WO2018040685A1 - Procédé de construction directionnelle d'hétérostructure par gravure sélective d'un matériau photocatalytique à base ferroélectrique - Google Patents
Procédé de construction directionnelle d'hétérostructure par gravure sélective d'un matériau photocatalytique à base ferroélectrique Download PDFInfo
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- WO2018040685A1 WO2018040685A1 PCT/CN2017/089681 CN2017089681W WO2018040685A1 WO 2018040685 A1 WO2018040685 A1 WO 2018040685A1 CN 2017089681 W CN2017089681 W CN 2017089681W WO 2018040685 A1 WO2018040685 A1 WO 2018040685A1
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- ferroelectric
- acid
- heterostructure
- selectively etching
- based photocatalytic
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- 239000000463 material Substances 0.000 title claims abstract description 73
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 28
- 238000005530 etching Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 24
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 27
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 12
- 239000004065 semiconductor Substances 0.000 claims abstract description 9
- 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
- 238000010276 construction Methods 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 claims abstract 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 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
- 150000002500 ions Chemical class 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910000462 iron(III) oxide hydroxide Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000969 carrier Substances 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 8
- 150000005837 radical ions Chemical class 0.000 abstract 1
- 229910000859 α-Fe Inorganic materials 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000002256 photodeposition Methods 0.000 description 10
- 238000004626 scanning electron microscopy Methods 0.000 description 9
- 238000000151 deposition Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000005684 electric field Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011941 photocatalyst Substances 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
- 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 4
- 230000010287 polarization Effects 0.000 description 4
- 230000002269 spontaneous effect Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 241000872931 Myoporum sandwicense Species 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910004042 HAuCl4 Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000007539 photo-oxidation reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Classifications
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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
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- 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
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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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
Definitions
- the invention relates to the field of photocatalysis, in particular to a method for selectively etching a ferroelectric-based photocatalytic material to orient a heterostructure.
- the spatial separation of photogenerated charges can effectively suppress the bulk recombination of photogenerated carriers and the occurrence of reverse reactions, which is a prerequisite for obtaining high quantum efficiency photocatalysts.
- the ferroelectric material has a spontaneous polarization at a temperature below the Curie temperature, and the spontaneous polarization can be reversed with an external electric field.
- the photocatalyst will generate photo-generated carriers under illumination conditions, and the spontaneous polarization will establish a small electric field inside the crystal grains.
- the electrons and holes are separated by the electric field, and the photo-generated charges can be more effectively promoted to migrate to the catalyst surface. Reduce the recombination rate of photogenerated charge during this bulk transport.
- the surface atomic structure of ferroelectric materials is generally not conducive to the decomposition reaction of water, and even if the photogenerated carriers are effectively separated and transported to the surface by the built-in electric field, the photocatalytic performance cannot be fully exerted due to the surface structure limitation.
- the construction of high catalytically active materials on the surface of ferroelectric materials is an effective means to give full play to the advantages of ferroelectric materials.
- the photogenerated electrons reach the surface to construct high-efficiency hydrogen-generating materials, and the photo-generated holes reach the surface to construct high-efficiency oxygen-generating materials.
- the orientation structure of the heterostructure is beneficial to the directional separation of photogenerated carriers, which can effectively improve the photocatalytic activity of heterostructures.
- a method for selectively etching a ferroelectric-based photocatalytic material to construct a heterostructure by using a ferroelectric field in a semiconductor ferroelectric material to induce a difference in surface charging properties, thereby causing preferentially selective adsorption of a negatively charged acid ion With a positively charged surface, the semiconductor ferroelectric material is placed in an aqueous solution containing an etchant acid, and a selective etching of the surface of the ferroelectric material is achieved by a hydrothermal treatment process, and a heterostructure is oriented on the surface of the ferroelectric substrate material. .
- the ferroelectric material is a variety of ternary or ternary metal compound ferroelectric materials.
- the ferroelectric material is lead titanate, barium titanate or barium ferrite.
- the etchable acid is a variety of inorganic acids or mixed acid solutions thereof.
- the etchable acid is one or a mixture of two or more of hydrofluoric acid, hydrochloric acid, sulfuric acid, and nitric acid.
- the molar concentration of the acid is from 0.1 mM to 5 M.
- the hydrothermal treatment temperature is 30 ° C to 300 ° C, and the hydrothermal treatment time is 10 min to 96 h.
- the invention utilizes the spontaneous polarization of the ferroelectric material to establish a built-in electric field inside the crystal, and the photogenerated electrons and holes are separated by the electric field, and can migrate to the catalyst surface more effectively, thereby reducing the photogenerated charge in the bulk transport process. Compound rate.
- the negatively charged acid ions are preferentially adsorbed on the positively charged surface to realize selective etching of the ferroelectric material surface to construct the heterostructure photocatalyst.
- Selectively build high-efficiency hydrogen production materials on the surface of photogenerated electrons which can effectively improve photo-generated charge separation, improve surface catalytic activity, and greatly improve the photocatalytic activity of heterostructures.
- the invention selectively etches a ferroelectric-based photocatalytic material to construct a heterostructure structure, and uses a ferroelectric material as a precursor to fully utilize the built-in ferroelectric field to effectively separate photo-generated carriers and induce surface charging properties.
- the difference is that the surface of the photogenerated electrons is selectively etched in situ to construct a highly efficient hydrogen generating active surface.
- the two basic processes of bulk transport separation and surface transfer of photogenerated charge in photocatalytic process are considered, which provides an effective reference for constructing high quantum efficiency photocatalyst system.
- FIG. 1 Scanning electron microscopy (SEM) photograph of lead titanate crystals; (a) is a SEM photograph of the original single-domain ferroelectric material lead titanate nanosheet crystals with (001) crystals exposed on the upper and lower surfaces. (b) SEM photograph of the lead titanate crystal after selective etching on the surface of the graph, where only a side (001) crystal plane is convex.
- SEM scanning electron microscopy
- FIG. 1 SEM photograph of the selective photodeposition of Au, MnO x and their co-deposition of lead titanate nano-plate crystals; (a) is a SEM photograph of selective photodeposition of Au by lead titanate crystal; (b) The figure is a SEM photograph of selective photodeposition of MnO x by lead titanate crystal; (c) is a SEM photograph of selective co-deposition of Au and MnO x of lead titanate crystal.
- FIG. 3 SEM photograph of selective photodeposition of Au, MnO x and co-deposition of single-domain ferroelectric material lead-acid (PbTiO 3 ) nano-platelet crystals with hydrofluoric acid selective etching;
- the figure is a selective photodeposition Au of hydrofluoric acid etched lead titanate crystal;
- (b) a selective photodeposition of MnO x of a hydrofluoric acid etched lead titanate crystal;
- the present invention utilizes a ferroelectric field in a semiconductor ferroelectric material (barium titanate, lead titanate, barium ferrite, etc.) to induce a difference in surface charging properties, resulting in preferentially selective adsorption of negatively charged acid ions.
- a method of selectively etching a ferroelectric material to construct a heterostructure photocatalyst is carried out, and the semiconductor ferroelectric material is placed in an aqueous solution containing an etchant acid, and the surface of the ferroelectric material is realized by a hydrothermal treatment process.
- the surface is oriented to construct a heterostructure, and the optimal photocatalytic performance is obtained by adjusting the type and concentration of the acid and the hydrothermal treatment temperature.
- the directional structure of heterogeneous structure is beneficial to the directional separation of photogenerated carriers, and can effectively improve the photocatalytic activity of heterostructures. It is the key research direction in the field of photocatalysis.
- the heterostructure is titanium oxide/lead titanate, titanium oxide/barium titanate, iron oxide/barium ferrite, and the like.
- a certain amount of ternary and ternary metal compound ferroelectric materials (material form: powder or film) are placed in an etchable acidic solution (type of solution: inorganic solution or organic solution), and then transferred to the reaction kettle.
- the inner tank material is PTFE material or other corrosion-resistant material. After sealing, the reaction kettle is heated to a predetermined temperature in an oven for a certain period of time. After cooling, the reaction vessel is opened, and the suspension after the reaction is collected.
- the aqueous solution is dried several times and then dried (the temperature is between 30 and 200 ° C) to obtain a crystal of a ferroelectric material having a convex surface on the surface of the (001) crystal plane, wherein the convex portion is newly formed from the ferroelectric matrix material.
- the ferroelectric material comprises various ternary and ternary metal compounds, such as lead titanate, barium titanate, barium ferrite, and the like.
- the etchable acid includes various inorganic acids and mixed acid solutions thereof, such as hydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, and the like.
- the molar concentration of the acid in the etchable acid aqueous solution is from 0.1 mM to 5 M (preferably from 0.5 mM to 2 M).
- the hydrothermal treatment temperature is from 30 ° C to 300 ° C (preferably from 100 ° C to 300 ° C), and the hydrothermal treatment time is from 10 min to 96 h (preferably from 1 h to 24 h).
- a prepared single-domain ferroelectric material lead titanate (PbTiO 3 ) flake crystal 300 mg (the morphology is shown in FIG. 1a) is weighed, and the single-domain lead titanate flake crystal is of a height. 150nm, length 600 ⁇ 1100nm, the upper and lower surface exposed crystal face is (001) crystal face, with different charges.
- the reactor was sealed, it was placed in an oven at 200 ° C for 3 h, and the reaction sample was taken out, washed with deionized water and dried at 80 ° C to obtain a lead titanate crystal having a convex surface on one side (001) crystal surface, wherein The protrusion is titanium oxide as shown in Fig. 1(b).
- Single-domain ferroelectric material lead titanate (PbTiO 3 ) plate crystal selective photodeposition Au 300mg of prepared ferroelectric material lead titanate crystals is placed in a mixture of 40ml of water and anhydrous methanol (water and anhydrous methanol volume ratio of 1: 3, using the effect of water was mixed with anhydrous methanol to provide electronic sacrificial agent), after 4 HAuCl4 was added thereto, the content of 4 HAuCl4 was 3wt% (HAuCl 4 to provide an optical effect Precursor of the reduction reaction).
- the system was photodeposited for 6 h under a xenon lamp, and the sample was washed with deionized water and dried at 80 ° C as shown in Fig. 2(a).
- Single-domain ferroelectric material lead titanate (PbTiO 3 ) plate crystal selective photodeposition MnO x 300mg of prepared ferroelectric material lead titanate crystals in 50ml containing 0.6g NaIO 3 aqueous solution (using NaIO 3 MnSO 4 ⁇ H 2 O (the role of MnSO 4 ⁇ H 2 O is to provide a precursor for photooxidation), and the content of MnSO 4 ⁇ H 2 O is 4wt. %.
- the system was photodeposited under a xenon lamp for 6 h, and the sample was washed with deionized water and dried at 80 ° C as shown in Figure 2 (b).
- Single-domain ferroelectric material lead titanate (PbTiO 3 ) plate crystal selective co-deposited Au and MnO x 300 mg of prepared ferroelectric material lead titanate crystals were placed in 50 ml of distilled water, and then HAuCl 4 was added thereto.
- MnSO 4 ⁇ H 2 O has a content of HAuCl 4 of 3 wt% and a content of MnSO 4 ⁇ H 2 O of 4 wt%.
- the system was light deposited under a xenon lamp for 6 h, and the sample was washed with deionized water and dried at 80 °C. As shown in Figure 2 (c).
- FIG 2 (c) and FIG. 3 (c) comparative As can be seen, larger crystals after etching, deposited on the surface of Au and MnO x density, more uniform distribution.
- the implementation results show that the invention utilizes the ferroelectric field in the semiconductor ferroelectric material to induce the difference in surface charging properties, so that the negatively charged acid ions are preferentially and selectively adsorbed on the positively charged surface, and the surface of the ferroelectric material can be selectively selectively engraved.
- the eccentricity constructs a heterostructure photocatalyst. Light-emitting single-domain ferroelectric material lead titanate nano-plate crystals built-in electric field effect downloading effective separation, photoreduction deposition of metal Au and photo-oxidation deposition of MnO x can selectively occur in single-domain ferroelectric material titanic acid Lead-like crystals have different charged properties on the (001) crystal plane.
- Hydrofluoric acid selectively etched single-domain ferroelectric material lead titanate (PbTiO 3 ) plate crystal which generates protrusions on the surface of one side (001) crystal surface to form TiO 2 nanoparticles, and hydrofluoric acid is confirmed by selective deposition.
- Etching the lead titanate crystals in an aqueous solution does not destroy the single-domain ferroelectric properties.
- the TiO 2 nanoparticle protrusion on the surface of the lead (001) crystal surface helps to improve the catalytic activity of the (001) crystal plane and further improve the photodegradation hydrogen production efficiency of lead titanate.
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Abstract
L'invention concerne également un procédé de construction directionnelle d'une hétérostructure par gravure sélective d'un matériau photocatalytique à base ferroélectrique, comprenant: en utilisant la caractéristique selon laquelle un champ ferroélectrique d'un matériau ferroélectrique semi-conducteur (titanate de baryum, titanate de plomb, ferrite de bismuth ou similaire) induit une différence de propriété de charge de surface, de sorte que les ions de radicaux acides chargés négativement soient préférentiellement et sélectivement adsorbés sur une surface chargée positivement, placer le matériau ferroélectrique semi-conducteur dans une solution aqueuse contenant de l'acide de gravure, et à graver sélectivement la surface du matériau ferroélectrique au moyen d'un procédé de traitement hydrothermique, pour construire directionnellement une hétérostructure sur la surface d'un matériau de substrat ferroélectrique. Au moyen du procédé, une performance photocatalytique optimale peut être obtenue par réglage du type et de la concentration d'acide, et d'une température de traitement hydrothermique. La construction directionnelle d'une hétérostructure facilite la séparation directionnelle de porteurs photogénérés, et peut améliorer efficacement l'activité photocatalytique de l'hétérostructure.
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CN201610801007.2 | 2016-09-05 | ||
CN201610801007.2A CN107790194A (zh) | 2016-09-05 | 2016-09-05 | 选择性刻蚀铁电基光催化材料以定向构筑异质结构的方法 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110227475A (zh) * | 2019-06-25 | 2019-09-13 | 长春工程学院 | 一种BiFeO3/Bi2Fe4O9异质结构催化剂的制备方法及其应用 |
CN113385169A (zh) * | 2021-06-21 | 2021-09-14 | 大连理工大学 | 一种高效降解有机污染物的新型压电光催化剂、制备方法及应用 |
CN114272917A (zh) * | 2021-12-17 | 2022-04-05 | 南京航空航天大学 | 一种压电光催化剂及其制备方法与应用 |
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CN110523411A (zh) * | 2018-05-25 | 2019-12-03 | 中国科学院金属研究所 | 在铁电光催化材料表面选择性沉积金属氧化物助催化剂的方法 |
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CN111203216A (zh) * | 2018-11-22 | 2020-05-29 | 中国科学院金属研究所 | 在铁电光催化材料表面选择性沉积Rh@Cr2O3核壳助催化剂的方法 |
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