CN103240072A - Core-shell structure nanoribbon photocatalyst and preparation method thereof - Google Patents
Core-shell structure nanoribbon photocatalyst and preparation method thereof Download PDFInfo
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- CN103240072A CN103240072A CN2013102077376A CN201310207737A CN103240072A CN 103240072 A CN103240072 A CN 103240072A CN 2013102077376 A CN2013102077376 A CN 2013102077376A CN 201310207737 A CN201310207737 A CN 201310207737A CN 103240072 A CN103240072 A CN 103240072A
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- 238000002360 preparation method Methods 0.000 title claims description 25
- 239000002074 nanoribbon Substances 0.000 title abstract 8
- 239000011258 core-shell material Substances 0.000 title abstract 4
- 239000011941 photocatalyst Substances 0.000 title abstract 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 70
- 239000000843 powder Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 238000003746 solid phase reaction Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910010251 TiO2(B) Inorganic materials 0.000 abstract 3
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 229910020293 Na2Ti3O7 Inorganic materials 0.000 abstract 1
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 abstract 1
- 238000005242 forging Methods 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 6
- 229910002115 bismuth titanate Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 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 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Abstract
The invention discloses a TiO2(B)@Bi20TiO32 core-shell structure nanoribbon photocatalyst, wherein the core-shell structure nanoribbon has the width size of 100nm-150nm, and the length of 10 micron-990 micron, and the nanoribbon is internally provided with TiO2(B), and is externally provided with Bi20TiO32. The photocatalyst provided by the invention is synthesized through low-temperature solid phase reaction, namely, Na2Ti3O7 is adopted within the nanoscale range as a reaction template and a reaction raw material, and is sufficiently mixed with pentahydrate bismuth nitrate hydrolysis suspension with certain concentration; and firstly a hybrid precursor nanoribbon is synthesized by utilizing electrostatic attraction among granules, and finally the TiO2(B)@Bi20TiO32 core-shell structure nanoribbon photocatalyst is obtained through low-temperature forging and synthesizing. Because the solid phase reaction is completed once at low temperature, and the technology device is simple, the obtained nanoribbon is narrow in width distribution, is controllable in length, is short in reaction cycle, has good repeatability, has a wide development prospect, and provides a simple and feasible synthesizing line for preparing other titanate nanoribbon materials by a solid phase reaction method.
Description
Technical field
The present invention relates to a kind of TiO
2(B) Bi
20TiO
32Nuclear shell structure nano band photochemical catalyst and preparation method thereof.
Background technology
The control that environment in recent years is polluted more and more comes into one's own with administering, and the environmental problem that goes from bad to worse presses for degrade pollutant in atmosphere and the water body of a kind of more environmental protection, cheap technology.Photocatalysis performance is one of special performance of Nano semiconductor.Nano semiconductor material by luminous energy is converted into chemical energy, impels the synthetic of compound or makes the process of compound (organic matter, inorganic matter) degraded be referred to as catalysis material under the irradiation of light.From then on, with TiO
2For the semiconductor light-catalyst that represents begins to grow up.But TiO
2Photocatalysis efficiency not high, and the photoresponse scope is at ultraviolet region, the sunshine utilization rate is low, has restricted its development.
Bi
2O
3And TiO
2Be compounded to form the composite oxides with multiple crystal phase structure: as Bi
4Ti
3O
12, Bi
2Ti
2O
7, Bi
2Ti
4O
11, Bi
12TiO
20, Bi
20TiO
32Deng, be referred to as the bismuth titanates compound.By studying these bismuth titanates compounds and P-25(anatase TiO
2Nano-powder) ultraviolet～visible scattered reflection spectrum finds that the energy gap of these several bismuth titanates materials is all less than 3eV, and ABSORPTION EDGE is 400～580nm, and TiO
2Energy gap be 3.2eV, ABSORPTION EDGE is 387.5nm, by contrast, " red shift " phenomenon has appearred in the ABSORPTION EDGE of bismuth titanates material, makes it have good photocatalytic effect in visible wavelength range.Bi wherein
20TiO
32Cause has high n type photoconduction and high carrier flowability, and possesses good ultraviolet～visible light catalytic effect.
Up to now, do not see relevant Bi as yet
20TiO
32The report of nanometer band preparation.[Hefeng Cheng, Baibiao Huang, Ying Dai et al.Visible-light photocatalytic activity of the metastable Bi such as Hefeng Cheng
20TiO
32Synthesized by a high-temperature quenching method[J] .Journal of Solid State Chemistry.2009,182:2274-2278.] under 1000 ℃, prepared Bi by solid reaction process
20TiO
32Nano particle, and its visible light catalytic performance studied, Bi shown
20TiO
32In visible wavelength range, methyl orange had good catalytic effect; [Tengfei Zhou and Juncheng Hu.Mass Production and Photocatalytic Activity of Highly Crystalline Metastable Single-Phase Bi such as Tengfei Zhou
20TiO
32Nanosheets[J] .Environ.Sci.Technol.2010,44:8698 – 8703.] gone out Bi by Prepared by Sol Gel Method
20TiO
32Nanometer sheet etc.But the Bi for preparing
20TiO
32Powder is that nano particle is difficult for recycling because of its pattern, and these methods or high to the equipment requirement, and equipment and instrument is relatively more expensive; Very little to utilization ratio of raw materials; Perhaps complex process, manufacturing cycle is long, and is repeatable poor.In order to reach the purpose of practicability, the Bi that necessary Development and Production cost is low, simple to operate, the cycle is short
20TiO
32The preparation technology of nanometer band.
Summary of the invention
At the deficiencies in the prior art, the problem that the present invention requires to solve provides a kind of TiO
2(B) Bi
20TiO
32Nuclear shell structure nano band photochemical catalyst and preparation method thereof.
TiO of the present invention
2(B) Bi
20TiO
32Nuclear shell structure nano band photochemical catalyst is characterized in that: described photochemical catalyst is that width dimensions is 100nm～150nm, and length is the TiO of 10 μ m～990 μ m
2(B) Bi
20TiO
32The nuclear shell structure nano band, wherein nanometer band the inside is TiO
2(B), the outside is Bi
20TiO
32
Described TiO of the present invention
2(B) Bi
20TiO
32The preparation method of nuclear shell structure nano band photochemical catalyst, step is:
(1) the nano titanium oxide P25 with reacting dose is dissolved in the NaOH solution of 10M, and is ultrasonic, stir each 0.5h and fall back in the thermal response still, and compactedness is controlled at 60～80% of reactor volume; Seal hydrothermal reaction kettle then, put it in the drying box, make hydrothermal temperature control at 200 ± 10 ℃, the reaction time is controlled at 24h～72h, and reaction naturally cools to room temperature after finishing, and the gained powder washes repeatedly with deionized water, and suction filtration makes Na then
2Ti
3O
7Powder, stand-by;
(2) with analytically pure five water bismuth nitrate (Bi (NO
3)
35H
2O) add in the distilled water, and constantly stir, be mixed with Bi
3+Concentration is the suspension of 2.5mmol/L～10mmol/L, and gained solution is designated as A solution;
(3) Na in molar ratio in the A solution
+: Bi
3+The ratio of=1:1 adds above-mentioned Na
2Ti
3O
7Powder, and constantly stir, forming precursor solution, gained solution is designated as B solution; Behind the B solution left standstill 48h with preparation, the gained powder washes repeatedly with deionized water, and suction filtration will make powder and place 60 ± 5 ℃ of drying 10～15h of drying box then;
(4) the dry good powder of step (3) is put into Muffle furnace and calcine 2～3h down at 450 ± 10 ℃, cool to room temperature then with the furnace, namely make TiO free from foreign meter
2(B) Bi
20TiO
32Nuclear shell structure nano band photochemical catalyst.
Above-mentioned TiO
2(B) Bi
20TiO
32Among the preparation method of nuclear shell structure nano band photochemical catalyst: the described Bi of step (2)
3+Concentration is preferably 2.5mmol/L～7mmol/L.
Above-mentioned TiO
2(B) Bi
20TiO
32Among the preparation method of nuclear shell structure nano band photochemical catalyst: the described powder of step (4) is put into Muffle furnace and is preferably calcined 2h down at 450 ℃.
The present invention adopts the simple low temperature solid reaction process, has prepared wide about 100nm-150nm, and length is at tens of TiO to hundreds of micrometer ranges
2(B) Bi
20TiO
32The nuclear shell structure nano band.Because this nanometer band is TiO
2(B) Bi
20TiO
32Nucleocapsid structure, the feature of this nuclear shell structure nano band are that the inside is TiO
2(B), the outside is Bi
20TiO
32, be conducive to the separation of carrier more, effectively raise the photocatalysis performance of this nanometer band, make its degradation rate to methyl orange under the ultraviolet radiation of 50min reach 96.89%.
TiO of the present invention
2(B) Bi
20TiO
32The nuclear shell structure nano band is to adopt Na in the nanoscale scope
2Ti
3O
7Be reaction template, synthesize by low-temperature solid phase reaction.Adopt this method can prepare wide about 100nm-150nm rapidly, length is at tens of TiO to hundreds of micrometer ranges
2(B) Bi
20TiO
32The nuclear shell structure nano band.Na in preparation
2Ti
3O
7The nanometer band for reaction titanium source, had been again nanometer band reaction template both.Five water bismuth nitrate (Bi (NO
3)
35H
2O) add in the distilled water, both generated BiONO
3Precipitation produces a large amount of H again simultaneously as reaction raw materials
+, be used for displacement Na
2Ti
3O
7In Na
+, kill two birds with one stone.Because this solid phase reaction is once finished at low temperatures, and process equipment is simple, gained nanometer bandwidth narrowly distributing, length controlled, reaction time is short, therefore good reproducibility has vast potential for future development, for solid reaction process prepares the synthetic route that other titanate nanometer carrying materials provide a simple possible.
To sum up, the invention has the beneficial effects as follows:
1. the TiO that makes of the inventive method
2(B) Bi
20TiO
32The nuclear shell structure nano band is conducive to the separation of carrier more, effectively raises the photocatalysis performance of this nanometer band.
2. this nanometer bandwidth narrow size distribution (100nm-150nm), length controlled (at tens of microns between hundreds of micrometer ranges).
3. technology preparation of the present invention is simple, and easy to operate, raw material is easy to get, and preparation cost is lower.
Description of drawings
Fig. 1 is the TiO of low-temperature solid-phase method preparation
2(B) Bi
20TiO
32The X-ray diffraction of nanometer band (XRD) collection of illustrative plates.
Fig. 2 is the TiO of low-temperature solid-phase method preparation
2(B) Bi
20TiO
32The field emission scanning electron microscope of nanometer band (FESEM) photo.
Fig. 3 is the TiO of low-temperature solid-phase method preparation
2(B) Bi
20TiO
32The transmission electron microscope of nanometer band (TEM) photo.
Fig. 4 is the TiO of low-temperature solid-phase method preparation
2(B) Bi
20TiO
32The nanometer band under UV-irradiation to the degraded figure of methyl orange.
The specific embodiment
Embodiment 1:
1. the nano titanium oxide P25 with 0.3g is dissolved in the NaOH solution of 60ml10M, and is ultrasonic, stir each 0.5h and pour in the hydrothermal reaction kettle, and compactedness is controlled 80%; Seal hydrothermal reaction kettle then, put it in the drying box.Hydrothermal temperature control is at 200 ℃, and the reaction time is controlled at 72h, and reaction naturally cools to room temperature after finishing, and the gained powder washes repeatedly with deionized water, and suction filtration makes Na then
2Ti
3O
7Powder, stand-by.
2. with analytically pure five water bismuth nitrate (Bi (NO
3)
35H
2O) add in the distilled water, and constantly stir, be mixed with Bi
3+Concentration is the solution of 2.5mmol/L, and gained solution is designated as A solution.
3. in A solution, add the Na that 1. step prepares
2Ti
3O
7Powder, and constantly stir, forming precursor solution, gained solution is designated as B solution.Behind the B solution left standstill 48h with preparation, the gained powder washes repeatedly with deionized water, and suction filtration then is with gained powder 60 ℃ of dry 10h in drying box.
4. drying is good powder is put into Muffle furnace calcining 2h under 450 ℃, cools to room temperature at last with the furnace, namely makes TiO free from foreign meter
2(B) Bi
20TiO
32Nuclear shell structure nano band photochemical catalyst.
TiO with gained
2(B) Bi
20TiO
32The nanometer band finds that with German Brooker D8X-x ray diffractometer x analytic sample product is the tetragonal crystal system Bi that JCPDS is numbered 42-0202
20TiO
32(Fig. 1).This sample is produced JEM2100 type transmission electron microscope (Fig. 3) with the field emission scanning electron microscope (Fig. 2) of HITACHI S-4800 and Japanese JEOL company observe, from photo prepared TiO as can be seen
2(B) Bi
20TiO
32The width distribution of nanometer band is narrow, is about 100-150nm; Distribution of lengths wider range is for tens of microns arrive hundreds of microns.The nuclear shell structure nano band of preparation is degraded (Fig. 4) to methyl orange under UV-irradiation, and degradation rate can reach 96.89% after the 50min irradiation.
Embodiment 2:
1. the nano titanium oxide P25 with 0.3g is dissolved in the NaOH solution of 60ml10M, and is ultrasonic, stir each 0.5h and fall back in the thermal response still, and compactedness is controlled 70%; Seal hydrothermal reaction kettle then, put it in the drying box.Hydrothermal temperature control is at 200 ℃, and the reaction time is controlled at 60h, and reaction naturally cools to room temperature, gained Na after finishing
2Ti
3O
7Powder is stand-by after deionized water washes suction filtration repeatedly.
2. with analytically pure five water bismuth nitrate (Bi (NO
3)
35H
2O) add in the distilled water, and constantly stir, be mixed with Bi
3+Concentration is the solution of 4mmol/L, and gained solution is designated as A solution.
3. in A solution, add the Na that 1. step prepares
2Ti
3O
7Powder, and constantly stir, forming precursor solution, gained solution is designated as B solution.Behind the B solution left standstill 48h with preparation, wash suction filtration repeatedly through deionized water, with gained powder 60 ℃ of dry 10h in drying box.
4. drying is good powder is put into Muffle furnace calcining 2h under 450 ℃, cools to room temperature at last with the furnace, namely makes TiO free from foreign meter
2(B) Bi
20TiO
32Nuclear shell structure nano band photochemical catalyst.
Embodiment 3:
1. the nano titanium oxide P25 with 0.3g is dissolved in the NaOH solution of 60ml10M, and is ultrasonic, stir each 0.5h and fall back in the thermal response still, and compactedness is controlled 60%; Seal hydrothermal reaction kettle then, put it in the drying box.Hydrothermal temperature control is at 200 ℃, and the reaction time is controlled at 48h, and reaction naturally cools to room temperature, gained Na after finishing
2Ti
3O
7Powder is stand-by after deionized water washes suction filtration repeatedly.
2. with analytically pure five water bismuth nitrate (Bi (NO
3)
35H
2O) add in the distilled water, and constantly stir, be mixed with Bi
3+Concentration is the solution of 7mmol/L, and gained solution is designated as A solution.
3. in A solution, add the Na that 1. step prepares
2Ti
3O
7Powder, and constantly stir, forming precursor solution, gained solution is designated as B solution.Behind the B solution left standstill 48h with preparation, wash suction filtration repeatedly through deionized water, with gained powder 60 ℃ of dry 10h in drying box.
4. drying is good powder is put into Muffle furnace calcining 2h under 450 ℃, cools to room temperature at last with the furnace, namely makes TiO free from foreign meter
2(B) Bi
20TiO
32Nuclear shell structure nano band photochemical catalyst.
Claims (4)
1. TiO
2(B) Bi
20TiO
32Nuclear shell structure nano band photochemical catalyst is characterized in that: described photochemical catalyst is that width dimensions is 100nm～150nm, and length is the TiO of 10 μ m～990 μ m
2(B) Bi
20TiO
32The nuclear shell structure nano band, wherein nanometer band the inside is TiO
2(B), the outside is Bi
20TiO
32
2. the described TiO of claim 1
2(B) Bi
20TiO
32The preparation method of nuclear shell structure nano band photochemical catalyst, step is:
(1) the nano titanium oxide P25 with reacting dose is dissolved in the NaOH solution of 10M, and is ultrasonic, stir each 0.5h and fall back in the thermal response still, and compactedness is controlled at 60～80% of reactor volume; Seal hydrothermal reaction kettle then, put it in the drying box, make hydrothermal temperature control at 200 ± 10 ℃, the reaction time is controlled at 24h～72h, and reaction naturally cools to room temperature after finishing, and the gained powder washes repeatedly with deionized water, and suction filtration makes Na then
2Ti
3O
7Powder, stand-by;
(2) with analytically pure five water bismuth nitrate (Bi (NO
3)
35H
2O) add in the distilled water, and constantly stir, be mixed with Bi
3+Concentration is the suspension of 2.5mmol/L～10mmol/L, and gained solution is designated as A solution;
(3) Na in molar ratio in the A solution
+: Bi
3+The ratio of=1:1 adds above-mentioned Na
2Ti
3O
7Powder, and constantly stir, forming precursor solution, gained solution is designated as B solution; Behind the B solution left standstill 48h with preparation, the gained powder washes repeatedly with deionized water, and suction filtration will make powder and place 60 ± 5 ℃ of drying 10～15h of drying box then;
(4) the dry good powder of step (3) is put into Muffle furnace and calcine 2～3h down at 450 ± 10 ℃, cool to room temperature then with the furnace, namely make TiO free from foreign meter
2(B) Bi
20TiO
32Nuclear shell structure nano band photochemical catalyst.
3. as TiO as described in the claim 2
2(B) Bi
20TiO
32The preparation method of nuclear shell structure nano band photochemical catalyst is characterized in that: the described Bi of step (2)
3+Concentration is 2.5mmol/L～7mmol/L.
4. as TiO as described in the claim 2
2(B) Bi
20TiO
32The preparation method of nuclear shell structure nano band photochemical catalyst is characterized in that: the described powder of step (4) is put into Muffle furnace and is calcined 2h down at 450 ℃.
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| CN109569569A (en) * | 2019-01-30 | 2019-04-05 | 辽宁石油化工大学 | A kind of photochemical catalyst and its preparation method and application with ternary heterojunction structure |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399427A (en) * | 2014-08-06 | 2016-03-16 | 国巨股份有限公司 | Titanium compound-containing core-shell powder, method for producing same, and titanium compound-containing sintered body |
| CN105399427B (en) * | 2014-08-06 | 2019-01-11 | 国巨股份有限公司 | Titanium compound-containing core-shell powder, method for producing same, and titanium compound-containing sintered body |
| CN109569569A (en) * | 2019-01-30 | 2019-04-05 | 辽宁石油化工大学 | A kind of photochemical catalyst and its preparation method and application with ternary heterojunction structure |
| CN109569569B (en) * | 2019-01-30 | 2021-08-03 | 辽宁石油化工大学 | Photocatalyst with ternary heterojunction structure and preparation method and application thereof |
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