphur source acid, and then is more easily dispersed in dissolved cadmium source, lead source and sulphur source In ethyl alcohol, on the other hand, cadmium source precursor solution, lead source precursor solution and sulphur source precursor solution are enabled to as far as possible Enter TiO2The inside of nanotube.
Further, referring to Figures 1 and 2, Fig. 1 is TiO obtained2The infiltration shape of nano-tube array in deionized water is surveyed Attempt, Fig. 2 is TiO obtained2Infiltration shape test chart of the nano-tube array in the second alcohol and water that volume ratio is 4:1.From Fig. 1 As can be seen that deionized water is in TiO2There is certain contact angle on nano-tube array surface, measured in experiment about 30~ 40 °, it can be seen that water can not be impregnated into TiO2In nanotube.From figure 2 it can be seen that the solution of second alcohol and water is in TiO2It receives Mitron array surface is sprawled rapidly, and contact angle is smaller, can be entered in pipe with complete wetting substantially, illustrates that this solution can be with base This complete wetting enters TiO2In nanotube, it is more advantageous to and ion is driven to enter the uniform modified structure of formation inside nanotube.
Step 3: carrying out continuous ionic layer using ultrasonic wave added is deposited in TiO2The inner and outer wall of nano-tube array is simultaneously Uniform CdS particle and PbS particle are formed, then after heat treatment obtains the TiO of the activity improvement of semiconductor2Nano-tube array composite wood Material.Specifically include following sub-step:
C1, by TiO2Nano-tube array is immersed vertically in the precursor solution of lead source, is clamped at this time with tweezers to be convenient to take Out, ultrasonic assistant soakage 15s is utilized and in the precursor solution of lead source, the power of ultrasonic wave added is 80W, during this, solution The inside for entering nanotube from the nozzle of nanotube, in TiO2The outer wall and inner wall of nano-tube array adhere to lead ion, then It is carried out repeated flushing 10 times using a large amount of solvent, then by the TiO after flushing2Nano-tube array immerse solvent in oscillate into Row rinses 10 times.
Wherein, it is rinsed primarily to removing TiO2The remaining ion in the outer surface of nano-tube array (including lead from Son, nitrate ion).During rinsing herein, solvent is in flow regime, and solvent immerses the inside of nanotube to remove TiO2 The ion of the internal residual of nanotube prevents the subsequent agglomeration that PbS occurs.Being rinsed and rinse solvent used is Volume ratio is the mixed solution of the second alcohol and water of 4:1, so that the solution can be easier the inside into nanotube.
C2, the outer wall obtained after rinsing in step c1 and inner wall are attached with the TiO of lead ion2Nano-tube array turns rapidly It moves and immerses in sulphur source precursor solution, and utilize ultrasonic assistant soakage 15s, the power of ultrasonic wave added in sulphur source precursor solution The deposition reaction of PbS occurs, and then in TiO in the process for 80W2The outer wall and inner wall of nano-tube array deposit to be formed PbS particle.
Then it is carried out repeated flushing 10 times using a large amount of solvent (the second alcohol and water that volume ratio is 4:1), to remove TiO2 The ion remained on surface of nano-tube array (including sulphion, sodium ion and does not enter inside nanotube and in remained on surface PbS).Again by the TiO after flushing2Nano-tube array, which immerses in solvent to oscillate, rinse 10 times, to remove TiO2Nanometer The ion of the internal residual of pipe prevents the agglomeration of PbS.
Using step c1 and c2 as the circulation circulation of deposition (i.e. a PbS), repetitive cycling step c1 and c2 totally 9 Secondary, at this point, the inner and outer wall in entire nanotube is respectively formed on uniform PbS particle, the PbS particle obtained at this time is most of For amorphous state.
C3, the TiO that the outer wall obtained after repetitive cycling and inner wall are deposited with to PbS particle2Nano-tube array immerses vertically In the precursor solution of cadmium source, and ultrasonic assistant soakage 15s being utilized in the precursor solution of cadmium source, the power of ultrasonic wave added is 80W, In TiO2The outer wall and inner wall of nano-tube array adhere to cadmium ion, then carry out repeated flushing and repeatedly rinse each 10 times.
C4, the outer wall obtained after rinsing in step c3 and inner wall are attached with the TiO of cadmium ion2Nano-tube array turns rapidly It moves and immerses in sulphur source precursor solution, and utilize ultrasonic assistant soakage 15s, the power of ultrasonic wave added in sulphur source precursor solution The deposition reaction of CdS occurs, and then in TiO in the process for 80W2The outer wall and inner wall of nano-tube array deposit to be formed Then CdS particle carries out repeated flushing and repeatedly rinses each 10 times.
Using step c3 and c4 as the circulation circulation of deposition (i.e. a CdS), repetitive cycling step c3 and c4 totally 15 Secondary, at this point, the inner and outer wall in entire nanotube is respectively formed on uniform CdS particle, the CdS particle obtained at this time is most of For amorphous state.
That is, the TiO obtained at this time2The outer wall and inner wall of nano-tube array are formed simultaneously with CdS particle and PbS Grain.Since the concentration of used cadmium source precursor solution, lead source precursor solution and sulphur source precursor solution is lower, because This, the less particle of amount of the CdS and PbS particle formed when recycling 1 time every time is smaller, therefore, using this few in the present embodiment The compound CdS and PbS particle of multiple method is measured, CdS and PbS can not only be made as much as possible to enter TiO2The inside of nanotube, What is be formed simultaneously is little particle, substantially increases the composite material to the utilization rate of sunlight.
C5, the TiO that CdS particle and PbS particle are formed simultaneously with to the outer wall and inner wall that obtain after repetitive cycling2Nanotube 30min is dried at 80 DEG C in array, is then placed in Muffle furnace, is warming up to 300 DEG C with the heating rate of 2 DEG C/min, into Row heat treatment 2h, in the process, amorphous CdS and PbS are changed into the CdS and PbS for being fully crystallized state, obtain CdS/PbS/ TiO2Nanotube array composite material (the i.e. TiO of the activity improvement of semiconductor2Nanotube array composite material).
Further, above-mentioned steps one specifically comprise the following steps:
A1, titanium sheet is pre-processed.
Specifically, titanium sheet selected by the present embodiment is industrially pure titanium TA0, and preprocessing process specifically comprises the following steps: Titanium sheet is first cut into 20 × 30mm2Specification size, then respectively successively deionized water, acetone, deionized water, isopropanol, Cleaning 10min is carried out using ultrasonic wave added in deionized water and dehydrated alcohol, be finally dried again (such as drying or baking It is dry), obtain pretreated titanium sheet.
Wherein, when being cleaned, acetone and isopropanol are primarily to remove the grease type of titanium plate surface, first with clear The stronger acetone of dynamics is washed, the isopropanol for recycling cleaning dynamics weaker with respect to acetone can clean more thoroughly.And it finally uses Dehydrated alcohol cleaned and and non-used deionized water, primarily to prevent cleaning after titanium sheet because have water presence and It causes to aoxidize.Therefore, dehydrated alcohol is finally used, one side dehydrated alcohol is volatile when the later period is dry, on the other hand anhydrous Ethyl alcohol is the oxidation that organic solvent does not easily cause titanium sheet.
A2, the phosphoric acid solution (H by 0.1mol/L3PO4) and 0.5wt% ammonium fluoride solution (NH4F it) is mixed, as The electrolyte of anodic oxidation.
Specifically, has the history of good decades in existing to the research of anodizing, different researchers are to formation Caliber, pipe range and the regular degree of nanotube have different research, the method for foring a generation, two generations and three generations.It is big at present Part uses newest three generations's method, i.e., is prepared, can be obtained using ethylene glycol, ammonium fluoride and distilled water as electrolyte system Longer pipe.But it is found by a large amount of experimental study, although the pipe that the method for three generations obtains is longer, due to titanium dioxide It is metal for semiconductor, titanium sheet matrix, the dilation performance difference of the two is larger, and this longer nanotube is in the later period to two When the heat treatment that titanium oxide is crystallized, the two expansibility and contractibility is different to be easily led to a nanometer tracheal rupture, loses and fall off Phenomena such as, while the ability for resisting the external world is weaker, carries out composite semiconductor particle according to ultrasonic wave added subsequent in this implementation, The breakage of entire nanotube is easily caused instead, or even can not be compound.
And the nanotube being prepared using HF solution as electrolyte system in generation method is although relatively solid, But pipe range is too short, respectively less than 500nm, and pipe range is too short mutually low to the absorptivity of sunlight, performance is weaker.Therefore, this implementation Being prepared in this method of a generation using phosphoric acid and ammonium fluoride as electrolyte system is used in example, although nanotube obtained It is slightly shorter compared to what three generations's method obtained, but its pipe range ratio HF is as long made from electrolyte, in 600~800nm, and It is firmer, and durability, corrosion resistance are stronger, it is stronger to resist extraneous ability, through Overheating Treatment or subsequent ultrasound Phenomena such as breakage of nanotube will not be caused when auxiliary, therefore there is superior performance.
A3, using pretreated titanium sheet as anode, graphite as cathode, using D.C. regulated power supply 20V voltage Anodic oxidation 1h is carried out, TiO is obtained2Nano-tube array presoma, the TiO obtained at this time2Nano-tube array presoma is largely Amorphous state.
Specifically, in this step, start continuous growing nano-tube in titanium sheet, in the growth course of nanotube, together When there are two kinds of chemical reactions: one is anodic oxidation, the oxygen in Titanium and water occurs chemical reaction and forms TiO2Nanotube； Another kind is field-enhanced dissolution, that is, the TiO formed2Nanotube is in F-Field-enhanced dissolution occurs in solution, therefore the length of nanotube is by this Two kinds are reacted while being determined.In the oxidation incipient stage, since anodic oxidation speed is greater than the solution rate of pipe, the length of pipe starts It is continuously increased.When pipe rises to certain length, since the two reaction reaches dynamic equilibrium, the oxidation rate of titanium and pipe at this time Solution rate maintains an equal level, then the length of nanotube and diameter are not further added by and keep constant value.
Wherein, the time of anodic oxidation will affect the pipe range of nanotube, under the constant pressure of 20V, grind by largely testing Study carefully discovery, in the 1h that oxidation starts, with the increase in reaction time, length of tube starts to increase, and when oxidization time is more than 1h, Pipe range reaches stationary value, will not increase in increase at any time.Therefore, in the present embodiment, the time for controlling anodic oxidation is 1h can make entirely reaction just reach dynamic balance, nanotube growth can be made more abundant, while performance is best.Most What is obtained eventually is relatively closer and high-sequential, rule the nanotube of same direction growth, arrangement along titanium sheet.
A4, by TiO2Nano-tube array presoma is put into Muffle furnace, is warming up to 500 DEG C with the heating rate of 2 DEG C/min, Heat treatment 3h is carried out, in the process, amorphous TiO2It is changed into the TiO of the crystalline state mainly presented with anatase2, obtain The TiO of crystallization2Nano-tube array.
Further, in this embodiment preparing TiO using anodizing2Nano-tube array, with it is existing in other preparation Method is compared, the existing middle TiO using preparations such as hydro-thermal method or sol-gal processes2Nano-tube array arrangement is more chaotic, benefit It will receive influence with the process for transmitting electronics when solar energy；And using TiO made from anodizing in the present embodiment2Nanometer Pipe array arranges high-sequential, and specific surface area is bigger, has higher quantum effect and structure effect, has superior property Energy.Meanwhile using the obtained nanotube of method in the present embodiment for shorter pipe (pipe range is respectively less than 1 μm), have stronger Durability, corrosion resistance and resist external world ability.
Further, referring to Fig. 3 and Fig. 4, TiO respectively obtained2The surface of nano-tube array and the SEM figure in section, Wherein, Fig. 3 is in acceleration voltage (HV)=10.00kV, operating distance (WD)=10.9mm, amplification factor (Mag)=50000x Under conditions of obtain.Fig. 4 is in acceleration voltage (HV)=10.00kV, operating distance (WD)=11.0mm, amplification factor (Mag) it is obtained under conditions of=60000x.
The TiO from Fig. 32It is more regular that the surface topography of nano-tube array can be seen that orifice configuration, nanotube tubulose knot Structure is very clear, and caliber is high-visible, and caliber is about 100nm, and tube wall is about 20nm.The TiO from Fig. 42Nano-tube array is cut It is about 700nm that face pattern, which can be seen that prepared nanotube length, and bottom end closure, and profile is obvious, and Bamboo-shaped is presented Growth, is a kind of tubular structure of comparison rule.
Further, referring to figure 5 and figure 6, CdS/PbS/TiO respectively obtained2The table of nanotube array composite material The SEM in face and section figure, wherein Fig. 5 is in acceleration voltage (HV)=15.00kV, operating distance (WD)=10.3mm, times magnification It is obtained under conditions of number (Mag)=150000x.Fig. 6 be acceleration voltage (HV)=15.00kV, operating distance (WD)= It is obtained under conditions of 10.2mm, amplification factor (Mag)=150000x.
The CdS/PbS/TiO from Fig. 52The surface topography of nanotube array composite material can be seen that surface have it is a large amount of small The presence of particle, and overall distribution is uniform, and surface concentrations are few, and do not occur the case where blocking nozzle, Bu Huiying Ring TiO2Absorption of the nano-tube array structure to light, and form more uniform multi-element heterogeneous structure.The CdS/ from Fig. 6 PbS/TiO2The interface topography that cuts of nanotube array composite material can be seen that inside nanotube that there is also a large amount of CdS and PbS Little particle is evenly distributed, in TiO2More uniform multi-element heterogeneous structure is formd on the wall of nanotube.This structure can rise To the effect for inhibiting photo-generate electron-hole compound, simultaneously because the effect of low energy gap CdS and PbS also can widen light abstraction width extremely Visible region.
It further, is CdS/PbS/TiO obtained referring to Fig. 72The EDS energy spectrum diagram of nanotube array composite material, it is main If having carried out Surface scan to material surface, the content of each element measured, can from Fig. 7 and table 1 referring to such as the following table 1 Out: the atom content that the atom content that the atom content of S is 7.23%, Cd is 5.3%, Pb is 3.79%, and in TiO2Nanometer The surface of pipe does not observe that too many particle exists, and thus explanation has more CdS and PbS ingredient to be present in TiO2Nanometer In pipe array.And the atomic ratio of the sum of atom total amount of Cd and Pb and S illustrate that the residual of excess ions is few close to 1:1, Cd, Pb and S are substantially to be existed in the form of CdS and PbS.
Table 1:CdS/PbS/TiO2Each element content in nanotube array composite material
Further, respectively to CdS/PbS/TiO obtained2Cadmium element in nanotube array composite material, lead element Surface scan test elements distribution situation is carried out with element sulphur, shows Cd, Pb and S these three Elemental redistributions more by test result Uniformly, the concentration phenomenon of some regions is not occurred.It further, is TiO obtained referring to Fig. 82Nano-tube array and CdS/PbS/TiO2The XRD diagram of nanotube array composite material, as can be seen from Figure 8, the angle of diffraction be 30 °, 45 °, 56 ° and Occur the diffraction maximum of CdS at 74 °, illustrates the CdS for being significantly present of crystalline phase in material.The angle of diffraction occurs when being 30 ° and 46 ° The diffraction maximum of PbS illustrates to be clearly present PbS in material.And for TiO2Nano-tube array wherein contains only Ti, anatase and gold The diffraction maximum of red stone, illustrates TiO2Composition be with anatase and the simultaneous mixed phase structure of rutile.
It further, is TiO obtained referring to Fig. 92Nano-tube array and CdS/PbS/TiO2Nano-tube array composite wood The ultraviolet-visible absorption spectroscopy figure of material.It can be seen in figure 9 that TiO2Nano-tube array can only absorb the ultraviolet of 320~380nm Light part, corresponding absorption edge are about 380nm, this is because the forbidden bandwidth of 3.2eV determines TiO2Spectral absorption model It encloses.PbS and CdS obtained compound TiO in the present embodiment2The absorption edge of nano-tube array has apparent red shift, ABSORPTION EDGE Edge is in the visible region of visible region 750nm or so.And modified sample has stronger absorption to some visible light, This is because determined using the relatively narrow forbidden bandwidth of CdS and PbS, the forbidden bandwidth of CdS and PbS are respectively 2.42eV and 0.3eV. Modified sample has in visible region significantly to fluctuate, this is because CdS and PbS and TiO2Between formed it is polynary Heterojunction structure capture charge carrier absorption superposition and caused by.
Further, for using nanotube closed at one end made from anodizing, because in pipe there are air due to nothing Method is compound to the inner wall progress of nanotube, is dexterously mutually tied using ultrasonic wave added method with continuous ionic sedimentation in the present embodiment It closes, solution can be made more uniform using the energy of ultrasonic wave, while can make to retain in nanotube by the energy of ultrasonic wave Air be effectively discharged, and then solution (i.e. cadmium source precursor solution, lead source precursor solution and sulphur source precursor solution) band Into the inside of nanotube, after solution drives the ion of the inside to enter the inside of nanotube, compound, and then shape is formed in internal and external walls At the multi-element heterogeneous knot of equably large area.
The concentration of cadmium source precursor solution, lead source precursor solution and sulphur source precursor solution when continuous ionic sedimentation simultaneously Relatively low, the number of circulation is more, using it is this it is a small amount of repeatedly deposit repeatedly by the way of and by repeat ultrasonic wave added by CdS, PbS and TiO2Nano-tube array progress is compound, is repeatedly capable of forming tiny particle on a small quantity, prevents the formation of large area big Grain, can be avoided that there is a phenomenon where reunite.And ultrasonic wave added can make solution be easier to enter the inside of nanotube and more It is even, therefore be easier to form the more tiny and uniform CdS and PbS particle of large area on the inside and outside wall of nanotube.
And pass through a large amount of experimental study and find, it is prepared if ultrasonic wave added is not added only with continuous ionic sedimentation, CdS the and PbS particle formed in ion infall process is easy to accumulate in nozzle, and this accumulation leads to the nozzle of entire nanotube The advantages of being blocked, largely effect on absorption of the inside to sunlight of nanotube, being unable to fully using nanotube specific surface area.
To sum up, ultrasonic wave added and continuous ionic sedimentation are combined carry out preparation CdS/PbS/TiO for the first time by the present embodiment2 Nanotube array composite material, be first first made with phosphoric acid and ammonium fluoride electrolyte using anodizing arrangement high-sequential and The TiO for having the ability of stronger durability, corrosion resistance and resistance external world2Nano-tube array.Recycle ultrasonic wave added Continuous ionic layer sedimentation is carried out by the way of repeatedly depositing repeatedly on a small quantity in the precursor solution of low concentration, can be discharged and receive Air inside mitron enables precursor solution more more uniformly to enter inside nanotube (i.e. the inside and outside wall of nanotube), And then large area, tiny and uniform CdS and PbS semiconductor grain are formed in the inside and outside wall of nanotube.
And CdS compares TiO with PbS2Not only have relatively narrow band-gap energy, while the band-gap degree between three compared with It is good.Therefore, final compound obtained CdS/PbS/TiO2Nanotube array composite material can successfully realize electrons and holes Between transfer, it is effective to inhibit the compound of hole and electronics, while can also improve the utilization rate to sunlight.
Embodiment 2
The present embodiment provides a kind of TiO of the activity improvement of semiconductor2The preparation method of nanotube array composite material, with embodiment 1 difference essentially consists in: first deposited in step 3 CdS and recycle 15 times, then redeposition PbS and circulation 9 times, remaining Procedure parameter is same as Example 1.Step one same as Example 1 and step 2 are not repeating herein in the present embodiment, Step three in the present embodiment is specific as follows:
C1 ', by TiO2Nano-tube array is immersed vertically in the precursor solution of cadmium source, and is utilized in the precursor solution of cadmium source The power of ultrasonic assistant soakage 15s, ultrasonic wave added are 80W, in TiO2The outer wall and inner wall of nano-tube array adhere to cadmium ion, so It is carried out repeated flushing 10 times using a large amount of solvent afterwards, then by the TiO after flushing2Nano-tube array, which immerses in solvent, to oscillate Rinse 10 times.
C2 ', the outer wall obtained after rinsing in step c1 ' and inner wall are attached with the TiO of cadmium ion2Nano-tube array is rapid Transfer is immersed in sulphur source precursor solution, and ultrasonic assistant soakage 15s, the function of ultrasonic wave added are utilized in sulphur source precursor solution Rate is 80W, in the process, the deposition reaction of CdS occurs, and then in TiO2The outer wall and inner wall of nano-tube array deposit to be formed CdS particle.
Using step c1 ' and c2 ' as a circulation (i.e. the circulation of CdS deposition), repetitive cycling step c1 ' and c2 ' Totally 15 times, at this point, the inner and outer wall in entire nanotube is respectively formed on uniform CdS particle, the CdS particle obtained at this time is big Part is amorphous state.
C3 ', the TiO that the outer wall obtained after repetitive cycling and inner wall are deposited with to CdS particle2Nano-tube array immerses vertically In the precursor solution of lead source, and ultrasonic assistant soakage 15s being utilized in the precursor solution of lead source, the power of ultrasonic wave added is 80W, In TiO2The outer wall and inner wall of nano-tube array adhere to lead cadmium ion, then carry out repeated flushing and repeatedly rinse each 10 times.
C4 ', the outer wall obtained after rinsing in step c3 ' and inner wall are attached with the TiO of lead ion2Nano-tube array is rapid Transfer is immersed in sulphur source precursor solution, and ultrasonic assistant soakage 15s, the function of ultrasonic wave added are utilized in sulphur source precursor solution Rate is 80W, in the process, the deposition reaction of PbS occurs, and then in TiO2The outer wall and inner wall of nano-tube array deposit to be formed Then PbS particle carries out repeated flushing and repeatedly rinses each 10 times.
Using step c3 ' and c4 ' as a circulation (i.e. the circulation of PbS deposition), repetitive cycling step c3 ' and c4 ' Totally 9 times, at this point, the inner and outer wall in entire nanotube is respectively formed on uniform PbS particle, the PbS particle obtained at this time is big Part is amorphous state.That is, the TiO obtained at this time2The outer wall and inner wall of nano-tube array be formed simultaneously with CdS particle and PbS particle.Wherein, in step c1 ', c2 ', c3 ' and c4 ', rinsing and rinse solvent used is the second that volume ratio is 4:1 Alcohol and water.
C5 ', the TiO that CdS particle and PbS particle are formed simultaneously with to the outer wall and inner wall that obtain after repetitive cycling2Nanometer 30min is dried at 80 DEG C in pipe array, is then placed in Muffle furnace, is warming up to 300 DEG C with the heating rate of 2 DEG C/min, Heat treatment 2h is carried out, CdS/PbS/TiO is obtained2Nanotube array composite material.
Embodiment 3
The present embodiment provides a kind of TiO of the activity improvement of semiconductor2The preparation method of nanotube array composite material, with embodiment 1 difference essentially consists in: being deposited by the way of layer by layer deposition PbS and CdS in step 3, remaining procedure parameter It is same as Example 1.Step one same as Example 1 and step 2 are not repeating herein in the present embodiment, the present embodiment In step three it is specific as follows:
C1, by TiO2Nano-tube array is immersed vertically in the precursor solution of lead source, and is utilized in the precursor solution of lead source The power of ultrasonic assistant soakage 15s, ultrasonic wave added are 80W, in TiO2The outer wall and inner wall of nano-tube array adhere to lead ion, so It is carried out repeated flushing 10 times using a large amount of solvent afterwards, then by the TiO after flushing2Nano-tube array, which immerses in solvent, to oscillate Rinse 10 times.
C2, the outer wall obtained after rinsing in step c1 and inner wall are attached with the TiO of lead ion2Nano-tube array turns rapidly It moves and immerses in sulphur source precursor solution, and utilize ultrasonic assistant soakage 15s, the power of ultrasonic wave added in sulphur source precursor solution The deposition reaction of PbS occurs, and then in TiO in the process for 80W2The outer wall and inner wall of nano-tube array deposit to be formed PbS particle.
C3, the outer wall obtained after rinsing in step c2 and inner wall are deposited with the TiO of PbS particle2Nano-tube array is vertical It immerses in the precursor solution of cadmium source, and utilizes ultrasonic assistant soakage 15s in the precursor solution of cadmium source, the power of ultrasonic wave added is 80W, in TiO2The outer wall and inner wall of nano-tube array adhere to cadmium ion, then carry out repeated flushing and repeatedly rinse each 10 times.
C4, the outer wall obtained after rinsing in step c3 and inner wall are attached with the TiO of cadmium ion2Nano-tube array turns rapidly It moves and immerses in sulphur source precursor solution, and utilize ultrasonic assistant soakage 15s, the power of ultrasonic wave added in sulphur source precursor solution The deposition reaction of CdS occurs, and then in TiO in the process for 80W2The outer wall and inner wall of nano-tube array deposit to be formed Then CdS particle carries out repeated flushing and repeatedly rinses each 10 times.
Using step c1, c2, c3 and c4 as a circulation (circulation of i.e. one PbS deposition and a CdS), repetitive cycling Step c1, c2, c3 and c4 totally 9 times, the TiO obtained at this time2The outer wall and inner wall of nano-tube array be formed simultaneously with CdS particle and PbS particle, and most of is amorphous state.Make CdS as far as possible by the way of a small amount of repeatedly layer by layer deposition this in the present embodiment Enter TiO with PbS2The inside of nanotube, and generate short grained CdS and PbS particle.Wherein, in step c1, c2, c3 and c4 In, rinsing and rinse solvent used is the second alcohol and water that volume ratio is 4:1.
C5, the TiO that CdS particle and PbS particle are formed simultaneously with to the outer wall and inner wall that obtain after repetitive cycling2Nanotube 30min is dried at 80 DEG C in array, is then placed in Muffle furnace, is warming up to 300 DEG C with the heating rate of 2 DEG C/min, into Row heat treatment 2h, obtains CdS/PbS/TiO2Nanotube array composite material.
Embodiment 4
The present embodiment provides a kind of TiO of the activity improvement of semiconductor2The preparation method of nanotube array composite material, including it is as follows Step:
Step 1: preparing TiO using anodizing2Nano-tube array.Specifically include following sub-step:
A1, titanium sheet is pre-processed.Selected titanium sheet and pretreated process and the basic phase in embodiment 1 Together, main difference is that ultrasonic wave added cleans 6min, and details are not described herein for detailed process.
A2, the H by 0.05mol/L3PO4The NH of solution and 0.2wt%4F solution is mixed, the electricity as anodic oxidation Solve liquid.
A3, using pretreated titanium sheet as anode, graphite as cathode, using D.C. regulated power supply 15V voltage Lower progress anodic oxidation 3h, obtains TiO2Nano-tube array presoma.
A4, by TiO2Nano-tube array presoma is put into Muffle furnace, is warming up to 450 DEG C with the heating rate of 2 DEG C/min, Heat treatment 5h is carried out, the TiO crystallized2Nano-tube array.
Step 2: by Cd (NO3)2It is dissolved in the cadmium for obtaining that concentration is 0.005mol/L in the mixed solution of second alcohol and water formation Source precursor solution, Pb (NO3)2It is dissolved in front of obtaining the lead source that concentration is 0.005mol/L in the mixed solution of second alcohol and water formation Liquid solution is driven, by Na2S be dissolved in second alcohol and water formation mixed solution in obtain concentration be 0.005mol/L sulphur source presoma it is molten Liquid, while ultrasonic wave added dissolution 6min is all made of during being prepared.Wherein, in the mixed solution used when preparing The volume ratio of second alcohol and water be 3.5:1.
Step 3: carrying out continuous ionic layer using ultrasonic wave added is deposited in TiO2The inner and outer wall of nano-tube array is simultaneously Uniform CdS particle and PbS particle are formed, then after heat treatment obtains the TiO of the activity improvement of semiconductor2Nano-tube array composite wood Material.Specifically include following sub-step:
C1, by TiO2Nano-tube array is immersed vertically in the precursor solution of lead source, and is utilized in the precursor solution of lead source Ultrasonic assistant soakage 8s, the power of ultrasonic wave added are 150W, then carry out repeated flushing using a large amount of solvent and repeatedly rinse Each 8 times.After being rinsed, then to the TiO after rinsing2Nano-tube array blows it using the hot wind function of common air-heater It is dry.During drying up herein, the solution in nanotube will do it volatilization, and the residual ion inside nanotube can be sent out herein During be carried over, and then achieve the purpose that remove nanotube inside survivor ion.
C2, the outer wall obtained after drying up in step c1 and inner wall are attached with the TiO of lead ion2Nano-tube array turns rapidly It moves and immerses in sulphur source precursor solution, and utilize ultrasonic assistant soakage 8s, the power of ultrasonic wave added in sulphur source precursor solution For 150W, repeated flushing then is carried out using a large amount of solvent and is repeatedly rinsed each 8 times.After being rinsed, then to rinsing after TiO2Nano-tube array dries up it using the hot wind function of common air-heater.
It is recycled using step c1 and c2 as one, repetitive cycling step c1 and c2 totally 12 times, at this time in entire nanotube Inner and outer wall is respectively formed on uniform PbS particle.
C3, the TiO that the outer wall obtained after repetitive cycling and inner wall are deposited with to PbS particle2Nano-tube array immerses vertically In the precursor solution of cadmium source, and ultrasonic assistant soakage 8s being utilized in the precursor solution of cadmium source, the power of ultrasonic wave added is 150W, Then repeated flushing is carried out using a large amount of solvent and repeatedly rinse each 8 times.After being rinsed, then to the TiO after rinsing2Nanometer Pipe array dries up it using the hot wind function of common air-heater.
C4, the outer wall obtained after drying up in step c3 and inner wall are attached with the TiO of cadmium ion2Nano-tube array turns rapidly It moves and immerses in sulphur source precursor solution, and utilize ultrasonic assistant soakage 8s, the power of ultrasonic wave added in sulphur source precursor solution For 150W, repeated flushing then is carried out using a large amount of solvent and is repeatedly rinsed each 8 times.After being rinsed, then to rinsing after TiO2Nano-tube array dries up it using the hot wind function of common air-heater.
It is recycled using step c3 and c4 as one, repetitive cycling step c3 and c4 totally 8 times, at this point, in entire nanotube Inner and outer wall is respectively formed on uniform CdS particle.That is, the TiO obtained at this time2The outer wall and inner wall of nano-tube array It is formed simultaneously with CdS particle and PbS particle.Wherein, in step c1, c2, c3 and c4, rinsing and rinse solvent used is Volume ratio is the second alcohol and water of 3.5:1.
C5, the TiO that CdS particle and PbS particle are formed simultaneously with to the outer wall and inner wall that obtain after repetitive cycling2Nanotube 100min is dried at 65 DEG C in array, is then placed in Muffle furnace, is warming up to 280 DEG C with the heating rate of 1 DEG C/min, into Row heat treatment 3h, obtains CdS/PbS/TiO2Nanotube array composite material.
Embodiment 5
The present embodiment provides a kind of TiO of the activity improvement of semiconductor2The preparation method of nanotube array composite material, including it is as follows Step:
Step 1: preparing TiO using anodizing2Nano-tube array.Specifically include following sub-step:
A1, titanium sheet is pre-processed.Selected titanium sheet and pretreated process and the basic phase in embodiment 1 Together, main difference is that ultrasonic wave added cleans 20min, and details are not described herein for detailed process.
A2, the H by 0.3mol/L3PO4The NH of solution and 0.8wt%4F solution is mixed, the electrolysis as anodic oxidation Liquid.
A3, using pretreated titanium sheet as anode, graphite as cathode, using D.C. regulated power supply 25V voltage Lower progress anodic oxidation 1h, obtains TiO2Nano-tube array presoma.
A4, by TiO2Nano-tube array presoma is put into Muffle furnace, is warming up to 600 DEG C with the heating rate of 5 DEG C/min, Heat treatment 2h is carried out, the TiO crystallized2Nano-tube array.
Step 2: by CdCl2It is dissolved in front of obtaining the cadmium source that concentration is 0.2mol/L in the mixed solution of second alcohol and water formation Drive liquid solution, PbCl2It is dissolved in the lead source precursor solution for obtaining that concentration is 0.2mol/L in the mixed solution of second alcohol and water formation, By thiocarbamide be dissolved in second alcohol and water formation mixed solution in obtain concentration be 0.2mol/L sulphur source precursor solution, while into Row is all made of ultrasonic wave added dissolution 20min during preparing.Wherein, the second alcohol and water in the mixed solution used when preparing Volume ratio be 8:1.
Step 3: carrying out continuous ionic layer using ultrasonic wave added is deposited in TiO2The inner and outer wall of nano-tube array is simultaneously Uniform CdS particle and PbS particle are formed, then after heat treatment obtains the TiO of the activity improvement of semiconductor2Nano-tube array composite wood Material.Specifically include following sub-step:
C1, by TiO2Nano-tube array is immersed vertically in the precursor solution of lead source, and is utilized in the precursor solution of lead source Ultrasonic assistant soakage 25s, the power of ultrasonic wave added are 100W, then carry out repeated flushing using a large amount of solvent and repeatedly rinse Each 25 times.
C2, the outer wall obtained after rinsing in step c1 and inner wall are attached with the TiO of lead ion2Nano-tube array turns rapidly It moves and immerses in sulphur source precursor solution, and utilize ultrasonic assistant soakage 25s, the power of ultrasonic wave added in sulphur source precursor solution For 100W, repeated flushing then is carried out using a large amount of solvent and is repeatedly rinsed each 25 times.
It is recycled using step c1 and c2 as one, repetitive cycling step c1 and c2 totally 5 times, at this time in entire nanotube Wall and outer wall are respectively formed on uniform PbS particle.
C3, the TiO that the outer wall obtained after repetitive cycling and inner wall are deposited with to PbS particle2Nano-tube array immerses vertically In the precursor solution of cadmium source, and ultrasonic assistant soakage 25s is utilized in the precursor solution of cadmium source, the power of ultrasonic wave added is Then 100W carries out repeated flushing using a large amount of solvent and repeatedly rinses each 25 times.
C4, the outer wall obtained after rinsing in step c3 and inner wall are attached with the TiO of cadmium ion2Nano-tube array turns rapidly It moves and immerses in sulphur source precursor solution, and utilize ultrasonic assistant soakage 25s, the power of ultrasonic wave added in sulphur source precursor solution For 100W, repeated flushing then is carried out using a large amount of solvent and is repeatedly rinsed each 25 times.
It is recycled using step c3 and c4 as one, repetitive cycling step c3 and c4 totally 16 times, at this point, in entire nanotube Inner and outer wall is respectively formed on uniform CdS particle.That is, the TiO obtained at this time2The outer wall and inner wall of nano-tube array It is formed simultaneously with CdS particle and PbS particle.Wherein, in step c1, c2, c3 and c4, rinsing and rinse solvent used is Volume ratio is the second alcohol and water of 8:1.
C5, the TiO that CdS particle and PbS particle are formed simultaneously with to the outer wall and inner wall that obtain after repetitive cycling2Nanotube 60min is dried at 90 DEG C in array, is then placed in Muffle furnace, is warming up to 400 DEG C with the heating rate of 4 DEG C/min, into Row heat treatment 0.5h, obtains CdS/PbS/TiO2Nanotube array composite material.
More than, it is only presently preferred embodiments of the present invention, is not the limitation for doing other forms to invention, it is any to be familiar with Professional and technical personnel is changed or is modified as the equivalence enforcement of equivalent variations possibly also with the technology contents of the disclosure above Example.But without departing from the technical solutions of the present invention, according to the technical essence of the invention to the above embodiments What simple modification, equivalent variations and remodeling, still falls within the protection scope of technical solution of the present invention.

Claims (10)

1. a kind of TiO of the activity improvement of semiconductor2The preparation method of nanotube array composite material, which is characterized in that including walking as follows It is rapid:
Step 1: preparing TiO using anodizing2Nano-tube array；
Step 2: cadmium source, lead source and sulphur source are dissolved in respectively in alcohols solvent, to obtain cadmium source precursor solution, lead source presoma molten Liquid and sulphur source precursor solution；
Wherein, the concentration of cadmium source precursor solution, the concentration of the concentration of lead source precursor solution and sulphur source precursor solution It is 0.005~0.2mol/L；
Step 3: carrying out continuous ionic layer using ultrasonic wave added is deposited in the TiO2The inner and outer wall of nano-tube array is simultaneously Uniform CdS particle and PbS particle are formed, then after heat treatment obtains the TiO of the activity improvement of semiconductor2Nano-tube array is compound Material；
Wherein, in step 3, the temperature of the heat treatment is 280~400 DEG C, and the heating rate when heat treatment is 1~4 DEG C/min, the time of the heat treatment is 0.5~3h.
2. the TiO of the activity improvement of semiconductor as described in claim 12The preparation method of nanotube array composite material, feature exist In in step 2:
The alcohols solvent is that second alcohol and water is the mixed solution that 3.5~8:1 is prepared by volume；
The cadmium source is Cd (NO3)2Or CdCl2, the lead source is Pb (NO3)2Or PbCl2, the sulphur source is Na2S or thiocarbamide；
Ultrasonic wave added dissolution is all made of when preparing cadmium source precursor solution, lead source precursor solution and sulphur source precursor solution 6~20min.
3. the TiO of the activity improvement of semiconductor as claimed in claim 22The preparation method of nanotube array composite material, feature exist In step 3 includes following sub-step:
C1, by the TiO2Nano-tube array immerses in the precursor solution of the lead source, and sharp in the precursor solution of the lead source With ultrasonic assistant soakage, in the TiO2The outer wall and inner wall of nano-tube array adhere to lead ion, are then rinsed and rinse；
C2, the outer wall obtained after rinsing in step c1 and inner wall are attached with the TiO of lead ion2Nano-tube array immerses the sulphur In the precursor solution of source, and ultrasonic assistant soakage is utilized in the sulphur source precursor solution, in the TiO2Nano-tube array Outer wall and inner wall deposit to form PbS particle, be then rinsed and rinse；
C3, the outer wall obtained after rinsing in step c2 and inner wall are deposited with the TiO of PbS particle2Nano-tube array immerses the cadmium In the precursor solution of source, and ultrasonic assistant soakage is utilized in the precursor solution of the cadmium source, in the TiO2Nano-tube array Outer wall and inner wall adhere to cadmium ion, be then rinsed and rinse；
C4, the outer wall obtained after rinsing in step c3 and inner wall are attached with the TiO of cadmium ion2Nano-tube array immerses the sulphur In the precursor solution of source, and ultrasonic assistant soakage is utilized in the sulphur source precursor solution, in the TiO2Nano-tube array Outer wall and inner wall deposit to form CdS particle, be then rinsed and rinse；
C5, the TiO that CdS particle and PbS particle are formed simultaneously with to the obtained outer wall of step c4 and inner wall2Nano-tube array carries out Dry and heat treatment, obtains CdS/PbS/TiO2Nanotube array composite material.
4. the TiO of the activity improvement of semiconductor as claimed in claim 32The preparation method of nanotube array composite material, feature exist In,
Before step c3, first repetitive cycling step c1 and c2 totally 5~12 times, then step c3 and c4 are carried out, then repeat step Rapid c3 and c4 totally 8~16 times, finally enter back into step c5；Or
After carrying out described step c1, c2, c3 and c4, first progress repetitive cycling step c1, c2, c3 and c4 totally 8~12 times, then Enter back into step c5.
5. the TiO of the activity improvement of semiconductor as claimed in claim 42The preparation method of nanotube array composite material, feature exist In,
In step c1, c2, c3 and c4, the power of ultrasonic wave added is 80~150W, equal using the time of ultrasonic assistant soakage For 8~25s, the solvent or ethyl alcohol for being all made of the formation of second alcohol and water carry out repeated flushing and repeatedly rinse.
6. the TiO of the activity improvement of semiconductor as claimed in claim 52The preparation method of nanotube array composite material, feature exist In in step c1, c2, c3 and c4:
When being rinsed and rinsed using the solvent of the formation of second alcohol and water, the volume ratio of the second alcohol and water is 3.5~8:1；
It repeated flushing and repeatedly rinses equal 8~25 times；And/or
After being rinsed, then to the TiO after rinsing2Nano-tube array is dried up.
7. the TiO of the activity improvement of semiconductor as claimed in claim 62The preparation method of nanotube array composite material, feature exist In,
In step c4, the temperature of the drying is 65~90 DEG C, and the time of the drying is 60~180min.
8. the TiO of the activity improvement of semiconductor as described in any one of claim 1 to 72The preparation method of nanotube array composite material, It is characterized in that, preparing TiO using anodizing2Nano-tube array includes following sub-step:
A1, titanium sheet is pre-processed；
A2, phosphoric acid solution and ammonium fluoride solution are mixed, the electrolyte as anodic oxidation；
A3, using pretreated titanium sheet as anode, it is certain that graphite as cathode, using D.C. regulated power supply carries out anodic oxidation Time obtains TiO2Nano-tube array presoma；
A4, to the TiO2Nano-tube array presoma is heat-treated, and the TiO is obtained2Nano-tube array.
9. the TiO of the activity improvement of semiconductor as claimed in claim 82The preparation method of nanotube array composite material, feature exist In,
In step a1, the pretreatment includes first by the titanium sheet respectively successively in deionized water, acetone, deionized water, different 6~20min of cleaning is carried out using ultrasonic wave added in propyl alcohol, deionized water and dehydrated alcohol, is then dried again；
In step a2, the concentration of phosphoric acid solution is 0.05~0.3mol/L, and the mass percentage concentration of the ammonium fluoride solution is 0.2~0.8%；
In step a3, voltage is 15~25V, and the time of anodic oxidation is 1~3h；
In step a4, the temperature of the heat treatment is 450~600 DEG C, the heating rate when heat treatment is 2~5 DEG C/ Min, the time of the heat treatment are 2~5h.
10. a kind of TiO of the activity improvement of semiconductor2Nanotube array composite material, which is characterized in that using such as claim 1 to 9 times Method described in one is prepared.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110592596A (en) * 2019-08-02 2019-12-20 西北师范大学 Ternary semiconductor composite film and preparation method and application thereof
CN110773108A (en) * 2019-10-15 2020-02-11 太原科技大学 Preparation method of titanium oxide hollow nanotube and application of titanium oxide hollow nanotube prepared by same
CN112076773A (en) * 2020-09-01 2020-12-15 常州工学院 WS (WS)2Nano-sheet modified TiN nanotube array composite material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102776513A (en) * 2012-07-13 2012-11-14 西南交通大学 Preparation process of TiO2 nanotube/PbS/CuS nanocomposite
CN102965645A (en) * 2012-11-13 2013-03-13 同济大学 Preparation method of CdTe/ZnS-nanocrystal-comodified TiO2 nanotube array

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102776513A (en) * 2012-07-13 2012-11-14 西南交通大学 Preparation process of TiO2 nanotube/PbS/CuS nanocomposite
CN102965645A (en) * 2012-11-13 2013-03-13 同济大学 Preparation method of CdTe/ZnS-nanocrystal-comodified TiO2 nanotube array

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LINGLING CHEN ETAL: "Effect of ultrasonic cold forging technology as the pretreatment on the corrosion resistance of MAO Ca/P coating on AZ31B Mg alloy", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110592596A (en) * 2019-08-02 2019-12-20 西北师范大学 Ternary semiconductor composite film and preparation method and application thereof
CN110773108A (en) * 2019-10-15 2020-02-11 太原科技大学 Preparation method of titanium oxide hollow nanotube and application of titanium oxide hollow nanotube prepared by same
CN110773108B (en) * 2019-10-15 2022-04-15 太原科技大学 Preparation method of titanium oxide hollow nanotube and application of titanium oxide hollow nanotube prepared by same
CN112076773A (en) * 2020-09-01 2020-12-15 常州工学院 WS (WS)2Nano-sheet modified TiN nanotube array composite material and preparation method thereof
WO2022048263A1 (en) * 2020-09-01 2022-03-10 常州工学院 Ws2 nanosheet modified tin nanotube array composite material and preparation method therefor

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