CN109078644A - Graphene-supported Bi-BiOCl-TiO2Photochemical catalyst and preparation method - Google Patents
Graphene-supported Bi-BiOCl-TiO2Photochemical catalyst and preparation method Download PDFInfo
- Publication number
- CN109078644A CN109078644A CN201810876147.5A CN201810876147A CN109078644A CN 109078644 A CN109078644 A CN 109078644A CN 201810876147 A CN201810876147 A CN 201810876147A CN 109078644 A CN109078644 A CN 109078644A
- Authority
- CN
- China
- Prior art keywords
- biocl
- tio
- graphene
- photochemical catalyst
- supported
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 106
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 60
- 239000000203 mixture Substances 0.000 claims abstract description 58
- 239000002245 particle Substances 0.000 claims abstract description 47
- 230000001699 photocatalysis Effects 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000007146 photocatalysis Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 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 9
- 239000011780 sodium chloride Substances 0.000 claims abstract description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 37
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000005119 centrifugation Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 15
- -1 stirred evenly Substances 0.000 claims description 11
- 239000011941 photocatalyst Substances 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229940085675 polyethylene glycol 800 Drugs 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 6
- 238000013019 agitation Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013067 intermediate product Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000013078 crystal Chemical group 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 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 3
- 229940012189 methyl orange Drugs 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 102000057593 human F8 Human genes 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 229940047431 recombinate Drugs 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
A kind of graphene-supported Bi-BiOCl-TiO2Photochemical catalyst and preparation method, belong to photocatalysis field.The graphene-supported Bi-BiOCl-TiO2Photochemical catalyst the preparation method comprises the following steps: by bismuth nitrate, polyethylene glycol, tetra-n-butyl titanate mixture, sodium chloride, citric acid are dissolved in the mixture of water, after mixing, in 2~4MPa, in 140~200 DEG C of heat preservations 8~16h, obtained Bi-BiOCl-TiO2Photocatalytic particle and graphene solution mixing are thick, and at 2~4MPa, in 100~150 DEG C of 1~5h of reaction, centrifugal drying obtains graphene-supported Bi-BiOCl-TiO2Photochemical catalyst.The photochemical catalyst can be effectively suppressed pure BiOCl electron hole pair Rapid Combination and improve visible light utilization efficiency, make BiOCl towards (001) oriented growth, photocatalysis efficiency greatly improves.This method preparation process is simple, at low cost, and time-consuming is few, can quickly produce.
Description
Technical field
The invention belongs to photocatalysis technology fields, and in particular to a kind of graphene-supported Bi-BiOCl-TiO2Photochemical catalyst
And preparation method.
Background technique
Photocatalytic Oxidation With Semiconductors technology, can effectively degrade a variety of environmentally harmful pollutants, make pollutant mine
Turn to CO2、H2The small molecules such as O are a kind of advanced oxidation processes, are one of the important methods of processing environment pollution problem in recent years.
TiO2The advantages that due to high with catalytic activity, oxidability is strong, chemical, physics and biological stability are good, nontoxic, has been found
For one of current classic semiconductor light-catalyst.TiO2Band-gap energy be 3.2eV, only wavelength be less than 387nm purple
Under outer light irradiation, TiO could be excited2Generate electron-hole pair.However, 400nm is below ultraviolet in the power spectrum of sunlight
Light is less than 5%, and the visible light that wavelength is 400~800nm then accounts for 43%.BiOCl is a kind of novel lamellar semiconducting compound,
Crystal structure is four directions PbFCl type, can also regard double X along C axis direction as-Layer and [Bi2O2]2+Layer is alternately arranged the stratiform of composition
Structure belongs to tetragonal crystal system.However, the light induced electron of BiOCl and hole are easy quickly to recombinate, it is anti-so as to cause photocatalysis
Efficiency is answered to reduce.
Graphene is to pass through sp by single layer of carbon atom2The hexagon cellular shape two dimensional crystal planar structure of hybridized orbit composition,
It is connected between carbon atom by very strong σ key, these C-C keys make graphene have excellent structural rigidity, parallel sheet direction
Intensity is higher.Graphene has excellent performance, such as high electron mobility, high-specific surface area, high intensity and higher Young mould
The performances such as amount.These excellent performances make graphene in nano electron device, gas sensor, energy stores and composite material etc.
Field has wide practical use.Graphene can occur chemically composited as excellent electronic conductor with photocatalytic particle.Work as light
When catalysed particulate light excites and generates electrons and holes, graphene can rapidly guide electronics, to block hole and electronics
It is compound, promote the generation of photohole, improve visible light photocatalysis ability.
Summary of the invention
It is that the present invention solves it is a key issue that providing a kind of graphene-supported Bi-BiOCl-TiO2Photochemical catalyst and preparation method.
The graphene-supported Bi-BiOCl-TiO2Pure BiOCl electron hole pair Rapid Combination can be effectively suppressed in photochemical catalyst and raising can
Light-exposed utilization rate makes BiOCl towards (001) oriented growth, compared with pure BiOCl photocatalysis performance, graphene-supported Bi-
BiOCl-TiO2Photochemical catalyst photocatalysis efficiency is greatly improved, and highest can be to 99.1%.
To achieve the goals above, the present invention uses following scheme:
A kind of graphene-supported Bi-BiOCl-TiO of the invention2The preparation method of photochemical catalyst, comprising the following steps:
Step 1: configuration reaction solution
(1) according to the ratio, raw material is weighed, bismuth nitrate, polyethylene glycol, tetra-n-butyl titanate are dissolved in deionized water, is stirred
Uniformly, mixture A is obtained；Wherein, by the solid-to-liquid ratio of each ingredient, bismuth nitrate: polyethylene glycol: tetra-n-butyl titanate: deionization
Water=(0.9~1) g:(0.1~0.2) g:(1~2) mL:(25~30) mL；
(2) according to the ratio, raw material is weighed, sodium chloride, citric acid are dissolved in deionized water, stirred evenly, mixture is obtained
B；Wherein, by the solid-to-liquid ratio of each ingredient, sodium chloride: citric acid: deionized water=(110~112) mg:(490~500) mg:
(25~30) mL；
(3) mixture A and mixture B is mixed, obtains reaction solution；Wherein, Ti in mixture A4+: Cl in mixture B-
=1:1；
Step 2: preparation Bi-BiOCl-TiO2Photocatalytic particle
(1) reaction solution is placed in autoclave, is contained in 2~4MPa in 140~200 DEG C of 8~16h of heat preservation
Bi-BiOCl-TiO2Photocatalytic particle mixture；
(2) Bi-BiOCl-TiO will be contained2The centrifugation of photocatalytic particle mixture cleans the solid product after centrifugation several
It is secondary, it is dry, obtain Bi-BiOCl-TiO2Photocatalytic particle；
Step 3: dispersed graphite alkene solution
(1) graphene is dissolved in the mixed solution of deionized water and dehydrated alcohol, ultrasonic disperse is uniform, and it is dense to obtain quality
Degree is 0.2~0.4mg/mL graphene solution；
(2) by graphene solution and Bi-BiOCl-TiO2Photocatalytic particle mixing, stirs evenly, obtains graphene and Bi-
BiOCl-TiO2The mixed solution of photocatalytic particle；Wherein, in mass ratio, graphene: Bi-BiOCl-TiO2Photocatalytic particle=
1:(100~20)；
Step 4: preparing graphene-supported Bi-BiOCl-TiO2Photochemical catalyst
(1) by graphene and Bi-BiOCl-TiO2The mixed solution of photocatalytic particle is placed in autoclave, 2~
Under 4MPa, in 100~150 DEG C of 1~5h of reaction, containing graphene load Bi-BiOCl-TiO is obtained2Photocatalyst mixture；
(2) containing graphene is loaded into Bi-BiOCl-TiO2Photocatalyst mixture centrifugation, will be graphene-supported after centrifugation
Bi-BiOCl-TiO2Photochemical catalyst is cleaned and dried, obtains graphene-supported Bi-BiOCl-TiO2Photochemical catalyst.
In the step 1 (1), the polyethylene glycol is preferably polyethylene glycol-800.
In the step 2 (1), in a high pressure reaction kettle, under acid and hydrothermal condition, part polyethylene glycol breakdown is obtained
To ethylene glycol, by Bi3+It is reduced into metal Bi.
In the step 2 (2), the drying, drying temperature is 60~90 DEG C.
Preferably, in the mixed solution of deionized water and dehydrated alcohol, by volume, being gone in the step 3 (1)
Ionized water: dehydrated alcohol=(1~2): 1.
In the step 3 (1), the ultrasonic disperse, supersonic frequency is 30~50KHz.
In the step 4 (2), the drying, drying temperature is 60~90 DEG C.
A kind of graphene-supported Bi-BiOCl-TiO of the invention2Photochemical catalyst is made using above-mentioned preparation method.
A kind of graphene-supported Bi-BiOCl-TiO of the invention2Photochemical catalyst, including graphene and Bi-BiOCl-TiO2
Photocatalytic particle, Bi-BiOCl-TiO2Photocatalytic nanometer piece is distributed in the inside and surface of graphene.
The graphene-supported Bi-BiOCl-TiO2The growth that BiOCl can be promoted to be orientated in photochemical catalyst along (001),
Highly exposed (001) is more advantageous to the formation of Lacking oxygen, will enhance photocatalysis performance.
The graphene-supported Bi-BiOCl-TiO2Highest photocatalysis efficiency of the photochemical catalyst in 50min reaches
99.1%.
Graphene-supported Bi-BiOCl-TiO2 photochemical catalyst of the invention and preparation method, it has the advantage that: changing stone herein
Black alkene and Bi-BiOCl-TiO2Mass ratio, Bi-BiOCl-TiO2It is respectively 1000:10,800:10,600 with graphene mass ratio:
10,400:10,200:10 are denoted as BBTR100, BBTR80, BBTR60, BBTR40, BBTR20 respectively, and this method is effectively by stone
Black alkene and Bi-BiOCl-TiO2It is combined together, in photo-catalytic degradation of methyl-orange experiment, degradation rate is up to after 50min
99.1%；Preparation process is simple, at low cost, and time-consuming is few, can quickly produce.
Detailed description of the invention
Fig. 1 is the graphene-supported Bi-BiOCl-TiO of the embodiment of the present invention 12The XRD diagram of photochemical catalyst and its intermediate product；
Fig. 2 is the graphene-supported Bi-BiOCl-TiO of the embodiment of the present invention 12The Raman of photochemical catalyst and its intermediate product
Map；
Fig. 3 is the graphene-supported Bi-BiOCl-TiO of the embodiment of the present invention 12Photochemical catalyst-BBTR-20 SEM picture.
Fig. 4 is the graphene-supported Bi-BiOCl-TiO of different ratio of the present invention2The drop of photochemical catalyst and its intermediate product
Solution rate.
Fig. 5 is that the present invention prepares graphene-supported Bi-BiOCl-TiO2The process flow chart of photochemical catalyst.
In the above figure, Bi/BiOCl/TiO2Represent graphene-supported Bi-BiOCl-TiO2Photochemical catalyst, Bi/BiOCl are represented
The Bi-BiOCl photochemical catalyst product of comparative example 1, BBTR-20 represent Bi-BiOCl-TiO2It is 200:10 with graphene mass ratio
Graphene-supported Bi-BiOCl-TiO2Photochemical catalyst, BBT represent graphene-supported Bi-BiOCl-TiO2Photochemical catalyst.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.
Embodiment 1
A kind of graphene-supported Bi-BiOCl-TiO2The preparation method of photochemical catalyst, process flow chart are shown in Fig. 5, including
Following steps:
Step 1: configuration reaction solution
(1) according to the ratio, raw material is weighed, 0.93g bismuth nitrate, 0.2g polyethylene glycol-800,2mL tetra-n-butyl titanate are dissolved in
In 30mL deionized water, magnetic agitation 30min is stirred evenly, and obtains mixture A；
(2) according to the ratio, raw material is weighed, 0.112g sodium chloride, 500mg citric acid are dissolved in 30mL deionized water, magnetic force
It stirs evenly, obtains mixture B；
(3) mixture A and mixture B is mixed, obtains reaction solution；Wherein, Ti in mixture A4+: Cl in mixture B-
=1:1；
Step 2: preparation Bi-BiOCl-TiO2Photocatalytic particle
(1) reaction solution is placed in autoclave, in 3MPa, in 160 DEG C of heat preservation 12h, is obtained containing Bi-BiOCl-
TiO2Photocatalytic particle mixture；
(2) Bi-BiOCl-TiO will be contained2The centrifugation of photocatalytic particle mixture cleans the solid product after centrifugation several
It is secondary, in 80 DEG C of dryings, obtain Bi-BiOCl-TiO2Photocatalytic particle；
Step 3: dispersed graphite alkene solution
(1) 10mg graphene is dissolved in the mixed solution of 20mL deionized water and 10mL dehydrated alcohol, using supersonic frequency
Rate is the ultrasonic disperse 30min of 40KHz, and after being uniformly dispersed, obtaining mass concentration is 0.33mg/mL graphene solution；
(2) by obtained graphene solution and 200mg Bi-BiOCl-TiO2Photocatalytic particle mixing, magnetic agitation 2h,
It is uniformly mixed, obtains graphene and Bi-BiOCl-TiO2The mixed solution of photocatalytic particle；Wherein, in mass ratio, graphene:
Bi-BiOCl-TiO2Photocatalytic particle=1:20；
Step 4: preparing graphene-supported Bi-BiOCl-TiO2Photochemical catalyst
(1) by graphene and Bi-BiOCl-TiO2The mixed solution of photocatalytic particle is placed in autoclave, in 3MPa
Under, in 120 DEG C of reaction 3h, obtain containing graphene load Bi-BiOCl-TiO2Photocatalyst mixture；
(2) containing graphene is loaded into Bi-BiOCl-TiO2Photocatalyst mixture centrifugation, will be graphene-supported after centrifugation
Bi-BiOCl-TiO2In 80 DEG C of dryings, it is negative several times with deionized water and washes of absolute alcohol to obtain graphene for photochemical catalyst
Carry Bi-BiOCl-TiO2Photochemical catalyst.
Graphene-supported Bi-BiOCl-TiO manufactured in the present embodiment2Photochemical catalyst, including graphene and Bi-BiOCl-
TiO2Photocatalytic particle, Bi-BiOCl-TiO2Photocatalytic nanometer piece is distributed in the inside and surface of graphene.
Graphene-supported Bi-BiOCl-TiO in the present embodiment2Photochemical catalyst-BBTR-20 SEM picture, is shown in Fig. 3, Fig. 3
Show Bi-BiOCl-TiO2It is grown in the surface RGO well.
Embodiment 2
A kind of graphene-supported Bi-BiOCl-TiO2Preparation method, comprising the following steps:
Step 1, reaction solution is prepared
(1) 1g bismuth nitrate, 0.1g polyethylene glycol-800 and 1ml tetra-n-butyl titanate are dissolved in 25mL deionized water beaker 1
In, 30~40min of magnetic agitation obtains mixture A；
(2) 110mg sodium chloride and 490mg citric acid are dissolved in 25ml deionized water beaker 2, mechanical stirring is uniform, obtains
To mixture B；
(3) the mixture B solution in beaker 2 is poured into the mixture A in beaker 1, is stirred evenly, keep it sufficiently anti-
It answers, obtains reaction solution.
Step 2, Bi-BiOCl-TiO is prepared2Photocatalytic particle
(1) reaction solution is poured into autoclave, at 4MPa, keeps the temperature 16h at 140 DEG C, obtained containing Bi-
BiOCl-TiO2Photocatalytic particle mixture；
(2) Bi-BiOCl-TiO will be contained2The centrifugation of photocatalytic particle mixture, by the solid product after centrifugation, uses deionization
Water and washes of absolute alcohol Bi-BiOCl-TiO2Several times, dry at 90 DEG C, obtain Bi-BiOCl-TiO2Photocatalytic particle.
Step 3, dispersed graphite alkene solution
(1) 10mg graphene is dissolved in 20ml deionized water and 20ml dehydrated alcohol, 30~40min of ultrasound, dispersion is equal
After even, obtaining mass concentration is 0.25mg/mL graphene solution；
(2) by 200mgBi-BiOCl-TiO2It is mixed with graphene solution, magnetic agitation 2h stirs evenly, obtains graphite
Alkene and Bi-BiOCl-TiO2The mixed solution of photocatalytic particle；Wherein, in mass ratio, graphene: Bi-BiOCl-TiO2Photocatalysis
Particle=1:20；
Step 4, graphene-supported Bi-BiOCl-TiO is prepared2Photochemical catalyst
(1) by graphene and Bi-BiOCl-TiO2The mixed solution of photocatalytic particle pours into autoclave, exists respectively
100 DEG C of heating 5h obtain containing graphene load Bi-BiOCl-TiO2Photocatalyst mixture.
(2) containing graphene is loaded into Bi-BiOCl-TiO2Photocatalyst mixture centrifugation, will be graphene-supported after centrifugation
Bi-BiOCl-TiO2Photochemical catalyst, it is several times with deionized water and washes of absolute alcohol, dry at 90 DEG C, obtain graphene
Load Bi-BiOCl-TiO2Photochemical catalyst.
Step 5, photocatalysis is tested
The photochemical catalyst prepared (30mg) is dispersed in the 50ml methyl orange aqueous solution that concentration is 20mg/L, in illumination
Before penetrating, by suspension magnetic agitation 30 minutes in the dark, to realize that the adsorption/desorption between photochemical catalyst and methyl orange is flat
Weighing apparatus.Then, it takes 4ml suspension and is centrifuged within every 10 minutes during irradiation.Record the solution of maximum absorption wavelength centrifugation.
Embodiment 3
A kind of graphene-supported Bi-BiOCl-TiO2Preparation method, comprising the following steps:
Step 1, reaction solution is prepared
(1) 0.93g bismuth nitrate, 0.2g polyethylene glycol 400 and 2ml tetra-n-butyl titanate are dissolved in 30ml deionized water beaker
In 1, mechanical stirring 30min obtains mixture A；
(2) 0.112g sodium chloride and 500mg citric acid are dissolved in 30ml deionized water beaker 2, magnetic agitation 30min,
Obtain mixture B；
(3) the mixture B solution in beaker 2 is poured into the mixture A of beaker 1, magnetic agitation 30min is reacted
Solution.
Step 2, Bi-BiOCl-TiO is prepared2Photocatalytic particle
(1) reaction solution is poured into autoclave, at 2MPa, keeps the temperature 12h at 160 DEG C, obtained containing Bi-
BiOCl-TiO2Photocatalytic particle mixture；
(2) Bi-BiOCl-TiO will be contained2The centrifugation of photocatalytic particle mixture, by the solid product after centrifugation, uses deionization
Water and washes of absolute alcohol Bi-BiOCl-TiO2Several times, dry at 80 DEG C, obtain Bi-BiOCl-TiO2Photocatalytic particle.
Step 3, dispersed graphite alkene solution
(1) 10mg graphene is dissolved in 15ml deionized water and 10ml dehydrated alcohol, ultrasonic 30min, after being uniformly dispersed,
Obtaining mass concentration is 0.4mg/mL graphene solution；
(2) by 200mgBi-BiOCl-TiO2It is mixed with graphene solution, magnetic agitation 2h, magnetic agitation 2h obtains stone
Black alkene and Bi-BiOCl-TiO2The mixed solution of photocatalytic particle；Wherein, in mass ratio, graphene: Bi-BiOCl-TiO2Light is urged
Change particle=1:20.
Step 4, graphene-supported Bi-BiOCl-TiO is prepared2Photochemical catalyst
(1) by graphene and Bi-BiOCl-TiO2The mixed solution of photocatalytic particle pours into autoclave, exists respectively
120 DEG C of heating 3h obtain containing graphene load Bi-BiOCl-TiO2Photocatalyst mixture.
(2) containing graphene is loaded into Bi-BiOCl-TiO2Photocatalyst mixture centrifugation, will be graphene-supported after centrifugation
Bi-BiOCl-TiO2Photochemical catalyst, it is several times with deionized water and washes of absolute alcohol, dry at 80 DEG C, obtain graphene
Load Bi-BiOCl-TiO2Photochemical catalyst.
Embodiment 4
A kind of graphene-supported Bi-BiOCl-TiO2The preparation method of photochemical catalyst, with embodiment 1, the difference is that,
In mass ratio, graphene: Bi-BiOCl-TiO2=1000:10.
Graphene-supported Bi-BiOCl-TiO manufactured in the present embodiment2Photochemical catalyst is BBTR100.
Embodiment 5
A kind of graphene-supported Bi-BiOCl-TiO2The preparation method of photochemical catalyst, with embodiment 1, the difference is that,
In mass ratio, graphene: Bi-BiOCl-TiO2=800:10.
Graphene-supported Bi-BiOCl-TiO manufactured in the present embodiment2Photochemical catalyst is BBTR80.
Embodiment 6
A kind of graphene-supported Bi-BiOCl-TiO2The preparation method of photochemical catalyst, with embodiment 1, the difference is that,
In mass ratio, graphene: Bi-BiOCl-TiO2=600:10.
Graphene-supported Bi-BiOCl-TiO manufactured in the present embodiment2Photochemical catalyst is BBTR60.
Embodiment 7
A kind of graphene-supported Bi-BiOCl-TiO2The preparation method of photochemical catalyst, with embodiment 1, the difference is that,
In mass ratio, graphene: Bi-BiOCl-TiO2=400:10.
Graphene-supported Bi-BiOCl-TiO manufactured in the present embodiment2Photochemical catalyst is BBTR40.
Comparative example 1
A kind of preparation method of Bi-BiOCl photocatalytic particle, comprising the following steps:
Step 1: configuration reaction solution
(1) according to the ratio, raw material is weighed, 0.93g bismuth nitrate, 0.2g polyethylene glycol-800 are dissolved in 30mL deionized water, magnetic
Power stirs 30min, stirs evenly, obtains mixture A；
(2) according to the ratio, raw material is weighed, 0.112g sodium chloride, 500mg citric acid are dissolved in 30mL deionized water, magnetic force
It stirs evenly, obtains mixture B；
(3) mixture A and mixture B is mixed, obtains reaction solution；Wherein, Ti in mixture A4+: Cl in mixture B-
=1:1；
Step 2: preparation Bi-BiOCl photocatalytic particle
(1) reaction solution is placed in autoclave, obtains light containing Bi-BiOCl in 160 DEG C of heat preservation 12h in 3MPa
Catalysed particulate mixture；
(2) centrifugation of Bi-BiOCl photocatalytic particle mixture will be contained, by the solid product after centrifugation, cleaning several times,
80 DEG C of dryings, obtain Bi-BiOCl photocatalytic particle.
Graphene-supported Bi-BiOCl-TiO prepared by embodiment 12Photochemical catalyst and the product of comparative example carry out XRD points
Analysis, the map after analysis is shown in Fig. 1, from Fig. 1, it can be deduced that: impurity is not detected in all samples, shows the product purity
Height, well-crystallized.It is worth noting that, with Bi/BiOCl and Bi/BiOCl/TiO2It compares, (001) peak highest of BBTR-20.
It should be the result shows that BiOCl should promote the growth along (001) orientation.Highly exposed (001) is more advantageous to the formation of Lacking oxygen, will
Enhance photocatalysis performance.
Graphene-supported Bi-BiOCl-TiO prepared by embodiment 12The Raman of photochemical catalyst and comparative example intermediate product
Map is shown in Fig. 2, and Raman map is in 90cm-1Place observes weaker band, this is because the single order of Bi scatters A1gMode.BiOCl has
Two typical characteristic peaks, are located at 153.2cm-1(AlgInternal Bi-Cl stretching mode) and 202.4cm-1(EgInternal Bi-Cl
Stretching vibration).Positioned at 399.1 (B1g), 510.2 (A1g+B1g) and 629.1cm-1(Eg) it is TiO2Characteristic peak.
The graphene-supported Bi-BiOCl-TiO that the different ratio of embodiment 1, embodiment 4-7 preparation is obtained2Photocatalysis
The degradation rate of agent and comparative example product is shown in Fig. 4, can intuitively, clearly find out that BBTR-20 shows highest light from Fig. 4
Catalytic performance.Graphene-supported Bi-BiOCl-TiO2Highest photocatalysis efficiency of the photochemical catalyst in 50min reaches 99.1%.
Claims (9)
1. a kind of graphene-supported Bi-BiOCl-TiO2The preparation method of photochemical catalyst, which comprises the following steps:
Step 1: configuration reaction solution
(1) according to the ratio, raw material is weighed, bismuth nitrate, polyethylene glycol, tetra-n-butyl titanate are dissolved in deionized water, stirred evenly,
Obtain mixture A；Wherein, by the solid-to-liquid ratio of each ingredient, bismuth nitrate: polyethylene glycol: tetra-n-butyl titanate: deionized water=
(0.9~1) g:(0.1~0.2) g:(1~2) mL:(25~30) mL；
(2) according to the ratio, raw material is weighed, sodium chloride, citric acid are dissolved in deionized water, stirred evenly, mixture B is obtained；Its
In, by the solid-to-liquid ratio of each ingredient, sodium chloride: citric acid: deionized water=(110~112) mg:(490~500) mg:(25~
30)mL；
(3) mixture A and mixture B is mixed, obtains reaction solution；Wherein, Ti in mixture A4+: Cl in mixture B-=1:
1；
Step 2: preparation Bi-BiOCl-TiO2Photocatalytic particle
(1) reaction solution is placed in autoclave, in 2~4MPa, in 140~200 DEG C of 8~16h of heat preservation, is obtained containing Bi-
BiOCl-TiO2Photocatalytic particle mixture；
(2) Bi-BiOCl-TiO will be contained2The centrifugation of photocatalytic particle mixture, by the solid product after centrifugation, cleaning several times, is done
It is dry, obtain Bi-BiOCl-TiO2Photocatalytic particle；
Step 3: dispersed graphite alkene solution
(1) graphene is dissolved in the mixed solution of deionized water and dehydrated alcohol, ultrasonic disperse is uniform, obtains mass concentration and is
0.2~0.4mg/mL graphene solution；
(2) by graphene solution and Bi-BiOCl-TiO2Photocatalytic particle mixing, stirs evenly, obtains graphene and Bi-
BiOCl-TiO2The mixed solution of photocatalytic particle；Wherein, in mass ratio, graphene: Bi-BiOCl-TiO2Photocatalytic particle=
1:(100~20)；
Step 4: preparing graphene-supported Bi-BiOCl-TiO2Photochemical catalyst
(1) by graphene and Bi-BiOCl-TiO2The mixed solution of photocatalytic particle is placed in autoclave, in 2~4MPa
Under, in 100~150 DEG C of 1~5h of reaction, obtain containing graphene load Bi-BiOCl-TiO2Photocatalyst mixture；
(2) containing graphene is loaded into Bi-BiOCl-TiO2Photocatalyst mixture centrifugation, by the graphene-supported Bi- after centrifugation
BiOCl-TiO2Photochemical catalyst is cleaned and dried, obtains graphene-supported Bi-BiOCl-TiO2Photochemical catalyst.
2. graphene-supported Bi-BiOCl-TiO as described in claim 12The preparation method of photochemical catalyst, which is characterized in that described
In step 1 (1), the polyethylene glycol is polyethylene glycol-800.
3. graphene-supported Bi-BiOCl-TiO as described in claim 12The preparation method of photochemical catalyst, which is characterized in that described
In step 2 (2), the drying, drying temperature is 60~90 DEG C.
4. graphene-supported Bi-BiOCl-TiO as described in claim 12The preparation method of photochemical catalyst, which is characterized in that described
In step 3 (1), in the mixed solution of deionized water and dehydrated alcohol, by volume, and deionized water: dehydrated alcohol=(1~2):
1。
5. graphene-supported Bi-BiOCl-TiO as described in claim 12The preparation method of photochemical catalyst, which is characterized in that described
In step 3 (1), the ultrasonic disperse, supersonic frequency is 30~50KHz.
6. graphene-supported Bi-BiOCl-TiO as described in claim 12The preparation method of photochemical catalyst, which is characterized in that described
In step 4 (2), the drying, drying temperature is 60~90 DEG C.
7. a kind of graphene-supported Bi-BiOCl-TiO2Photochemical catalyst, using graphene described in claim 1~2 any one
Load Bi-BiOCl-TiO2The preparation method of photochemical catalyst is made.
8. a kind of graphene-supported Bi-BiOCl-TiO2Photochemical catalyst, which is characterized in that the graphene-supported Bi-BiOCl-TiO2
Photochemical catalyst includes graphene and Bi-BiOCl-TiO2Photocatalytic particle, Bi-BiOCl-TiO2Photocatalytic nanometer piece is distributed in stone
The inside and surface of black alkene.
9. graphene-supported Bi-BiOCl-TiO as claimed in claim 7 or 82Photochemical catalyst, which is characterized in that the stone
Black alkene loads Bi-BiOCl-TiO2Highest photocatalysis efficiency of the photochemical catalyst in 50min reaches 99.1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810876147.5A CN109078644B (en) | 2018-08-03 | 2018-08-03 | Graphene-loaded Bi-BiOCl-TiO2Photocatalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810876147.5A CN109078644B (en) | 2018-08-03 | 2018-08-03 | Graphene-loaded Bi-BiOCl-TiO2Photocatalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109078644A true CN109078644A (en) | 2018-12-25 |
| CN109078644B CN109078644B (en) | 2021-09-28 |
Family
ID=64833397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810876147.5A Active CN109078644B (en) | 2018-08-03 | 2018-08-03 | Graphene-loaded Bi-BiOCl-TiO2Photocatalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109078644B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112452344A (en) * | 2020-12-14 | 2021-03-09 | 北京科技大学 | In-situ synthesis of monatomic Bi0Bridged TiO2Method for preparing @ BiOCl composite photocatalytic material |
| CN113351231A (en) * | 2021-06-08 | 2021-09-07 | 常州大学 | Preparation method and catalytic application of high-performance bismuth oxyhalide/graphene nanocomposite |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101947463A (en) * | 2010-08-06 | 2011-01-19 | 上海师范大学 | Preparation method and application of high-efficiency ultraviolet visible full-spectrum photocatalytic material |
| US20110167913A1 (en) * | 2009-10-15 | 2011-07-14 | Nexgen Semi Holding, Inc. | Imaging devices for measuring the structure of a surface |
| CN104190448A (en) * | 2014-07-29 | 2014-12-10 | 南开大学 | Preparation method and application of visible light photocatalyst, namely BiOCl nanosheets |
| CN104646037A (en) * | 2015-01-12 | 2015-05-27 | 内蒙古科技大学 | BiOXs pholocatalyst, grapheme-compounded BiOXs pholocatalyst and preparation method thereof |
| CN104874811A (en) * | 2015-05-22 | 2015-09-02 | 武汉工程大学 | Preparing method of simple substance bismuth/bismuth compound nanocomposite with oxygen vacancies |
| CN105452169A (en) * | 2013-08-05 | 2016-03-30 | 耶路撒冷希伯来大学伊萨姆研究开发有限公司 | Zeolite, and production method and use therefor |
| CN106334568A (en) * | 2016-10-08 | 2017-01-18 | 合肥工业大学 | Method for adopting solvothermal one-step method to synthesize Bi/BiOCl composite nanostructure |
-
2018
- 2018-08-03 CN CN201810876147.5A patent/CN109078644B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110167913A1 (en) * | 2009-10-15 | 2011-07-14 | Nexgen Semi Holding, Inc. | Imaging devices for measuring the structure of a surface |
| CN101947463A (en) * | 2010-08-06 | 2011-01-19 | 上海师范大学 | Preparation method and application of high-efficiency ultraviolet visible full-spectrum photocatalytic material |
| CN105452169A (en) * | 2013-08-05 | 2016-03-30 | 耶路撒冷希伯来大学伊萨姆研究开发有限公司 | Zeolite, and production method and use therefor |
| CN104190448A (en) * | 2014-07-29 | 2014-12-10 | 南开大学 | Preparation method and application of visible light photocatalyst, namely BiOCl nanosheets |
| CN104646037A (en) * | 2015-01-12 | 2015-05-27 | 内蒙古科技大学 | BiOXs pholocatalyst, grapheme-compounded BiOXs pholocatalyst and preparation method thereof |
| CN104874811A (en) * | 2015-05-22 | 2015-09-02 | 武汉工程大学 | Preparing method of simple substance bismuth/bismuth compound nanocomposite with oxygen vacancies |
| CN106334568A (en) * | 2016-10-08 | 2017-01-18 | 合肥工业大学 | Method for adopting solvothermal one-step method to synthesize Bi/BiOCl composite nanostructure |
Non-Patent Citations (3)
| Title |
|---|
| WEI LI ET AL.: "Novel BiOCl/TiO2hierarchical composites: Synthesis, characterizationand application on photocatalysis", 《APPLIED CATALYSIS A: GENERAL》 * |
| WEI LI ET AL.: "Synthesis of Bi/BiOCl-TiO2-CQDs quaternary photocatalyst with enhanced visible-light photoactivity and fast charge migration", 《CATALYSIS COMMUNICATIONS》 * |
| XIAN-XIAN WEI ET AL.: ""Advanced visible-light-driven photocatalyst BiOBr–TiO2–graphene composite with graphene as a nano-filler"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112452344A (en) * | 2020-12-14 | 2021-03-09 | 北京科技大学 | In-situ synthesis of monatomic Bi0Bridged TiO2Method for preparing @ BiOCl composite photocatalytic material |
| CN112452344B (en) * | 2020-12-14 | 2021-09-14 | 北京科技大学 | In-situ synthesis of monatomic Bi0Bridged TiO2Method for preparing @ BiOCl composite photocatalytic material |
| CN113351231A (en) * | 2021-06-08 | 2021-09-07 | 常州大学 | Preparation method and catalytic application of high-performance bismuth oxyhalide/graphene nanocomposite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109078644B (en) | 2021-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | One-step synthesis of unique thorn-like BaTiO3–TiO2 composite nanofibers to enhance piezo-photocatalysis performance | |
| CN102000584A (en) | Method for preparing cobalt-doped improved beta-bismuth oxide photocatalyst | |
| CN106268908A (en) | A kind of graphite-phase C removing removal organic polluter3n4doping TiO2float type ecological restoration material of load expanded perlite and preparation method thereof | |
| CN106902890A (en) | A kind of Cu BTC/ pucherites/SWCNTs ternary heterojunction structure photochemical catalysts and preparation method and application | |
| CN111729682A (en) | Photocatalyst g-C3N4/RGO/Bi2O3And method for preparing the same | |
| CN113210003A (en) | Preparation method of composite visible-light-driven photocatalyst graphene quantum dot/graphite-phase nitrogen carbide | |
| CN109078644A (en) | Graphene-supported Bi-BiOCl-TiO2Photochemical catalyst and preparation method | |
| Hu et al. | Controllable construction of hierarchical TiO2 supported on hollow rGO/P-HC heterostructure for highly efficient photocatalysis | |
| CN109092340A (en) | Graphene-supported bismuth oxychloride-basic carbonate bismuth oxide photocatalyst and its preparation method | |
| CN111229279B (en) | Carbon nitride quantum dot-loaded hierarchical-pore inverse opal structure CuO-SiO 2 Preparation and use thereof | |
| CN109078654A (en) | PVP modified graphene loads BiOCl photochemical catalyst and preparation method thereof | |
| CN106179315B (en) | A kind of preparation method of the graphene-supported Bi photochemical catalysts with 40 shape of octahedron | |
| CN109663612A (en) | A kind of Fe/N/S tri- adulterates double-layer hollow meso-porous carbon material and the preparation method and application thereof | |
| CN107051480A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN113731390A (en) | Spherical HCNs @ TiO2Preparation method of photocatalyst and application of photocatalyst in dye wastewater | |
| CN115254161A (en) | MnO (MnO) 2-x /Ti 2 C 3 Preparation method of MXene catalytic ozonation material | |
| CN117205953A (en) | Nonmetal nitrogen-phosphorus co-doped porous carbon catalyst and preparation method and application thereof | |
| CN109317132A (en) | A kind of photochemical catalyst nano material and preparation method thereof | |
| CN110510701A (en) | The method for bending Electrocatalysis Degradation waste water containing dye | |
| CN107008354A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN117414817A (en) | High-efficiency niobium pentoxide photocatalytic material and etching preparation method and application thereof | |
| CN107008357A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107159247A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN106984341A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN106984347A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |