CN107020142B - 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
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- CN107020142B CN107020142B CN201710267045.9A CN201710267045A CN107020142B CN 107020142 B CN107020142 B CN 107020142B CN 201710267045 A CN201710267045 A CN 201710267045A CN 107020142 B CN107020142 B CN 107020142B
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- 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 84
- 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 10
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000006260 foam Substances 0.000 claims abstract description 39
- 239000006185 dispersion Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 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 12
- 239000007788 liquid Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000003756 stirring 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
- 239000004575 stone 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
- 238000007254 oxidation reaction 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
- 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 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000002957 persistent organic pollutant Substances 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 10
- 238000007146 photocatalysis Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 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
- 238000012360 testing method Methods 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
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process 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
- 238000010586 diagram Methods 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
- 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
- 238000004064 recycling Methods 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
- 239000000126 substance Substances 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis 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
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 230000006378 damage 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
- 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
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000005855 radiation Effects 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
- 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 calcined to obtain g-C3N4Nanometer sheet is acidified in 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 cleans, dries, and is placed in g-C3N4It is submerged in/graphene oxide dispersion, realizes that the load of catalyst so in triplicate must load g-C3N4The nickel foam of/graphene oxide；By it in reducing agent solution heating water bath, dry to obtain load g-C3N4The nickel foam of/reduced graphene.The present invention realizes g-C3N4In the load of solid support surface, firm binding force, products obtained therefrom under visible light section, can organic pollutant in catalytic degradation water body, and there is good cycle performance.
Description
Technical field
The invention belongs to photocatalysis fields, and in particular to a kind of foamed nickel supported g-C3N4Reduced graphene photochemical catalyst
Method.
Background technique
With the development of modern society and the acceleration of process of industrialization, environmental pollution becomes a topic being on the rise.
Wherein, water pollution directly threatens the health and modernization of China resident, also has serious destruction to ecological environment.How
Handle Recalcitrant chemicals micro in water body, it has also become a project paid close attention to.Since the 1970s
Fujishima and Honda are in TiO2Since realizing that the photodissociation of water produces hydrogen on electrode, photocatalysis technology gradually causes the pass of people
Note also becomes an effective method using the pollutant in photocatalysis technology degradation water body.For general semiconductor
Material, when it, which is absorbed into photon energy, is more than or equal to the photon for absorbing threshold value, valence band can transit to conduction band, and inspire electricity
Son and hole.Electron-hole is extremely unstable, can reach semiconductor material surface, and point on oxidation or reducing material surface rapidly
Son forms the free radicals such as hydroxyl radical free radical, superoxide anion.Free radical is equally extremely unstable, can with extremely strong oxidisability
Certain groups of attack contaminant molecule are allowed to break to form small molecule, and so on, complete the degradation of pollutant.Exist at present
The more mature photochemical catalyst of industrial application (titanium dioxide, zinc oxide etc.) belongs to wide band gap semiconducter, only can absorb
Ultraviolet light section in sunlight, and this section only accounts for very little ratio in sunlight, therefore limits these catalyst
Photocatalytic activity.
g-C3N4Belong to novel metalloid photochemical catalyst, forbidden bandwidth 2.7eV.By hot soarfing from g-C3N4Block material
Material, can be obtained g-C3N4Nanometer sheet further increases its specific surface area, to enhance its photocatalytic activity.However, preparation at present
G-C3N4Mostly powder body material, there is suspend with being not easily recycled in liquid phase photocatalytic system；Preparation process need to be into
Row repeatedly calcining, it is difficult to the fabricated in situ on matrix, and finished product is poor in solid phase surface adhesion.
Graphene is the two-dimensional surface crystal being made of carbon atom, has excellent electric conductivity and adsorptivity.Pure graphene
Bad dispersibility in water.After crystalline flake graphite is handled with strong oxidizer, it can be removed through ultrasonic disperse, obtain graphene oxide
Dispersion liquid, then handled with reducing agent and reduced graphene can be obtained.
Nickel foam is a kind of metal material with porous structure, because of its biggish surface area, stronger mechanical performance with
The cost of relative moderate, is widely used in industrial circle.
Summary of the invention
The purpose of the present invention is statuses in view of the above technology, it is desirable to provide a kind of simple process, products therefrom have excellent
Photocatalytic activity and circulation catalytic performance foamed nickel supported carbon nitrogen/reduced graphene photochemical catalyst preparation method.
The implementation of the object of the invention is the preparation method of foamed nickel supported carbon nitrogen/reduced graphene photochemical catalyst, tool
Steps are as follows for body:
1) by 0.1g-0.5g g-C3N4Block is placed in alumina ceramic crucible, with the heating of 5 DEG C/min in Muffle furnace
Rate is warming up to 520 DEG C, keeps the temperature 2h, subsequent natural cooling, obtain hot soarfing from g-C3N4Nanometer sheet；By 0.5g g-C3N4Nanometer
Piece is placed in the nitric acid of 50ml 0.1M-0.5M, is taken out after stirring 2h, is filtered and be washed with deionized until pH=7, and
It is dried at 50 DEG C；
2) 10ml is taken, concentration is the graphene oxide aqueous dispersions of 2mg/ml, with 1M hydrochloric acid and 1M sodium hydroxide solution tune
Section takes the resulting g-C of 60mg-220mg step 1) to pH=6-83N4Nanometer 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 the fritter of 25mm*25mm*1mm, uses acetone, ethyl alcohol, deionized water ultrasonic vibration respectively
5min is cleaned, and after drying in 50 DEG C of baking ovens, is placed in the resulting g-C of step 2)3N4It is submerged in/reduced graphene dispersion liquid
10min makes suspension in matrix surface Load Balanced by lifting；It takes out and is dried in 50 DEG C, is then again dipped into, repeat three
It is secondary；Load g-C can be obtained after drying3N4The nickel foam of/graphene oxide；
4) by the resulting load g-C of step 3)3N4It is 0.2g/L-4g/L that the nickel foam of/graphene oxide, which is placed in 50ml concentration,
Reducing agent solution in, at 60 DEG C -80 DEG C water-bath restore 1h, take out, be washed with deionized water, spontaneously dry, can be obtained
g-C3N4The nickel foam photochemical catalyst of/reduced graphene load；
The solute of the reducing agent solution is hydrazine hydrate, ascorbic acid or sodium citrate.
The present invention is based on the g-C of graphene oxide and acidification3N4The electrical property difference of nanometer sheet is completed two kinds in the solution and is received
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, achievable g-C3N4/ graphene oxide foam nickel surface load, and
Using certain reducing solution, completing graphene oxide in the reduction of foam nickel surface enhances graphite to remove moieties
The electric conductivity of alkene, to obtain foamed nickel supported g-C3N4/ reduced graphene photochemical catalyst under visible light can catalytic degradation water
Organic pollutant in body.
The present invention has the following advantages:
1, using the good absorption property of graphene, electrical property difference in big specific surface area and solution, in aqueous solution
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
It carries；
2, using the characteristic of graphene bigger serface, make g-C3N4In stannic oxide/graphene nano piece, and utilize oxygen
The characteristic of graphite alkene bigger serface, makes g-C3N4/ graphene oxide compound, which is further spread out, to be coated on basis material,
Realize the fixation of powder catalyst；Product surface has one layer of uniform photocatalyst film, more sharp compared with powder catalyst
In recycling and it is recycled；
3, the adsorptivity and electric conductivity excellent using graphene enhance it to the adsorption capacity of pollutant and photoproduction electricity
Son-hole separating rate has stronger photocatalysis performance and repetitive cycling catalytic performance in visible light section.Make pollutant point
Son is easier to be adsorbed on catalyst surface, improves the efficiency of degradation of contaminant.
Gained photochemical catalyst of the invention has wider spectrum respective range, has stronger photocatalysis living in visible light region
Property, be easy to cut out and recycle, and be recycled for multiple times repeatability it is stronger, have industrial application value.
Detailed description of the invention
Fig. 1 is the UV-visible absorption spectrum of photochemical catalyst in embodiment 1- example 4
Fig. 2 a is the XRD diagram spectrogram of photochemical catalyst in embodiment 1- example 4,
Fig. 2 b is existing g-C in map3N4The partial enlarged view at peak,
Fig. 3 a-d is 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 figure,
Fig. 5 is 3 photochemical catalyst reperformance test figure of embodiment.
Specific embodiment
Under certain pH, surface of graphene oxide is negatively charged, by g-C3N4Nanometer sheet is after mineral acid treatment, surface
It can be positively charged.The present invention utilizes graphene oxide in solution and acidification g-C3N4Nanometer sheet electrical property difference is completed compound；Same time slice
Shape graphene oxide coats g-C3N4Nanometer sheet is simultaneously adsorbed in foam nickel surface, is restored, dries to form relatively firm photocatalysis
Agent film.
The present invention utilizes g-C3N4With the electrical property difference of graphene oxide, g-C is completed in aqueous solution3N4Nanometer 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 is handled with reducing agent and obtain foamed nickel supported g-C3N4/ reduced graphene
Photochemical catalyst.
The present invention electric conductivity excellent using graphene, accelerates the separation in light induced electron and hole, enhances g-C3N4's
Photocatalytic activity, the foamed nickel supported g-C3N4/ reduced graphene photochemical catalyst surface of gained are covered with uniform catalyst film,
The photocatalytic activity still with higher after 4 times are recycled.
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 crucible of 25ml, with 5 DEG C/min's in Muffle furnace
Heating rate is warming up to 520 DEG C, keeps the temperature 2h, subsequent natural cooling, obtain hot soarfing from g-C3N4Nanometer sheet；By 0.5g g-C3N4
Nanometer sheet is placed in the nitric acid of 50ml 0.1M, is taken out after stirring 2h, is filtered and be washed with deionized until pH=7, and
It is dried at 50 DEG C；
2) 10ml is taken, concentration is the graphene oxide aqueous dispersions of 2mg/ml, with 1M hydrochloric acid and 1M sodium hydroxide solution tune
Section takes the resulting g-C of 60mg step 1) to pH=63N4Nanometer 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 the fritter of 25mm*25mm*1mm, uses acetone, ethyl alcohol, deionized water ultrasonic vibration respectively
5min is cleaned, and after 50 DEG C of drying, is placed in the resulting g-C of step 2)3N410min is submerged in/reduced graphene dispersion liquid, passes through rotation
Turning lifting makes suspension in matrix surface Load Balanced；It takes out and is dried in 50 DEG C, is then again dipped into, in triplicate；After drying
Load g-C can be obtained3N4The nickel foam of/graphene oxide；
4) by the resulting load g-C of step 3)3N4The nickel foam of/graphene oxide is placed in the water that 50ml concentration is 0.2g/L
It closes in hydrazine solution, water-bath restores 1h at 60 DEG C, takes out, is washed with deionized water, and spontaneously dries, g-C can be obtained3N4/ reduction
Graphene-supported nickel foam photochemical catalyst.
Embodiment 2, with embodiment 1, unlike,
1) by 0.2g g-C3N4Block is placed in the common alumina ceramic crucible of 25ml, and 520 DEG C are warming up in Muffle furnace,
Keep the temperature 2h, natural cooling, obtain hot soarfing from g-C3N4Nanometer sheet；By 0.5g g-C3N4Nanometer sheet is placed in the nitre of 50ml 0.2M
In acid, is taken out after stirring 2h, filter and be washed with deionized until pH=7, and dried at 50 DEG C；
2) 10ml is taken, concentration is the graphene oxide aqueous dispersions of 2mg/ml, with 1M hydrochloric acid and 1M sodium hydroxide solution tune
Section takes the resulting g-C of 140mg step 1) to pH=6.53N4Nanometer 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, is cleaned respectively with acetone, ethyl alcohol, deionized water ultrasonic vibration 5min, after 50 DEG C of drying, set
In the resulting g-C of step 2)3N4It is submerged in/reduced graphene dispersion liquid, loads suspension in matrix surface by rotary pulling
Uniformly；Drying, is again dipped into, in triplicate；Load g-C can be obtained after drying3N4The nickel foam of/graphene oxide；
4) by the resulting load g-C of step 3)3N4It 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 restores 1h at 70 DEG C, takes out, and deionized water is cleaned, and spontaneously dries, g-C can be obtained3N4/ reduction stone
The nickel foam photochemical catalyst of black alkene load.
Embodiment 3, with embodiment 1, unlike,
1) by 0.4g g-C3N4Block is placed in the common alumina ceramic crucible of 25ml, and 520 DEG C are warming up in Muffle furnace,
Keep the temperature 2h, natural cooling, obtain hot soarfing from g-C3N4Nanometer sheet；By 0.5g g-C3N4Nanometer sheet is placed in the nitre of 50ml 0.5M
In acid, is taken out after stirring 2h, filter and be washed with deionized until pH=7, and dried at 50 DEG C；
2) 10ml is taken, concentration is the graphene oxide aqueous dispersions of 2mg/ml, with 1M hydrochloric acid and 1M sodium hydroxide solution tune
Section takes the resulting g-C of 180mg step 1) to pH=73N4Nanometer 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, is cleaned respectively with acetone, ethyl alcohol, deionized water ultrasonic vibration 5min, after 50 DEG C of drying, set
In the resulting g-C of step 2)3N4It is submerged in/reduced graphene dispersion liquid, loads suspension in matrix surface by rotary pulling
Uniformly；Drying, is again dipped into, in triplicate；Load g-C can be obtained after drying3N4The nickel foam of/graphene oxide；
4) by the resulting load g-C of step 3)3N4It 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 restores 1h at 70 DEG C, takes out, and deionized water is cleaned, and spontaneously dries, g-C can be obtained3N4/ reduction stone
The nickel foam photochemical catalyst of black alkene load.
Embodiment 4, with embodiment 1, unlike,
1) by 0.5g g-C3N4Block is placed in the common alumina ceramic crucible of 25ml, and 520 DEG C are warming up in Muffle furnace,
Keep the temperature 2h, natural cooling, obtain hot soarfing from g-C3N4Nanometer sheet；By 0.5g g-C3N4Nanometer sheet is placed in the nitre of 50ml 0.2M
In acid, is taken out after stirring 2h, filter and be washed with deionized until pH=7, and dried at 50 DEG C；
2) 10ml is taken, concentration is the graphene oxide aqueous dispersions of 2mg/ml, with 1M hydrochloric acid and 1M sodium hydroxide solution tune
Section takes the resulting g-C of 220mg step 1) to pH=83N4Nanometer 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, is cleaned respectively with acetone, ethyl alcohol, deionized water ultrasonic vibration 5min, after 50 DEG C of drying, set
In the resulting g-C of step 2)3N4It is submerged in/reduced graphene dispersion liquid, loads suspension in matrix surface by rotary pulling
Uniformly；Drying, is again dipped into, in triplicate；Load g-C can be obtained after drying3N4The nickel foam of/graphene oxide；
4) by the resulting load g-C of step 3)3N4The nickel foam of/graphene oxide is placed in the lemon that 50ml concentration is 4g/L
In acid sodium solution, water-bath restores 1h at 80 DEG C, takes out, and deionized water is cleaned, and spontaneously dries, g-C can be obtained3N4/ reduction stone
The nickel foam photochemical catalyst of black alkene load.
The applicant is to 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 are g-C for sample3N4Absorption peak,
In it is the most obvious with NF-4 with NF-3, be because of its g-C3N4The more reason of content.XRD analysis is 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 absorption peak of more nickel, this is the absorption peak of basis material.And Fig. 2
(b) be Fig. 2 (a) partial enlargement diagram, it is seen that with pure reduced graphene load nickel foam compared with, all samples exist
27.5 ° there is diffraction maximum, g-C in this peak and 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
For sample under 100x amplification factor, surface is all covered with thin film shape structure.With g-C3N4Adding proportion raising
(i.e. according to Fig. 3 (a)-(d) sequence), the granular substance on surface also increases further, this i.e. g-C3N44The load of/reduced graphene
Nickel foam photochemical catalyst typical pattern.
The applicant is to g-C prepared by embodiment 1-43N4The nickel foam photochemical catalyst of/reduced graphene load has made light
Catalytic performance test.Using 300W xenon lamp as light source, 400nm wavelength cut-off piece controls visible light region, with to methyl orange (MO)
It degrades.
Method is as follows: one piece of (25mm*25mm*1mm) finished catalyst being placed in 50ml beaker, 20ml 5mg/L is 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, reaches adsorption equilibrium.2ml solution is then taken out, ultraviolet-uisible spectrophotometer is utilized
Concentration determination is carried out, using its result as initial concentration.It then turns on light source and is sampled test concentrations every 20min,
Solution is refunded in reaction system to avoid error caused by solution loss after being completed.
After radiation of visible light 180min of the wavelength greater than 400nm, it is seen that all samples have catalysis methyl orange degradation
Effect, degradation rate are respectively 59.0% (BG-1), 78.6% (BG-2), 96.7% (BG-3) and 91.9% (BG-4) (see figure
4).Illustrate g-C of the invention3N4The nickel foam photochemical catalyst of/reduced graphene load has preferable photocatalysis effect, wherein
With BG-3, that is, reduced graphene and g-C3N4Mass ratio is that the photochemical catalyst effect of 1:9 is best.
The applicant is to g-C prepared by embodiment 1-43N4The nickel foam photochemical catalyst of/reduced graphene load weighs
Renaturation test, result are as shown in Figure 5.
It is 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, carry out four tests altogether, and result is as shown in figure 5, hereafter
In reaction, degradation efficiency is respectively 92.3%, 90.5%, 87.5%.Illustrate the g-C of Ordering-the embodiment preparation3N4/ reduced graphene
The nickel foam photochemical catalyst of load has preferable recycling performance.
Claims (2)
1. a kind of foamed nickel supported g-C3N4The preparation method of/reduced graphene photochemical catalyst, it is characterised in that: specific steps are such as
Under:
1) by 0.1g-0.5g g-C3N4Block is placed in alumina ceramic crucible, with the heating rate of 5 DEG C/min in Muffle furnace
Be warming up to 520 DEG C, keep the temperature 2h, subsequent natural cooling, obtain hot soarfing from g-C3N4Nanometer sheet；By 0.5g g-C3N4Nanometer sheet is set
In the nitric acid of 50ml0.1M-0.5M, is taken out after stirring 2h, filter and be washed with deionized until pH=7, and at 50 DEG C
Lower drying；
2) 10ml is taken, concentration is the graphene oxide aqueous dispersions of 2mg/ml, is adjusted to 1M hydrochloric acid and 1M sodium hydroxide solution
PH=6-8 takes the resulting g-C of 60mg-220mg step 1)3N4Nanometer sheet is placed in graphene oxide aqueous dispersions, and ultrasonic 1h is obtained
To catalyst precursor g-C3N4/ graphene oxide dispersion；Wherein, the g-C3N4Oxidation stone in nanometer sheet and dispersion liquid
Black alkene mass ratio is 1:3-1:11；
3) nickel foam is cut into the fritter of 25mm*25mm*1mm, uses acetone, ethyl alcohol, deionized water ultrasonic vibration 5min respectively
It cleans, after drying in 50 DEG C of baking ovens, is placed in the resulting g-C of step 2)3N410min is submerged in/graphene oxide dispersion, is led to
Crossing lifting makes suspension in matrix surface Load Balanced；It takes out and is dried in 50 DEG C, is then again dipped into, in triplicate；Drying
After foamed nickel supported g-C can be obtained3N4/ graphene oxide；
4) by the resulting foamed nickel supported g-C of step 3)3N4/ graphene oxide is placed in the reduction that 50ml concentration is 0.2g/L-4g/L
In agent solution, water-bath restores 1h at 60 DEG C -80 DEG C, takes out, is washed with deionized water, and spontaneously dries, nickel foam can be obtained
Load g-C3N4/ reduced graphene photochemical catalyst；
The solute of the reducing agent solution is hydrazine hydrate, ascorbic acid or sodium citrate.
2. a kind of foamed nickel supported g-C according to claim 13N4The preparation method of/reduced graphene photochemical catalyst,
It is characterized in that: by 0.1g-0.5g g-C3N4Block is placed in the common alumina ceramic crucible of 25ml.
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| 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 |
| CN110148713B (en) * | 2018-02-12 | 2021-02-05 | 澳门大学 | Carbon-coated nitrogen-rich g-C3N4And anode 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 |
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| 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 |
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