CN105879855A - Graphene-gamma-bismuth molybdate nano-composite material, method for preparing same and application of graphene-gamma-bismuth molybdate nano-composite material - Google Patents
Graphene-gamma-bismuth molybdate nano-composite material, method for preparing same and application of graphene-gamma-bismuth molybdate nano-composite material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 36
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 17
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 17
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 17
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 14
- 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 abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
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- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims description 20
- 229910052797 bismuth Inorganic materials 0.000 claims description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 3
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- 238000005516 engineering process Methods 0.000 abstract description 6
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- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 8
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- 235000012054 meals Nutrition 0.000 description 7
- 239000002131 composite material Substances 0.000 description 5
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 230000009514 concussion Effects 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 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 4
- 239000004065 semiconductor Substances 0.000 description 4
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
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- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
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- 241000220317 Rosa Species 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a method for preparing a graphene-gamma-bismuth molybdate nano-composite material. The method includes steps of 1), carrying out solvent thermal reaction on graphene, bismuth nitrate and ethylene glycol to obtain reaction products and filtering, washing and drying the reaction products to obtain graphene-ethylene glycol bismuth compounds; 2), uniformly dispersing the compounds in sodium molybdate aqueous solution to obtain a solution system, regulating a pH (potential of hydrogen) value of the obtained solution system until the pH value is 0-3, then carrying out hydrothermal reaction on the solution system to obtain reaction products and filtering, washing and drying the reaction products to obtain the graphene-gamma-bismuth molybdate nano-composite material. The method has the advantages that the graphene-gamma-bismuth molybdate nano-composite material is mainly prepared from graphene, bismuth nitrate, sodium molybdate and ethylene glycol by the aid of solvent thermal processes and hydrothermal processes which are combined with one another; technologies and equipment for preparing the graphene-gamma-bismuth molybdate nano-composite material are simple, reaction conditions are mild, the method is low in energy consumption, the technologies are novel, and the graphene-gamma-bismuth molybdate nano-composite material prepared by the aid of the method has large specific surface area and is excellent in visible light photocatalytic performance.
Description
Technical field
The invention belongs to environmental friendly material field, be specifically related to a kind of Graphene-γ-bismuth molybdate nano composite material and preparation side thereof
Method and application.
Background technology
The seriousness of environmental pollution, it has also become a direct threat human survival, needs the focal issue of solution badly.Photocatalysis technology
As a branch of Green Chemistry, this technology can make the organic pollution generation oxidative decomposition in environment, is finally degraded to
CO2, the small-molecule substance such as water and inorganic ions, non-secondary pollution, palliating degradation degree are high it is considered to be at the most promising pollution
Reason method.But traditional TiO2Photocatalyst, band gap length, mainly absorb ultraviolet light, only with the ultraviolet light in sunlight,
Low to the utilization rate of sunlight.Exploitation can utilize the nanometer new material of visible light photocatalysis as high catalytic activity, can make full use of
The photocatalyst of sunlight, is one of method controlling environmental pollution most prospect.Therefore exploitation design new and effective, stable and
Visible light-responded semiconductor light-catalyst is the focus of current photocatalysis research.
Nanometer γ-bismuth molybdate (Bi2MoO6) be rose in recent years, degree of receiving significant attention one visible ray semiconductor catalyst,
It has good photocatalytic activity under visible light, can be used for degrading environmental organic pollutant, photocatalysis oxygen and photocatalysis also
Former carbon dioxide etc..But its major defect is bismuth based semiconductor photocatalyst all exist photo-generate electron-hole easily in conjunction with, greatly
Limit the large-scale application of bismuth series photocatalyst.Therefore, it is necessary to take certain measure to improve light induced electron transport efficiency,
Effectively limit electron hole in conjunction with.Graphene is a kind of efficient electron acceptor material, itself and γ-bismuth molybdate (Bi2MoO6)
Semiconductors coupling is conducive to improving the separation efficiency of electron-hole under illumination, reduce electron hole in conjunction with, thus improve composite wood
The photocatalytic activity of material, therefore Graphene-γ-bismuth molybdate nano composite material has light more higher than simple nanometer γ-bismuth molybdate and urges
Change efficiency.The preparation method developing a kind of technique simple Graphene-γ-bismuth molybdate nano composite material is significant.
Summary of the invention
It is an object of the invention to provide a kind of Graphene-γ-bismuth molybdate nano composite material and preparation method thereof, the method relates to
Process equipment is simple, reaction condition is gentle, energy consumption is little, and the Graphene-γ of preparation-bismuth molybdate nano composite material specific surface area is big,
Visible light photocatalysis excellent performance.
For achieving the above object, the technical solution used in the present invention is: the preparation of a kind of Graphene-γ-bismuth molybdate nano composite material
Method, comprises the following steps: 1) by Graphene, bismuth nitrate is solvent thermal reaction together with ethylene glycol, then through filtering, washing,
Dry to obtain Graphene-ethylene glycol bismuth complex；2) being dispersed in sodium molybdate aqueous solution by gained complex, regulation gained is molten
The pH value of liquid system is 0-3, then carries out hydro-thermal reaction, then through filtering, wash, dry and to obtain Graphene-γ-bismuth molybdate nanometer
Composite.
By such scheme, described Graphene is the 0.5-5% of bismuth nitrate quality.
By such scheme, described bismuth nitrate concentration in ethylene glycol is 10-100g/L.
By such scheme, described solvent thermal reaction condition is: be heated to 160-180 DEG C of insulation reaction 2-24 hour, then natural
It is cooled to room temperature.
By such scheme, described sodium molybdate is (0.35-0.5) with the quality of Graphene-ethylene glycol bismuth complex: 1.
By such scheme, the concentration of described sodium molybdate aqueous solution is 20-100g/L.
By such scheme, described hydrothermal reaction condition is for being heated to 150-200 DEG C of insulation reaction 1-24 hour.
By such scheme, step 1) described drying temperature is 80-100 DEG C；Step 2) described drying temperature is 80-120 DEG C.
Graphene-γ-bismuth molybdate nano composite material that preparation method described above prepares, it is nanocrystalline lamellar, and wafer thickness is
10-40nm, specific surface area is 30-60m2/g。
Described Graphene-γ-bismuth molybdate nano composite material is as the application of catalysis material.
The mechanism of the present invention: owing to Graphene has a monolayer two-dimensional structure, high conductivity, excellent electron mobility and high
The characteristics such as specific surface area so that it is quasiconductor-Graphene hetero-junctions can be constructed to strengthen visible light catalysis activity.The graphite of load
Alkene is conducive to transfer and the storage of electronics, can effectively shift photo-generated carrier, suppression photoproduction electricity after γ-bismuth molybdate Material cladding
Son-hole, to being combined, provides big specific surface area simultaneously, and the light of the Graphene-γ of improvement-bismuth molybdate nano-composite catalyst is urged
Change activity, and the oxygen-containing functional group at graphene edge has strong adsorptivity to organic pollutant, also can strengthen composite
Photocatalytic activity.
The invention have the benefit that the present invention, with Graphene, bismuth nitrate, ethylene glycol, sodium molybdate as primary raw material, uses molten
Agent heat and hydro-thermal method prepare Graphene-γ-bismuth molybdate nano composite material, and the composite chemical composition obtained is homogeneous, Graphene
High degree of dispersion, owing to Graphene has high electron acceptability, γ-bismuth molybdate composite when photocatalysis, electron-hole
Separation rate is high, and photocatalysis effect significantly improves than compound phase ratio.This preparation technology equipment is simple simultaneously, reaction condition is gentle, energy
Consume low.
Detailed description of the invention
In order to be more fully understood that the present invention, it is further elucidated with present disclosure below in conjunction with embodiment, but the present invention not only office
It is limited to the following examples.
Following example as no specific instructions, the commercially available chemical reagent of reagent of employing or industrial products.
Embodiment 1
The preparation method of Graphene-γ-bismuth molybdate nano composite material, comprises the following steps:
1) 100g bismuth nitrate is dissolved in 1L ethylene glycol, is subsequently adding 0.5g Graphene powder and is uniformly mixed, stablized
Suspension, transfers to this solution in the autoclave that volume is 2L, is heated to 160 DEG C and is incubated 24 hours；Question response still is cold
But to room temperature, filter and by washing with alcohol 3 times, be then dried 12 hours at 80 DEG C, obtain Graphene-ethylene glycol bismuth meal body；
2) take 25g sodium molybdate to be dissolved in 250ml deionized water, then by 1) in prepare Graphene-ethylene glycol powder 50g and add
In above-mentioned sodium molybdate aqueous solution, ultrasonic wave concussion stirring makes it be uniformly dispersed, and regulates solution ph extremely with concentrated nitric acid and concentrated hydrochloric acid
Between 0-3, then gained mixed liquor is transferred in the autoclave that volume is 500mL, is warming up to 200 DEG C and is incubated 1 hour,
Question response still is cooled to room temperature, by deionized water and washing with alcohol 5 times after filtration, then is dried 4 hours at 120 DEG C, obtains stone
Ink alkene-bismuth molybdate sodium nano composite material.
The present embodiment products therefrom γ-bismuth molybdate nanometer wafer average thickness is 10nm, and specific surface area is 60m2/ g, in concentration
During 1.0g/L, it is seen that light irradiate under can in 30min degradable 0.02g/L rhodamine.
Embodiment 2
The preparation method of Graphene-γ-bismuth molybdate nano composite material, comprises the following steps:
1) 50g bismuth nitrate is dissolved in 1L ethylene glycol, is subsequently adding 2.5g Graphene powder and is uniformly mixed, stablized
Suspension, transfers to this solution in the autoclave that volume is 2L, is heated to 180 DEG C and is incubated 2 hours；Question response still cools down
To room temperature, filter and by washing with alcohol 3 times, be then dried 6 hours at 80 DEG C, obtain Graphene-ethylene glycol bismuth meal body；
2) take 4g sodium molybdate to be dissolved in 200ml deionized water, then by 1) in prepare Graphene-ethylene glycol bismuth meal end 10g and add
In above-mentioned sodium molybdate aqueous solution, ultrasonic wave concussion stirring makes it be uniformly dispersed, and regulates solution ph extremely with concentrated nitric acid and concentrated hydrochloric acid
Between 0-3, then gained mixed liquor is transferred in the autoclave that volume is 500mL, is warming up to 150 DEG C and is incubated 24 hours,
Question response still is cooled to room temperature, by deionized water and washing with alcohol 2 times after filtration, then is dried 12 hours at 80 DEG C, obtains stone
Ink alkene-bismuth molybdate sodium nano composite material.
The present embodiment products therefrom γ-bismuth molybdate nanometer wafer average thickness is 12nm, and specific surface area is 55m2/ g, in concentration
During 1.0g/L, it is seen that light irradiate under can in 30min degradable 0.02g/L rhodamine.
Embodiment 3
The preparation method of Graphene-γ-bismuth molybdate nano composite material, comprises the following steps:
1) 50g bismuth nitrate is dissolved in 1L ethylene glycol, is subsequently adding 2g Graphene powder and is uniformly mixed, stably hanged
Turbid liquid, transfers to this solution in the autoclave that volume is 2L, is heated to 170 DEG C and is incubated 12 hours；Question response still cools down
To room temperature, filter and by washing with alcohol 3 times, be then dried 4 hours at 100 DEG C, obtain Graphene-ethylene glycol bismuth meal body；
2) take 3.5g sodium molybdate to be dissolved in 100ml deionized water, then by 1) in prepare Graphene-ethylene glycol bismuth meal end 10g and add
Entering in above-mentioned sodium molybdate aqueous solution, ultrasonic wave concussion stirring makes it be uniformly dispersed, and regulates solution ph with concentrated nitric acid and concentrated hydrochloric acid
Between 0-3, then gained mixed liquor is transferred in the autoclave that volume is 200mL, is warming up to 180 DEG C of insulations 12 little
Time, question response still is cooled to room temperature, by deionized water and washing with alcohol 3 times after filtration, then is dried 12 hours at 100 DEG C,
Obtain Graphene-bismuth molybdate sodium nano composite material.
The present embodiment products therefrom γ-bismuth molybdate nanometer wafer average thickness is 20nm, and specific surface area is 40m2/ g, in concentration
During 1.0g/L, it is seen that light irradiate under can in 30min degradable 0.02g/L rhodamine.
Embodiment 4
The preparation method of Graphene-γ-bismuth molybdate nano composite material, comprises the following steps:
1) 10g bismuth nitrate is dissolved in 1L ethylene glycol, is subsequently adding 0.5g Graphene powder and is uniformly mixed, stablized
Suspension, transfers to this solution in the autoclave that volume is 2L, is heated to 160 DEG C and is incubated 24 hours；Question response still is cold
But to room temperature, filter and by washing with alcohol 3 times, be then dried 4 hours at 100 DEG C, obtain Graphene-ethylene glycol bismuth meal body；
2) take 2.5g sodium molybdate to be dissolved in 100ml deionized water, then by 1) in prepare Graphene-ethylene glycol bismuth meal end 5g and add
Entering in above-mentioned sodium molybdate aqueous solution, ultrasonic wave concussion stirring makes it be uniformly dispersed, and regulates solution ph with concentrated nitric acid and concentrated hydrochloric acid
Between 0-3, then gained mixed liquor is transferred in the autoclave that volume is 200mL, is warming up to 200 DEG C of insulations 24 little
Time, question response still is cooled to room temperature, by deionized water and washing with alcohol 3 times after filtration, then is dried 12 hours at 100 DEG C,
Obtain Graphene-bismuth molybdate sodium nano composite material.
The present embodiment products therefrom γ-bismuth molybdate nanometer wafer average thickness is 40nm, and specific surface area is 30m2/ g, in concentration
During 1.0g/L, it is seen that light irradiate under can in 60min degradable 0.02g/L rhodamine.
Each proportioning raw materials cited by the present invention can realize the present invention, and the bound value of each raw material, interval value can be real
The existing present invention, the bound value of the technological parameter of the present invention and interval value can realize the present invention, reality numerous to list herein
Execute example.
Claims (10)
1. a preparation method for Graphene-γ-bismuth molybdate nano composite material, comprises the following steps: 1) by Graphene, bismuth nitrate is solvent thermal reaction together with ethylene glycol, then through filtering, wash, dry and to obtain Graphene-ethylene glycol bismuth complex；2) being dispersed in sodium molybdate aqueous solution by gained complex, the pH value of regulation gained solution system is 0-3, then carries out hydro-thermal reaction, then through filtering, wash, dry and to obtain Graphene-γ-bismuth molybdate nano composite material.
Preparation method the most according to claim 1, it is characterised in that described Graphene is the 0.5-5% of bismuth nitrate quality.
Preparation method the most according to claim 1, it is characterised in that described bismuth nitrate concentration in ethylene glycol is 10-100g/L.
Preparation method the most according to claim 1, it is characterised in that described solvent thermal reaction condition is: is heated to 160-180 DEG C of insulation reaction 2-24 hour, then naturally cools to room temperature.
Preparation method the most according to claim 1, it is characterised in that described sodium molybdate is (0.35-0.5) with the quality of Graphene-ethylene glycol bismuth complex: 1.
Preparation method the most according to claim 1, it is characterised in that the concentration of described sodium molybdate aqueous solution is 20-100g/L.
Preparation method the most according to claim 1, it is characterised in that described hydrothermal reaction condition is for being heated to 150-200 DEG C of insulation reaction 1-24 hour.
Preparation method the most according to claim 1, it is characterised in that step 1) described drying temperature is 80-100 DEG C；Step 2) described drying temperature is 80-120 DEG C.
9. Graphene-γ-bismuth molybdate nano composite material that preparation method described in any one of claim 1～8 prepares, it is nanocrystalline lamellar, and wafer thickness is 10-40nm, and specific surface area is 30-60m2/g。
10. Graphene-the γ described in claim 9-bismuth molybdate nano composite material is as the application of catalysis material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610268468.8A CN105879855B (en) | 2016-04-27 | 2016-04-27 | A kind of graphene-γ-bismuth molybdate nanocomposite and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610268468.8A CN105879855B (en) | 2016-04-27 | 2016-04-27 | A kind of graphene-γ-bismuth molybdate nanocomposite and its preparation method and application |
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| CN108031467A (en) * | 2017-12-08 | 2018-05-15 | 浙江工业大学 | Bi2MoO6Clad halloysite nanotube composite material and preparation method and application thereof |
| CN111450822A (en) * | 2020-04-09 | 2020-07-28 | 浙江工业大学 | Preparation method of bismuth molybdate coated tourmaline composite photocatalyst |
| CN113789090A (en) * | 2021-09-16 | 2021-12-14 | 广州特种承压设备检测研究院 | Graphene modified photocatalytic water-based paint and preparation method and application thereof |
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| CN111450822A (en) * | 2020-04-09 | 2020-07-28 | 浙江工业大学 | Preparation method of bismuth molybdate coated tourmaline composite photocatalyst |
| CN113789090A (en) * | 2021-09-16 | 2021-12-14 | 广州特种承压设备检测研究院 | Graphene modified photocatalytic water-based paint and preparation method and application thereof |
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