CN106861732A - A kind of boron nickel titanium dioxide/nitridation carbon composite photocatalyst, and application thereof and preparation method - Google Patents
A kind of boron nickel titanium dioxide/nitridation carbon composite photocatalyst, and application thereof and preparation method Download PDFInfo
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- CN106861732A CN106861732A CN201710055783.7A CN201710055783A CN106861732A CN 106861732 A CN106861732 A CN 106861732A CN 201710055783 A CN201710055783 A CN 201710055783A CN 106861732 A CN106861732 A CN 106861732A
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- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 title description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title description 3
- XRPIYRHZVDSLQE-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].[Ni+2].[B+3] Chemical compound [O-2].[O-2].[Ti+4].[Ni+2].[B+3] XRPIYRHZVDSLQE-UHFFFAOYSA-N 0.000 title description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims description 32
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229960005091 chloramphenicol Drugs 0.000 claims description 12
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims description 7
- 230000000593 degrading effect Effects 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 238000012546 transfer Methods 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001055 reflectance spectroscopy Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
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- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
The present invention relates to a kind of B Ni TiO2/g‑C3N4Composite photo-catalyst, and application thereof and preparation method.The present invention builds a composite visible light photocatalytic system.Strengthen its absorbability to visible ray by forming heterojunction structure, improve photocatalytic activity of the photochemical catalyst in visible region.Photochemical catalyst after compound can promote electro transfer, suppress electronics and hole to being combined, and improve photochemical catalyst in visible region absorbability and photocatalytic activity.
Description
Technical field
The present invention relates to a kind of photochemical catalyst, and in particular to the composite photo-catalyst and its use of a kind of degradable antibiotic
Way and preparation method.
Background technology
TiO2Because with good chemical stability, abrasion resistance, the advantages of inexpensive and by research extensively and profoundly.
However, TiO2With energy gap (3.0 to 3.2eV) higher, thus its can only absorbing wavelength less than 387.5nm sunshine,
3% to 5% up to the solar energy of the earth can only be so used, and the visible ray for accounting for energy 43% is not used.This
Outward, TiO2The recombination rate of middle light induced electron and photohole is relatively large, reduces the quantum efficiency in light-catalyzed reaction, causes
Reduce photocatalysis efficiency.
In order to further improve TiO2Photocatalytic activity, reduces the recombination rate in its photoelectron-hole, by changing
Property or doping other elements and compound different semiconductors improve its utilization rate to visible ray, reach enhancing TiO2Light
Catalysis activity.
Although having been disclosed for some in existing document to TiO2Linguistic term, to overcome this material to exist not
Foot, but property of the material after this improvement in terms of stability, Degradation of Antibiotics still has much room for improvement.
The content of the invention
The main object of the present invention is to provide one kind has catalysis activity in visible region, stable in properties, in antibiosis
The photochemical catalyst of plain degraded aspect good properties.
In order to complete above-mentioned purpose, the invention provides a kind of composite photo-catalyst, the composite photo-catalyst is B-Ni-
TiO2/g-C3N4 composite photo-catalysts.
Such scheme has the beneficial effect that：The present invention builds a composite visible light photocatalytic system.It is heterogeneous by being formed
Junction structure strengthens its absorbability to visible ray, improves photocatalytic activity of the photochemical catalyst in visible region.After compound
Photochemical catalyst can promote electro transfer, suppress electronics and hole to be combined, improve photochemical catalyst in visible region absorption
Ability and photocatalytic activity.
One preferred scheme is, composite photo-catalyst as chloramphenicol degrading purposes.
A kind of B-Ni-TiO2/g-C3N4The preparation method of composite photo-catalyst, is carried out according to the following steps：
Step (1):The butyl titanate and absolute ethyl alcohol of measured amounts are well mixed respectively is made A liquid；It is another to take necessarily
The absolute ethyl alcohol of amount, concentrated hydrochloric acid solution, deionized water, boric acid and six water nickel nitrates are sufficiently mixed uniformly, obtain B liquid；By the transfer of A liquid
To magnetic stirring apparatus, stirred under 35 DEG C to 45 DEG C water baths, after after A liquid stirring certain hour, B liquid is slowly instilled into A liquid
In；After completion of dropping, continue magnetic agitation, until solution is into gel；Done after the gel is placed in into thermostatic drying chamber drying
Gel, by the xerogel grind into powder, then is placed on calcining in Muffle furnace, and B-Ni-TiO is obtained2Photochemical catalyst；
Step (2)：Weigh a certain amount of melamine to be put into crucible with cover, then heated in Muffle furnace, one
Determine temperature lower calcination, be cooled to room temperature, g-C is obtained after flaxen solid is milled3N4Photochemical catalyst；
Step (3)：The g-C that will be prepared3N4And B-Ni-TiO2It is added in absolute ethyl alcohol according to different proportion, with heating back
The method of stream is combined；The temperature of heating is generally 80 DEG C to 100 DEG C, and backflow refers to absolute ethyl alcohol evaporative condenser after the heating
After be back in reaction bulb, magnetic stirring structure is provided with reaction bulb, for example with magnetic stirring apparatus；Product after centrifugation is placed on
Dried in drying box and B-Ni-TiO is obtained2/g-C3N4Composite photo-catalyst.
Such scheme produce technique effect be：Using the reactions steps, with reference to B-Ni-TiO2And g-C3N4It is respective excellent
Gesture, B-Ni-TiO is prepared using sol-gel process and calcination method respectively2And g-C3N4Photochemical catalyst, then by being heated to reflux legal system
Standby B-Ni-TiO2/g-C3N4Composite photo-catalyst, the TiO after doping2The light abstraction width of photochemical catalyst is extended to visible region,
Photochemical catalyst after compound can prevent electron-hole recombination rate, be conducive to improving its photocatalytic activity under visible light.
One preferred scheme is that boric acid, six water nickel nitrates and the butyl titanate molar ratio added in step (1) are
1：0.9-1.1：9-11, the temperature conditionss of Muffle furnace are 500 DEG C to 550 DEG C.
One preferred scheme is that the time calcined described in step (2) is 3 hours to 5 hours；Calcining heat is 550
DEG C to 600 DEG C.
One preferred scheme is in step (3), to be heated to reflux using water-bath mode, bath temperature be 70 DEG C extremely
90 DEG C, the reaction time is 6 hours to 8 hours, obtained B-Ni-TiO2/g-C3N4G-C in composite photo-catalyst3N4And B-Ni-
TiO2Molar ratio be 1：10 to 40：10.
Such scheme has the beneficial effect that, under equal conditions, during using the program, the B-Ni-TiO that obtains2/g-C3N4
The property of composite photo-catalyst is most stable, the efficiency highest of chloramphenicol degrading.
Brief description of the drawings
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
Fig. 1 is the g-C of the embodiment of the present invention 13N4、B-Ni-TiO2And B-Ni-TiO2/g-C3N4The XRD of composite photo-catalyst
Figure.
Fig. 2 is the g-C of the embodiment of the present invention 13N4(Fig. 2 a) and B-Ni-TiO2/g-C3N4Composite photo-catalyst (Fig. 2 b)
TEM schemes.
Fig. 3 is the g-C of the embodiment of the present invention 13N4、B-Ni-TiO2And B-Ni-TiO2/g-C3N4Composite photo-catalyst is consolidated
Body UV Diffuse Reflectance Spectroscopy figure.
Fig. 4 is the g-C of the embodiment of the present invention 13N4、B-Ni-TiO2And B-Ni-TiO2/g-C3N4The light of composite photo-catalyst
Degradation effect figure.
Fig. 5 is the B-Ni-TiO of the embodiment of the present invention 12/g-C3N4The recovery light degradation design sketch of composite photo-catalyst.
Specific embodiment
With reference to the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Ground description.Many details are elaborated in the following description in order to fully understand the present invention, but the present invention can be with
Other manner described here is different from using other to implement, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by following public specific embodiment.
Embodiment 1：
The B-Ni-TiO of the present embodiment2/g-C3N4The preparation method of composite photo-catalyst includes following step.
Step (1)：The absolute ethyl alcohol of the butyl titanate and 40mL that measure 10mL (milliliter) with graduated cylinder respectively pours into 200mL
It is well mixed in beaker and is made A liquid.Separately take 40mL absolute ethyl alcohols to be put into beaker, it is the dense of 0.01mol/L to be separately added into concentration
Hydrochloric acid solution 0.3mL, 3.5mL deionized water, the boric acid of 0.721g (gram) and the six water nickel nitrates of 0.854g are simultaneously sufficiently mixed,
Obtain B liquid.A liquid is transferred on magnetic stirring apparatus, is persistently stirred under 40 DEG C of water baths, when A liquid stirs 30min (minute),
During B liquid slowly instilled into A liquid, the speed for slowly instilling can be 1 drop per second, 2 drop per second or drip for every two seconds 1.Entirely titrated
Journey needs offer 25min.After completion of dropping, continue magnetic agitation, until solution is into gel.Constant temperature is done at the gel is placed in into 80 DEG C
Xerogel is obtained after dry case 24h (hour) drying, by xerogel agate mortar grind into powder, then 500 DEG C is placed on
Muffle furnace in calcine 3h, be obtained B-Ni-TiO2(boron-nickel-titanium dioxide) photochemical catalyst.
Step (2)：The melamine for weighing 2g is put into crucible with cover, is then heated in Muffle furnace, with 5 DEG C/min
Speed heat up, calcine 3h at 550 DEG C, be cooled to room temperature, it is i.e. prepared after flaxen solid is milled in agate mortar
g-C3N4Photochemical catalyst (graphite phase carbon nitride photochemical catalyst).
Step (3)：Under 80 DEG C of water baths, magnetic agitation under certain rotating speed, with the method for backflow by obtained g-C3N4
And B-Ni-TiO2It is 1 according to mol ratio:1 is combined.Product after centrifugation dries 24h in being placed on 80 DEG C of drying box, is finally obtained
B-Ni-TiO2/g-C3N4(g-C3N4With B-Ni-TiO2Molar ratio be 1:1) composite photo-catalyst.
Sample B-Ni-TiO obtained in the present embodiment2/g-C3N4XRD (X-ray diffraction) figure such as Fig. 1 of composite photo-catalyst
It is shown.It can be seen that nethermost lines spectrogram is g-C3N4, middle lines spectrogram is B-Ni-TiO2, topmost
Lines spectrogram be B-Ni-TiO2/g-C3N4Composite photo-catalyst.Wherein, B-Ni-TiO2Spectrogram contain TiO2Feature spread out
Peak is penetrated, in B-Ni-TiO2/g-C3N4G-C can be simultaneously seen in the XRD spectrum of composite photo-catalyst3N4And TiO2Feature diffraction
Peak.This explanation B-Ni-TiO2/g-C3N4Composite photo-catalyst is successfully prepared.
The g-C of the present embodiment step (2)3N4(Fig. 2 a), obtained sample B-Ni-TiO2/g-C3N4Composite photo-catalyst (figure
TEM (transmission electron microscope) figure 2b) is as shown in Figure 2.As shown in Figure 2 a, g-C3N4It is laminated structure；In Fig. 2 (b), can
There is B-Ni-TiO to see2Spherical particle is grown in the g-C of sheet3N4Body structure surface, this explanation B-Ni-TiO2And g-C3N4Success
It is compound, and this composite effect shows good property on microcosmic.
Sample B-Ni-TiO obtained in the present embodiment2/g-C3N4The UV Diffuse Reflectance Spectroscopy of composite photo-catalyst such as Fig. 3 institutes
Show, as can be seen from the figure B-Ni-TiO2/g-C3N4The light absorpting ability of composite photo-catalyst is remarkably reinforced, its Absorption edge hair
Red shift is given birth to, this is conducive to improving its photocatalytic activity.Therefore, B-Ni-TiO2/g-C3N4Composite photo-catalyst shines in visible ray
Penetrate it is lower to chloramphenicol have the disposal efficiency higher.
Sample B-Ni-TiO obtained in the present embodiment2/g-C3N4Composite photo-catalyst has also carried out photocatalysis performance evaluation.
Photocatalysis performance evaluation is carried out in light-catalyzed reaction instrument, the antibiotic light that photochemical catalyst prepared by the above method is used in water
Catalytic degradation, and recycling is carried out to the photochemical catalyst after catalysis.
Specifically, B-Ni-TiO obtained in 0.02g the present embodiment is weighed2/g-C3N4Composite photo-catalyst, using photocatalysis
Reaction instrument carries out degradation experiment, and different photochemical catalysts are observed to chloramphenicol degradation capability with this.Meanwhile, B-Ni- in step (1)
TiO2, the g-C in step (2)3N4Light-catalysed contrast experiment has been carried out, and they are tested at identical conditions.
Blank control group experiment is also added into addition, in blank control group experiment, chlorine of degrading to be used for without any photochemical catalyst is added
Mycin.
Fig. 4 is the light degradation design sketch for adding various photocatalyst for degrading chloramphenicol, and as can be seen from the figure chloramphenicol is empty
More stable under light illumination, simple g-C in white experimental group3N4Photochemical catalyst is relatively low to the degradation rate of chloramphenicol, and this is attributed to it
Light induced electron and hole are easy to be combined what is caused.B-Ni-TiO2And g-C3N4The B-Ni-TiO prepared after compound2/g-C3N4It is compound
The photocatalytic activity of photochemical catalyst is remarkably reinforced.When irradiation time (irradiation time) is about 30 minutes, C/
C0About 0.5, when irradiation time is about 60 minutes, C/C0About 0.3, when irradiation time is about 85 minutes, C/
C0About 0.17, when irradiation time is about 120 minutes, C/C0About 0.10, when irradiation time is 150 minutes,
C/C0About 0.05, when irradiation time is about 180 minutes, C/C0-About 0.04.
By the B-Ni-TiO of light degradation above2/g-C3N4Composite photo-catalyst is reclaimed and is repeated light degradation examination
Test, to verify the stability of this material.Concretely comprise the following steps：First, the B-Ni-TiO of most original in the preceding paragraph2/g-C3N4It is multiple
Closing catalyst is used for the degradation curve of chloramphenicol degrading as the 5a (B-Ni-TiO in Fig. 42/g-C3N4Composite catalyst degraded chlorine
The curve of mycin).Above for the B-Ni-TiO after chloramphenicol degradation experiment2/g-C3N4Composite photo-catalyst, spend from
Sub- water washing obtains the B-Ni-TiO for reclaiming for the first time after drying2/g-C3N4Composite photo-catalyst.0.02g is weighed to return for the first time
The B-Ni-TiO of receipts2/g-C3N4Composite photo-catalyst, reuses light-catalyzed reaction instrument and carries out degradation experiment and obtain Fig. 5 b curves.
Then, B-Ni-TiO is reclaimed again2/g-C3N4Composite catalyst, reclaiming the B-Ni-TiO that obtains for the second time2/g-C3N4It is compound
Catalyst carries out chloramphenicol light degradation experiment again, obtains Fig. 5 c curves.The like, then obtain third time recovery, return for the 4th time
The B-Ni-TiO of receipts2/g-C3N4Composite catalyst, and obtain curve map 5c, 5d and 5e of corresponding chloramphenicol degraded.This is several
Individual curve is aggregated into Fig. 5.From figure 5 it can be seen that by after multiple recovery again degradation experiment, B-Ni-TiO2/g-
C3N4There is not change substantially in the degradation property of composite photo-catalyst, and this turns out this material has good stability.This
Sample illustrates that this material can be recycled, and belongs to a kind of environmentally friendly material.
Embodiment 2：
The B-Ni-TiO of the present embodiment2/g-C3N4The preparation method of composite photo-catalyst includes following step.
Step (1)：The absolute ethyl alcohol of the butyl titanate and 40mL that measure 10mL with graduated cylinder respectively is poured into 200mL beakers
It is well mixed to be made A liquid.Separately take 40mL absolute ethyl alcohols to be put into beaker, be separately added into concentration for 0.01mol L-1Concentrated hydrochloric acid it is molten
Liquid 0.3mL, 3.5mL deionized water, the boric acid of 0.721g and the six water nickel nitrates of 0.854g are simultaneously sufficiently mixed uniformly, obtain B liquid.Will
A liquid is transferred on magnetic stirring apparatus, and stirring is opened in 40 DEG C of water-baths, when A liquid stirs 30min, during B liquid slowly instilled into A liquid.It is whole
Individual titration process needs about 25min.After completion of dropping, continue magnetic agitation, until solution is into gel.The gel is placed in 80 DEG C
Xerogel is obtained after lower thermostatic drying chamber 24h drying, by xerogel agate mortar grind into powder, then 500 is placed on
DEG C Muffle furnace in calcine 3h, prepared B-Ni-TiO is obtained2Photochemical catalyst.
Step (2)：The melamine for weighing 2g is put into crucible with cover, is then heated in Muffle furnace, with 5 DEG C of min-1
Speed heat up, calcine 3h at 550 DEG C, be cooled to room temperature, it is i.e. prepared after flaxen solid is milled in agate mortar
g-C3N4Photochemical catalyst.
Step (3)：In 80 DEG C of water-baths, magnetic agitation under certain rotating speed, the g-C that will be made with the method for backflow3N4And B-Ni-
TiO2It is 4 according to mol ratio:1 compound TiO2Photochemical catalyst.Product after centrifugation dries 24h i.e. in being placed on 80 DEG C of drying box
B-Ni-TiO is obtained2/g-C3N4(g-C3N4The molar ratio for occupying is 80%, that is, g-C3N4With B-Ni-TiO2Material
The ratio of amount is 4:1) composite photo-catalyst.
Embodiment 3：
The B-Ni-TiO of the present embodiment2/g-C3N4The preparation method of composite photo-catalyst includes following step.
Step (1)：The absolute ethyl alcohol of the butyl titanate and 40mL that measure 10mL with graduated cylinder respectively is poured into 200mL beakers
It is well mixed to be made A liquid.Separately take 40mL absolute ethyl alcohols to be put into beaker, be separately added into concentration for 0.01mol L-1Concentrated hydrochloric acid it is molten
(other embodiments are liquid 0.3mL：0.25mL to 0.35mL), (other embodiments are 3.5mL deionized waters：3.0mL is extremely
3.5mL), the six water nickel nitrates of the boric acid of 0.721g and 0.854g and it is sufficiently mixed uniform, obtains B liquid.A liquid is transferred into magnetic force to stir
Mix on device, 40 DEG C (other embodiments are：35 DEG C to 45 DEG C) water-bath opens stirring, treats that (other embodiments are A liquid stirring 30min：
15 minutes to 1 hour) when, during B liquid slowly instilled into A liquid.Whole titration process needs about 25min, and (other embodiments are：20 points
Clock was to 30 minutes).After completion of dropping, continue magnetic agitation, until solution is into gel.The gel is placed in 80 DEG C of (other implementations
Example be：50 DEG C of minutes are to 90 DEG C) under thermostatic drying chamber 24h drying after obtain xerogel, the xerogel is ground with agate mortar
Into powder, then it is placed in 500 DEG C of Muffle furnace and calcines 3h, prepared B-Ni-TiO2Photochemical catalyst.
Step (2)：The melamine for weighing 2g is put into crucible with cover, is then heated in Muffle furnace, with 5 DEG C
min-1Speed heat up, calcine 3h at 550 DEG C, be cooled to room temperature, after flaxen solid is milled in agate mortar i.e.
G-C is obtained3N4Photochemical catalyst.
Step (3)：In 80 DEG C of water-baths, magnetic agitation under certain rotating speed, the g-C that will be made with the method for backflow3N4And B-Ni-
TiO2In absolute ethyl alcohol according to mol ratio be 1:9 compound TiO2Photochemical catalyst.Product after centrifugation is placed on 80 DEG C of drying box
In dry 24h i.e. be obtained B-Ni-TiO2/g-C3N4(g-C3N4The molar ratio for occupying is 10%, that is, g-C3N4With B-Ni-
TiO2Material amount ratio be 1:9) composite photo-catalyst.In step (3), absolute ethyl alcohol addition is g-C3N4And B-Ni-
TiO2The twice of weight is to five times.
Obviously, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
Claims (7)
1. a kind of composite photo-catalyst, it is characterised in that the composite photo-catalyst is B-Ni-TiO2/g-C3N4Composite photocatalyst
Agent.
2. composite photo-catalyst according to claim 1, it is characterised in that the B-Ni-TiO2/g-C3N4Complex light is urged
G-C in agent3N4With B-Ni-TiO2Molar ratio be 1：10 to 40：10.
3. composite photo-catalyst according to claim 1 as chloramphenicol degrading purposes.
4. a kind of B-Ni-TiO2/g-C3N4The preparation method of composite photo-catalyst, is carried out according to the following steps：
Step (1):The butyl titanate and absolute ethyl alcohol of measured amounts are well mixed respectively is made A liquid；Separately take a certain amount of
Absolute ethyl alcohol, concentrated hydrochloric acid solution, deionized water, boric acid and six water nickel nitrates are sufficiently mixed uniformly, obtain B liquid；A liquid is transferred to magnetic
On power agitator, stirred under 35 DEG C to 45 DEG C water baths, after after A liquid stirring certain hour, during B liquid slowly instilled into A liquid；Drop
Add after finishing, continue magnetic agitation, until solution is into gel；Xerogel is obtained after the gel is placed in into thermostatic drying chamber drying,
By the xerogel grind into powder, then calcining in Muffle furnace is placed on, B-Ni-TiO is obtained2Photochemical catalyst；
Step (2)：Weigh a certain amount of melamine to be put into crucible with cover, then heated in Muffle furnace, in a constant temperature
The lower calcining of degree, is cooled to room temperature, and g-C is obtained after flaxen solid is milled3N4Photochemical catalyst；
Step (3)：The g-C that will be prepared3N4And B-Ni-TiO2It is added in absolute ethyl alcohol according to different proportion, with what is be heated to reflux
Method is combined；Product after centrifugation dries i.e. prepared B-Ni-TiO in being placed on drying box2/g-C3N4Composite photo-catalyst.
5. B-Ni-TiO according to claim 42/g-C3N4The preparation method of composite photo-catalyst, it is characterised in that step
Suddenly boric acid, six water nickel nitrates and the butyl titanate molar ratio for being added in (1) are 1：0.9-1.1：9-11, the temperature of Muffle furnace
Condition is 500 DEG C to 550 DEG C.
6. B-Ni-TiO according to claim 42/g-C3N4The preparation method of composite photo-catalyst, it is characterised in that step
Suddenly the time calcined described in (2) is 3 hours to 5 hours；Calcining heat is 550 DEG C to 600 DEG C.
7. the B-Ni-TiO according to any one of claim 4 to 62/g-C3N4The preparation method of composite photo-catalyst, its
It is characterised by, in step (3), is heated to reflux using water-bath mode, bath temperature is 70 DEG C to 90 DEG C, and the reaction time is 6
Hour to 8 hours, obtained B-Ni-TiO2/g-C3N4G-C in composite photo-catalyst3N4And B-Ni-TiO2Molar ratio be
1：10 to 40：10.
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| CN109461590A (en) * | 2018-09-30 | 2019-03-12 | 江苏理工学院 | A kind of porous g-C3N4/NiWO4The preparation method of composite material |
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| CN109603886A (en) * | 2019-01-09 | 2019-04-12 | 扬州工业职业技术学院 | A kind of novel Fe3O4/g-C3N4Composite material and its application as catalyst |
| CN111111727A (en) * | 2019-12-12 | 2020-05-08 | 西安建筑科技大学 | Ternary magnetic composite visible light catalytic nano material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109461590A (en) * | 2018-09-30 | 2019-03-12 | 江苏理工学院 | A kind of porous g-C3N4/NiWO4The preparation method of composite material |
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| CN109603887A (en) * | 2019-01-09 | 2019-04-12 | 扬州工业职业技术学院 | A kind of Fe of nickel doping3O4/g-C3N4The preparation method of composite material and its application in catalytic hydrogenation |
| CN109603886A (en) * | 2019-01-09 | 2019-04-12 | 扬州工业职业技术学院 | A kind of novel Fe3O4/g-C3N4Composite material and its application as catalyst |
| CN111111727A (en) * | 2019-12-12 | 2020-05-08 | 西安建筑科技大学 | Ternary magnetic composite visible light catalytic nano material and preparation method and application thereof |
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