CN106367738A - Preparation method of ZnTiO3 film for photoelectrocatalysis - Google Patents

Preparation method of ZnTiO3 film for photoelectrocatalysis Download PDF

Info

Publication number
CN106367738A
CN106367738A CN201610902287.6A CN201610902287A CN106367738A CN 106367738 A CN106367738 A CN 106367738A CN 201610902287 A CN201610902287 A CN 201610902287A CN 106367738 A CN106367738 A CN 106367738A
Authority
CN
China
Prior art keywords
zntio
thin film
preparation
conductive glass
sol
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
Application number
CN201610902287.6A
Other languages
Chinese (zh)
Inventor
刘志华
张晶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin Chengjian University
Original Assignee
Tianjin Chengjian University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tianjin Chengjian University filed Critical Tianjin Chengjian University
Priority to CN201610902287.6A priority Critical patent/CN106367738A/en
Publication of CN106367738A publication Critical patent/CN106367738A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C23C18/1254—Sol or sol-gel processing
    • 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
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • 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

Abstract

To further simplify a preparation method of a ZnTiO3 film, the invention discloses a preparation method of the ZnTiO3 film for photoelectrocatalysis. The preparation method comprises the following steps: firstly, preparing ZnTiO3 precursor sol by using a sol-gel method, then, adopting a dip-coating method to finish film coating on ITO conductive glass, and finally, carrying out late annealing treatment on the ITO conductive glass to obtain the ZnTiO3 film. The ZnTiO3 film is illuminated by light and energy is absorbed, and when the energy hv is equal or greater than the self forbidden bandwidth, electrons on a valence band are motivated and jump to an empty conduction band, and a photoproduction electron hole is left on the valence band to form a photoproduction electron hole pair (e<->-h<+>), and the photoproduction electron hole and the electron motivated by light on the surface of a semiconductor photocatalyst have high oxidizing capacity and reducing capacity.

Description

A kind of zntio for photoelectrocatalysiss3The preparation method of thin film
Technical field
The invention belongs to technical field of material, specially a kind of zntio for photoelectrocatalysiss3The preparation side of thin film Method.
Background technology
Photoelectrocatalysiss hydrogen production by water decomposition is to prepare one of desirable route of fuel using solar energy, since nearly half a century, Various countries' scientists unremitting effort, is devoted to developing efficient, stable solar energy electrocatalytic decomposition aqueous systems.Research team exists While deployment solar energy photocatalytic decomposes wate research, start the research of solar energy electrocatalytic decomposition water, the pass of photoelectrocatalysiss The design of key section light anode system and preparation aspect are study hotspots.Traditional optoelectronic pole material zno and tio2It is Dan Jin Belong to ion Binary-phase oxide semiconductor.According to pertinent literature, the semi-conducting material of many metal ions is compared with monometallic ion Material has more superior photocatalysis performance.Particularly prominent in the photocatalysis performance of titanate many metal semiconductors material among these Go out, this is because metatitanic acid salt form quasiconductor usually has perovskite structure, and perovskite structure abo3In, b cation is ti+In catalysis activity in the highest flight, ti in conventional experiment+Photocatalysis performance have been obtained for the height of all circles and recognize Can.In addition, a ion can produce impact for b ion to a great extent, improves its photoresponse scope.And in this base On plinth, zn2+Ion as second generation catalysis material comform de- in polyion draw, and existing ti4+Ion population becomes zntio3Ca-Ti ore type semi-conducting material because have simple preparation technology, excellent optical property and cause the wide of people General concern.
Existing zntio3The preparation method of thin film needs to simplify further.
Content of the invention
In order to simplify zntio further3The preparation method of thin film, it is an object of the invention to propose one kind urge for photoelectricity The zntio changing3The preparation method of thin film.
A kind of zntio for photoelectrocatalysiss that the present invention provides3The preparation method of thin film is as follows: coagulates first by colloidal sol Glue method prepares zntio3Precursor sol, then completes plated film using dipping-pulling method, finally to it on ito electro-conductive glass The annealing carrying out the later stage obtains zntio3Thin film.
The present invention is given at the specific process parameter on the basis of said method further:
First, prepare zntio3The technological parameter of precursor sol:
Using sol-gal process, under magnetic agitation, configuration zinc concentration is 0.02～0.03mol l-1Dehydrated alcohol molten Liquid, adds acid on a small quantity and adjusts ph value to 5；It is added dropwise over c thereto16h36o4Ti solution, the mol ratio making ti and zn is 1:1, Magnetic agitation 2～5h obtains shallow yellow transparent solution；It is hydrolyzed at normal temperatures and pressures formation zntio after 24h3Presoma is molten Glue.
2nd, prepare zntio3The technological parameter of thin film:
Using dipping-pulling method on ito electro-conductive glass membrane, after completing membrane process by glass be placed in baking oven be dried Appropriate time.Repeat the above steps carry out second membrane to ito electro-conductive glass, and put into and carry out in fabric resistor stove at heat Reason, obtains one layer of fine and close zntio on electro-conductive glass3Thin film.
The mechanism of action of the present invention is: when the energy h ν that semiconductor light-catalyst is absorbed by illumination is equal to or more than During the energy gap of itself, the electrons in valence band are excited on the conduction band transitting to sky, and leave photohole in valence band, Thus forming photo-generate electron-hole to (e--h+).The photohole on semiconductor light-catalyst surface excited by light and electronics are respectively There is very strong oxidability and reducing power.
Beneficial effect
1st, with respect to traditional catalysis material such as tio2, zno, zntio3Have narrower energy gap, about 3.06ev, energy needed for its electron transition is less, is more also easy to produce photo-generated carrier.Simultaneously because zntio3Belong to bimetallic ion The ternary system of oxide, its abundant phase structure gives its more probability changing and improving in terms of photocatalysis.Right Visible ray respective capabilities are strong, and photoelectrocatalysiss effect is good.
2nd, perovskite structure is titanium typical structure present in nature, and perovskite structure makes it be easy to and other gold Belong to ion and be doped modified its light-catalysed characteristic extra-high, and zntio3The PhotoelectrocatalytiPerformance Performance of thin film has good application Prospect.
3rd, a kind of zntio for photoelectrocatalysiss3The preparation method of thin film, the material feedstock of employing is enriched, using process Pollution-free.
4th, a kind of zntio for photoelectrocatalysiss3The preparation method of thin film, further simplify zntio3The preparation of thin film Technique, the zntio preparing3Thin film has good PhotoelectrocatalytiPerformance Performance.
Brief description
Fig. 1 is the zntio of gained in embodiment3Thin film and traditional tio2, zno quasiconductor can carry schematic diagram.
Fig. 2 is the zntio of gained in embodiment3The scanning electron microscope image of thin film.
Fig. 3 is the zntio of gained in embodiment3Thin film and traditional tio2, zno quasiconductor is through UV-Vis spectrophotometry luminosity Measure test result.
Specific embodiment
The following examples can make those skilled in the art be more completely understood by the present invention, but limits never in any form The present invention.
Embodiment 1
First, prepare zntio using sol-gal process3Precursor sol, by the zn (ch of 0.3g3coo)2·2h2O adds To in dehydrated alcohol, make 0.027mol l-1Ethanol solution 50ml, wherein add a small amount of hydrochloric acid to 5, adjust ph It is worth to 5；It is added dropwise over c more thereto16h36o4Ti (mol ratio of ti and zn is 1:1), magnetic agitation 2h obtains light yellow clear Solution；Shallow yellow transparent solution is hydrolyzed at normal temperatures and pressures formation zntio after 24h3Precursor sol.Using dipping-lifting Method membrane on ito electro-conductive glass, electro-conductive glass fixation is dipped vertically into zntio with the speed of 1mm/s3In colloidal sol and quiet Put after 20s takes out and be placed in 60 DEG C of dryings in baking oven.Repeat the above steps carry out to ito electro-conductive glass putting into fibre after second membrane Carry out heat treatment in dimension resistance furnace to be made annealing treatment with 550 DEG C, obtain zntio3Thin film.
The zntio that the present invention is obtained3Thin film, it can be with schematic diagram as shown in figure 1, can be observed prepared zntio3 Thin film energy gap is less than tio2, zno, can effectively absorb visible ray.The zntio that the present invention is obtained3Thin film, dense uniform, survey Test result is as shown in Figure 2.The zntio that the present invention is obtained3Thin film, with traditional tio2, zno quasiconductor compare its photon absorbing intensity with And band-gap energy all increases, test result is as shown in Figure 3.
Embodiment 2
First, prepare zntio using sol-gal process3Precursor sol, using znso4Preparation zinc concentration is 0.02mol l-1Ethanol solution 50ml, add a small amount of hydrochloric acid, adjust ph value to 5；It is added dropwise over c thereto16h36o4Ti (ti and zn Mol ratio be 1:1), magnetic agitation 3h obtains shallow yellow transparent solution.It is hydrolyzed at normal temperatures and pressures and is formed after 24h zntio3Precursor sol.Using dipping-pulling method on ito electro-conductive glass membrane, by electro-conductive glass fixation with the speed of 1mm/s Degree is dipped vertically into zntio3In colloidal sol, and stand 20s take out after be placed in 60 DEG C of dryings in baking oven.Repeat the above steps are to ito Electro-conductive glass is put into after carrying out second membrane in fabric resistor stove and is carried out heat treatment and made annealing treatment with 550 DEG C, obtains zntio3Thin film.
Embodiment 3
First, prepare zntio using sol-gal process3Precursor sol, using zn (ch3coo)2·2h2It is dense that o prepares zinc Spend for 0.03mol l-1Ethanol solution 50ml, add a small amount of hydrochloric acid, adjust ph value to 5；It is added dropwise over thereto c16h36o4Ti (mol ratio of ti and zn is 1:1), magnetic agitation 5h obtains shallow yellow transparent solution.By its water at normal temperatures and pressures Form zntio after solution 24h3Precursor sol.Using dipping-pulling method on ito electro-conductive glass membrane, electro-conductive glass is fixed Zntio is dipped vertically into the speed of 1mm/s3In colloidal sol, and stand 20s take out after be placed in 60 DEG C of dryings in baking oven.On repeating State step and ito electro-conductive glass is carried out put into after second membrane and carry out heat treatment in fabric resistor stove and annealed with 550 DEG C Process, obtain zntio3Thin film.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto, Any those familiar with the art the invention discloses technical scope in, the change or replacement that can readily occur in, All should be included within the scope of the present invention.Therefore, protection scope of the present invention should be with scope of the claims It is defined.

Claims (5)

1. a kind of zntio for photoelectrocatalysiss3The preparation method of thin film is it is characterised in that prepare first by sol-gal process zntio3Precursor sol, then completes plated film on ito electro-conductive glass using dipping-pulling method, finally carries out the later stage to it Annealing obtain zntio3Thin film.
2. a kind of zntio for photoelectrocatalysiss as claimed in claim 13The preparation method of thin film is it is characterised in that prepare Described zntio3The technological parameter of precursor sol is: adopt sol-gal process, under magnetic agitation, configuration zinc concentration be 0.02～ 0.03mol·l-1Ethanol solution, add acid on a small quantity and adjust ph value to 5；It is added dropwise over c thereto16h36o4Ti is molten Liquid, the mol ratio making ti and zn is 1:1, obtains shallow yellow transparent solution after magnetic agitation 2～5h；By its water at normal temperatures and pressures Solution 24h forms zntio3Precursor sol.
3. a kind of zntio for photoelectrocatalysiss as claimed in claim 13The preparation method of thin film is it is characterised in that prepare Described zntio3The technological parameter of thin film is: using dipping-pulling method on ito electro-conductive glass membrane, using dipping-pulling method Membrane on ito electro-conductive glass, electro-conductive glass fixation is dipped vertically into zntio with the speed of 1mm/s3In colloidal sol, and stand 20s is placed in 60 DEG C of dryings in baking oven after taking out；Repeat the above steps carry out second membrane to ito electro-conductive glass, and put into fibre Carry out heat treatment in dimension resistance furnace, one layer of fine and close zntio is obtained on electro-conductive glass3Thin film.
4. a kind of zntio for photoelectrocatalysiss as claimed in claim 23The preparation method of thin film is it is characterised in that prepare Described zntio3Precursor sol adopt for zn (ch3coo)2·2h2O or znso4.
5. a kind of zntio for photoelectrocatalysiss as claimed in claim 33The preparation method of thin film is it is characterised in that described Carrying out heat treatment in fabric resistor stove is to be annealed under conditions of 550 DEG C.
CN201610902287.6A 2016-10-17 2016-10-17 Preparation method of ZnTiO3 film for photoelectrocatalysis Pending CN106367738A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610902287.6A CN106367738A (en) 2016-10-17 2016-10-17 Preparation method of ZnTiO3 film for photoelectrocatalysis

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610902287.6A CN106367738A (en) 2016-10-17 2016-10-17 Preparation method of ZnTiO3 film for photoelectrocatalysis

Publications (1)

Publication Number Publication Date
CN106367738A true CN106367738A (en) 2017-02-01

Family

ID=57895497

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610902287.6A Pending CN106367738A (en) 2016-10-17 2016-10-17 Preparation method of ZnTiO3 film for photoelectrocatalysis

Country Status (1)

Country Link
CN (1) CN106367738A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3794717A (en) * 1971-03-26 1974-02-26 Fuji Photo Film Co Ltd Method of preparing compound oxides of titanium and zinc
CN101054266A (en) * 2007-05-30 2007-10-17 北京科技大学 Method of preparing photoelectrocatalysis material zinc ferrite film from lead-zinc tailings
CN101367035A (en) * 2008-09-24 2009-02-18 中国科学院广州地球化学研究所 Preparation method for nano-titanium dioxide film photocatalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3794717A (en) * 1971-03-26 1974-02-26 Fuji Photo Film Co Ltd Method of preparing compound oxides of titanium and zinc
CN101054266A (en) * 2007-05-30 2007-10-17 北京科技大学 Method of preparing photoelectrocatalysis material zinc ferrite film from lead-zinc tailings
CN101367035A (en) * 2008-09-24 2009-02-18 中国科学院广州地球化学研究所 Preparation method for nano-titanium dioxide film photocatalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陈亮: ""TiO2和钛酸盐的制备及光催化性能的研究"", 《中国优秀硕士学位论文全文数据库（电子期刊）工程Ⅰ辑》 *

Similar Documents

Publication Publication Date Title
CN109402656B (en) Preparation method of cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode
Kudo Z-scheme photocatalyst systems for water splitting under visible light irradiation
JP5641499B2 (en) Photocatalytic photocatalytic electrode
KR101981658B1 (en) Photoelectrochemical cell and manufacturing method thereof, water electrolysis system and manufacturing method thereof
CN109338391B (en) Preparation method of substrate for hydrogen production by photoelectrochemical decomposition of water, product and application thereof
CN110655656A (en) Cobalt metal organic framework material and preparation method and application thereof
CN103409778A (en) Method used for preparing TiO2/Cu2O nano heterojunction by composite mask method
CN106637285B (en) Cu2The TiO 2 nanotubes modified optoelectronic pole of O quantum dot and its preparation and application
CN104383950A (en) Bi2O3-BiOI heterojunction visible-light response photocatalyst and preparation method thereof
CN106268813A (en) A kind of CuFeO for photoelectrocatalysis2the preparation method of nano material
CN112941557A (en) Ce-BiVO4/g-C3N4Composite material for hydrogen production by photolysis of water and preparation method thereof
CN102909008A (en) Preparation method for TiO2/SiO2-Ag-SiO2 nanocomposite film
JP6270884B2 (en) Method for producing electrode for photohydrolysis reaction
Wang et al. Influence of grain size on photoelectrocatalytic performance of CuBi2O4 photocathodes
CN101734866A (en) Method for preparing nano tungsten trioxide thin film
JP5641981B2 (en) Photoelectric conversion element that can be manufactured by a method suitable for mass production
CN110911170B (en) Photo-anode material with molybdenum sulfide modified bismuth oxybromide in two-dimensional structure and preparation method thereof
CN104928648B (en) A kind of zinc oxide photo-anode film and its preparation method and application
CN109225245B (en) Three-dimensional flower-shaped CuWO for photoelectrocatalysis4Preparation method of/NiOOH film
CN111020501A (en) Preparation method of copper bismuthate film
CN106367738A (en) Preparation method of ZnTiO3 film for photoelectrocatalysis
CN107804900B (en) Titanium-based stable photoelectric electrode and preparation method and application thereof
CN106975501B (en) Visible light response type photocatalytic film and preparation method and application thereof
CN109487291A (en) A kind of photocathode preparation method, photocathode and its photoelectrochemical cell
CN104190451B (en) A kind of preparation method of silver orthophosphate film

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170201