CN107790194A - Selective etch ferroelectricity base optic catalytic material is to orient the method for constructing heterojunction structure - Google Patents
Selective etch ferroelectricity base optic catalytic material is to orient the method for constructing heterojunction structure Download PDFInfo
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- ferroelectricity
- heterojunction structure
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- 239000000463 material Substances 0.000 title claims abstract description 80
- 230000005621 ferroelectricity Effects 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 34
- 238000005530 etching Methods 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 239000004065 semiconductor Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 5
- 229910000765 intermetallic Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000011260 aqueous acid Substances 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 description 46
- 238000000151 deposition Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 230000008021 deposition Effects 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 229910001868 water Inorganic materials 0.000 description 14
- 229910016978 MnOx Inorganic materials 0.000 description 12
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 7
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 7
- 229910004042 HAuCl4 Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 230000005684 electric field Effects 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910003781 PbTiO3 Inorganic materials 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000002269 spontaneous effect Effects 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 241000872931 Myoporum sandwicense Species 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000007539 photo-oxidation reaction Methods 0.000 description 2
- 238000007540 photo-reduction reaction Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011697 sodium iodate Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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Abstract
The present invention relates to photocatalysis field, specially a kind of selective etch ferroelectricity base optic catalytic material is to orient the method for constructing heterojunction structure.Difference of the surface with electrical properties is induced using the ferroelectricity field in semiconductor ferroelectric material (barium titanate, lead titanates, bismuth ferrite etc.), adsorb on positively charged surface with causing the acid ion preference of negatively charged, realize and heterojunction structure photochemical catalyst is constructed to ferroelectric material surface selective etch orientation.Semiconductor ferroelectric material is put into the aqueous solution containing etching property acid, the selective etch on ferroelectric material surface is realized by hydrothermal treatment process, heterojunction structure is constructed in ferroelectricity substrate material surface orientation, the species, concentration and hydro-thermal process temperature for adjusting acid obtain optimal photocatalysis performance.The orientation of heterojunction structure constructs the directional separation for being advantageous to photo-generated carrier, can effectively improve the photocatalytic activity of heterojunction structure, is the focus on research direction of photocatalysis field.
Description
Technical field
The present invention relates to photocatalysis field, specially a kind of selective etch ferroelectricity base optic catalytic material with orient construct it is different
The method of matter structure.
Background technology
Being spatially separating of photogenerated charge can effectively suppress photo-generated carrier body phase is compound and the generation of back reaction, be
Obtain the prerequisite of high-quantum efficiency photochemical catalyst.Ferroelectric material has spontaneous polarization effect when less than Curie temperature, and
And spontaneous polarization strength can invert with external electric field.Photochemical catalyst will produce photo-generated carrier under illumination condition, and spontaneous
Polarization will establish small electrical field, electronics and hole under the electric field driven in intra-die and separate, and can more effectively promote light
Raw charge migration reduces recombination rate of the photogenerated charge in this body phase transmitting procedure to catalyst surface.But ferroelectric material
Surface Layer Atomic Structure is generally not favored the decomposition reaction of induction water, effectively divides under built-in electric field action even in photo-generated carrier
From and be transported to surface, its photocatalysis performance is limited by surface texture and can not given full play to.
It is the effective means for giving full play to ferroelectric material advantage in ferroelectric material surface construction high catalytic activity material, in light
Raw electronics reaches surface construction highly effective hydrogen yield material, reaches surface construction in photohole and efficiently produces oxygen material.We carry accordingly
Go out selective etch ferroelectricity base optic catalytic material to orient the method for constructing heterojunction structure, the orientation of heterojunction structure, which is constructed, to be advantageous to
The directional separation of photo-generated carrier, the photocatalytic activity of heterojunction structure can be effectively improved.
The content of the invention
It is an object of the invention to provide a kind of selective etch ferroelectricity base optic catalytic material to construct heterojunction structure to orient
Method, can under conditions of photo-generated carrier efficiently separates, further improve ferroelectric material superficial catalytic activation.
The technical scheme is that：
A kind of selective etch ferroelectricity base optic catalytic material utilizes semiconductor ferroelectricity to orient the method for constructing heterojunction structure
In material ferroelectricity field induction difference of the surface with electrical properties, cause negatively charged acid ion preference adsorb
The characteristics of positively charged surface, semiconductor ferroelectric material is put into the aqueous solution containing etching property acid, passes through hydro-thermal process mistake
Cheng Shixian constructs heterojunction structure to the selective etch on ferroelectric material surface in ferroelectricity substrate material surface orientation.
Described ferroelectric material is various ternarys or ternary above metallic compound ferroelectric material.
Preferably, described ferroelectric material is lead titanates, barium titanate or bismuth ferrite.
Described etching acid is various inorganic acids or its mixed acid solution.
Preferably, described etching acid is one of hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid or two or more mixing.
In described etching aqueous acid, sour molar concentration is 0.1mM~5M.
Described hydro-thermal process temperature is 30 DEG C~300 DEG C, and hydrothermal conditions are 10min~96h.
The design philosophy of the present invention is as follows：
The present invention establishes built in field, light induced electron and hole in the electricity using ferroelectric material spontaneous polarization in crystals
Field driving is lower to be separated, and can more effectively be migrated to catalyst surface, and it is compound in body phase transport process to reduce photogenerated charge
Rate.Also, difference of the surface with electrical properties induced with reference to built in field, utilizes the acid ion preference of negatively charged
Ground is adsorbed on positively charged surface, is realized and is constructed heterojunction structure photochemical catalyst to ferroelectric material surface selective etch orientation.Choosing
Selecting property reaches surface construction highly effective hydrogen yield material in light induced electron, while can effectively improving photogenerated charge separation, improves surface
Catalytic activity, increase substantially the photocatalytic activity of heterojunction structure.
Advantages of the present invention and beneficial effect are：
Selective etch ferroelectricity base optic catalytic material of the present invention to orient the method for constructing heterojunction structure, using ferroelectric material as
Presoma, its built-in ferroelectricity field is made full use of to efficiently separate the characteristic and induction difference of the surface with electrical properties of photo-generated carrier
Surface in situ etching structure highly effective hydrogen yield active surface that is different, optionally being reached in light induced electron.Photocatalysis is taken into account simultaneously
During photogenerated charge body phase Mass Transport Separation and surface shift two big basic processes, to construct high-quantum efficiency photochemical catalyst
System provides effectively reference.
Brief description of the drawings
SEM (SEM) photo of Fig. 1 metatitanic acid leading crystals；Wherein, (a) figure is original single electricdomain ferroelectricity material
Expect the SEM photograph of lead titanates nano-sheet crystal, upper and lower surface exposure is (001) crystal face；(b) after the selective etch of chart face
Metatitanic acid leading crystal SEM photograph, produced only in side (001) crystal plane surface raised.
Fig. 2 lead titanates nano-sheet crystallographic selectivity light depositions Au, MnOxAnd the SEM photograph of the two co-deposition；Wherein,
(a) figure is lead titanates crystallographic selectivity light deposition Au SEM photograph；(b) figure is lead titanates crystallographic selectivity light deposition MnOx's
SEM photograph；(c) figure is that lead titanates crystallographic selectivity is co-deposited Au and MnOxSEM photograph.
Single electricdomain ferroelectric material lead titanates (PbTiO of Fig. 3 hydrofluoric acid selective etch3) nano-sheet crystal selection
Property light deposition Au, MnOxAnd the SEM photograph of the two co-deposition；Wherein, (a) figure is the selection of the metatitanic acid leading crystal of hf etching
Property light deposition Au；(b) the selective light deposition MnO of the metatitanic acid leading crystal of figure hf etchingx；(c) figure is hf etching
The selectivity of metatitanic acid leading crystal is co-deposited Au and MnOxSEM photograph.
Embodiment
In specific implementation process, the present invention is utilized in semiconductor ferroelectric material (barium titanate, lead titanates, bismuth ferrite etc.)
Ferroelectricity field induce difference of the surface with electrical properties, cause negatively charged acid ion preference adsorb positively charged
Surface, realize and heterojunction structure photocatalytic method is constructed to ferroelectric material selective etch orientation, semiconductor ferroelectric material is put
Enter in the aqueous solution containing etching property acid, the selective etch on ferroelectric material surface is realized by hydrothermal treatment process, in ferroelectricity
Substrate material surface orientation constructs heterojunction structure, and optimal light is obtained by the species, concentration and hydro-thermal process temperature that adjust acid
Catalytic performance.The orientation of heterojunction structure constructs the directional separation for being advantageous to photo-generated carrier, can effectively improve the light of heterojunction structure
Catalytic activity, it is the focus on research direction of photocatalysis field.
Described heterojunction structure is titanium oxide/lead titanates, titanium oxide/barium titanate, iron oxide/barium ferrite etc..Will be a certain amount of
Ternary and ternary more than metallic compound ferroelectric material (material forms：Powder or film) it is put into etching property acid solution
(the species of solution：Inorganic solution or organic solution), being then transferred to reactor, (inner bag material is polytetrafluoro material or other corrosion resistants
Corrosion material) in, reactor is heated to predetermined temperature in an oven after closed, the regular hour is incubated, is opened after cooling anti-
Kettle is answered, collects reacted suspension, (temperature is between 30~200 DEG C) is dried after being cleaned multiple times with the aqueous solution, obtains one side
(001) crystal plane surface has the ferroelectric material crystal of projection, and wherein bossing is binary newly-generated from ferroelectricity fertile material
Oxide, so as to obtain a kind of unique heterojunction structure being made up of fertile material and protrusion.
Wherein, the ferroelectric material includes various ternarys and ternary above metallic compound, such as：Lead titanates, barium titanate, iron
Sour bismuth etc..The etching property acid includes various inorganic acids and its mixed acid solution, such as：Hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid etc..Institute
State in etching property aqueous acid, sour molar concentration is 0.1mM~5M (being preferably 0.5mM~2M).Described hydro-thermal process temperature
It is 10min~96h (being preferably 1h~24h) to spend for 30 DEG C~300 DEG C (being preferably 100 DEG C~300 DEG C), hydrothermal conditions.
Describe the present invention in detail with reference to the accompanying drawings and examples.
Embodiment
In the present embodiment, the single electricdomain ferroelectric material lead titanates (PbTiO prepared is weighed3) flat crystal 300mg (shapes
Looks are as shown in Figure 1a), single electricdomain lead titanates flat crystal size is height 150nm, 600~1100nm of length, and upper and lower surface is sudden and violent
Dew crystal face is (001) crystal face, with different electric charges.Put it into equipped with (molar concentration 1M) in hydrofluoric acid aqueous solution, be transferred to
Using polytetrafluoroethylene (PTFE) as in the 80mL stainless steel cauldrons of liner.After reactor sealing, baking oven is put into 200 DEG C of hydro-thermal process
3h, response sample is taken out, cleaned with deionized water and dried at 80 DEG C, obtaining unilateral (001) crystal plane surface has the metatitanic acid of projection
Leading crystal, wherein protrusion are titanium oxide, as shown in Fig. 1 (b).
Single electricdomain ferroelectric material lead titanates (PbTiO3) flat crystal selective light deposition Au：The ferroelectricity material that will have been prepared
Material metatitanic acid leading crystal 300mg is put into that 40ml is aqueous, (volume ratio of water and absolute methanol is 1 in mixed liquor of absolute methanol:3, adopt
The effect mixed with water with absolute methanol is to provide electronics sacrifice agent), after add HAuCl thereto4, make HAuCl4Content be
3wt% (HAuCl4Effect be to provide the presoma of photoreduction).System light deposition 6h under xenon lamp, obtain sample use
Deionized water is cleaned and dried at 80 DEG C, as shown in Fig. 2 (a).
Single electricdomain ferroelectric material lead titanates (PbTiO of hydrofluoric acid selective etch3) flat crystal selective light deposition
Au：The raised metatitanic acid leading crystal 300mg of (001) crystal plane surface prepared adds to 40ml is aqueous, mixing of absolute methanol
(volume ratio of water and absolute methanol is 1 in liquid:3) HAuCl is added after, thereto4, make HAuCl4Content be 3wt%.The body
Light deposition 6h under xenon lamp is tied up to, sample is obtained and is cleaned with deionized water and dried at 80 DEG C, as shown in Fig. 3 (a).
By Fig. 2 (a) compared with Fig. 3 (a) as can be seen that it is etched after crystal, surface deposition Au grain densities it is higher.
Single electricdomain ferroelectric material lead titanates (PbTiO of hydrofluoric acid selective etch3) flat crystal selective light deposition
MnOx：The raised metatitanic acid leading crystal 300mg of (001) crystal plane surface prepared is added into 50ml NaIO containing 0.6g3The aqueous solution
In, after add MnSO thereto4·H2O, make MnSO4·H2O content is 4wt%.System light deposition 6h under xenon lamp, is obtained
Cleaned with deionized water to sample and dried at 80 DEG C, as shown in Fig. 3 (b).
Single electricdomain ferroelectric material lead titanates (PbTiO3) flat crystal selective light deposition MnOx：The ferroelectricity that will have been prepared
Material metatitanic acid leading crystal 300mg is put into 50ml NaIO containing 0.6g3The aqueous solution (uses NaIO3Function as hole sacrifice agent)
In, after add MnSO thereto4·H2O(MnSO4·H2O effect is to provide the presoma of photooxidation reaction), make MnSO4·
H2O content is 4wt%.System light deposition 6h under xenon lamp, obtain sample and cleaned with deionized water and dried at 80 DEG C, such as
Shown in Fig. 2 (b).
By Fig. 2 (b) compared with Fig. 3 (b) as can be seen that it is etched after crystal, surface deposition MnOxNanometer sheet is distributed
It is more uniform.
Single electricdomain ferroelectric material lead titanates (PbTiO3) flat crystal selectively co-deposition Au and MnOx：By what is prepared
Ferroelectric material metatitanic acid leading crystal 300mg is put into 50ml distilled water, after add HAuCl thereto4、MnSO4·H2O, make HAuCl4
Content be 3wt%, MnSO4·H2O content is 4wt%.System light deposition 6h under xenon lamp, obtains sample deionization
Water cleans and in 80 DEG C of drying.As shown in Fig. 2 (c).
Single electricdomain ferroelectric material lead titanates (PbTiO of hydrofluoric acid selective etch3) flat crystal selectivity be co-deposited
Au and MnOx：The raised metatitanic acid leading crystal of (001) crystal plane surface prepared is added in 50ml distilled water, after thereto plus
Enter HAuCl4、MnSO4·H2O, make HAuCl4Content be 3wt%, MnSO4·H2O content is 4wt%.The system is in xenon lamp
Lower light deposition 6h, obtain sample and cleaned with deionized water and dried at 80 DEG C, as shown in Fig. 3 (c).
By Fig. 2 (c) compared with Fig. 3 (c) as can be seen that it is etched after crystal, surface deposition Au and MnOxDensity is more
Greatly, it is more evenly distributed.
Result of implementation shows that the present invention utilizes ferroelectricity field induction difference of the surface with electrical properties in semiconductor ferroelectric material
It is different, cause negatively charged acid ion preference adsorb on positively charged surface, can be achieved to ferroelectric material surface
Selective etch orientation constructs heterojunction structure photochemical catalyst.Under illumination including single electricdomain ferroelectric material lead titanates nano-sheet crystal
Build carrier under electric field action to efficiently separate, photo-reduction deposited metal Au and photooxidation deposition MnOxGeneration that can be selective exists
On (001) crystal face of single electricdomain ferroelectric material lead titanates flat crystal different band electrical properties.Single electricity of hydrofluoric acid selective etch
Farmland ferroelectric material lead titanates (PbTiO3) flat crystal, produce raised generation TiO in one side (001) crystal plane surface2Nano particle,
Confirm that hydrofluoric acid aqueous solution etches metatitanic acid leading crystal and do not destroy its single electricdomain ferroelectric properties by selective deposition.Meanwhile titanium
The TiO of lead plumbate (001) crystal plane surface2Nano particle projection is favorably improved the catalytic activity of (001) crystal face, further improves titanium
The light of lead plumbate decomposes hydrogen generation efficiency.Carrier efficiently separates the raising with plane of crystal photocatalytic activity, the effective combination of the two
Make single electricdomain ferroelectric material lead titanates (PbTiO of hydrofluoric acid selective etch3) photocatalytic activity of flat crystal significantly carries
Height, the further design for other ferroelectricity base optic catalytic materials or photoelectrocatalysis device provide important references.
Claims (7)
1. a kind of selective etch ferroelectricity base optic catalytic material is to orient the method for constructing heterojunction structure, it is characterised in that：Utilize
Ferroelectricity field induction difference of the surface with electrical properties in semiconductor ferroelectric material, cause the acid ion prioritizing selection of negatively charged
Property adsorb the positively charged surface the characteristics of, semiconductor ferroelectric material is put into the aqueous solution containing etching property acid, passed through
Hydrothermal treatment process realizes the selective etch to ferroelectric material surface, and hetero-junctions is constructed in ferroelectricity substrate material surface orientation
Structure.
2. according to the selective etch ferroelectricity base optic catalytic material described in claim 1 to orient the method for constructing heterojunction structure,
It is characterized in that：Described ferroelectric material is various ternarys or ternary above metallic compound ferroelectric material.
3. according to the selective etch ferroelectricity base optic catalytic material described in claim 1 to orient the method for constructing heterojunction structure,
It is characterized in that：Preferably, described ferroelectric material is lead titanates, barium titanate or bismuth ferrite.
4. according to the selective etch ferroelectricity base optic catalytic material described in claim 1 to orient the method for constructing heterojunction structure,
It is characterized in that：Described etching acid is various inorganic acids or its mixed acid solution.
5. according to the selective etch ferroelectricity base optic catalytic material described in claim 1 to orient the method for constructing heterojunction structure,
It is characterized in that：Preferably, described etching acid is one of hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid or two or more mixing.
6. according to the selective etch ferroelectricity base optic catalytic material described in claim 1 to orient the method for constructing heterojunction structure,
It is characterized in that：In described etching aqueous acid, sour molar concentration is 0.1mM~5M.
7. according to the selective etch ferroelectricity base optic catalytic material described in claim 1 to orient the method for constructing heterojunction structure,
It is characterized in that：Described hydro-thermal process temperature is 30 DEG C~300 DEG C, and hydrothermal conditions are 10min~96h.
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| PCT/CN2017/089681 WO2018040685A1 (en) | 2016-09-05 | 2017-06-23 | Method for directionally constructing heterostructure by selectively etching ferroelectric-based photocatalytic material |
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| CN113908827A (en) * | 2021-10-18 | 2022-01-11 | 青岛科技大学 | Preparation method and application of tungsten oxide @ bismuth tungstate heterojunction piezoelectric catalytic material |
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| CN113908827A (en) * | 2021-10-18 | 2022-01-11 | 青岛科技大学 | Preparation method and application of tungsten oxide @ bismuth tungstate heterojunction piezoelectric catalytic material |
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