CN110523411A - In the method for ferroelectricity catalysis material surface selective deposition metal oxide promoters - Google Patents
In the method for ferroelectricity catalysis material surface selective deposition metal oxide promoters Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 93
- 230000005621 ferroelectricity Effects 0.000 title claims abstract description 41
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 40
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 40
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 38
- 230000008021 deposition Effects 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 19
- 230000010287 polarization Effects 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000004044 response Effects 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- -1 ion forms metal oxide Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910002902 BiFeO3 Inorganic materials 0.000 claims description 3
- 229910003334 KNbO3 Inorganic materials 0.000 claims description 3
- 229910003327 LiNbO3 Inorganic materials 0.000 claims description 3
- 229910015667 MoO4 Inorganic materials 0.000 claims description 3
- 229910020696 PbZrxTi1−xO3 Inorganic materials 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000003426 co-catalyst Substances 0.000 abstract description 28
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 230000033228 biological regulation Effects 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 description 23
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 21
- 229910003781 PbTiO3 Inorganic materials 0.000 description 13
- 239000000843 powder Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 230000028161 membrane depolarization Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- SNUFURQFLHHQQS-UHFFFAOYSA-N chembl1488131 Chemical compound CC1=[N+]([O-])[N+]([O-])=C(C)C2=[N+]([O-])ON=C12 SNUFURQFLHHQQS-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000006557 surface reaction Methods 0.000 description 3
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000002305 electric material Substances 0.000 description 2
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- 230000002269 spontaneous effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
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- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/628—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with lead
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
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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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- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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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
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Abstract
The present invention relates to field of photocatalytic material, specially a kind of method in ferroelectricity catalysis material surface selective deposition metal oxide promoters.Using ferroelectric material as matrix, it takes and is fitted into the reaction kettle of the solution containing different metal ions in right amount, reaction kettle is sealed after uniform stirring, it is placed in baking oven heat treatment, take out response sample, it is cleaned and is dried with deionized water, the ferroelectricity catalysis material of metal oxide promoters selective deposition is obtained in metal ion solution system.Metal ion of the present invention is that co-catalyst presoma directly adsorbs on the opposite polarizations face of ferroelectric material, hydrothermal growth goes out the catalysis material of selective load cocatalyst, and the co-catalyst and clearly selective deposition on its surface can be recognized by scanning electron microscope.To realize modification of the ferroelectric material to the selective regulation and co-catalyst of co-catalyst to ferroelectricity catalysis material, effectively improve the photocatalysis performance of ferroelectricity catalysis material.
Description
Technical field
The present invention relates to field of photocatalytic material, and specially one kind is in ferroelectricity catalysis material surface selective deposition metal
The method of oxide promoter, by water-heat process, before being co-catalyst as matrix, metal ion using ferroelectricity catalysis material
Drive the ferroelectricity catalysis material that body Direct Hydrothermal prepares surface selective deposition metal oxide promoters.
Background technique
In photocatalysis field, efficiently separating photo-generated carrier and realizing that it is efficiently utilized is the pass for obtaining high photocatalysis efficiency
Key.Perovskite structure (ABO3) imbalance of the ferroelectric material due to B metal cations on lattice sites, lead to Symmetrical
Center is not overlapped so as to cause spontaneous polarization electric field, the hole that illumination can be accelerated to excite using this depolarization field, electronics
Directional separation reduces recombination probability.But shortcoming is: the superficial catalytic activation of ferroelectric material is weak, generally requires and passes through load
Co-catalyst provides more reactivity sites to improve reactivity, and conventional deposition method includes light deposition, impregnating
Method.
We have found that the unique polarization characteristic of available iron electric material realizes that the selectivity of ion is inhaled on different polarization surfaces
Attached, which can induce metal oxide promoters hydrothermal growth on different planes of polarization, can improve light and urge
Change material to the transformation efficiency of solar energy.
Summary of the invention
The purpose of the present invention is to provide one kind to help in ferroelectricity catalysis material surface selective deposition metal oxide
The method of catalyst can be realized regulation of the ferroelectricity catalysis material to co-catalyst under temperate condition, to improve ferroelectricity light
The separative efficiency and surface reaction activity of photo-generated carrier in catalysis material.
Technical solution of the present invention:
A method of in ferroelectricity catalysis material surface selective deposition metal oxide promoters, with ferroelectric material
It for matrix, is loaded into the reaction kettle of the neutral solution containing different metal ions, after stirring evenly sealing reaction kettle, is placed in baking
Case heat treatment, takes out response sample, is cleaned and dried with deionized water, urged to obtain selective deposition metal oxide and help
The ferroelectric material of agent.
The ferroelectric material is the PbTiO of different-shape3、BaTiO3、BiFeO3、LiNbO3、KNbO3、Bi4Ti3O12、
Bi2SiO5、Bi5FeTi3O15、PbZrxTi1-xO3Or the compound of related derivative.
In the neutral solution containing different metal ions, metal ion is Ru3+、Ir3+、Cr2+、Cr3+、Ni2+、Ag+、Co2 +、Mn2+、Rh3+、IrCl6 2-、CrO4 2-、Cr2O7 2-、MoO4 2-、PtCl6 2-、AuCl4 -、MnO4 -、MnO4 2-、RuO4 -、RuO4 2-In one
Kind is two or more, and the molar concentration of metal ion in the solution is 0.01mmol/L~10mmol/L.
The method in ferroelectricity catalysis material surface selective deposition metal oxide promoters, relative to base
Body material, the mass percent of the metal oxide of deposition are 0.05%~20%wt.
The method in ferroelectricity catalysis material surface selective deposition metal oxide promoters, relative to base
Body material, the mass percent of the metal oxide of deposition are preferably 0.25%~5%wt.
The method in ferroelectricity catalysis material surface selective deposition metal oxide promoters is dried being placed in
When case heats, heating temperature is 50~350 DEG C, and heating time is 0.2~240h.
The method in ferroelectricity catalysis material surface selective deposition metal oxide promoters is dried being placed in
When case heats, heating temperature is preferably 160~220 DEG C, and heating time is preferably 6~for 24 hours.
The method in ferroelectricity catalysis material surface selective deposition metal oxide promoters, passes through hydro-thermal
Adjusting and controlling growth metal oxide is in the selective distribution on ferroelectric material surface, and under the action of ferroelectricity depolarization field, ion is by quiet
The plane of polarization that electrical forces are preferentially adsorbed to opposite-sign forms metal oxide, of the metal oxide promoters of load
Grain distribution is 1nm~100nm.
Design philosophy of the invention is as follows:
Ferroelectric material meets corresponding thermodynamic condition, and resource is extensive since they have good band structure,
So the candidate of catalysis material can be become, but be more attributed to the fact that spontaneous polarization electric field existing for ferroelectric material, it can be in light
It is reached on reduction or the oxidation activity site on surface according to lower directional separation light induced electron, hole, induces light-catalyzed reaction.But iron
The surface reaction activity of electric material is limited, and the active site for improving ferroelectric material surface is not to the application of ferroelectricity catalysis material
It is evitable.On the other hand, ferroelectric material is usually ternary or multi-element compounds, and due to the presence of depolarization field, choosing
Mild condition is selected to be necessary the modification of ferroelectric material.Take into account this two o'clock, hydro-thermal selective growth metal oxide
Co-catalyst is for promoting ferroelectric material surface-active site highly significant.Compared with conventional method deposits co-catalyst, this hair
Bright step is simple and is suitable for all kinds of oxide promoters, and different conditions can be obtained under acting on by ferroelectricity depolarization field
Co-catalyst, to explore the influence of ferroelectric material and co-catalyst coupling to light-catalyzed reaction.
The invention has the advantages and beneficial effects that:
1, this invention address that solving general catalysis material simultaneously does not have high reaction selectivity, high reaction activity not
Foot obtains the ferroelectricity catalysis material of selective load cocatalyst by completely new method.
2, the present invention uses environmental-friendly, the simple synthetic method of step, is conducive to large-scale production.
3, the matrix that the present invention uses is resourceful for solid-state material, is easy to store, use.
4, material prepared of the present invention has high active site, high reaction selectivity, high surface-active.
Detailed description of the invention
The XRD spectrum of 1 resulting materials of Fig. 1 embodiment, abscissa are 2 θ of the angle of diffraction, and unit is angle, and ordinate is diffraction
Peak intensity, arbitrary unit.
The XRD spectrum of 1 resulting materials of Fig. 2 embodiment, abscissa are 2 θ of the angle of diffraction, and unit is angle, and ordinate is diffraction
Peak intensity, arbitrary unit.
The SEM photograph of 1 resulting materials of Fig. 3 embodiment.
The SEM photograph of 2 resulting materials of Fig. 4 embodiment.
The SEM photograph of 3 resulting materials of Fig. 5 embodiment.
The SEM photograph of 3 resulting materials of Fig. 6 embodiment.
Specific embodiment
The present invention provide it is a kind of can be in the side of ferroelectricity catalysis material surface selective deposition metal oxide promoters
Method takes and is loaded into the reaction kettle of the solution containing different metal ions in right amount, seal after mixing evenly using ferroelectric material as matrix
Reaction kettle is placed in baking oven heat treatment, takes out response sample, cleaned and dried with deionized water.To molten in metal ion
In liquid system, the ferroelectricity catalysis material of metal oxide promoters selective deposition is obtained, is specifically characterized by:
1, the matrix used PbTiO for various powders commercializations or experiment preparation3、BaTiO3、BiFeO3、LiNbO3、KNbO3、
Bi4Ti3O12、Bi2SiO5、Bi5FeTi3O15、PbZrxTi1-xO3Deng and related derivative compound, powder granularity range is
50nm~5 μm.
2, in the solution used containing different metal ions, a certain amount of deionized water is added, metal ion is Ru3+、Ir3+、
Cr2+、Cr3+、Ni2+、Ag+、Co2+、Mn2+、Rh3+、IrCl6 2-、CrO4 2-、Cr2O7 2-、MoO4 2-、PtCl6 2-、AuCl4 -、MnO4 -、
MnO4 2-、RuO4 -、RuO4 2-Deng one or more of, the molar concentration of metal ion in the solution be 0.01mmol/L~
10mmol/L, metal ion is added can be using conventional chloride, Li salt, Na salt, K salt or Ca salt etc..
3, in the reaction system, the metal oxide of load and ferroelectricity basis material mass ratio be 0.01mg/200mg~
40mg/200mg (preferably 0.5mg/200mg~10mg/200mg).
4, when being placed in baking oven heat treatment, heating temperature is 50~350 DEG C (preferably 160~220 DEG C), heating time
For 0.2~240h (preferably 6~for 24 hours).
In the present invention, metal oxide is regulated and controled in the selective distribution on ferroelectric material surface, in ferroelectricity by hydrothermal growth
Under the action of depolarization field, ion forms metal oxide by the plane of polarization that electrostatic force is preferentially adsorbed to opposite-sign, bears
The particle distribution range of the metal oxide promoters of load is 1nm~100nm.
In the following, in conjunction with the embodiments next, the present invention will be described in detail.
Embodiment 1
Weigh the ferroelectricity single domain material PbTiO of laboratory preparation3(in the present embodiment, PbTiO3Preparation method sees reference document
Doi:10.1002/anie.201204792) powder 200mg, powder granularity are about 1 μm or so, put it into and contain equipped with 30mL
0.677mM RuCl3Aqueous solution in, using polytetrafluoroethylene (PTFE) to stir evenly in the 80mL stainless steel cauldron of liner.Reaction
After kettle sealing, baking oven is put into 200 DEG C of heat treatment 12h, takes out response sample, is cleaned with deionized water and is dried at 60 DEG C,
Obtain surface selective deposition RuO2The PbTiO of co-catalyst3Material.In the present embodiment, ferroelectric material selective growth co-catalysis
Agent, co-catalyst RuO2Content relative to ferroelectricity basis material mass ratio be 1.35%.
As shown in Figure 1, prepared material is surface selective growth RuO2The PbTiO of co-catalyst3, from XRD diffraction maximum
Intensity illustrates PbTiO3Peak do not change, also without the generation of other new peaks；
As shown in Fig. 2, hydrothermal growth RuO2PbTiO afterwards3400 degree of heat treatment 2h, corresponding XRD spectrum are in air
PTO-RuO2- 400 and original PTO-RuO2There are two new peaks after the discovery heat treatment that compares in the diffracting spectrum of sample.Through looking into this
New peak comes from RuO2, it was demonstrated that the RuO of hydrothermal growth2It is amorphous or low-crystallinity, RuO2The PbTiO of modification3Show height
Photocatalysis performance.The RuO prepared using hydrothermal method2State with other methods (such as infusion process etc.) obtained by RuO2Shape
State is dramatically different；
As shown in figure 3, bulky grain is tetragonal phase PbTiO3, size is about 1 μm or so, and on its surface, the little particle of growth is
RuO2, size distribution is 5nm~20nm.
Embodiment 2
Weigh the ferroelectric material PbTiO of experiment preparation3(in the present embodiment, PbTiO3Preparation method sees reference document doi:
10.1002/anie.201204792) powder 200mg, powder granularity is about 1 μm or so, is put it into equipped with 30mL containing 1.02mM
RuCl3Aqueous solution in, using polytetrafluoroethylene (PTFE) to stir evenly in the 80mL stainless steel cauldron of liner.After reaction kettle sealing,
Baking oven is put into 200 DEG C of heat treatment 12h, takes out response sample, is cleaned with deionized water and is dried at 60 DEG C, obtains surface choosing
Selecting property deposits RuO2The PbTiO of co-catalyst3Material.In the present embodiment, ferroelectric material grows co-catalyst, RuO2Co-catalyst
Content relative to matrix PbTiO3Mass percent is 2%.
As shown in figure 4, bulky grain is tetragonal phase PbTiO3, on its surface, the little particle of growth is RuO2, granularity is about 5nm
~20nm.
Embodiment 3
Weigh the ferroelectric material PbTiO of experiment preparation3(in the present embodiment, PbTiO3Preparation method sees reference document doi:
10.1002/anie.201204792) powder 200mg, powder granularity is about 1 μm or so, puts it into and contains equipped with 30mL
0.677mM RuCl3、0.877mM K2CrO4Aqueous solution in, using polytetrafluoroethylene (PTFE) as in the 80mL stainless steel cauldron of liner,
It stirs evenly.After reaction kettle sealing, baking oven is put into 200 DEG C of heat treatment 12h, response sample is taken out, is cleaned with deionized water
And dried at 60 DEG C, obtain the RuO of positive polarization face preferential deposition2And the Cr of negative polarization face preferential deposition2O3Co-catalyst modification
PbTiO3Material.In the present embodiment, ferroelectric material grows co-catalyst, RuO2And Cr2O3The content of co-catalyst is relative to iron
Electric basis material mass ratio is respectively 1.35%, 1%.
As shown in figure 5, bulky grain is tetragonal phase PbTiO3, it is Cr in its positive polarization long little particle of looking unfamiliar2O3, negative at it
The little particle of plane of polarization growth is RuO2, granularity is about 5nm~20nm.
Embodiment 4
Weigh the epitaxial growth TiO of experiment preparation2PbTiO3(in the present embodiment, PbTiO3Preparation method bibliography
Doi.org/10.1016/j.joule.2018.03.006, and it is denoted as FPTO) powder 200mg, powder PbTiO3Granularity is about 1 μ
M, surface TiO2Granularity is about 10nm~50nm, is put it into equipped with 30mL RuCl containing 1.002mM3Aqueous solution in, with poly- four
Vinyl fluoride is to stir evenly in the 80mL stainless steel cauldron of liner.After reaction kettle sealing, baking oven is put at 200 DEG C of heating
12h is managed, response sample is taken out, cleaned with deionized water and is dried at 60 DEG C, negative polarization face preference deposition RuO is obtained2
The FPTO material of co-catalyst.In the present embodiment, ferroelectric material grows co-catalyst, RuO2The content of co-catalyst relative to
FPTO basis material mass percent is 2%.
As shown in fig. 6, bulky grain is tetragonal phase PbTiO3, it is TiO in positive polarization long little particle of looking unfamiliar2, in negative polarization face
The little particle of preferred growth is RuO2, granularity is about 5nm~20nm.
Embodiment the result shows that, be co-catalyst forerunner by matrix, metal ion of ferroelectric material by water-heat process
Body directly adsorbs on the opposite polarizations face of ferroelectric material, and hydrothermal growth goes out metal oxide promoters selective modification
Ferroelectricity catalysis material can recognize the co-catalyst and clearly selective deposition on its surface by scanning electron microscope.
The co-catalyst of selective deposition is able to ascend the carrier separation efficiency of ferroelectricity catalysis material and improves surface reaction and lives
Property.To, realize modification of the ferroelectric material to the selective regulation and co-catalyst of co-catalyst to ferroelectricity catalysis material,
Effectively improve the photocatalysis performance of ferroelectricity catalysis material.
Claims (8)
1. a kind of method in ferroelectricity catalysis material surface selective deposition metal oxide promoters, which is characterized in that
It using ferroelectric material as matrix, is loaded into the reaction kettle of the neutral solution containing different metal ions, stirs evenly sealing reaction
After kettle, it is placed in baking oven heat treatment, response sample is taken out, is cleaned and dried with deionized water, to obtain selective deposition gold
Belong to the ferroelectric material of oxide promoter.
2. the side described in accordance with the claim 1 in ferroelectricity catalysis material surface selective deposition metal oxide promoters
Method, which is characterized in that the ferroelectric material is the PbTiO of different-shape3、BaTiO3、BiFeO3、LiNbO3、KNbO3、
Bi4Ti3O12、Bi2SiO5、Bi5FeTi3O15、PbZrxTi1-xO3Or the compound of related derivative.
3. the side described in accordance with the claim 1 in ferroelectricity catalysis material surface selective deposition metal oxide promoters
Method, which is characterized in that in the neutral solution containing different metal ions, metal ion is Ru3+、Ir3+、Cr2+、Cr3+、Ni2+、
Ag+、Co2+、Mn2+、Rh3+、IrCl6 2-、CrO4 2-、Cr2O7 2-、MoO4 2-、PtCl6 2-、AuCl4 -、MnO4 -、MnO4 2-、RuO4 -、RuO4 2-
One or more of, the molar concentration of metal ion in the solution is 0.01mmol/L~10mmol/L.
4. the side described in accordance with the claim 1 in ferroelectricity catalysis material surface selective deposition metal oxide promoters
Method, which is characterized in that relative to basis material, the mass percent of the metal oxide of deposition is 0.05%~20%wt.
5. the side described in accordance with the claim 1 in ferroelectricity catalysis material surface selective deposition metal oxide promoters
Method, which is characterized in that relative to basis material, the mass percent of the metal oxide of deposition is preferably 0.25%~5%wt.
6. the side described in accordance with the claim 1 in ferroelectricity catalysis material surface selective deposition metal oxide promoters
Method, which is characterized in that when being placed in baking oven heat treatment, heating temperature is 50~350 DEG C, and heating time is 0.2~240h.
7. the side described in accordance with the claim 1 in ferroelectricity catalysis material surface selective deposition metal oxide promoters
Method, which is characterized in that when being placed in baking oven heat treatment, heating temperature is preferably 160~220 DEG C, and heating time is preferably 6~
24h。
8. the side described in accordance with the claim 1 in ferroelectricity catalysis material surface selective deposition metal oxide promoters
Method, which is characterized in that metal oxide is regulated and controled in the selective distribution on ferroelectric material surface by hydrothermal growth, moves back pole in ferroelectricity
Under the action of changing field, ion forms metal oxide by the plane of polarization that electrostatic force is preferentially adsorbed to opposite-sign, load
The particle distribution range of metal oxide promoters is 1nm~100nm.
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