CN107020142A - The preparation method of foamed nickel supported carbon nitrogen/reduced graphene photochemical catalyst - Google Patents
The preparation method of foamed nickel supported carbon nitrogen/reduced graphene photochemical catalyst Download PDFInfo
- Publication number
- CN107020142A CN107020142A CN201710267045.9A CN201710267045A CN107020142A CN 107020142 A CN107020142 A CN 107020142A CN 201710267045 A CN201710267045 A CN 201710267045A CN 107020142 A CN107020142 A CN 107020142A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- nickel foam
- graphene
- photochemical catalyst
- reduced graphene
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 108
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 81
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 239000006260 foam Substances 0.000 claims abstract description 41
- 239000006185 dispersion Substances 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 239000008236 heating water Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 230000001699 photocatalysis Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 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 5
- 229940012189 methyl orange Drugs 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- -1 hydroxyl radical free radical Chemical class 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 241000196171 Hydrodictyon reticulatum Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004153 renaturation Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B01J35/39—
-
- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/60—
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
Abstract
The present invention relates to a kind of preparation method of foamed nickel supported carbon nitrogen/reduced graphene photochemical catalyst, g C3N4Block is through calcining to obtain g C3N4It is acidified in nanometer sheet, juxtaposition nitric acid, filtering and washing drying.Graphene oxide aqueous dispersions are adjusted to certain pH, then by g C3N4Nanometer sheet is placed in one ultrasonic g C3N4/ graphene oxide dispersion；Nickel foam cuts and cleaned, dries, and is placed in g C3N4Submerged in/graphene oxide dispersion, realize the load of catalyst, so in triplicate, g C must be loaded3N4The nickel foam of/graphene oxide；By it in reductant solution heating water bath, g C must be loaded by drying3N4The nickel foam of/reduced graphene.The present invention realizes g C3N4In the load of solid support surface, firm binding force, products obtained therefrom is under visible ray section, organic pollution that can be in catalytic degradation water body, and with good cycle performance.
Description
Technical field
The invention belongs to photocatalysis field, and in particular to a kind of foamed nickel supported g-C3N4Reduced graphene photochemical catalyst
Method.
Background technology
With the development and the acceleration of process of industrialization of modern society, environmental pollution turns into a topic being on the rise.
Wherein, water pollution directly threatens the health and modernization of China resident, also has heavy damage to ecological environment.How
Handle micro Recalcitrant chemicals in water body, it has also become the problem paid close attention to.Since 1970s
Fujishima and Honda are in TiO2Since the photodissociation production hydrogen that water is realized on electrode, photocatalysis technology gradually causes the pass of people
Pollutant in note, water body of being degraded using photocatalysis technology also turns into an effective method.For general semiconductor
Material, when it, which is absorbed to photon energy, is more than or equal to the photon for absorbing threshold value, its valence band can transit to conduction band, and inspire electricity
Son and hole.Electron-hole is extremely unstable, and semiconductor material surface, and point on oxidation or reducing material surface can be reached rapidly
Son, forms the free radicals such as hydroxyl radical free radical, superoxide anion.Free radical is equally extremely unstable, and it has extremely strong oxidisability, can
Some groups of attack contaminant molecule, are allowed to break to form small molecule, and so on, complete the degraded of pollutant.Exist at present
The photochemical catalyst (titanium dioxide, zinc oxide etc.) of industrial application more maturation belongs to wide band gap semiconducter, only can absorb
Ultraviolet light section in sunshine, and this section only accounts for very little ratio in sunshine, therefore limit these catalyst
Photocatalytic activity.
g-C3N4Belong to novel metalloid photochemical catalyst, its energy gap is 2.7eV.By hot soarfing from g-C3N4Block material
Material, can obtain g-C3N4Nanometer sheet, further increases its specific surface area, so as to strengthen its photocatalytic activity.However, preparing at present
G-C3N4Mostly powder body material, haves the shortcomings that to suspend with being not easily recycled in liquid phase photocatalytic system；Preparation technology need to enter
Row repeatedly calcining, it is difficult to the fabricated in situ on matrix, and finished product is poor in solid phase surface tack.
Graphene is the two dimensional surface crystal being made up of carbon atom, with excellent electric conductivity and adsorptivity.Pure graphene
The bad dispersibility in water.After crystalline flake graphite is handled with strong oxidizer, it can be peeled off through ultrasonic disperse, obtain graphene oxide
Dispersion liquid, then it is that can obtain reduced graphene to be handled with reducing agent.
Nickel foam is a kind of metal material with loose structure, because of its larger surface area, stronger mechanical performance with
The cost of relative moderate, is widely used in industrial circle.
The content of the invention
The purpose of the present invention is to be directed to the above-mentioned state of the art, it is desirable to provide a kind of technique is simple, and products therefrom has excellent
Photocatalytic activity with circulation catalytic performance foamed nickel supported carbon nitrogen/reduced graphene photochemical catalyst preparation method.
The implementation of the object of the invention is that the preparation method of foamed nickel supported carbon nitrogen/reduced graphene photochemical catalyst has
Body step is as follows：
1) by 0.1g-0.5g g-C3N4Block is placed in alumina ceramic crucible, with 5 DEG C/min heating in Muffle furnace
Speed is warming up to 520 DEG C, is incubated 2h, subsequent natural cooling, obtain hot soarfing from g-C3N4Nanometer sheet；By 0.5g g-C3N4Nanometer
Piece is placed in 50ml 0.1M-0.5M nitric acid, is taken out after stirring 2h, suction filtration is simultaneously washed with deionized untill pH=7, and
Dried at 50 DEG C；
2) 10ml is taken, concentration is 2mg/ml graphene oxide aqueous dispersions, is adjusted with 1M hydrochloric acid and 1M sodium hydroxide solutions
Section to pH=6-8, take 60mg-220mg steps 1) obtained by g-C3N4Nanometer sheet is placed in graphene oxide aqueous dispersions, ultrasound
1h obtains catalyst precursor g-C3N4/ graphene oxide dispersion；；Wherein, the g-C3N4With the graphite oxide in dispersion liquid
Alkene mass ratio is 1:3-1:11；
3) nickel foam is cut into 25mm*25mm*1mm fritter, respectively with acetone, ethanol, deionized water ultrasonic vibration
5min clean, in 50 DEG C of baking ovens dry after, be placed in step 2) obtained by g-C3N4Submerged in/reduced graphene dispersion liquid
10min, makes suspension in matrix surface Load Balanced by lifting；Take out in 50 DEG C of drying, be then again dipped into, repeat three
It is secondary；It can obtain loading g-C after drying3N4The nickel foam of/graphene oxide；
4) by step 3) obtained by load g-C3N4The nickel foam of/graphene oxide is placed in 50ml concentration for 0.2g/L-4g/L
Reductant solution in, water-bath reduces 1h at 60 DEG C -80 DEG C, takes out, and is washed with deionized water net, spontaneously dries, you can obtain
g-C3N4The nickel foam photochemical catalyst of/reduced graphene load；
The solute of the reductant solution is hydrazine hydrate, ascorbic acid or sodium citrate.
G-C of the present invention based on graphene oxide and acidifying3N4The electrical property difference of nanometer sheet, completes two kinds in the solution and receives
Rice piece it is compound, and form relatively stable dispersion.Nickel foam is porous metal material cheap and easy to get, and nickel foam is soaked
In g-C3N4In/graphene oxide solution dispersion system, g-C can be completed3N4/ graphene oxide foam nickel surface load, and
Using certain reducing solution, reduction of the graphene oxide in foam nickel surface is completed, to remove moieties, strengthens graphite
The electric conductivity of alkene, so as to obtain foamed nickel supported g-C3N4/ reduced graphene photochemical catalyst, under visible light, can catalytic degradation water
Organic pollution in body.
The invention has the advantages that：
1st, using the good absorption property of graphene, the electrical property difference in big specific surface area and solution, in aqueous
Realize g-C3N4With the inclusion of stannic oxide/graphene nano piece, g-C is completed3N4Powder body material is in the negative of solid support surface
Carry；
2nd, using the characteristic of graphene bigger serface, g-C is made3N4In stannic oxide/graphene nano piece, and utilize oxygen
The characteristic of graphite alkene bigger serface, makes g-C3N4/ graphene oxide compound is further spread out being coated on matrix material,
Realize the fixation of powder catalyst；Product surface is more sharp than powder catalyst with one layer of uniform photocatalyst film
In recovery and recycling；
3rd, using graphene excellent adsorptivity and electric conductivity, its adsorption capacity and photoproduction electricity to pollutant is enhanced
Son-hole separating rate, has stronger photocatalysis performance and repetitive cycling catalytic performance in visible ray section.Make pollutant point
Son is easier to absorption in catalyst surface, improves the efficiency of degradation of contaminant.
Gained photochemical catalyst of the invention has wider spectrum respective range, has stronger photocatalysis to live in visible region
Property, it is easy to cut out and reclaim, and be recycled for multiple times repeatability it is stronger, with industrial application value.
Brief description of the drawings
Fig. 1 is the UV-visible absorption spectrum of photochemical catalyst in embodiment 1- examples 4
Fig. 2 a are the XRD spectrogram of photochemical catalyst in embodiment 1- examples 4,
Fig. 2 b are existing g-C in collection of illustrative plates3N4The partial enlarged drawing at peak,
Fig. 3 a-d are respectively the field emission scanning electron microscope figure of photochemical catalyst in embodiment 1-4,
Fig. 4 is embodiment 1-4 photocatalyst for degrading methyl orange performance test figures,
Fig. 5 is the photochemical catalyst reperformance test figure of embodiment 3.
Embodiment
Under certain pH, surface of graphene oxide is negatively charged, by g-C3N4Nanometer sheet is after mineral acid treatment, its surface
Can be positively charged.The present invention utilizes graphene oxide in solution and acidifying g-C3N4Nanometer sheet electrical property difference completes compound；Same time slice
Shape graphene oxide coats g-C3N4Nanometer sheet is simultaneously adsorbed in foam nickel surface, through reduction, dries the more firm photocatalysis of formation
Agent film.
The present invention utilizes g-C3N4With the electrical property difference of graphene oxide, g-C is completed in aqueous3N4Nanometer sheet and oxygen
Graphite alkene it is compound while, using the ultra-slim features and excellent absorption property of grapheme material, by g-C3N4/ oxidation stone
Black alkene complex is adsorbed in the surface of nickel foam, then it is to obtain foamed nickel supported g-C3N4/ reduced graphenes to be handled with reducing agent
Photochemical catalyst.
The present invention is accelerated the separation in light induced electron and hole, is enhanced g-C using the excellent electric conductivity of graphene3N4's
Photocatalytic activity, the foamed nickel supported g-C3N4/ reduced graphenes photochemical catalyst its surface of gained is covered with uniform catalyst film,
Still there is higher photocatalytic activity after being recycled through 4 times.
The present invention is described in detail with specific embodiment below.
Embodiment 1,
1) by 0.1g g-C3N4Block is placed in the common alumina ceramic crucibles of 25ml, with 5 DEG C/min's in Muffle furnace
Heating rate is warming up to 520 DEG C, is incubated 2h, subsequent natural cooling, obtain hot soarfing from g-C3N4Nanometer sheet；By 0.5g g-C3N4
Nanometer sheet is placed in 50ml 0.1M nitric acid, is taken out after stirring 2h, suction filtration is simultaneously washed with deionized untill pH=7, and
Dried at 50 DEG C；
2) 10ml is taken, concentration is 2mg/ml graphene oxide aqueous dispersions, is adjusted with 1M hydrochloric acid and 1M sodium hydroxide solutions
Section to pH=6, take 60mg steps 1) obtained by g-C3N4Nanometer sheet is placed in graphene oxide aqueous dispersions, and ultrasonic 1h is urged
Agent presoma g-C3N4/ graphene oxide dispersion；
3) nickel foam is cut into 25mm*25mm*1mm fritter, respectively with acetone, ethanol, deionized water ultrasonic vibration
5min clean, 50 DEG C drying after, be placed in step 2) obtained by g-C3N410min is submerged in/reduced graphene dispersion liquid, passes through rotation
Turning lifting makes suspension in matrix surface Load Balanced；Take out in 50 DEG C of drying, be then again dipped into, in triplicate；After drying
It can obtain loading g-C3N4The nickel foam of/graphene oxide；
4) by step 3) obtained by load g-C3N4The nickel foam of/graphene oxide is placed in the water that 50ml concentration is 0.2g/L
Close in hydrazine solution, water-bath reduces 1h at 60 DEG C, takes out, net, natural drying, you can obtain g-C is washed with deionized water3N4/ reduction
Graphene-supported nickel foam photochemical catalyst.
Embodiment 2, be the same as Example 1, unlike,
1) by 0.2g g-C3N4Block is placed in the common alumina ceramic crucibles of 25ml, and 520 DEG C are warming up in Muffle furnace,
Be incubated 2h, natural cooling, obtain hot soarfing from g-C3N4Nanometer sheet；By 0.5g g-C3N4Nanometer sheet is placed in 50ml 0.2M nitre
In acid, taken out after stirring 2h, suction filtration is simultaneously washed with deionized untill pH=7, and dried at 50 DEG C；
2) 10ml is taken, concentration is 2mg/ml graphene oxide aqueous dispersions, is adjusted with 1M hydrochloric acid and 1M sodium hydroxide solutions
Section to pH=6.5, take 140mg steps 1) obtained by g-C3N4Nanometer sheet is placed in graphene oxide aqueous dispersions, and ultrasonic 1h is obtained
Catalyst precursor g-C3N4/ graphene oxide dispersion；
3) nickel foam is cut, cleaned respectively with acetone, ethanol, deionized water ultrasonic vibration 5min, after 50 DEG C of drying, put
In step 2) obtained by g-C3N4Submerged in/reduced graphene dispersion liquid, suspension is loaded in matrix surface by rotary pulling
Uniformly；Drying, is again dipped into, in triplicate；It can obtain loading g-C after drying3N4The nickel foam of/graphene oxide；
4) by step 3) obtained by load g-C3N4It is the anti-bad of 2g/L that the nickel foam of/graphene oxide, which is placed in 50ml concentration,
In hematic acid solution, water-bath reduces 1h at 70 DEG C, takes out, and deionized water is cleaned, and spontaneously dries, you can obtain g-C3N4/ reduction stone
The nickel foam photochemical catalyst of black alkene load.
Embodiment 3, be the same as Example 1, unlike,
1) by 0.4g g-C3N4Block is placed in the common alumina ceramic crucibles of 25ml, and 520 DEG C are warming up in Muffle furnace,
Be incubated 2h, natural cooling, obtain hot soarfing from g-C3N4Nanometer sheet；By 0.5g g-C3N4Nanometer sheet is placed in 50ml 0.5M nitre
In acid, taken out after stirring 2h, suction filtration is simultaneously washed with deionized untill pH=7, and dried at 50 DEG C；
2) 10ml is taken, concentration is 2mg/ml graphene oxide aqueous dispersions, is adjusted with 1M hydrochloric acid and 1M sodium hydroxide solutions
Section to pH=7, take 180mg steps 1) obtained by g-C3N4Nanometer sheet is placed in graphene oxide aqueous dispersions, and ultrasonic 1h is urged
Agent presoma g-C3N4/ graphene oxide dispersion；
3) nickel foam is cut, cleaned respectively with acetone, ethanol, deionized water ultrasonic vibration 5min, after 50 DEG C of drying, put
In step 2) obtained by g-C3N4Submerged in/reduced graphene dispersion liquid, suspension is loaded in matrix surface by rotary pulling
Uniformly；Drying, is again dipped into, in triplicate；It can obtain loading g-C after drying3N4The nickel foam of/graphene oxide；
4) by step 3) obtained by load g-C3N4It is the anti-bad of 4g/L that the nickel foam of/graphene oxide, which is placed in 50ml concentration,
In hematic acid solution, water-bath reduces 1h at 70 DEG C, takes out, and deionized water is cleaned, and spontaneously dries, you can obtain g-C3N4/ reduction stone
The nickel foam photochemical catalyst of black alkene load.
Embodiment 4, be the same as Example 1, unlike,
1) by 0.5g g-C3N4Block is placed in the common alumina ceramic crucibles of 25ml, and 520 DEG C are warming up in Muffle furnace,
Be incubated 2h, natural cooling, obtain hot soarfing from g-C3N4Nanometer sheet；By 0.5g g-C3N4Nanometer sheet is placed in 50ml 0.2M nitre
In acid, taken out after stirring 2h, suction filtration is simultaneously washed with deionized untill pH=7, and dried at 50 DEG C；
2) 10ml is taken, concentration is 2mg/ml graphene oxide aqueous dispersions, is adjusted with 1M hydrochloric acid and 1M sodium hydroxide solutions
Section to pH=8, take 220mg steps 1) obtained by g-C3N4Nanometer sheet is placed in graphene oxide aqueous dispersions, and ultrasonic 1h is urged
Agent presoma g-C3N4/ graphene oxide dispersion；
3) nickel foam is cut, cleaned respectively with acetone, ethanol, deionized water ultrasonic vibration 5min, after 50 DEG C of drying, put
In step 2) obtained by g-C3N4Submerged in/reduced graphene dispersion liquid, suspension is loaded in matrix surface by rotary pulling
Uniformly；Drying, is again dipped into, in triplicate；It can obtain loading g-C after drying3N4The nickel foam of/graphene oxide；
4) by step 3) obtained by load g-C3N4The nickel foam of/graphene oxide is placed in the lemon that 50ml concentration is 4g/L
In acid sodium solution, water-bath reduces 1h at 80 DEG C, takes out, and deionized water is cleaned, and spontaneously dries, you can obtain g-C3N4/ reduction stone
The nickel foam photochemical catalyst of black alkene load.
The applicant is to the g-C prepared by embodiment 1-43N4The nickel foam photochemical catalyst of/reduced graphene load has made purple
Outside-visible absorption spectra experiment, as shown in Figure 1, it is seen that at 350-400nm, there is g-C in sample3N4Absworption peak, its
In it is the most obvious with NF-3 and NF-4, be because of its g-C3N4The more reason of content.XRD analysis are carried out to sample, as shown in Fig. 2
Fig. 2 (a) is XRD spectrum of the sample at 5 ° -80 °, it is seen that the absworption peak of more nickel, and this is the absworption peak of matrix material.And Fig. 2
(b) be Fig. 2 (a) close-up schematic view, it is seen that with pure reduced graphene load nickel foam compared with, all samples exist
27.5 ° there is diffraction maximum, this peak and g-C in existing literature3N4002 crystallographic plane diffraction peak it is consistent, it was demonstrated that contain g- in sample
C3N4, and other peaks are the intrinsic diffraction maximum of nickel.Field emission scanning electron microscope analysis is carried out to sample, as shown in Figure 3, it is seen that all
Sample is under 100x multiplication factors, and its surface is all covered with thin film shape structure.With g-C3N4Adding proportion raising
(i.e. according to Fig. 3 (a)-(d) orders), the granular material on its surface also increases further, and this is g-C3N44/ reduced graphene is loaded
Nickel foam photochemical catalyst typical pattern.
The applicant is to the g-C prepared by embodiment 1-43N4The nickel foam photochemical catalyst of/reduced graphene load has made light
Catalytic performance test.Using 300W xenon lamps as light source, 400nm wavelength cut-offs piece control visible region, with to methyl orange (MO)
Degraded.
Method is as follows：One piece of (25mm*25mm*1mm) finished catalyst is placed in 50ml beakers, 20ml 5mg/L are included
Methyl orange aqueous solution.Reaction system is tested in the quartzy photo catalysis reactor with condensation function.Before illumination,
System is placed in camera bellows and reacts 30min, adsorption equilibrium is reached.2ml solution is then taken out, ultraviolet-uisible spectrophotometer is utilized
Concentration determination is carried out, initial concentration is used as using its result.Then turn on light source and be sampled test concentrations every 20min,
Solution is refunded into the error in reaction system to avoid solution loss from causing after being completed.
After wavelength is more than 400nm radiation of visible light 180min, it is seen that all samples have catalysis methyl orange degradation
Effect, its degradation rate is respectively 59.0% (BG-1), 78.6% (BG-2), 96.7% (BG-3) and 91.9% (BG-4) (see figure
4).Illustrate the g-C of the present invention3N4The nickel foam photochemical catalyst of/reduced graphene load has preferable photocatalysis effect, wherein
It is reduced graphene and g-C with BG-33N4Mass ratio is 1:9 photochemical catalyst best results.
The applicant is to the g-C prepared by embodiment 1-43N4The nickel foam photochemical catalyst of/reduced graphene load is weighed
Renaturation is tested, and its result is as shown in Figure 5.
Examined using the NF-3 of embodiment 3 as circulation catalytic performance.Solution after first set reaction is discarded, sample is cleaned
Product, carry out second and test after natural drying, and so on, and four tests, its result are carried out altogether as shown in figure 5, thereafter
In reaction, degradation efficiency is respectively 92.3%, 90.5%, 87.5%.Illustrate g-C prepared by Ordering-the embodiments3N4/ reduced graphene
The nickel foam photochemical catalyst of load, which has, preferably recycles performance.
Claims (2)
1. the preparation method of foamed nickel supported carbon nitrogen/reduced graphene photochemical catalyst, it is characterised in that：Comprise the following steps that：
1) by 0.1g-0.5g g-C3N4Block is placed in alumina ceramic crucible, with 5 DEG C/min heating rate in Muffle furnace
Be warming up to 520 DEG C, be incubated 2h, subsequent natural cooling, obtain hot soarfing from g-C3N4Nanometer sheet；By 0.5g g-C3N4Nanometer sheet is put
In 50ml 0.1M-0.5M nitric acid, taken out after stirring 2h, suction filtration is simultaneously washed with deionized untill pH=7, and 50
Dried at DEG C；
2) take 10ml, concentration is 2mg/ml graphene oxide aqueous dispersions, adjusted with 1M hydrochloric acid and 1M sodium hydroxide solutions to
PH=6-8, takes 60mg-220mg steps 1) obtained by g-C3N4Nanometer sheet is placed in graphene oxide aqueous dispersions, and ultrasonic 1h is obtained
To catalyst precursor g-C3N4/ graphene oxide dispersion；Wherein, the g-C3N4With the graphene oxide matter in dispersion liquid
Amount is than being 1:3-1:11；
3) nickel foam is cut into 25mm*25mm*1mm fritter, respectively with acetone, ethanol, deionized water ultrasonic vibration 5min
Clean, in 50 DEG C of baking ovens dry after, be placed in step 2) obtained by g-C3N410min is submerged in/reduced graphene dispersion liquid, is led to
Crossing lifting makes suspension in matrix surface Load Balanced；Take out in 50 DEG C of drying, be then again dipped into, in triplicate；After drying
It can obtain loading g-C3N4The nickel foam of/graphene oxide；
4) by step 3) obtained by load g-C3N4The nickel foam of/graphene oxide is placed in 50ml concentration going back for 0.2g/L-4g/L
In former agent solution, water-bath reduces 1h at 60 DEG C -80 DEG C, takes out, and net, natural drying, you can obtain g- is washed with deionized water
C3N4The nickel foam photochemical catalyst of/reduced graphene load；
The solute of the reductant solution is hydrazine hydrate, ascorbic acid or sodium citrate.
2. the preparation method and application of foamed nickel supported carbon nitrogen/reduced graphene photochemical catalyst according to claim 1, its
It is characterised by：By 0.1g-0.5g g-C3N4Block is placed in the common alumina ceramic crucibles of 25ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710267045.9A CN107020142B (en) | 2017-04-21 | 2017-04-21 | The preparation method of foamed nickel supported carbon nitrogen/reduced graphene photochemical catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710267045.9A CN107020142B (en) | 2017-04-21 | 2017-04-21 | The preparation method of foamed nickel supported carbon nitrogen/reduced graphene photochemical catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107020142A true CN107020142A (en) | 2017-08-08 |
| CN107020142B CN107020142B (en) | 2019-08-20 |
Family
ID=59528003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710267045.9A Expired - Fee Related CN107020142B (en) | 2017-04-21 | 2017-04-21 | The preparation method of foamed nickel supported carbon nitrogen/reduced graphene photochemical catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107020142B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107597168A (en) * | 2017-11-06 | 2018-01-19 | 西南石油大学 | A kind of catalysis material of visible light-responded load dispersant carbonitride and preparation method and application |
| CN107876078A (en) * | 2017-11-06 | 2018-04-06 | 西南石油大学 | A kind of graphene, TiO2Catalysis material of carbonitride load nickel foam and preparation method and application |
| CN108579786A (en) * | 2018-04-24 | 2018-09-28 | 辽宁师范大学 | Fe3O4@g-C3N4/ RGO composite photo-catalysts and preparation method |
| CN109453610A (en) * | 2018-10-30 | 2019-03-12 | 湖北工业大学 | A kind of air purifier making full use of sunlight |
| CN109701582A (en) * | 2019-02-19 | 2019-05-03 | 上海师范大学 | A kind of foam-like visible light catalytic material, preparation method and its usage |
| CN110148713A (en) * | 2018-02-12 | 2019-08-20 | 澳门大学 | A kind of carbon-coated richness nitrogen g-C3N4 and negative electrode material and preparation method thereof |
| CN110538672A (en) * | 2019-07-25 | 2019-12-06 | 广东工业大学 | Composite visible light response photocatalyst material and preparation method and application thereof |
| CN110694664A (en) * | 2019-10-22 | 2020-01-17 | 邢台学院 | Preparation method and application of graphite-phase carbon nitride/graphene composite photocatalyst |
| CN113856757A (en) * | 2021-11-04 | 2021-12-31 | 广东工业大学 | Polydopamine-modified carbon nitride/titanium dioxide-loaded foam nickel composite photocatalyst and preparation method and application thereof |
| CN114988515A (en) * | 2022-04-21 | 2022-09-02 | 南京林业大学 | Method for removing Cr (VI) and g-C adopted by same 3 N 4 Composite foam/cellulose/GO |
| CN115121274A (en) * | 2022-05-20 | 2022-09-30 | 湖南大学 | Palladium-modified carbon nitrogen compound-loaded foam metal visible-light-induced photocatalyst and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266774A (en) * | 2011-06-07 | 2011-12-07 | 广东工业大学 | Semiconductor nano photocatalysis material and preparation method thereof |
-
2017
- 2017-04-21 CN CN201710267045.9A patent/CN107020142B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266774A (en) * | 2011-06-07 | 2011-12-07 | 广东工业大学 | Semiconductor nano photocatalysis material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| WEE-JUN ONG, ET AL.: "Surface charge modification via photonation of graphitic carbon nitride (g-C3N4) for electrostatic self-assembly construction of 2D/2D reduced graphene oxide (rGO)/g-C3N4 nanostructures toward enhanced photocatalytic reduction of carbon dioxide to methane", 《NANO ENERGY》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107876078A (en) * | 2017-11-06 | 2018-04-06 | 西南石油大学 | A kind of graphene, TiO2Catalysis material of carbonitride load nickel foam and preparation method and application |
| CN107597168A (en) * | 2017-11-06 | 2018-01-19 | 西南石油大学 | A kind of catalysis material of visible light-responded load dispersant carbonitride and preparation method and application |
| CN110148713B (en) * | 2018-02-12 | 2021-02-05 | 澳门大学 | Carbon-coated nitrogen-rich g-C3N4And anode material and preparation method thereof |
| CN110148713A (en) * | 2018-02-12 | 2019-08-20 | 澳门大学 | A kind of carbon-coated richness nitrogen g-C3N4 and negative electrode material and preparation method thereof |
| CN108579786B (en) * | 2018-04-24 | 2020-10-13 | 辽宁师范大学 | Fe3O4@g-C3N4/RGO composite photocatalyst and preparation method thereof |
| CN108579786A (en) * | 2018-04-24 | 2018-09-28 | 辽宁师范大学 | Fe3O4@g-C3N4/ RGO composite photo-catalysts and preparation method |
| CN109453610A (en) * | 2018-10-30 | 2019-03-12 | 湖北工业大学 | A kind of air purifier making full use of sunlight |
| CN109701582A (en) * | 2019-02-19 | 2019-05-03 | 上海师范大学 | A kind of foam-like visible light catalytic material, preparation method and its usage |
| CN109701582B (en) * | 2019-02-19 | 2021-08-27 | 上海师范大学 | Foamed visible light catalytic material, preparation method and application thereof |
| CN110538672A (en) * | 2019-07-25 | 2019-12-06 | 广东工业大学 | Composite visible light response photocatalyst material and preparation method and application thereof |
| CN110694664A (en) * | 2019-10-22 | 2020-01-17 | 邢台学院 | Preparation method and application of graphite-phase carbon nitride/graphene composite photocatalyst |
| CN113856757A (en) * | 2021-11-04 | 2021-12-31 | 广东工业大学 | Polydopamine-modified carbon nitride/titanium dioxide-loaded foam nickel composite photocatalyst and preparation method and application thereof |
| CN113856757B (en) * | 2021-11-04 | 2023-08-22 | 广东工业大学 | Polydopamine modified carbon nitride/titanium dioxide supported foam nickel composite photocatalyst and preparation method and application thereof |
| CN114988515A (en) * | 2022-04-21 | 2022-09-02 | 南京林业大学 | Method for removing Cr (VI) and g-C adopted by same 3 N 4 Composite foam/cellulose/GO |
| CN115121274A (en) * | 2022-05-20 | 2022-09-30 | 湖南大学 | Palladium-modified carbon nitrogen compound-loaded foam metal visible-light-induced photocatalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107020142B (en) | 2019-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107020142B (en) | The preparation method of foamed nickel supported carbon nitrogen/reduced graphene photochemical catalyst | |
| Li et al. | Insight into photocatalytic activity, universality and mechanism of copper/chlorine surface dual-doped graphitic carbon nitride for degrading various organic pollutants in water | |
| Jiang et al. | Novel ternary BiOI/g-C3N4/CeO2 catalysts for enhanced photocatalytic degradation of tetracycline under visible-light radiation via double charge transfer process | |
| Jiang et al. | Constructing graphite-like carbon nitride modified hierarchical yolk–shell TiO 2 spheres for water pollution treatment and hydrogen production | |
| Momeni et al. | Preparation of TiO2 and WO3–TiO2 nanotubes decorated with PbO nanoparticles by chemical bath deposition process: a stable and efficient photo catalyst | |
| Yang et al. | Preparation and enhanced visible-light photocatalytic activity of silver deposited graphitic carbon nitride plasmonic photocatalyst | |
| Zhang et al. | Fly ash cenospheres supported visible-light-driven BiVO4 photocatalyst: synthesis, characterization and photocatalytic application | |
| Kim et al. | Application of a photostable silver-assisted Z-scheme NiTiO3 nanorod/g-C3N4 nanocomposite for efficient hydrogen generation | |
| Hu et al. | Simple synthesis of 3D flower-like g-C3N4/TiO2 composite microspheres for enhanced visible-light photocatalytic activity | |
| Wu et al. | Band-gap tailoring and visible-light-driven photocatalytic performance of porous (GaN) 1− x (ZnO) x solid solution | |
| Liu et al. | Fabrication of highly efficient heterostructured Ag-CeO2/g-C3N4 hybrid photocatalyst with enhanced visible-light photocatalytic activity | |
| CN103506141A (en) | Method for preparing visible light photocatalytic material and application thereof | |
| CN103949234A (en) | Preparation method of boron-doped graphene/TiO2 nanorod photocatalytic material | |
| Liao et al. | A novel g-C3N4/BiOI/Ag2WO4 heterojunction for efficient degradation of organic pollutants under visible light irradiation | |
| CN101966989B (en) | Method for realizing photocatalytic reduction of graphene oxide by quadrangular zinc oxide | |
| CN113262808A (en) | Water-soluble graphite-phase carbon nitride nanosheet catalyst for efficiently removing formaldehyde at room temperature and preparation method thereof | |
| CN108654607A (en) | The preparation method of silver nano-grain/carbon/nano titania compound of nucleocapsid | |
| Liu et al. | S-scheme heterojunction ZnO/g-C3N4 shielding polyester fiber composites for the degradation of MB | |
| Zhu et al. | Fabrication of noble-metal-free NiS 2/gC 3 N 4 hybrid photocatalysts with visible light-responsive photocatalytic activities | |
| Liu et al. | Construction of ternary hollow TiO2-ZnS@ ZnO heterostructure with enhanced visible-light photoactivity | |
| CN104801308A (en) | NiFe2O4/TiO2/sepiolite composite photocatalyst and preparation method thereof | |
| CN107598150B (en) | A kind of nano metal/red phosphorus composite material and preparation method | |
| Gu et al. | Construction of dual Z-scheme UNiMOF/BiVO4/S-C3N4 photocatalyst for visible-light photocatalytic tetracycline degradation and Cr (VI) reduction | |
| Fan et al. | Preparation of g-C3N4/MoS2 composite material and its visible light catalytic performance | |
| Hu et al. | Heterojunction Cu 2 O/RGO/BiVO 4 ternary nanocomposites with enhanced photocatalytic activities towards degradation of rhodamine B and tetracycline hydrochloride |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190820 |