CN109107598A - A kind of h-BN/TiO with high photocatalysis performance2The preparation method of composite material - Google Patents
A kind of h-BN/TiO with high photocatalysis performance2The preparation method of composite material Download PDFInfo
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- CN109107598A CN109107598A CN201811091155.5A CN201811091155A CN109107598A CN 109107598 A CN109107598 A CN 109107598A CN 201811091155 A CN201811091155 A CN 201811091155A CN 109107598 A CN109107598 A CN 109107598A
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- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000020477 pH reduction Effects 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000010936 titanium Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 7
- 230000005012 migration Effects 0.000 abstract description 6
- 238000013508 migration Methods 0.000 abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052719 titanium Inorganic materials 0.000 abstract description 5
- 229910003074 TiCl4 Inorganic materials 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 2
- 238000000919 Fourier transform infrared map Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910003089 Ti–OH Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- -1 hydroxyl Free radical Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 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 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007281 self degradation Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
Abstract
The invention discloses a kind of h-BN/TiO with high photocatalysis performance2The preparation method of composite material, comprising the following steps: step 1), with H3BO3With CO (NH2)2For raw material, the h-BN of class graphene-structured is synthesized；Step 2) pre-processes the powder h-BN sample obtained in step 1)；Step 3), with TiCl4H-BN/TiO is synthesized as titanium source with TBOT2Composite material.The present invention passes through in TiO2Covalent bond is constructed between non-metal semiconductive h-BN, will pass through the migration for promoting light induced electron between interface, improves the photocatalysis efficiency of material；And by TiO2In adulterate two kinds of nonmetalloids of N, F simultaneously, change TiO2Forbidden bandwidth and light induced electron interface migration rate, so as to improve TiO2Photocatalytic activity.
Description
Technical field
The present invention relates to nano material synthesis technical fields, and in particular to a kind of h-BN/ with high photocatalysis performance
TiO2The preparation method of composite material.
Background technique
With the development of society, having pushed industrialized process to meet the needs of people.But industrialized appearance
It is usually associated with the water environment pollution that serious environmental pollution, especially people depend on for existence.Organic pollutant in water body, it is main
If phenols, antibiotic etc., these pollutants are difficult to be decomposed in vivo, and trace level will threaten the strong of people
Health, how removing the pollutant that these stability are high, toxicity is big and obtaining clean water resource is considered as one global
Challenge.Traditional sewage water treatment method mainly has absorption method, microbial degradation method, Coagulation Method etc., although these methods are ok
Remove a part of pollutant.But all there are some problems, such as pollutant cannot be removed thoroughly, complex process, equipment requirement
It is higher and be easy to cause secondary pollution etc..Therefore, the presence of these problems pushes researcher to seek a kind of efficient, environment friend
The technology of good type completely removes the organic pollutant in water body.
Since the beginning of the seventies in last century, Frank and Bard et al. discovery TiO under the action of light2It can be by the cyaniding in water
Object decomposes, and CN- is made to be oxidized to OCN-, provides new direction to handle the development of water pollution.Photocatalysis technology has attracted one
Scientific researches scholar's extensive concern such as large quantities of environment, catalysis and biochemistry.Photocatalysis technology is as a kind of economic, environmental protection Wastewater Treatment Technology
Art.The research core of photocatalysis technology is the preparation of high efficiency photocatalyst, and the photon in light can be absorbed in catalysis material, in turn
It generates electronics (e-) and hole (h+), these e- and h+ are located on the conduction band (CB) and valence band (VB) of catalyst for restoring
And oxidation reaction.And TiO2Because the advantages that it has economic benefits height, high catalytic efficiency, strong and nontoxic photostability, is considered as
Excellent photochemical catalyst.TiO2E- and h+ in catalyst are respectively provided with excellent reduction and oxidability, can make the overwhelming majority
Organic pollutant completely removes and decomposes aquatic products hydrogen.For example, the Ce3+-TiO of Bharatvaj et al. preparation2Photochemical catalyst,
There is preferable decomposition water H2-producing capacity under the Hg lamp irradiation of 150W and hydrogen-producing speed is up to 6789 μm of ol/h；Wang Hao et al. system
Standby nano-TiO2Catalysis material can decompose aquatic products hydrogen and good light stability under the Hg lamp irradiation of 500W；Kim et al. at
Function is prepared for Zn-TiO2Composite material completely removes methyl orange under sunlight.In addition, many inorganic compounds and again
Metal can also be in TiO2Surface is restored by light induced electron and generates the lesser product of nontoxic or toxicity.Therefore, TiO2It is organic degrading
Object, pollution control of water, production hydrogen etc. have relatively broad application prospect.
However, TiO2Itself also there are limitation, TiO2Larger of band gap have a response to ultraviolet light, it is ultraviolet in solar spectrum
Light only occupies 5%；In addition, TiO2The e- and h+ generated after excitation is easy to happen compound；Limit TiO2Fortune in practice
With being difficult to be commercialized by the catalysis material of substrate of titanium dioxide to hinder.Therefore, the sub- efficiency of preparation higher amount and
The TiO of efficient responding to visible light2It is considered as a vital step in entire photocatalytic process.Currently, scientific research scholar is
Itd is proposed number of ways for solving TiO2There are the shortcomings that.
Wherein non-metal semiconductive composite Ti O2Method of modifying have the advantages that it is a variety of: by change semi-conductor nano particles
Size, the band gap and optical response range of controllable catalysis material；Semiconductor composite can be surface modified
Increase photostability；The light absorption of semiconductor composite shows band edge type, increases to photoresponse intensity.
Non-metal semiconductive and TiO2The interfacial contact of composite material is loose, cause light induced electron migrated between interface compared with
Slowly and it is easy to happen accumulation；On the other hand, nonmetallic codope TiO2Middle nonmetalloid is in the work for improving catalyst activity
With and it is indefinite.
Summary of the invention
Problem to be solved by this invention is: providing a kind of h-BN/TiO with high photocatalysis performance2Composite material
The preparation method present invention in order to solve the above problem provided by technical solution are as follows: a kind of h- with high photocatalysis performance is provided
BN/TiO2The preparation method of composite material, comprising the following steps:
Step 1), with H3BO3With CO (NH2)2For raw material, the h-BN of class graphene-structured is synthesized: by H3BO3With CO (NH2)2
It is dissolved in distilled water, it is dry in the environment of 70 DEG C, it then goes in calcining vessel and is calcined, powder is obtained after natural cooling
The h-BN sample of last shape；
Step 2) pre-processes the powder h-BN sample obtained in step 1): the powder h- that will be obtained in step 1)
BN is added to HNO3In be acidified, place into Vltrasonic device by ultrasonic wave act on 2h after place into centrifugal device from
Then h-BN precipitating after gains in depth of comprehension to acidification, washing are dried to neutrality, add dehydrated alcohol, then place into super
Uniform dispersion liquid is obtained after ultrasonic wave acts on 30min in acoustic device；
TiCl4 and TBOT is slowly added dropwise in dispersion liquid obtained into step 2) in step 3), is stirred for 15min；Then it drips
Add deionized water, be transferred in the reaction kettle containing polytetrafluoroethyllining lining after being stirred for 30min, is placed in 65 DEG C of thermostatic drying chambers
12h；After natural cooling, the sample of collection, which is pulverized, to be transferred to calcine in calciner plant obtains h-BN/TiO2Composite material
Sample.
Preferably, the calcining in the step 1) is divided into two steps, before this in N2Then the lower calcining of protection, natural cooling exist
It is calcined again under air atmosphere, natural cooling.It is heated using two steps, can adequately eliminate the influence of residual impurity.
Preferably, in N2Lower calcination parameter is that heating rate is 2 DEG C/min, and constant temperature is 900 DEG C, calcination time 5h.
Preferably, the parameter calcined under air atmosphere is that heating rate is 2 DEG C/min, and constant temperature is 550 DEG C, calcination time
For 5h.
Preferably, the H in the step 1)3BO3With CO (NH2)2Molar ratio be 1:48.
Preferably, h-BN, HNO in the step 2)3Molar ratio with dehydrated alcohol is 1:5:2.
Preferably, TiCl in the step 3)4, TBOT molar ratio be 4:7.
Compared with prior art, the invention has the advantages that
(1) through the invention the prepared h-BN/TiO of preparation method2Composite material passes through in TiO2With nonmetallic half
Covalent bond is constructed between conductor h-BN, will pass through the migration for promoting light induced electron between interface, improves the photocatalysis of material
Efficiency；And by TiO2In adulterate two kinds of nonmetalloids of N, F simultaneously, change TiO2Forbidden bandwidth and light induced electron on boundary
The migration rate in face, so as to improve TiO2Photocatalytic activity.
(2) in h-BN/TiO2In composite material preparation, using two kinds of titanium sources of TiCl4 and TBOT, prepared TiO2Than
Single titanium source is more stable, and specific surface area is bigger.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present invention, constitutes a part of the invention, this hair
Bright illustrative embodiments and their description are used to explain the present invention, and are not constituted improper limitations of the present invention.
A and b is 1wt%h-BN/TiO of the invention in Fig. 12- 300 DEG C of TEM figure；
A is 1wt%h-BN/TiO in Fig. 22- 300 DEG C of XPS all band figure, b is 1wt%h-BN/TiO2- 300 DEG C, physics
Mix (1wt%h-BN+TiO2- 300 DEG C) and h-BN B1s Momentum profiles figure, c is 1wt%h-BN/TiO2- 300 DEG C, physics it is mixed
Close (1wt%h-BN+TiO2- 300 DEG C) and h-BN N1s Momentum profiles figure, d is O1s Momentum profiles figure, and e is Ti 2p combination energy
Spectrogram；
Fig. 3 is x wt%h-BN/TiO2- 300 DEG C of (x=0,0.5,1,1.5,2.5), physical mixed (1wt%h-BN+
TiO2- 300 DEG C) and h-BN FT-IR map；
A is catalyst 1wt%h-BN/TiO under visible light in Fig. 42- 300 DEG C degradation 4NP (p-nitrophenol) it is ultraviolet-
It can be seen that all band scanning figure, b is the degradation speed of 4NP photocatalysis and dark reaction absorption at radiation of visible light 3h (ph=4.11)
Rate.
Specific embodiment
Carry out the embodiment that the present invention will be described in detail below in conjunction with accompanying drawings and embodiments, how the present invention is applied whereby
Technological means solves technical problem and reaches the realization process of technical effect to fully understand and implement.
Embodiment 1
Step 1), with H3BO3With CO (NH2)2For raw material, the h-BN of class graphene-structured is synthesized: by 0.1855g H3BO3With
8.6486gCO(NH2)2It is dissolved in 50mL distilled water, it is dry in the environment of 70 DEG C, it then goes in calcining vessel and is forged
It burns, obtains powdered h-BN sample after natural cooling；
Step 2) pre-processes the powder h-BN sample obtained in step 1): the powder h- that will be obtained in step 1)
BN is added to 20mLHNO3In be acidified, place into Vltrasonic device by ultrasonic wave act on 2h after place into centrifugation dress
The h-BN precipitating after centrifugation is acidified is set, then washing is dried to neutrality, adds 25mL dehydrated alcohol, then again
It is put into Vltrasonic device and obtains uniform dispersion liquid after ultrasonic wave acts on 30min；
0.5mL TiCl is slowly added dropwise in dispersion liquid obtained into step 2) in step 3)4With 2.5mL TBOT, it is stirred for
15min；Then 3.6mL deionized water is added dropwise, is stirred for being transferred to capacity after 30min being 100mL containing polytetrafluoroethyllining lining
Reaction kettle in, be placed in 12h in 65 DEG C of thermostatic drying chambers；After natural cooling, the sample of collection is pulverized and is transferred to calcining
Calcining obtains h-BN/TiO in device2The sample of composite material.
Embodiment 2
Step 1), with H3BO3With CO (NH2)2For raw material, the h-BN of class graphene-structured is synthesized: by 0.1855gH3BO3With
8.6486gCO(NH2)2It is dissolved in 50mL distilled water, it is dry in the environment of 70 DEG C, it then calcines, rises under N2 protection before this
Warm rate is 2 DEG C/min, and constant temperature is 900 DEG C, calcination time 5h, then natural cooling is forged again under air atmosphere
It burns, heating rate is 2 DEG C/min, and constant temperature is 550 DEG C, calcination time 5h.Natural cooling.It is obtained after natural cooling powdered
H-BN sample；
Step 2) pre-processes the powder h-BN sample obtained in step 1): the powder h- that will be obtained in step 1)
BN is added to 20mLHNO3In be acidified, place into Vltrasonic device by ultrasonic wave act on 2h after place into centrifugation dress
The h-BN precipitating after centrifugation is acidified is set, then washing is dried to neutrality, adds 25mL dehydrated alcohol, then again
It is put into Vltrasonic device and obtains uniform dispersion liquid after ultrasonic wave acts on 30min；
0.5mL TiCl is slowly added dropwise in dispersion liquid obtained into step 2) in step 3)4With 2.5mL TBOT, it is stirred for
15min；Then 3.6mL deionized water is added dropwise, is stirred for being transferred to capacity after 30min being 100mL containing polytetrafluoroethyllining lining
Reaction kettle in, be placed in 12h in 65 DEG C of thermostatic drying chambers；After natural cooling, the sample of collection, which is pulverized, is transferred to corundum earthenware
In crucible, calcining obtains h-BN/TiO in Muffle furnace2The sample of composite material.
Wherein, the H in step 1)3BO3With CO (NH2)2Molar ratio be 1:48；H-BN, HNO in step 2)3With it is anhydrous
The molar ratio of ethyl alcohol is 1:5:2；TiCl in step 3)4, TBOT molar ratio be 4:7.
A and b is 1wt%h-BN/TiO in Fig. 12- 300 DEG C of TEM figure, from the figure, it can be seen that three kinds of different lattices
Striped, middle d=0.33nm belong to the lattice fringe of (002) crystal face of h-BN；D=0.352nm is to belong to anatase TiO2's
(101) lattice fringe of crystal face；And d=0.29nm then belongs to brockite TiO2(211) crystal face lattice fringe, this and 2-1
(b) analysis of XRD is consistent in.In addition, what can be apparent from Fig. 1-b sees TiO2It is very tight with the interfacial contact of h-BN
Close, this may be due to TiO2It is to be connected to make to contact very between interface by Ti-O-B covalent bond between h-BN
Closely, natural.
The present invention has carried out really the successful preparation of composite photo-catalyst using XPS (x-ray photoelectron spectroscopy) and FT-IR
Fixed: a is 1wt%h-BN/TiO in Fig. 22- 300 DEG C of XPS all band figure.In order to compare, while giving physical mixed
(1wt%h-BN+TiO2- 300 DEG C), h-BN and TiO2- 300 DEG C of XPS spectrum figure.From the figure, it can be seen that 1wt%h-BN/
TiO2- 300 DEG C and 1wt%h-BN+TiO2There are the peak XPS of Ti 2p, B 1s, N 1s and O 1s in -300 DEG C of catalyst simultaneously, says
Bright 1wt%h-BN/TiO2- 300 DEG C and physical mixed (1wt%h-BN+TiO2- 300 DEG C) in all there is h-BN.
B is 1wt%h-BN/TiO in Fig. 22- 300 DEG C, physical mixed (1wt%h-BN+TiO2- 300 DEG C) and h-BN B1s
Momentum profiles figure.From the figure, it can be seen that the peak of the 190.5eV of h-BN belongs to B-N key, the peak of 191.5eV is due to preparing
Caused by the B-OH key that the surface that water or hydroxyl are attached to h-BN during catalyst is formed, and 1wt%h-BN/TiO2-
The peak of 300 DEG C of 192.2eV then belongs to B-O-Ti, this with it is reported in the literature consistent.To 1wt%h-BN/TiO2In -300 DEG C
The formation of B-O-Ti key is speculated: firstly, since there are unsaturated bonds to pass through HNO in h-BN3After acidification, easy and hydroxyl
Free radical (.OH) combines and forms B-OH key；Secondly, TiO2Presoma TBOT (butyl titanate) self condensing and recrystallizing shape
At TiO2During will form the macromolecular that Ti-O-Ti key is connected；Finally, TBOT is mixed with the h-BN of acidification, make B-OH
It is contacted with the Ti-O-Ti macromolecular being connected and polycondensation reaction occurs and then forms B-O-Ti key.
C is 1wt%h-BN/TiO in Fig. 22- 300 DEG C, physical mixed (1wt%h-BN+TiO2- 300 DEG C) and h-BN N1s
Momentum profiles figure.It can be seen from the figure that the peak that three kinds of catalyst all have 398.1eV belongs to the N3- in h-BN；And
1wt%h-BN/TiO2The peak of the 400.2eV occurred in -300 DEG C of catalyst then belongs to N-B-O-Ti key.D is that O1s is combined in Fig. 2
Energy spectrum diagram, the B-OH key that the peak at 532.3eV belongs to h-BN surface adsorption water or hydroxyl is formed；530.2eV,
Peak at 531.4eV is respectively belonging to TiO2In Ti-O-Ti and Ti-OH key；But in 1wt%h-BN/TiO2- 300 DEG C are urged
But occur the new peak being located at 532.9eV in agent, this is because caused by the presence of B-O-Ti key, with Artiglia
That reports is consistent.
E is Ti 2p Momentum profiles figure in Fig. 2.From the figure, it can be seen that there are two being located at 458.9eV and 464.5eV
Peak is respectively belonging to the characteristic peak of Ti 2p3/2 and the Ti 2p1/2 of Ti4+.Sample 1wt%h-BN/TiO2- 300 DEG C and physics
Mix (1wt%h-BN+TiO2- 300 DEG C) it compares, two characteristic peaks of Ti 2p combine energy direction to deviate slightly towards height, this may
It is due to 1wt%h-BN/TiO2In -300 DEG C caused by the presence of Ti-O-B key.Therefore, by XPS analysis it is known that
1wt%h-BN/TiO2TiO in -300 DEG C2It with h-BN is connected by Ti-O-B covalent bond.
Fig. 3 is x wt%h-BN/TiO2- 300 DEG C of (x=0,0.5,1,1.5,2.5), physical mixed (1wt%h-BN+
TiO2- 300 DEG C) and h-BN FT-IR map.From the figure, it can be seen that h-BN at 772cm-1 and 1387cm-1 there are two compared with
Big vibration peak is respectively belonging to the stretching vibration of B-N-B and the bending vibration of B-N-B；X wt%h-BN/TiO2-300℃(x
=0.5,1,1.5,2.5) and physical mixed (1wt%h-BN+TiO2- 300 DEG C) catalyst exist at 1387cm-1 it is apparent
Vibration peak, and the vibration peak at 772cm-1 may be by TiO2The vibration peak of itself is sheltered, and illustrates x wt%h-BN/TiO2-300
DEG C (x=0.5,1,1.5,2.5) and physical mixed (1wt%h-BN+TiO2- 300 DEG C) all contain h-BN in catalyst.
A is catalyst 1wt%h-BN/TiO under visible light in Fig. 42- 300 DEG C degradation 4-NP (p-nitrophenol) it is ultraviolet-
It can be seen that all band scanning figure, scanning range 200-600nm.It is known that 4-NP characteristic absorption peak appears in 317nm from figure
Place, with the increase of illumination reaction time, the absorbance at the wavelength is gradually reduced, and is illustrated with the increase with light application time
4-NP is gradually degraded.
As shown in the b in Fig. 4,1wt%h-BN/TiO2- 300 DEG C, physical mixed (1wt%h-BN+TiO2-300℃)、
TiO2The degradation curve of -300 DEG C and h-BN degradation 4-NP.Sample reaches absorption-after dark reaction 1h as can be observed from Figure
Desorption equilibrium.In radiation of visible light 3h, 4-NP can not self-degradation；And 1wt%h-BN/TiO2The degradation of -300 DEG C of catalysis 4-NP
Rate is 99.7%, is 6.4 times of P25, is physical mixed (1wt%h-BN/TiO2- 300 DEG C) 1.2 times, illustrate 1wt%h-
BN/TiO2The presence of Ti-O-B covalent bond has the photocatalytic activity for being conducive to improve catalyst in -300 DEG C.
The beneficial effects of the present invention are:
(1) through the invention the prepared h-BN/TiO of preparation method2Composite material passes through in TiO2With nonmetallic half
Covalent bond is constructed between conductor h-BN, will pass through the migration for promoting light induced electron between interface, improves the photocatalysis of material
Efficiency；And by TiO2In adulterate two kinds of nonmetalloids of N, F simultaneously, change TiO2Forbidden bandwidth and light induced electron on boundary
The migration rate in face, so as to improve TiO2Photocatalytic activity.
(2) in h-BN/TiO2In the preparation of composite material, using TiCl4With two kinds of titanium sources of TBOT, prepared TiO2It wants
More stable than single titanium source, specific surface area is bigger.
Only highly preferred embodiment of the present invention is described above, but is not to be construed as limiting the scope of the invention.This
Invention is not only limited to above embodiments, and specific structure is allowed to vary.All protection models in independent claims of the present invention
Interior made various change is enclosed to all fall in the scope of protection of the present invention.
Claims (7)
1. a kind of h-BN/TiO with high photocatalysis performance2The preparation method of composite material, it is characterised in that: including following step
It is rapid:
Step 1), with H3BO3With CO (NH2)2For raw material, the h-BN of class graphene-structured is synthesized: by H3BO3With CO (NH2)2Dissolution
It is dry in the environment of 70 DEG C in distilled water, it then goes in calcining vessel and is calcined, obtained after natural cooling powdered
H-BN sample；
Step 2) pre-processes the powder h-BN sample obtained in step 1): the powder h-BN obtained in step 1) is added
Enter to HNO3In be acidified, place into Vltrasonic device and place into centrifugal device after ultrasonic wave acts on 2h and be centrifuged
Then h-BN precipitating after to acidification, washing are dried to neutrality, add dehydrated alcohol, then place into ultrasound dress
It sets and obtains uniform dispersion liquid after ultrasonic wave acts on 30min；
TiCl is slowly added dropwise in dispersion liquid obtained into step 2) in step 3)4And TBOT, it is stirred for 15min；Then it is added dropwise and goes
Ionized water is transferred in the reaction kettle containing polytetrafluoroethyllining lining after being stirred for 30min, is placed in 12h in 65 DEG C of thermostatic drying chambers；
After natural cooling, the sample of collection, which is pulverized, to be transferred to calcine in calciner plant obtains h-BN/TiO2The sample of composite material
Product.
2. a kind of h-BN/TiO with high photocatalysis performance according to claim 12The preparation method of composite material,
Be characterized in that: the calcining in the step 1) is divided into two steps, before this in N2The lower calcining of protection, natural cooling, then in air atmosphere
It is calcined again under enclosing, natural cooling.
3. a kind of h-BN/TiO with high photocatalysis performance according to claim 22The preparation method of composite material,
It is characterized in that: in N2Lower calcination parameter is that heating rate is 2 DEG C/min, and constant temperature is 900 DEG C, calcination time 5h.
4. a kind of h-BN/TiO with high photocatalysis performance according to claim 22The preparation method of composite material,
Be characterized in that: the parameter calcined under air atmosphere is that heating rate is 2 DEG C/min, and constant temperature is 550 DEG C, calcination time 5h.
5. a kind of h-BN/TiO with high photocatalysis performance according to claim 12The preparation method of composite material,
It is characterized in that: the H in the step 1)3BO3With CO (NH2)2Molar ratio be 1:48.
6. a kind of h-BN/TiO with high photocatalysis performance according to claim 12The preparation method of composite material,
It is characterized in that: h-BN, HNO in the step 2)3Molar ratio with dehydrated alcohol is 1:5:2.
7. a kind of h-BN/TiO with high photocatalysis performance according to claim 12The preparation method of composite material,
It is characterized in that: TiCl in the step 3)4, TBOT molar ratio be 4:7.
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| CN110560138A (en) * | 2019-09-27 | 2019-12-13 | 南昌航空大学 | Preparation method of N/F co-doped titanium dioxide photocatalyst with high photocatalytic performance |
| CN113181893A (en) * | 2021-04-28 | 2021-07-30 | 四川大学 | B-TiO2Preparation method of/LDH photocatalyst and H removal2S applications |
| CN113351238A (en) * | 2021-07-01 | 2021-09-07 | 中国环境科学研究院 | Boron nitride series material for photocatalytic degradation of perfluorinated compounds and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560138A (en) * | 2019-09-27 | 2019-12-13 | 南昌航空大学 | Preparation method of N/F co-doped titanium dioxide photocatalyst with high photocatalytic performance |
| CN113181893A (en) * | 2021-04-28 | 2021-07-30 | 四川大学 | B-TiO2Preparation method of/LDH photocatalyst and H removal2S applications |
| CN113351238A (en) * | 2021-07-01 | 2021-09-07 | 中国环境科学研究院 | Boron nitride series material for photocatalytic degradation of perfluorinated compounds and application thereof |
| CN113351238B (en) * | 2021-07-01 | 2023-08-15 | 中国环境科学研究院 | Boron nitride material for photocatalytic degradation of perfluorinated compounds and application thereof |
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