CN109999888A - The preparation of copper and nitrogen co-doped modified titanium dioxide photocatalyst and the application for toluene of degrading - Google Patents
The preparation of copper and nitrogen co-doped modified titanium dioxide photocatalyst and the application for toluene of degrading Download PDFInfo
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 87
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000010949 copper Substances 0.000 title claims abstract description 37
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract 8
- 230000000593 degrading effect Effects 0.000 title abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 120
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 35
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004202 carbamide Substances 0.000 claims abstract description 26
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229960000583 acetic acid Drugs 0.000 claims abstract description 17
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 17
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 230000032683 aging Effects 0.000 claims abstract description 10
- 238000006731 degradation reaction Methods 0.000 claims abstract description 4
- 230000015556 catabolic process Effects 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000007146 photocatalysis Methods 0.000 claims description 7
- 230000001699 photocatalysis Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 89
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 51
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 11
- 239000004408 titanium dioxide Substances 0.000 abstract description 10
- 230000031700 light absorption Effects 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 48
- 239000000243 solution Substances 0.000 description 48
- 238000013019 agitation Methods 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000003760 magnetic stirring Methods 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000006798 recombination Effects 0.000 description 6
- 238000005215 recombination Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 238000000103 photoluminescence spectrum Methods 0.000 description 4
- 238000001055 reflectance spectroscopy Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229960004424 carbon dioxide Drugs 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- -1 printing Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 208000014644 Brain disease Diseases 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 208000032274 Encephalopathy Diseases 0.000 description 1
- 229910002661 O–Ti–O Inorganic materials 0.000 description 1
- 229910002655 O−Ti−O Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 239000000356 contaminant Substances 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses the preparation of a kind of copper and nitrogen co-doped modified titanium dioxide photocatalyst and the applications for toluene of degrading, and are mixed in order by dehydrated alcohol, copper nitrate, butyl titanate and glacial acetic acid, are stirred evenly, obtain solution A；Urea is dissolved in deionized water, obtains B solution；B solution instills solution A, is uniformly mixing to obtain Cu-N-TiO2Colloidal sol, it is dry after ageing, it grinds, copper and nitrogen co-doped modified titanium dioxide photocatalyst is made in roasting.Photochemical catalyst obtained is for explaining toluene.Copper and nitrogen are successfully doped in titanium dioxide by preparation method of the present invention using simple sol-gel method, have been expanded the visible light light absorption range of titanium dioxide, have been increased the utilization rate to sunlight.Photochemical catalyst obtained is used in the reaction of Photocatalytic Degradation of Toluene, is compared to pure titanium oxide and is only adulterated Cu or N, copper and nitrogen co-doped modified titanic oxide degradation of toluene rate with higher, has reached 38%.
Description
Technical field
The invention belongs to nanocomposite technical fields, are related to a kind of Cu and N codope modification TiO2Photochemical catalyst
Preparation；The photochemical catalyst is mainly used in the photocatalytic degradation reaction of toluene.
Background technique
Volatile organic matter (VOC) is one of main gaseous contamination source in environment, and Long Term Contact can cause human body sternly
The harm of weight.And toluene is common one of volatile organic compounds, usually mainly as solvent or diluent for painting, rubber,
In the industries such as leather, printing, insulating materials.If human body is chronically in the environment of a certain concentration toluene, will cause in chronic
Poison leads to encephalopathy and hepatorenal damage, or even has carcinogenesis.Currently, mainly by photochemical catalytic oxidation, chemical oxidation, burning and
VOC in the non-destructive methods control environment such as the disruptive methods such as biofiltration and absorption, absorption and film filtering.In recent years
Come, photocatalysis technology is widely used in removal organic polluter because of the features such as reaction condition is mild, secondary pollution is small.Ultraviolet
Or under the irradiation of visible light, photochemical catalyst generates electrons and holes and is further converted to hydroxyl radical free radical (OH), superoxide anion
(•O2 −) isoreactivity group.VOCs can be aoxidized by these active groups and be generated CO2、H2O and other inorganic molecules.Therefore, light
Catalysis technique is the technology for solving the problems, such as the most development potentiality of organic contamination.
Titanium dioxide (TiO2) it is a kind of excellent conductor photocatalysis material.With nontoxic, chemical property is relatively stable,
Catalytic activity is high, oxidability is strong, it is cheap, can reuse, can be CO by organic pollutant degradation2、H2O etc. is nontoxic
The advantages that oxide is the environmental type photochemical catalyst of current most development prospect.However, TiO2Forbidden band it is wider
(3.2eV), absorption spectrum ranges are relatively narrow, only in response to ultraviolet light；Secondly, TiO2Internal and surface light induced electron has with hole
High recombination rate, results in TiO2Photocatalysis degradation organic contaminant performance it is lower.Therefore, light induced electron and hole are reduced
Recombination rate and expansion become TiO in the optical response range of visible light region2The Main way of Photocatalyst.Currently, TiO2
Doping with element has proved to be effectively by spectral response from the ultraviolet method for expanding to visible light-responded range, effectively drops
The recombination rate of low light induced electron and hole.For example, N adulterates TiO2Visible light-responded range can be widened, this is because N2p and
Interaction between O2p track, results in TiO2Valence band location move up.Ag adulterates TiO2Photoproduction can be significantly improved
Electron transport ability reduces the recombination rate in light induced electron and hole, improves the catalytic activity of photochemical catalyst.
Summary of the invention
The object of the present invention is to provide the preparation methods of a kind of copper and nitrogen co-doped modified titanium dioxide photocatalyst, are made
Cu-N-T iO2Nano material.
It is a further object to provide nano materials made from a kind of above-mentioned preparation method to drop as photocatalysis
Solve the application in toluene.
To achieve the above object, the technical scheme adopted by the invention is that: a kind of copper and nitrogen co-doped modified titanic oxide
The preparation method of photochemical catalyst, specifically sequentially includes the following steps:
1) 1 ︰, 8~10 ︰ 2~3 by volume takes butyl titanate, dehydrated alcohol and glacial acetic acid respectively, then presses four fourth of 5mL metatitanic acid
The ratio of 0.06~0.08g copper nitrate is added in ester, takes copper nitrate；Urea, the quality of taken urea and taken copper nitrate are taken again
Than for 4~6 ︰ 1；
Dehydrated alcohol, copper nitrate, butyl titanate and glacial acetic acid are mixed in order, it is molten to obtain A by 30~50 min of magnetic agitation
Liquid；
Taken urea is dissolved completely in deionized water, is stirred evenly, B solution is obtained；
2) B solution is slowly dropped into solution A, stirs 2~3 h, obtains Cu-N-TiO2Colloidal sol；
3) by Cu-N-TiO2After colloidal sol is aged 22~24 h, in 80 DEG C~100 DEG C of at a temperature of 10~12h of drying, after grinding,
In 500 DEG C~550 DEG C of 2~4h of roasting temperature, copper and nitrogen co-doped modified titanium dioxide photocatalyst (Cu-N- is made
TiO2Nano material).
Another technical solution of the present invention is: a kind of above-mentioned copper and nitrogen co-doped modified titanic oxide photocatalysis
Application of the agent in Photocatalytic Degradation of Toluene.
Preparation method of the present invention is successfully prepared Cu-N-TiO using simple sol-gel method2Photochemical catalyst, and by its
Visible light photocatalytic degradation for toluene.Photochemical catalyst is characterized using technologies such as XRD, SEM, UV-vis and PL.It is right
Material has carried out the performance test of Photocatalytic Degradation of Toluene, and excellent Photocatalytic Degradation Property is shown by test result,
This has a very important significance the research and application of semiconductor light-catalyst.
Detailed description of the invention
Fig. 1 is TiO made from comparative example 12Cu-TiO made from catalyst, comparative example 22Made from catalyst, comparative example 3
N-TiO2Cu-N-TiO made from catalyst and embodiment 12The scanning electron microscope (SEM) photograph of catalyst.
Fig. 2 is TiO made from comparative example 12Cu-TiO made from catalyst, comparative example 22Made from catalyst, comparative example 3
N-TiO2Cu-N-TiO made from catalyst and embodiment 12The X ray diffracting spectrum of catalyst.
Fig. 3 is TiO made from comparative example 12Cu-TiO made from catalyst, comparative example 22Made from catalyst, comparative example 3
N-TiO2Cu-N-TiO made from catalyst and embodiment 12The UV Diffuse Reflectance Spectroscopy figure of catalyst.
Fig. 4 is TiO made from comparative example 12Cu-TiO made from catalyst, comparative example 22Made from catalyst, comparative example 3
N-TiO2Cu-N-TiO made from catalyst and embodiment 12The forbidden bandwidth figure of catalyst.
Fig. 5 is TiO made from comparative example 12Cu-TiO made from catalyst, comparative example 22Made from catalyst, comparative example 3
N-TiO2Cu-N-TiO made from catalyst and embodiment 12The infrared spectrogram of catalyst.
Fig. 6 is TiO made from comparative example 12Cu-TiO made from catalyst, comparative example 22Made from catalyst, comparative example 3
N-TiO2Cu-N-TiO made from catalyst and embodiment 12The photoluminescence spectra figure of catalyst.
Fig. 7 is TiO made from comparative example 12Cu-TiO made from catalyst, comparative example 22Made from catalyst, comparative example 3
N-TiO2Cu-N-TiO made from catalyst and embodiment 12The comparison diagram of catalyst generation amount of carbon dioxide.
Fig. 8 is TiO made from comparative example 12Cu-TiO made from catalyst, comparative example 22Made from catalyst, comparative example 3
N-TiO2Cu-N-TiO made from catalyst and embodiment 12The performance comparison figure of catalyst Photocatalytic Degradation of Toluene.
Specific embodiment
Below by the drawings and specific embodiments, the present invention will be further described.
Comparative example 1
40mL dehydrated alcohol, 5mL butyl titanate and 10mL acetic acid are sequentially added into beaker, beaker is placed on magnetic agitation
Magnetic agitation 30min on device obtains the first solution；Then 10mL deionized water is slowly dropped into the first solution, stirs 2h, obtains
TiO2Colloidal sol after ageing for 24 hours, in 80 DEG C of at a temperature of drying 12h, after grinding, in 500 DEG C of Muffle kiln roasting 2h, obtains TiO2It urges
Agent.
Photochemical properties test: the TiO made from comparative example 12The conversion ratio of catalyst Photocatalytic Degradation of Toluene, toluene is
10%。
Comparative example 2
40mL dehydrated alcohol, 0.071g copper nitrate, 5mL butyl titanate and 10mL glacial acetic acid are sequentially added into beaker,
Magnetic agitation 30min on magnetic stirring apparatus, obtains solution A；Then 10mL deionized water is slowly dropped into solution A, stirs 2h, obtains
Cu -TiO2Colloidal sol, ageing for 24 hours, in 80 DEG C of at a temperature of drying, after grinding, in 500 DEG C of Muffle kiln roasting 2h, obtain Cu-TiO2
Catalyst.
Photochemical properties test: the Cu-TiO made from comparative example 22Catalyst Photocatalytic Degradation of Toluene, the conversion of toluene
Rate is 27.5%.
Comparative example 3
40mL dehydrated alcohol, 5mL butyl titanate and 10mL glacial acetic acid are sequentially added into beaker, beaker is placed on magnetic force and is stirred
Magnetic agitation 30min on device is mixed, the second solution is obtained.0.353g urea is added in 10mL deionized water, is completely dissolved, obtains B solution,
B solution is slowly dropped into the second solution, 2h is stirred, obtains N-TiO2Colloidal sol, after ageing for 24 hours, in 80 DEG C of at a temperature of drying
12h after grinding, in 500 DEG C of 2 h of Muffle kiln roasting, obtains N-TiO2Catalyst.
Photochemical properties test: the N-TiO made from comparative example 32Catalyst Photocatalytic Degradation of Toluene, the conversion ratio of toluene
It is 28%.
Embodiment 1
40mL dehydrated alcohol, 0.071g copper nitrate, 5mL butyl titanate and 10mL glacial acetic acid are sequentially added into beaker, it will
Beaker is placed on magnetic agitation 30min on magnetic stirring apparatus, obtains solution A；0.353g urea is added in 10mL deionized water, glass bar
Stirring, is completely dissolved urea, obtains B solution；B solution is slowly dropped into solution A, 2h is stirred, obtains Cu-N-TiO2Colloidal sol, it is old
After changing for 24 hours, in 80 DEG C of at a temperature of dry 12h, after grinding, in 500 DEG C of Muffle kiln roasting 2h, copper is made and nitrogen co-doped repairs
Adorn titanium dioxide optical catalyst (Cu-N-TiO2Catalyst).
Photochemical properties test: the photochemical catalyst Photocatalytic Degradation of Toluene made from embodiment 1, the conversion ratio of toluene are
38%。
The characterization of copper made from embodiment 1 and nitrogen co-doped modified titanium dioxide photocatalyst:
1, SEM is tested
The scanning electron microscope (SEM) photograph of catalyst made from comparative example 1, comparative example 2, comparative example 3 and embodiment 1, as shown in Figure 1.Comparative example
1 TiO2The Cu-TiO of catalyst (Fig. 1 a), comparative example 22The N-TiO of catalyst (Fig. 1 b), comparative example 32Catalyst (Fig. 1 c) and
The Cu-N-TiO of embodiment 12Catalyst (Fig. 1 d).It can be clearly seen that sample bolus is got together from figure, this is attributed to
TiO2It the surface of nano particle can be very big, it is easy to reunite.Therefore, that observe in Electronic Speculum is TiO2Particle size
Rather than crystallite dimension.As seen from Figure 1, pure TiO2Particle it is maximum, Cu-N-TiO2Particle is minimum.Suitable Cu's and N
Incorporation can change TiO2Surface nature, make TiO2Surface can reduce, and then reduce TiO2Reunion between particle, shows
The incorporation of Cu and N can inhibit the reunion of crystal grain well.
2, XRD diagram spectrum analysis
Fig. 2 is TiO made from comparative example 12Cu-TiO made from catalyst, comparative example 22N- made from catalyst, comparative example 3
TiO2Cu-N-TiO made from catalyst and embodiment 12The XRD of catalyst schemes.X-ray diffraction analysis (XRD) is for measuring crystalline substance
Type structure, crystal form composition, crystallinity and crystallite dimension.It analyzes from Fig. 2 it is found that prepared sample shows stronger TiO2It is sharp
Titanium ore characteristic diffraction peak (101) peak, Cu-TiO in figure2、N-TiO2And Cu-N-TiO2XRD spectrum it is identical, illustrate
These three nano materials do not have any difference in terms of crystalline structure and particle size.Cu-TiO2、N-TiO2And Cu-N-TiO2With it is pure
TiO2The sample crystallinity that compares becomes smaller, it is seen that the incorporation of Cu and N changes TiO2Size.
3, UV Diffuse Reflectance Spectroscopy figure and forbidden bandwidth atlas analysis
UV Diffuse Reflectance Spectroscopy is usually used in nano-TiO2The diffusing reflection of powder surface is analyzed, according to sample at different wavelengths anti-
Rate is penetrated to detect the absorption spectrum under catalyst ultraviolet-visible light.TiO made from comparative example 12Made from catalyst, comparative example 2
Cu-TiO2N-TiO made from catalyst, comparative example 32Cu-N-TiO made from catalyst and embodiment 12The ultraviolet of catalyst is overflow
Reflectance spectrum figure, as shown in Figure 3.Pure TiO2Catalyst is most weak in the absorption of visibility region, and Cu-TiO2Catalyst, N-TiO2
Catalyst and Cu-N-TiO2Red Shift Phenomena, Cu-N-TiO all has occurred in catalyst ABSORPTION EDGE2Catalyst UV Diffuse Reflectance Spectroscopy figure
It shows most strong in visible region absorption.Light absorption threshold value is from pure TiO2400 nm extend to 550 nm, Cu-TiO2Catalysis
Agent and Cu-N-TiO2Catalyst has stronger absorption in 400~550 nm of visible light region.The above phenomenon possible cause
Be: suitable Cu doping can be in TiO2Valence band and conduction band between form intermediate level, make light induced electron and hole that transition occur
The energy of Shi Suoxu reduces；And N doping can also cause TiO2Band gap narrows, to make TiO2Optical response range red shift to visible
Light region.According to shock, you calculate band gap magnitude: (α hv)2=A(hv-Eg), wherein α, h, A and v correspond respectively to absorption coefficient,
The characteristic constant and light frequency of Planck's constant, semiconductor material.Such as Fig. 4, TiO2Adulterate the semiconductor material after Cu and N
Forbidden bandwidth narrows, and equally illustrates that material enhances the utilization rate of visible light.Semiconductor is calculated using the λ formula of Eg=1240/
Band gap magnitude TiO2、N-TiO2、Cu-TiO2And Cu-N-TiO2Forbidden bandwidth be respectively 3.11 eV, 3.03 eV, 2.51
EV and 2.28 eV.
4, infrared and photoluminescence spectra map analysis
TiO made from comparative example 12Cu-TiO made from catalyst, comparative example 22N-TiO made from catalyst, comparative example 32Catalysis
Cu-N-TiO made from agent and embodiment 12The infrared spectrogram of catalyst, as shown in Figure 5.From fig. 5, it can be seen that being in wave number
3400 cm-1、1600 cm-1With 500~800 cm-1There is strong absworption peak respectively in place, in 3437 cm-1The absorption peak of left and right is answered
TiO2The O-H stretching vibration of surface hydroxyl and absorption water, 1627 cm-1The absorption peak of left and right is TiO2The O-H of surface adsorption water
Bending vibration, 500~800 cm-1The absorption peak of left and right is the characteristic peak of O-Ti-O.But from N-TiO2And Cu-N-TiO2's
Do not occur the absorption peak of N-O in map, it may be possible to which, since doping is very little, signal is too weak not to be detected.
The service life of the photo-generated carrier of semiconductor catalyst is usually characterized with photoluminescence spectra, and fluorescence is usually utilized
The power of intensity determines photo-generated carrier recombination rate height, and fluorescence intensity is weaker, and recombination rate is lower.TiO made from comparative example 12
Cu-TiO made from catalyst, comparative example 22N-TiO made from catalyst, comparative example 32Cu- made from catalyst and embodiment 1
N-TiO2The photoluminescence spectra figure of catalyst, as shown in Figure 6.It is observed that Cu-N-TiO2Fluorescence intensity than other
Sample will be weak, show that the incorporation of Cu and N can effectively inhibit the compound of photo-generated carrier.
2The test of nano material photochemical properties:
Firstly, by the Cu-N-TiO of 0.1g2Nano material is put into reactor, is then injected into 20mL molal volume concentration and is
The toluene aqueous solution of 0.05mol/L, is passed through the oxygen of a period of time, is sufficiently stirred half an hour on magnetic stirring apparatus and is adsorbed
Processing finally opens light source and carries out illumination reaction.Every 30min that crosses detects gas concentration lwevel in reactor, wherein two
The concentration of carbonoxide uses nitrogen enterprising as the gas-chromatography (GC-2080) of carrier gas with thermal conductivity detector (TCD) (TCD)
Row detection.The gas in 0.6 mL reactor is taken with glass syringe, injects gas-chromatography.Toluene is calculated using following formula
Conversion ratio:
Toluene conversion: Conversion %=(C0-C)/C0 × 100%
In formula, C0 is the initial concentration of toluene, and C is a certain concentration of toluene in reaction process.
By Fig. 7 it can be observed that the CO of the growth all samples with light application time2Yield be continuously increased, in illumination
It is observed that Cu-N-TiO after two hours2CO2Yield reached 5800(ppm) left and right, be compared to pure TiO2
Improve nearly four times.This may be because when Cu mixes TiO2In, surface nature is improved, and intergranular reunion is reduced
Phenomenon increases the specific surface area of particle, and Cu appropriate2+Capture trap can be formed and capture light induced electron, make light induced electron with
Preferable separation is realized in hole, to improve Cu-N-TiO2Photocatalytic activity.Similarly, when N mixes TiO2In, N
It may replace the O in Ti-O key, generate corresponding O vacancy, these O vacancies are conducive to TiO2The separation of middle light induced electron and hole,
To be conducive to light-catalyzed reaction；And then improve Cu-N-TiO2Photocatalytic activity.
With pure TiO2For comparing, Cu-TiO2Catalyst, N-TiO2Catalyst and Cu-N-TiO2Catalyst is all shown
Preferable catalytic performance.Light-catalyzed reaction 120 min, Cu-N-TiO2Catalyst has reached 38% to the conversion ratio of toluene, than phase
Pure TiO under the conditions of2Catalytic activity improves nearly 4 times, as shown in Figure 8.
Embodiment 2
40mL dehydrated alcohol, 0.06g copper nitrate, 5mL butyl titanate and 15mL glacial acetic acid are sequentially added into beaker, will be burnt
Cup is placed on magnetic agitation 50min on magnetic stirring apparatus, obtains solution A；0.24g urea is added in deionized water, and glass bar stirring makes
Urea is completely dissolved, and obtains B solution；B solution is slowly dropped into solution A, 3h is stirred, obtains Cu-N-TiO2Colloidal sol, after being aged 22h,
In 100 DEG C of at a temperature of drying 10h, after grinding, in 550 DEG C of Muffle kiln roasting 2h, copper and nitrogen co-doped modification dioxy is made
Change titanium photochemical catalyst.
Embodiment 3
40mL dehydrated alcohol, 0.08g copper nitrate, 5mL butyl titanate and 12.5mL glacial acetic acid are sequentially added into beaker, it will
Beaker is placed on magnetic agitation 40min on magnetic stirring apparatus, obtains solution A；0.32g urea is added in deionized water, glass bar stirring,
It is completely dissolved urea, obtains B solution；B solution is slowly dropped into solution A, 2.5h is stirred, obtains Cu-N-TiO2Colloidal sol, ageing
After 23h, in 90 DEG C of at a temperature of drying 11h, after grinding, in 525 DEG C of Muffle kiln roasting 3h, copper and nitrogen co-doped modification is made
Titanium dioxide optical catalyst.
Embodiment 4
50mL dehydrated alcohol, 0.07g copper nitrate, 5mL butyl titanate and 10mL glacial acetic acid are sequentially added into beaker, will be burnt
Cup is placed on magnetic agitation 35min on magnetic stirring apparatus, obtains solution A；0.35g urea is added in deionized water, and glass bar stirring makes
Urea is completely dissolved, and obtains B solution；B solution is slowly dropped into solution A, 2h is stirred, obtains Cu-N-TiO2Colloidal sol, after being aged 23h,
In 90 DEG C of at a temperature of drying 11h, after grinding, in 525 DEG C of Muffle kiln roasting 4h, copper and nitrogen co-doped modification titanium dioxide is made
Titanium photochemical catalyst.
Embodiment 5
50mL dehydrated alcohol, 0.07g copper nitrate, 5mL butyl titanate and 15mL glacial acetic acid are sequentially added into beaker, will be burnt
Cup is placed on magnetic agitation 45min on magnetic stirring apparatus, obtains solution A；0.42g urea is added in deionized water, and glass bar stirring makes
Urea is completely dissolved, and obtains B solution；B solution is slowly dropped into solution A, 3h is stirred, obtains Cu-N-TiO2Colloidal sol, after ageing for 24 hours,
In 100 DEG C of at a temperature of drying 10h, after grinding, in 500 DEG C of Muffle kiln roasting 3h, copper and nitrogen co-doped modification dioxy is made
Change titanium photochemical catalyst.
Embodiment 6
50mL dehydrated alcohol, 0.065g copper nitrate, 5mL butyl titanate and 12.5mL glacial acetic acid are sequentially added into beaker,
Beaker is placed on magnetic agitation 50min on magnetic stirring apparatus, obtains solution A；0.325g urea is added in deionized water, and glass bar stirs
It mixes, is completely dissolved urea, obtain B solution；B solution is slowly dropped into solution A, 2.5h is stirred, obtains Cu-N-TiO2Colloidal sol, it is old
After changing 22.5h, in 85 DEG C of at a temperature of drying 11.5h, after grinding, in 520 DEG C of Muffle kiln roasting 2.5h, copper is made and nitrogen is total
Doping and modification titanium dioxide optical catalyst.
Embodiment 7
45mL dehydrated alcohol, 0.075g copper nitrate, 5mL butyl titanate and 10mL glacial acetic acid are sequentially added into beaker, it will
Beaker is placed on magnetic agitation 50min on magnetic stirring apparatus, obtains solution A；0.3g urea is added in deionized water, glass bar stirring,
It is completely dissolved urea, obtains B solution；B solution is slowly dropped into solution A, 3.5h is stirred, obtains Cu-N-TiO2Colloidal sol, ageing
After 23.5h, in 95 DEG C of at a temperature of drying 10.5h, after grinding, in 530 DEG C of Muffle kiln roasting 3.5h, copper is made and nitrogen is co-doped with
Miscellaneous modified titanium dioxide photocatalyst.
Embodiment 8
45mL dehydrated alcohol, 0.08g copper nitrate, 5mL butyl titanate and 15mL glacial acetic acid are sequentially added into beaker, will be burnt
Cup is placed on magnetic agitation 50min on magnetic stirring apparatus, obtains solution A；0.48g urea is added in deionized water, and glass bar stirring makes
Urea is completely dissolved, and obtains B solution；B solution is slowly dropped into solution A, 3.5h is stirred, obtains Cu-N-TiO2Colloidal sol, ageing
After 23.5h, in 95 DEG C of at a temperature of drying 10.5h, after grinding, in 530 DEG C of Muffle kiln roasting 3.5h, copper is made and nitrogen is co-doped with
Miscellaneous modified titanium dioxide photocatalyst.
Embodiment 9
45mL dehydrated alcohol, 0.072g copper nitrate, 5mL butyl titanate and 12.5mL glacial acetic acid are sequentially added into beaker,
Beaker is placed on magnetic agitation 50min on magnetic stirring apparatus, obtains solution A；0.282g urea is added in deionized water, and glass bar stirs
It mixes, is completely dissolved urea, obtain B solution；B solution is slowly dropped into solution A, 3.5h is stirred, obtains Cu-N-TiO2Colloidal sol, it is old
After changing 23.5h, in 95 DEG C of at a temperature of drying 10.5h, after grinding, in 530 DEG C of Muffle kiln roasting 3.5h, copper is made and nitrogen is total
Doping and modification titanium dioxide optical catalyst.
Claims (5)
1. the preparation method of a kind of copper and nitrogen co-doped modified titanium dioxide photocatalyst, which is characterized in that specifically press following step
It is rapid to carry out:
1) 1 ︰, 8~10 ︰ 2~3 by volume takes butyl titanate, dehydrated alcohol and glacial acetic acid respectively, then presses four fourth of 5mL metatitanic acid
The ratio of 0.06~0.08g copper nitrate is added in ester, takes copper nitrate；Urea, the quality of taken urea and taken copper nitrate are taken again
Than for 4~6 ︰ 1；
Dehydrated alcohol, copper nitrate, butyl titanate and glacial acetic acid are mixed in order, stirs, obtains solution A；
Taken urea is dissolved completely in deionized water, is stirred evenly, B solution is obtained；
2) B solution is slowly dropped into solution A, stirs, obtains Cu-N-TiO2Colloidal sol；
3) by Cu-N-TiO2It is dry after colloidal sol ageing, it grinds, copper and nitrogen co-doped modified titanic oxide photocatalysis is made in roasting
Agent.
2. the preparation method of copper as described in claim 1 and nitrogen co-doped modified titanium dioxide photocatalyst, which is characterized in that
In the step 3), Cu-N-TiO2Colloidal sol is aged 22~24 h.
3. the preparation method of copper as described in claim 1 and nitrogen co-doped modified titanium dioxide photocatalyst, which is characterized in that
In the step 3), Cu-N-TiO2After colloidal sol ageing, in 80 DEG C~100 DEG C of at a temperature of 10~12h.
4. the preparation method of copper as described in claim 1 and nitrogen co-doped modified titanium dioxide photocatalyst, which is characterized in that
In the step 3), in 500 DEG C~550 DEG C of 2~4h of roasting temperature after grinding.
5. copper made from preparation method described in a kind of claim 1 and nitrogen co-doped modified titanium dioxide photocatalyst are in photocatalysis
Application in degradation toluene.
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