CN108745336A - Titanium dioxide nanoplate/reduced graphene composite photo-catalyst and preparation method thereof - Google Patents
Titanium dioxide nanoplate/reduced graphene composite photo-catalyst and preparation method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 99
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 38
- 239000002055 nanoplate Substances 0.000 title claims abstract description 33
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 150000003608 titanium Chemical class 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 16
- 238000007146 photocatalysis Methods 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 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 6
- 229940012189 methyl orange Drugs 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- -1 graphite Alkene Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 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 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer 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
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
Abstract
The present invention relates to photocatalysis technology fields, and in particular to a kind of preparation method of titanium dioxide nanoplate/reduced graphene composite photo-catalyst.Include the following steps：Step 1) TiO 2 precursor, hydrofluoric acid and graphene oxide are mixed；Step 2) by step 1) obtained mixed liquor is transferred to hydrothermal reaction kettle, reaction 12 at 120~200 DEG C~for 24 hours；Step 3) by step 2) product of reaction gained is once purged dry obtains titanium dioxide nanoplate/reduced graphene composite photo-catalyst.Further relate to the titanium dioxide nanoplate made from above-mentioned preparation method/reduced graphene composite photo-catalyst.Raw material prepared by the present invention is commonly easy to get, of low cost, and preparation process is simple, environmentally protective, and titanium dioxide nanoplate is made to be uniformly distributed in graphene surface.Meanwhile obtaining excellent photocatalytic activity and recycling performance, there is potential application value in field of environment protection.
Description
Technical field
The present invention relates to photocatalysis technology fields, and in particular to a kind of titanium dioxide nanoplate/reduced graphene complex light
Catalyst and preparation method thereof.
Background technology
1972, Fujishima et al. was found that the TiO under illumination condition2The redox reaction of water occurs for surface energy,
Open the new page of light-catalyzed reaction research.TiO2Since its is of low cost, chemical property is stable, advantages of environment protection,
It is to study one of widest photochemical catalyst at present, photocatalytic degradation capability is all shown to various organic pollutions.It is natural
TiO in boundary2There are three types of common crystal form, anatase, rutile and brockites, wherein Detitanium-ore-type TiO for tool2Because having high ratio
Example (101) crystal face, shows excellent performance in terms of photocatalysis degradation organic contaminant.But due to TiO2Be adsorbed in its table
The organic pollution in face occur the time needed for chemical action be more than electron-hole pair that light excitation generates it is compound required when
Between, lead to TiO2Photocatalysis efficiency it is relatively low.Therefore, by adding noble metal, conductor oxidate, carbon nanotube, graphene
Etc. components obtain TiO2Base composite photocatalyst is one of the effective way for improving photocatalysis efficiency.These composite photo-catalysts have
There is different electron energy levels so that separation of charge can be enhanced by internal electric field driving force.
Graphene, because its large specific surface area, conductivity is high, electric charge carrier transfer ability is strong the advantages that, not only contribute to
Target contaminant is improved in the adsorption capacity on its surface, the transmission of light induced electron in composite material can also be promoted, is effectively reduced
The combined efficiency of photo-generate electron-hole, and absorbability of the composite material to ultraviolet light can be expanded, its photocatalysis performance is improved,
It is widely used in preparing TiO2Base composite photocatalyst material.Graphene oxide (GO) is to prepare various graphite due to being readily synthesized
One of the main precursor of alkenyl catalysis material.But it is led there are a large amount of oxygen-containing functional group such as hydroxyl and epoxides in GO
Its Electronic Performance is caused to be greatly reduced.Therefore, in order to prepare the efficiently TiO based on graphene2GO need to be reduced to by photochemical catalyst
Reduced graphene (rGO), to obtain excellent carrier mobility.Wherein, hydrazine hydrate and sodium borohydride can be used as efficiently also
Former agent restores GO, but toxicity itself is stronger, and secondary pollution can be caused to environment after reaction.Alcohol be used as reducing agent itself
There is no toxicity, but reproducibility is weaker, it can only partial reduction GO.
Currently, about titanium dioxide/reduced graphene (TiO2/ rGO) composite photo-catalyst report in TiO2Mainly to receive
Based on rice grain.(Qiu B, Zhou Y, Ma Y, the et al.Facile synthesis of the Ti3+self- such as Qiu
doped TiO2-graphene nanosheet composites with enhanced
photocatalysis.Scientific reports,2015,5:Vacuum activating method 8591-8596) is used, by GO obtained
Commercially P25 (TiO2Nano-particle) mixing, 3h is reacted in 300 DEG C under vacuum, GO is made to be reduced to rGO to obtain
TiO2/ rGO composite materials.This method condition is harsh, need to complete under vacuum.(Wang P, Wang J, the Wang X, et such as Wang
al.One-step synthesis of easy-recycling TiO2-rGO nanocomposite photocatalysts
with enhanced photocatalytic activity.Applied Catalysis B:Environmental,2013,
132:452-459) GO and commercially P25 are mixed and obtain TiO after reacting under hydrothermal conditions2/ rGO composite materials.This method is adopted
With between hydro-thermal method research P25 particles and rGO interaction and photocatalysis performance, unmodified P25 nano-particles are multiple
Reunite in condensation material apparent.
Therefore, TiO is developed2The green and simple synthesis of base graphene composite photocatalyst material are still one huge
Challenge.
Invention content
The technical problem to be solved in the present invention is to provide a kind of simple and effective titanium dioxide nanoplate/reduction stone
Black alkene composite photo-catalyst and preparation method thereof, makes titanium dioxide nanoplate be uniformly distributed in graphene surface, has than pure two
The more efficient photocatalytic activity of TiOx nano piece.
The invention is realized in this way：
Present invention firstly provides a kind of preparation method of titanium dioxide nanoplate/reduced graphene composite photo-catalyst,
Include the following steps：
Step 1) TiO 2 precursor, hydrofluoric acid and graphene oxide are uniformly mixed；
Step 2) by step 1) obtained mixed liquor is transferred to hydrothermal reaction kettle, reaction 12 at 120~200 DEG C~for 24 hours；
Step 3) by step 2) product of reaction gained is once purged dry obtains titanium dioxide nanoplate/reduction graphite
Alkene composite photo-catalyst.
Further to improve, the TiO 2 precursor is titanium salt.It is highly preferred that the titanium salt includes four fourth of metatitanic acid
Ester, titanium tetrachloride or isopropyl titanate.
Further to improve, the additive amount of graphene oxide is 0~6wt%.The mass percent of graphene oxide be with
On the basis of the quality of obtained titanium dioxide nanoplate.Preferably, the additive amount of graphene oxide is 1~6wt%.
Further to improve, step 1) described in the volume ratio of TiO 2 precursor and hydrofluoric acid be 9~5：1.
Further to improve, step 3) cleaning, it is respectively washed 2~3 times with deionized water, acetone and absolute ethyl alcohol,
It is highly preferred that the cleaning is to be centrifuged repeatedly cleaning with supercentrifuge.
Further to improve, step 3) drying be dry 6 at 40~80 DEG C of vacuum~for 24 hours.
Then the present invention uses hydro-thermal method one-step synthesis dioxy by mixing graphene oxide with TiO 2 precursor
Change titanium nanometer sheet/reduced graphene composite photo-catalyst.
The raw material graphene oxide that the present invention uses can be powdered, sheet or solution shape for commercial product.
The present invention also provides the titanium dioxide nanoplate made from the preparation method/reduced graphene composite photocatalysts
Agent, graphene oxide reduction is complete, titanium dioxide nanoplate favorable dispersibility.It is showed in terms of photocatalysis degradation organic contaminant
Go out excellent performance, the organic pollution that can be used for handling includes：Methyl orange, methylene blue, phenol, rhodamine B etc..
The invention has the advantages that：Raw material prepared by the present invention is commonly easy to get, of low cost, and preparation process is simple, green
Colour circle is protected.During the formation of complexes, titanium dioxide nanoplate growth in situ and graphene film surface, the two are dispersed in
Between due to structure it is similar, there are stronger active forces between piece and piece, avoid titanium dioxide nanoplate because dimensional effect is brought
Reunion, also effectively prevent the accumulation again of graphene sheet layer.Meanwhile obtaining excellent photocatalytic activity and recycling
Can, there is potential application value in field of environment protection.
Description of the drawings
The present invention is further illustrated in conjunction with the embodiments with reference to the accompanying drawings.
Fig. 1 is that the TEM and HRTEM of photochemical catalyst scheme.Wherein a：TiO2Nanometer sheet；b：Graphene oxide；c：TiO2/rGO-
1%；d：TiO under high-resolution2/ rGO-1%.
Fig. 2 is the XRD diagram of graphene oxide and different graphene additive amount (0-6%) composite photo-catalysts.Wherein a：Oxygen
Graphite alkene；b：TiO2Nanometer sheet；c：TiO2/ rGO-1%；d：TiO2/ rGO-3%；e：TiO2/ rGO-6%.
Fig. 3 is the XPS figures of graphene oxide and composite photo-catalyst.Wherein a：Graphene oxide；b:TiO2/ rGO-1%.
Fig. 4 is that the degrade when m- degradation rate of methyl orange solution of ultraviolet catalytic of photochemical catalyst under different cycle-indexes closes
System's figure；
Fig. 4 a：TiO2Nanometer sheet；
Fig. 4 b：TiO2/ rGO-1%；
Fig. 4 c：TiO2/ rGO-3%；
Fig. 4 d：TiO2/ rGO-6%.
Fig. 5 is four degradation cycle efficieny figures of composite photo-catalyst of different graphene additive amounts.
Specific implementation mode
Embodiment 1
12.5mL butyl titanates and 1.5mL hydrofluoric acid are uniformly mixed, 100mL polytetrafluoroethylene (PTFE) hydro-thermal reactions are transferred to
In kettle, constant temperature is for 24 hours at 180 DEG C.It waits being cooled to room temperature after the completion of reacting.By product supercentrifuge turning in 10000rpm
Speed is lower to centrifuge 10min, uses deionized water, acetone and washes of absolute alcohol respectively, at 60 DEG C of vacuum it is dry for 24 hours, obtain titanium dioxide
Titanium nanosheet photocatalyst (TiO2)。
Embodiment 2-4
Other steps are constant, and the mass percentage that graphene oxide is added in mix stages is respectively 1%, 3%, 6%,
Obtained titanium dioxide nanoplate/reduced graphene composite photo-catalyst is respectively labeled as TiO2/ rGO-1%, TiO2/rGO-
3%, TiO2/ rGO-6%.
Embodiment 5
Titanium dioxide nanoplate/reduced graphene composite photo-catalyst be applied to methyl orange photocatalytic degradation, and with it is pure
Anatase phase titanium dioxide nanometer sheet carries out photocatalysis performance comparison.It is as follows：30mg composite photo-catalysts are disperseed
In the methyl orange solution of 100mL 10mg/L, and the magnetic agitation 30min under darkroom, so that methyl orange is reached adsorption equilibrium.?
Light degradation reaction is carried out under 300W xenon source systems, wave-length coverage is 200~400nm, and light source and the distance for reacting liquid level are
10cm.Photocatalytic degradation liquid is drawn every 7min, centrifuges composite photo-catalyst, remaining methyl orange concentration in supernatant liquor
Tracking and measuring is carried out by ultraviolet-visible spectrophotometer, to obtain the degradation rate of each period methyl orange.
To 1~4 gained titanium dioxide nanoplate of above-described embodiment and titanium dioxide nanoplate/reduced graphene using transmission
The instruments such as electron microscope (TEM), X-ray diffractometer (XRD), x-ray photoelectron spectroscopy instrument (XPS) carry out structural analysis to product.
By embodiment 5, photocatalytic degradation experiment is carried out by target dyestuff of methyl orange solution, passes through ultraviolet-visible spectrophotometer
Absorbance is measured, to assess its photocatalytic activity.Specific test result is as shown in Fig. 1~5.
Fig. 1 is that the TEM and HRTEM of obtained photochemical catalyst scheme.It can be seen that pure TiO2It is nano flake (in Fig. 1
A), size about 60~120nm, and increase with the increase of hydrofluoric acid dosage.Graphene oxide is in gauze-like (b in Fig. 1), shape
At larger two-dimension plane structure, unique physical and chemical performance can effectively adsorb organic pollution and electron-transport.In Fig. 1
C, TiO2Nanometer sheet is equably supported on the surface of graphene oxide being reduced, and the fold of graphene edge part is high-visible.
It can be calculated the TiO in compound in HRTEM (d in Fig. 1)2Nano lamellite interplanar distance is 0.335nm, corresponds to Anatase
TiO2(101) crystal face, show the TiO generated in the compound2Nanometer sheet is Detitanium-ore-type.
Fig. 2 is the XRD diagram of graphene oxide and different graphene additive amount composite photo-catalysts.As can be seen that oxidation stone
Nearby there is (001) characteristic diffraction peak (a in Fig. 2) at 11.04 ° in black alkene, but in the composite material obtained after hydro-thermal method restores
Do not occur this feature peak, shows hydro-thermal reaction while generating anatase phase titanium dioxide nanometer sheet, it effectively will oxidation
Graphene is changed into reduced graphene (c~e in Fig. 2).The ratio of (001) crystal face is big in titanium dioxide nanoplate, crystal face tool
There are more chemism points (b in Fig. 2).First principle shows that the fluorine ion in hydrofluoric acid can be by titanium dioxide (001) crystalline substance
The surface in face can significantly reduce.Fluorine ion plays a crucial role in the formation on exposed (001) surface.When hydrofluoric acid volume increases
Greatly, titanium dioxide nanoplate becomes large-sized, and the ratio in (001) face also greatly improves.In fig. 2 in b~e, 2 angles θ in
There is feature diffraction at 25.3 °, 36.9 °, 48.0 °, 53.9 °, 55.0 °, 62.7 °, 70.3 °, 75.0 °, 76.0 °, 82.7 °
Peak corresponds respectively to Detitanium-ore-type TiO2(101), (004), (200), (105), (211), (204), (220), (215) and
(224) crystal face shows obtained pure TiO2And the TiO in composite material2It is Detitanium-ore-type.
Fig. 3 is the XPS figures of graphene oxide and titanium dioxide nanoplate/reduced graphene.It can be seen that graphene oxide
Absorption peak at 286.6eV and 288.7eV corresponds respectively to ehter bond, hydroxyl and carboxyl, with TiO2Nanometer sheet forms compound
Intensity significantly reduces after object, shows that the graphene oxide introduced in hydrothermal reaction process is effectively reduced into graphene.
Fig. 4 is that the degrade when m- degradation rate of methyl orange solution of ultraviolet catalytic of photochemical catalyst under different cycle-indexes closes
System's figure.It can be seen that pure TiO2The 1st degradation rate of nanometer sheet is 78.9%, illustrates that it has preferable degrading activity to methyl orange.
But it is fast that circulation experiment finds that its photocatalytic activity declines, after cycle 3 times degradation efficiency only have the 1st time 56.8%.Add graphite
After alkene, the ultraviolet catalytic activity of titanium dioxide nanoplate/reduced graphene compound compares TiO2The height of nanometer sheet, wherein
With graphene additive amount be 6% when activity it is optimal.With TiO2TiO prepared by nano-particle2/ rGO composite materials are compared, photocatalysis
Performance is suitable, but recycles performance and improve.
Fig. 5 is 4 degradation cycle efficieny figures of composite photo-catalyst of different graphene additive amounts.As can be seen that working as graphite
When alkene additive amount is 3%, degrading activity keeps best, and the 4th degradation rate is 0.789 times of the 1st time.Show that this is compound
Photochemical catalyst is with good stability and repeats the feature of utilizing.
Although specific embodiments of the present invention have been described above, those familiar with the art should manage
Solution, we are merely exemplary described specific embodiment, rather than for the restriction to the scope of the present invention, it is familiar with this
The technical staff in field modification and variation equivalent made by the spirit according to the present invention, should all cover the present invention's
In scope of the claimed protection.
Claims (8)
1. a kind of preparation method of titanium dioxide nanoplate/reduced graphene composite photo-catalyst, it is characterised in that：Including as follows
Step：
Step 1) TiO 2 precursor, hydrofluoric acid and graphene oxide are uniformly mixed；
Step 2) by step 1) obtained mixed liquor is transferred to hydrothermal reaction kettle, reaction 12 at 120~200 DEG C~for 24 hours；
Step 3) by step 2) once purged dry to obtain titanium dioxide nanoplate/reduced graphene multiple for the product of reaction gained
Closing light catalyst.
2. the preparation method of titanium dioxide nanoplate according to claim 1/reduced graphene composite photo-catalyst, special
Sign is：The TiO 2 precursor is titanium salt.
3. the preparation method of titanium dioxide nanoplate according to claim 2/reduced graphene composite photo-catalyst, special
Sign is：The titanium salt includes butyl titanate, titanium tetrachloride or isopropyl titanate.
4. the preparation method of titanium dioxide nanoplate according to claim 1/reduced graphene composite photo-catalyst, special
Sign is：The additive amount of graphene oxide is 0~6wt%, and the mass percent of graphene oxide is the titanium dioxide to obtain
On the basis of the quality of nanometer sheet.
5. the preparation method of titanium dioxide nanoplate according to claim 1/reduced graphene composite photo-catalyst, special
Sign is：Step 1) described in the volume ratio of TiO 2 precursor and hydrofluoric acid be 9~5：1.
6. the preparation method of titanium dioxide nanoplate according to claim 1/reduced graphene composite photo-catalyst, special
Sign is：Step 3) cleaning, it is respectively washed 2~3 times with deionized water, acetone and absolute ethyl alcohol.
7. the preparation method of titanium dioxide nanoplate according to claim 1/reduced graphene composite photo-catalyst, special
Sign is：Step 3) drying be dry 6 at 40~80 DEG C of vacuum~for 24 hours.
8. titanium dioxide nanoplate made from the preparation method as described in Arbitrary Term in claim 1-7/reduced graphene complex light
Catalyst.
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| CN110026173A (en) * | 2019-04-28 | 2019-07-19 | 苏州科技大学 | Nano-ZnO/TiO2Composite photo-catalyst and its preparation method and application |
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| CN110801857A (en) * | 2019-12-02 | 2020-02-18 | 山东建筑大学 | Method for preparing titanium dioxide-nitrogen doped graphene composite photocatalytic material |
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| CN110743585B (en) * | 2019-11-20 | 2022-02-18 | 南通纺织丝绸产业技术研究院 | Preparation method of graphene-based nano titanium dioxide sheet for enhancing visible light catalysis |
| CN110801857A (en) * | 2019-12-02 | 2020-02-18 | 山东建筑大学 | Method for preparing titanium dioxide-nitrogen doped graphene composite photocatalytic material |
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