CN106276839B - A kind of preparation of phosphoric acid antimony nano-superstructure and its photocatalysis new opplication - Google Patents
A kind of preparation of phosphoric acid antimony nano-superstructure and its photocatalysis new opplication Download PDFInfo
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- CN106276839B CN106276839B CN201610596907.8A CN201610596907A CN106276839B CN 106276839 B CN106276839 B CN 106276839B CN 201610596907 A CN201610596907 A CN 201610596907A CN 106276839 B CN106276839 B CN 106276839B
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- WOJYMMRSNJJSRF-UHFFFAOYSA-N [Sb].P(O)(O)(O)=O Chemical compound [Sb].P(O)(O)(O)=O WOJYMMRSNJJSRF-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 title abstract description 11
- 238000007146 photocatalysis Methods 0.000 title abstract description 7
- 239000000243 solution Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 12
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 11
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 229960003330 pentetic acid Drugs 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 230000001376 precipitating effect Effects 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000005352 clarification Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 4
- 239000010935 stainless steel Substances 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000006193 liquid solution Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000011534 incubation Methods 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 1
- 229910052787 antimony Inorganic materials 0.000 abstract 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract 1
- 238000002835 absorbance Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229910001439 antimony ion Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 210000005252 bulbus oculi Anatomy 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- -1 laser eye Eyeball Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000007281 self degradation Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The present invention relates to a kind of preparation of phosphoric acid antimony nano-superstructure and its photocatalysis new opplications, and diethylenetriamine pentaacetic acid and antimony trichloride are successively dissolved in deionized water, under 60 DEG C of water bath conditions, are sufficiently stirred；Then ammonium dihydrogen phosphate is added, is sufficiently stirred, forms precursor mixed solution, filtering precursor mixed solution obtains precursor solution and presoma precipitating；Precursor solution is stood into 10~20min in 60 DEG C of water-baths, forms suspension system；The suspending clarification liquid and whole presoma precipitatings for taking part in suspension system pour into polytetrafluoroethyllining lining stainless steel hydrothermal reaction kettle, and incubation water heating reacts 10h at 160 DEG C, and centrifuge washing is dry, obtains product.Phosphoric acid antimony nano-superstructure preparation method of the invention is simple, and the phosphoric acid antimony being prepared has preferable photocatalytic activity, extends the type of photochemical catalyst, the pattern type of phosphoric acid antimony and preparation method.
Description
Technical field
The present invention relates to field of photocatalytic material, and in particular to a kind of preparation and its photocatalysis of phosphoric acid antimony nano-superstructure
New opplication.
Background technique
Since semiconductor material has excellent photocatalysis performance, there is good application in terms of environmental contaminants degradation
Prospect, therefore paid close attention to by people, the photochemical catalyst for finding and reporting is also growing day by day.Nanostructure is by zero dimension or one-dimensional aggregation
At multidimensional nano-superstructure when, new performance can occur, such as: optics, electricity, magnetics and catalytic performance.Nano unit
The nano-superstructure being assembled into is already known to current one of research hotspot, such as: hollow sphere, three-dimensional flower-shaped nanostructure etc..
Since semiconductor material has excellent photocatalytic applications performance, the photochemical catalyst for being found and reporting is also growing day by day.
Phosphoric acid antimony belongs to monoclinic system, due in antimony ion there are lone pair electrons, so phosphoric acid antimony have good absorption,
The characteristics such as lubrication, nonlinear optics, doping, magnetism and electric conductivity are widely used in low-loss optically fiber wave guide, glass, laser eye
Eyeball, additive of stratified material etc..Liu Hua equality (CN105238018A) has invented a kind of seamless wall of environment-friendly type of phosphoric acid antimony
The plant type flexible polyurethane foams of paper.The anti-aging that Zhang Youji etc. (CN105034132A) has invented a kind of phosphoric acid antimony is useless
Old tire modifying rubber powder bamboo fiberboard.However, the preparation method for the phosphoric acid antimony reported at present it is perhaps cumbersome or
Raw material is difficult to obtain.Application report still without phosphoric acid antimony in terms of photocatalysis at present.
Summary of the invention
The object of the present invention is to provide a kind of simple preparation methods of phosphoric acid antimony nano-superstructure photochemical catalyst and its light to urge
Change performance.
In order to achieve the above objectives, present invention provide the technical scheme that
A kind of preparation method of phosphoric acid antimony nano-superstructure, comprising the following steps:
(1) diethylenetriamine pentaacetic acid and antimony trichloride are successively dissolved in deionized water, under 60 DEG C of water bath conditions, are filled
Divide stirring；Then ammonium dihydrogen phosphate is added, is sufficiently stirred, forms precursor mixed solution, filtering precursor mixed solution obtains
Precursor solution and presoma precipitating；
(2) precursor solution is stood to 10~20min in 60 DEG C of water-baths, forms suspension system；Take suspension system top
The suspending clarification liquid and whole presoma precipitatings divided pours into polytetrafluoroethyllining lining stainless steel hydrothermal reaction kettle, at 160 DEG C
Lower incubation water heating reacts 10h, and centrifuge washing is dry, obtains product.
The diethylenetriamine pentaacetic acid: antimony trichloride: the molar ratio of ammonium dihydrogen phosphate is 1:1:1.
Preparation-obtained nano-superstructure is the sphere that nanometer chip assembles, and diameter is 15~35 μm, nanometer sheet
With a thickness of 0.15 μm or so.
The volume of the suspending clarification liquid is the half of suspension system.
The addition sequence of reaction raw materials are as follows: pentaacetic acid, antimony trichloride, ammonium dihydrogen phosphate, and Diethylenetriamine is being added
After pentaacetic acid and antimony trichloride, after 1h is sufficiently stirred, ammonium dihydrogen phosphate is added, then 0.5h is sufficiently stirred.
The amount that diethylenetriamine pentaacetic acid, antimony trichloride, ammonium dihydrogen phosphate are added is respectively 5mmol, the addition of deionized water
Amount is 65mL.
Washing described in step (2) is successively respectively to be washed three times with dehydrated alcohol and deionized water.
It is dry in 60 DEG C of vacuum drying 12h described in step (2).
Application the present invention also provides the phosphoric acid antimony nano-superstructure of above-mentioned preparation as photochemical catalyst.
The utility model has the advantages that
Phosphoric acid antimony nano-superstructure preparation method of the invention is simple, and the phosphoric acid antimony being prepared has preferable photocatalysis
Activity extends the type of photochemical catalyst, the pattern type of phosphoric acid antimony and preparation method.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) figure of phosphoric acid antimony nano-superstructure.
Fig. 2 is X-ray diffraction (XRD) figure of phosphoric acid antimony nano-superstructure.
Fig. 3 is the photocatalytic degradation rhodamine B of phosphoric acid antimony nano-superstructure and the activity of blank assay (catalyst is not added)
Contrast curve chart.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment
65mL water is added in beaker, 1.967g diethylenetriamine pentaacetic acid and 1.141g antimony trichloride are sequentially added, 60
1h is sufficiently stirred under DEG C water-bath；Then 0.575g ammonium dihydrogen phosphate is added, 0.5h is sufficiently stirred, forms precursor mixed solution,
Filtering precursor mixed solution obtains precursor solution and presoma precipitating.Precursor solution stands to 10 in 60 DEG C of water-baths~
20min forms suspension system；The suspending clarification liquid and whole presoma precipitatings for taking part in suspension system pour into 50mL poly- four
In vinyl fluoride inner liner stainless steel hydrothermal reaction kettle, the volume of the suspending clarification liquid is the half of suspension system, permanent at 160 DEG C
Warm water thermal response 10h, centrifuge washing is dry, obtains product.
Electron microscope observation and X-ray diffraction measure have been carried out to the phosphoric acid antimony nano-superstructure being prepared.
It can be seen from figure 1 that phosphoric acid antimony nano-superstructure prepared by the present invention is the microballoon assembled by nanometer chip, diameter
It is 15~35 μm, nanometer sheet thickness is 0.15 μm or so.
As it is clear from fig. 2 that the nano-superstructure product is pure SbPO compared with XRD standard card No.35-08294。
Test case
Phosphoric acid antimony nano-superstructure photochemical catalyst made from embodiment is used to rhodamine B degradation (RhB) solution.
Prepare the RhB solution that 200mL concentration is 0.01g/L.The phosphoric acid antimony sample to be tested that 0.1g is weighed with electronic balance, adds
Enter above-mentioned solution, 30min is stirred under conditions of being protected from light, reaches solution and adsorb-desorb balance.After 30min, it is up to absorption
The solution sampling of balance is centrifuged, and supernatant liquor is measured with absorbance of the UV-vis to RhB solution, and trap is denoted as C0。
Ultraviolet light carried out to the above-mentioned solution for reaching adsorption equilibrium under stiring, carries out light-catalyzed reaction, lamp current 15A, lamp away from
Analysis is sampled for 15cm, every minor tick 10min.It is first centrifuged after sampling, obtains supernatant liquor with UV-vis to RhB solution
Absorbance measure, according to Lambert-Beer law, the variation of organic matter characteristic absorption peak intensity can be calculated quantitatively
The variation of its concentration.When extinction material is identical, thickness is identical, the change of solution concentration can be directly indicated with the variation of absorbance
Change.Therefore, absorbance is directly denoted as to concentration symbol: C1, C2, C3.By the absorbance of the RhB solution measured every 10min, draw
Catalytic activity curve processed (curve SbPO in Fig. 34), analyze the ability of the photocatalytic degradation RhB of sample.As shown in figure 3, and RhB
Self-degradation curve (curve blank experiment in Fig. 3) under ultraviolet light compares, the phosphoric acid antimony that the present invention is prepared
With preferable photocatalytic activity.
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, any ripe
Professional and technical personnel is known, without departing from the scope of the present invention, according to the technical essence of the invention, to the above reality
Any simple modifications, equivalent substitutions and improvements etc. made by example are applied, it is fallen within the scope of protection of the technical scheme of the present invention
It is interior.
Claims (5)
1. a kind of preparation method of phosphoric acid antimony nano-superstructure, it is characterised in that: the following steps are included:
(1) diethylenetriamine pentaacetic acid and antimony trichloride are successively dissolved in deionized water, 60oUnder C water bath condition, sufficiently stir
It mixes；Then ammonium dihydrogen phosphate is added, is sufficiently stirred, forms precursor mixed solution, filtering precursor mixed solution obtains forerunner
Liquid solution and presoma precipitating；
(2) by precursor solution 60o10 ~ 20min is stood in C water-bath, forms suspension system；Take the outstanding of part in suspension system
Floating clarified solution and whole presoma precipitatings are poured into polytetrafluoroethyllining lining stainless steel hydrothermal reaction kettle, 160oConstant temperature under C
Hydro-thermal reaction 10h, centrifuge washing is dry, obtains product；
The diethylenetriamine pentaacetic acid: antimony trichloride: the molar ratio of ammonium dihydrogen phosphate is 1:1:1；
The volume of the suspending clarification liquid is the half of suspension system；
The addition sequence of reaction raw materials are as follows: diethylenetriamine pentaacetic acid, antimony trichloride, ammonium dihydrogen phosphate, and Diethylenetriamine is being added
After pentaacetic acid and antimony trichloride, after 1h is sufficiently stirred, ammonium dihydrogen phosphate is added, then 0.5h is sufficiently stirred；
The amount that diethylenetriamine pentaacetic acid, antimony trichloride, ammonium dihydrogen phosphate are added is respectively 5mmol, and the additional amount of deionized water is
65mL。
2. the preparation method of phosphoric acid antimony nano-superstructure as described in claim 1, it is characterised in that: preparation-obtained nanometer
Superstructure is the sphere that nanometer chip assembles, and diameter is 15 ~ 35 μm, and nanometer sheet thickness is 0.15 μm.
3. the preparation method of phosphoric acid antimony nano-superstructure as described in claim 1, it is characterised in that: step is washed described in (2)
It washs successively respectively to be washed three times with dehydrated alcohol and deionized water.
4. the preparation method of phosphoric acid antimony nano-superstructure as described in claim 1, it is characterised in that: done described in step (2)
Dry is in 60 DEG C of vacuum drying 12h.
5. application of the phosphoric acid antimony nano-superstructure as photochemical catalyst prepared by claim 1.
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| CN201610596907.8A CN106276839B (en) | 2016-07-26 | 2016-07-26 | A kind of preparation of phosphoric acid antimony nano-superstructure and its photocatalysis new opplication |
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| CN201610596907.8A CN106276839B (en) | 2016-07-26 | 2016-07-26 | A kind of preparation of phosphoric acid antimony nano-superstructure and its photocatalysis new opplication |
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| CN110190280A (en) * | 2019-05-21 | 2019-08-30 | 中南大学 | A kind of preparation method of ball top shape polyanion negative electrode material phosphoric acid antimony |
| CN110589789B (en) * | 2019-09-07 | 2023-02-17 | 中南大学 | Preparation method of negative electrode material nano needle-shaped antimony phosphate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102139869A (en) * | 2011-03-09 | 2011-08-03 | 超威电源有限公司 | Method for preparing spherical iron phosphate by combining sedimentation method and hydrothermal method |
| CN102491301A (en) * | 2011-12-04 | 2012-06-13 | 中国科学院福建物质结构研究所 | Bismuth phosphate nanometer powder body and preparation method thereof |
| CN103111315A (en) * | 2013-03-15 | 2013-05-22 | 南开大学 | Preparation method of bismuth phosphate (BiPO4) photocatalysts differing in structure |
| CN104843661A (en) * | 2015-04-29 | 2015-08-19 | 岭南师范学院 | Preparation method for template-free synthesis of phosphoric acid microspheres |
-
2016
- 2016-07-26 CN CN201610596907.8A patent/CN106276839B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102139869A (en) * | 2011-03-09 | 2011-08-03 | 超威电源有限公司 | Method for preparing spherical iron phosphate by combining sedimentation method and hydrothermal method |
| CN102491301A (en) * | 2011-12-04 | 2012-06-13 | 中国科学院福建物质结构研究所 | Bismuth phosphate nanometer powder body and preparation method thereof |
| CN103111315A (en) * | 2013-03-15 | 2013-05-22 | 南开大学 | Preparation method of bismuth phosphate (BiPO4) photocatalysts differing in structure |
| CN104843661A (en) * | 2015-04-29 | 2015-08-19 | 岭南师范学院 | Preparation method for template-free synthesis of phosphoric acid microspheres |
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