CN107511145A - A kind of bar-shaped hierarchical organization pucherite material of corn of nano-particle accumulation and preparation method thereof - Google Patents
A kind of bar-shaped hierarchical organization pucherite material of corn of nano-particle accumulation and preparation method thereof Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 41
- 240000008042 Zea mays Species 0.000 title claims abstract description 40
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 title claims abstract description 40
- 235000002017 Zea mays subsp mays Nutrition 0.000 title claims abstract description 40
- 235000005822 corn Nutrition 0.000 title claims abstract description 40
- 230000008520 organization Effects 0.000 title claims abstract description 34
- 238000009825 accumulation Methods 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910003206 NH4VO3 Inorganic materials 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 8
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 20
- 229910002915 BiVO4 Inorganic materials 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 3
- -1 wide 400~700nm Substances 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000007146 photocatalysis Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 238000007431 microscopic evaluation Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
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Abstract
The invention provides the bar-shaped hierarchical organization pucherite material of corn and preparation method of a kind of nano-particle accumulation.Long 500nm~the 900nm of corn club shaped structure of the material, wide 400~700nm, nano particle diameter is 50~120nm.Its preparation method includes：(1) by Bi (NO3)3·5H2O is dissolved in water-miscible organic solvent, NH4VO3Soluble in water, then both are well mixed obtains suspension, (2) and then suspension is transferred into microwave hydrothermal retort, controls reaction condition, then filtered, washs, dries, be placed in baking oven and be dried to obtain pucherite material.The present invention, as organic solvent, the bar-shaped hierarchical organization BiVO of corn of nano-particle accumulation is successfully synthesized in different microwave hydrothermal conditions using glycerine4Catalyst, effectively increase the specific surface area of catalyst, there is provided more photocatalytic activity sites, reduce the compound of light induced electron and hole, so as to improve BiVO4The efficiency of photocatalytic degradation methylene blue.
Description
Technical field
The invention belongs to photocatalysis and dye wastewater degradation technical field, and in particular to a kind of corn of nano-particle accumulation
Bar-shaped hierarchical organization pucherite material and preparation method thereof.
Background technology
In past ten years, photocatalysis is applied to solve the energy and problem of environmental pollution, such as：Solar energy
Conversion and the removal of pollutant.But most of photochemical catalyst can only utilize the ultraviolet light of sunshine, and ultraviolet light only accounts for the sun
The 4% of light energy, and visible ray accounts for 43%, thus find under visible light the semi-conducting material with superior photocatalytic activity into
For the study hotspot of photocatalysis field in recent years.As the non-TiO to receive much concern recently2Based photocatalyst, BiVO4Semiconductor material
Material has that nontoxic, chemical stability is good, solar energy effective rate of utilization is high, band gap narrow (about 2.4eV) and oxidation-reduction potential
The advantages that suitable, there is great application prospect in the field such as clean energy resource and environmental improvement.
BiVO4Although having good visible light photocatalysis performance, due to its narrower energy gap, cause photoproduction electric
Son and hole are easily compound, reduce photocatalysis efficiency.In order to improve BiVO4Photocatalysis performance, some researchers prepare
The BiVO of different-shape4Sample, and it is modified, so that being improved in degradable organic pollutant ability.It is but existing
Some modification BiVO4It is excessive or too small specific surface area to be present in catalyst, the problems such as quantum efficiency is low, causes degradation efficiency not high.
The content of the invention
To there is provided corn that a kind of high nano-particle of degradation efficiency accumulates bar-shaped etc. to solve above-mentioned technical problem by the present invention
Level structure pucherite material and preparation method thereof.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that：
A kind of bar-shaped hierarchical organization pucherite material of corn of nano-particle accumulation, the long 500nm of corn club shaped structure
~900nm, wide 400~700nm, nano particle diameter are 50~120nm.
The preparation method of the bar-shaped hierarchical organization pucherite material of corn of described nano-particle accumulation, it is characterised in that
Comprise the following steps：
(1) by Bi (NO3)3·5H2O is dissolved in the Bi (NO that 0.01~0.2mol/L is obtained in water-miscible organic solvent3)3It is molten
Liquid, by NH4VO3It is dissolved in water and obtains 0.01~0.2mol/L NH4VO3Solution, the volume ratio of the water-miscible organic solvent and water
For 5~25:15~35；By NH4VO3Solution is slowly dropped into the Bi (NO3)3In solution, stirring is described in yellow suspension
Water-miscible organic solvent is glycerine；
(2) yellow suspension that step (1) obtains is transferred to progress microwave hydrothermal reaction in microwave hydrothermal retort, treated
The bar-shaped grade knot of corn of nano-particle accumulation is obtained after filtered room temperature, washing, drying process are naturally cooled to after having reacted
Structure pucherite material.
In such scheme, the microwave hydrothermal control condition described in step (2) is 100~220 DEG C of temperature, the reaction time 5~
80min, 300~500W of power.
In such scheme, temperature is 160~180 DEG C.
In such scheme, the reaction time is 40~80min.
In such scheme, power 300W.
In such scheme, the volume ratio of the water-miscible organic solvent and water is 2:3.
The bar-shaped hierarchical organization pucherite material of corn of described nano-particle accumulation is in photocatalytic degradation methylene blue
Application.
Beneficial effects of the present invention are：The present invention uses glycerine as organic solvent, in the success of different microwave hydrothermal conditions
The bar-shaped hierarchical organization BiVO of corn of nano-particle accumulation is synthesized4Catalyst, the specific surface area of catalyst is effectively increased, is carried
More photocatalytic activity sites have been supplied, have reduced the compound of light induced electron and hole, so as to improve BiVO4 photocatalytic degradations
The efficiency of methylene blue.
Brief description of the drawings
Fig. 1 is the bar-shaped hierarchical organization BiVO of corn that nano-particle accumulation prepared by embodiment 1 forms4XRD；
Fig. 2 is the bar-shaped hierarchical organization BiVO of corn that nano-particle accumulation prepared by embodiment 1 forms4SEM overall diagrams；
Fig. 3 is the bar-shaped hierarchical organization BiVO of corn that nano-particle accumulation prepared by embodiment 1 forms4SEM Local maps.
Embodiment
With reference to specific embodiment, the present invention will be further described, but does not produce any restrictions to the present invention.
To make those skilled in the art be better understood from technical scheme, with reference to embodiment and accompanying drawing to this
Invention is described in further detail.
Embodiment 1
Prepare the bar-shaped hierarchical organization BiVO of corn of nano-particle accumulation4Catalyst, step are as follows：
(1) by 1mmolBi (NO3)3·5H2O is dissolved in 16ml glycerine, by 1mmolNH4VO324ml deionized waters are dissolved in, then
By NH4VO3Solution is slowly dropped into Bi (NO3)3·5H2In O solution, both are well mixed, magnetic agitation half an hour, in yellow suspension
Liquid.
(2) yellow suspension that step (1) obtains is transferred in microwave hydrothermal retort, controls the microwave reaction condition to be
180 DEG C, 20min, 300W, it is filtered then to naturally cool to room temperature, after water and ethanol are respectively washed three times, is placed in thermostatic drying chamber
In in 70 DEG C of dry 10h, that is, obtain the bar-shaped hierarchical organization BiVO of corn of nano-particle accumulation4Photochemical catalyst.
Product made from the present embodiment determines and monocline scheelite BiVO through X-ray diffraction analysis4Crystalline phase matches, crystallinity
Preferably, its X-ray diffractogram is shown in Fig. 1.Scanning electron microscope analysis result, which is shown, sees Fig. 2, and products therefrom is nano-particle heap
The bar-shaped hierarchical organization of corn that product forms, wide 400nm, long 600nm or so, particle diameter is on 50~70nm, the bar-shaped surface of corn
And there are many pore structures inside, by the bar-shaped hierarchical organization BiVO of corn of nano-particle accumulation made from this example4Photocatalysis
Agent is degraded 5mg/L methylene blue solutions under visible light illumination, shows high degradation efficiency, 50min degradation efficiencies are
96.86%.It is shown in Table 1.
Embodiment 2
Prepare the bar-shaped hierarchical organization BiVO of corn of nano-particle accumulation4Catalyst, step are as follows：
(1) by 1mmolBi (NO3)3·5H2O is dissolved in 20ml glycerine, by 1mmolNH4VO320ml deionized waters are dissolved in, then
By NH4VO3Solution is slowly dropped into Bi (NO3)3·5H2In O solution, both are well mixed, magnetic agitation half an hour, in yellow suspension
Liquid.
(2) yellow suspension that step (1) obtains is transferred in microwave hydrothermal retort, controls the microwave reaction condition to be
160 DEG C, 20min, 400W, it is filtered then to naturally cool to room temperature, after water and ethanol are respectively washed three times, is placed in thermostatic drying chamber
In in 70 DEG C of dry 10h, that is, obtain the bar-shaped hierarchical organization BiVO of corn of nano-particle accumulation4Photochemical catalyst.
Product made from the present embodiment determines and monocline scheelite BiVO through X-ray diffraction analysis4Crystalline phase matches, scanning electricity
Sub- microscopic analysis result shows that products therefrom is the bar-shaped hierarchical organization of corn that nano-particle accumulation forms, and wide 600nm is long
800nm or so, particle diameter is in 60~80nm, the bar-shaped hierarchical organization BiVO of corn that nano-particle made from this example is accumulated4Light
Catalyst is degraded 5mg/L methylene blue solutions under visible light illumination, shows good degradation efficiency, 50min degradation efficiencies are
92.39%.It is shown in Table 1.
Embodiment 3
Prepare the bar-shaped hierarchical organization BiVO of corn of nano-particle accumulation4Catalyst, step are as follows：
(1) by 1mmolBi (NO3)3·5H2O is dissolved in 20ml glycerine, by 1mmol NH4VO320ml deionized waters are dissolved in, so
Afterwards by NH4VO3Solution is slowly dropped into Bi (NO3)3·5H2In O solution, both are well mixed, magnetic agitation half an hour, are hanged in yellow
Supernatant liquid.
(2) yellow suspension that step (1) obtains is transferred in microwave hydrothermal retort, controls the microwave reaction condition to be
200 DEG C, 40min, 300W, then naturally cool to room temperature and be placed in after filtering, washing in thermostatic drying chamber in 70 DEG C of dryings
10h, that is, obtain the bar-shaped hierarchical organization BiVO of corn of nano-particle accumulation4Photochemical catalyst.
Product made from the present embodiment determines and monocline scheelite BiVO through X-ray diffraction analysis4Crystalline phase matches, scanning electricity
Sub- microscopic analysis result shows that products therefrom is nano-particle, wide 700nm, long 900nm or so, particle diameter in 100~120nm,
The bar-shaped hierarchical organization BiVO of corn that nano-particle made from the present embodiment is accumulated4Photochemical catalyst is degraded under visible light illumination
5mg/L methylene blue solutions, show good degradation efficiency, and 50min degradation efficiencies are 90.18%.It is shown in Table 1.
Comparative example 1
Prepare the bar-shaped hierarchical organization BiVO of corn of nano-particle accumulation4Catalyst, step are as follows：
(1) by 1mmolBi (NO3)3·5H2O is dissolved in 16ml diethylene glycols, by 1mmolNH4VO324ml deionized waters are dissolved in,
Then by NH4VO3Solution is slowly dropped into Bi (NO3)3·5H2In O solution, both are well mixed, magnetic agitation half an hour, in yellow
Suspension；
(2) yellow suspension that step (1) obtains is transferred in microwave hydrothermal retort, controls the microwave reaction condition to be
180 DEG C, 20min, 300W, room temperature is then naturally cooled to through filtering, washing, being placed in thermostatic drying chamber in 70 DEG C of dry 10h,
Obtain microspheroidal BiVO4Catalyst.
Product made from the present embodiment determines and monocline scheelite BiVO through X-ray diffraction analysis4Crystalline phase matches, scanning electricity
Sub- microscopic analysis result shows products therefrom as scattered nano-particle, and particle diameter is in 100~150nm, by made from this example
Nanoparticulate BiVO4Photochemical catalyst is degraded 5mg/L methylene blue solutions under visible light illumination, and 50min degradation efficiencies are
83.56%.It is shown in Table 1.
Comparative example 2
Prepare the bar-shaped hierarchical organization BiVO of corn of nano-particle accumulation4Catalyst, step are as follows：
(1) by 1mmolBi (NO3)3·5H2O is dissolved in 16ml ethanol, by 1mmolNH4VO324ml deionized waters are dissolved in, will
NH4VO3Solution is slowly dropped into Bi (NO3)3·5H2In O solution, both are well mixed, magnetic agitation half an hour, in yellow suspension
Liquid.
(2) yellow suspension that step (1) obtains is transferred in microwave hydrothermal retort, controls the microwave reaction condition to be
180 DEG C, 20min, 300W, room temperature is then naturally cooled to through filtering, washing, being placed in thermostatic drying chamber in 70 DEG C of dry 10h,
Obtain microspheroidal BiVO4Catalyst.
Product made from the present embodiment determines and cubic Zircon cut BiVO through X-ray diffraction analysis4Crystalline phase matches, scanning electricity
Sub- microscopic analysis result shows that products therefrom is the homogeneous microspheroidal of pattern, and diameter is at 3~5 μm.By made from the present embodiment
Microspheroidal BiVO4Photochemical catalyst is degraded 5mg/L methylene blue solutions under visible light illumination, and degradation efficiency is general, 50min degradeds
Efficiency is 81.32%.It is shown in Table 1.
Table 1
。
Claims (8)
- A kind of 1. bar-shaped hierarchical organization pucherite material of corn of nano-particle accumulation, it is characterised in that the bar-shaped knot of corn Long 500nm~the 900nm of structure, wide 400~700nm, nano particle diameter is 50~120nm.
- 2. the preparation method of the bar-shaped hierarchical organization pucherite material of corn of nano-particle accumulation according to claim 1, It is characterised in that it includes following steps：(1) by Bi (NO3)3·5H2O is dissolved in the Bi (NO that 0.01~0.2mol/L is obtained in water-miscible organic solvent3)3Solution, will NH4VO3It is dissolved in water and obtains 0.01~0.2mol/L NH4VO3Solution, the volume ratio of the water-miscible organic solvent and water for 5~ 25:15~35；By NH4VO3Solution is slowly dropped into the Bi (NO3)3In solution, stirring is described water-soluble in yellow suspension Property organic solvent is glycerine；(2) yellow suspension that step (1) obtains is transferred to progress microwave hydrothermal reaction, question response in microwave hydrothermal retort The bar-shaped hierarchical organization vanadium of corn of nano-particle accumulation is obtained after filtered room temperature, washing, drying process are naturally cooled to after complete Sour bismuth material.
- 3. the preparation method of the bar-shaped hierarchical organization pucherite material of corn of nano-particle accumulation according to claim 2, Characterized in that, the microwave hydrothermal control condition described in step (2) is 100~220 DEG C, 5~80min of reaction time of temperature, work( 300~500W of rate.
- 4. the preparation method of the bar-shaped hierarchical organization pucherite material of corn of nano-particle accumulation according to claim 2, Characterized in that, temperature is 160~180 DEG C.
- 5. the preparation method of the bar-shaped hierarchical organization pucherite material of corn of nano-particle accumulation according to claim 2, Characterized in that, the reaction time is 40~80min.
- 6. the preparation method of the bar-shaped hierarchical organization pucherite material of corn of nano-particle accumulation according to claim 2, Characterized in that, power is 300W.
- 7. the preparation method of the bar-shaped hierarchical organization pucherite material of corn of nano-particle accumulation according to claim 2, Characterized in that, the volume ratio of the water-miscible organic solvent and water is 2:3.
- 8. the bar-shaped hierarchical organization pucherite material of corn of nano-particle accumulation according to claim 1 is in photocatalytic degradation Application in methylene blue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710683734.8A CN107511145A (en) | 2017-08-11 | 2017-08-11 | A kind of bar-shaped hierarchical organization pucherite material of corn of nano-particle accumulation and preparation method thereof |
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| CN111330567A (en) * | 2020-03-25 | 2020-06-26 | 陕西科技大学 | One-step solvothermal method for preparing rose-structured Bi2O3/BiVO4/GO nano composite photocatalytic material and application thereof |
| CN114433066A (en) * | 2021-12-30 | 2022-05-06 | 江西科技师范大学 | Nanometer bismuth-based material and preparation method and application thereof |
| CN115028185A (en) * | 2022-05-18 | 2022-09-09 | 广东粤港澳大湾区黄埔材料研究院 | Corn-rod-shaped cerium oxide and preparation method and application thereof |
| CN116143170A (en) * | 2023-01-03 | 2023-05-23 | 西京学院 | Nanometer sheet assembled porous rod-shaped BiVO 4 Triangular prism material and preparation method thereof |
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| CN103112896A (en) * | 2013-02-06 | 2013-05-22 | 长安大学 | Method for preparing octahedral nano bismuth vanadate photocatalyst by microwave process |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111330567A (en) * | 2020-03-25 | 2020-06-26 | 陕西科技大学 | One-step solvothermal method for preparing rose-structured Bi2O3/BiVO4/GO nano composite photocatalytic material and application thereof |
| CN114433066A (en) * | 2021-12-30 | 2022-05-06 | 江西科技师范大学 | Nanometer bismuth-based material and preparation method and application thereof |
| CN114433066B (en) * | 2021-12-30 | 2023-11-10 | 江西科技师范大学 | Nano bismuth-oxide-based material and preparation method and application thereof |
| CN115028185A (en) * | 2022-05-18 | 2022-09-09 | 广东粤港澳大湾区黄埔材料研究院 | Corn-rod-shaped cerium oxide and preparation method and application thereof |
| CN115028185B (en) * | 2022-05-18 | 2023-08-04 | 广州飞雪芯材有限公司 | Corn cob cerium oxide and preparation method and application thereof |
| CN116143170A (en) * | 2023-01-03 | 2023-05-23 | 西京学院 | Nanometer sheet assembled porous rod-shaped BiVO 4 Triangular prism material and preparation method thereof |
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