CN106268903B - A kind of preparation method of the visible light catalyst of the surface nitrogen modifying titanium dioxide nano particle based on ALD technique - Google Patents
A kind of preparation method of the visible light catalyst of the surface nitrogen modifying titanium dioxide nano particle based on ALD technique 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 70
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 title claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 47
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 210000002381 plasma Anatomy 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010936 titanium Substances 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000012159 carrier gas Substances 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 10
- 229910052786 argon Inorganic materials 0.000 claims abstract description 9
- 229910010037 TiAlN Inorganic materials 0.000 claims abstract description 5
- 230000002000 scavenging effect Effects 0.000 claims abstract description 5
- 239000010409 thin film Substances 0.000 claims abstract description 5
- 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 abstract description 5
- 239000006227 byproduct Substances 0.000 claims abstract description 3
- 210000004027 cell Anatomy 0.000 claims abstract description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 25
- 230000008021 deposition Effects 0.000 claims description 12
- 239000010408 film Substances 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 abstract description 2
- 238000000231 atomic layer deposition Methods 0.000 description 21
- 235000010215 titanium dioxide Nutrition 0.000 description 19
- 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 15
- 229940012189 methyl orange Drugs 0.000 description 15
- 238000000151 deposition Methods 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- MNWRORMXBIWXCI-UHFFFAOYSA-N tetrakis(dimethylamido)titanium Chemical compound CN(C)[Ti](N(C)C)(N(C)C)N(C)C MNWRORMXBIWXCI-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000802 nitrating effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 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 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000739 chaotic effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- -1 metals cation Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 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
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000007736 thin film deposition technique Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000010148 water-pollination Effects 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
-
- 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
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The preparation method of the visible light catalyst of the invention discloses a kind of surface nitrogen modifying titanium dioxide nano particle based on ALD technique, is transferred to ALD reative cells by titania powder first, the depositional packages of ultra-thin TiAlN thin film is carried out to its surface, package parameters are：Reaction chamber temperature 100 500oC；Titanium source：Titanium tetrachloride, four dimethylamino titaniums or isopropyl titanate；Nitrogen source：Ammonia or ammonia plasmas；Carrier gas：Titanium source uses high pure nitrogen or argon gas as carrier gas, and flow is 50 200 sccm；Nitrogen source uses high-purity argon gas as carrier gas, and flow is 50 200 sccm；Pulse and scavenging period：Titanium source pulse is 0.1 10 s；After each inorganic source pulse all and then 2 60 s are cleaned with high pure nitrogen；Nitrogen source pulse is 5 60s, and then cleans 2 60 s with high pure nitrogen, washes out byproduct of reaction and remaining reaction source.This method is simple and practicable, and the visible light catalytic performance of product significantly increases.
Description
Technical field
The present invention relates to a kind of preparation methods for realizing efficient visible light catalyst using technique for atomic layer deposition, belong to new
Type nano-functional material prepares and photocatalysis field.
Background technology
With making constant progress for human society, the problem of environmental pollution faced is increasingly serious.TiO2Because it is cheap,
Safe and non-toxic, the advantages that stability is good, catalytic activity is high, research extensively and profoundly is obtained as catalysis material.But due to
TiO2It is broad-band gap（3.2 eV) semi-conducting material, it can only absorb the ultraviolet light less than 5% in sunlight, and the 50% of solar spectrum
For visible light, therefore TiO2Very low to the absorption efficiency of most visible lights in sunlight, application is very limited.
In order to make full use of sunlight, the doping vario-property of traditional photocatalytic semiconductor material is had been a great deal of attention.Such as
In TiO2Middle doping metals cation（Fe, Co, Ni, V, Mo etc.）Or nonmetallic ion（N, C, B, S, F etc.）It can effectively carry
High TiO2Photocatalytic activity under visible light, the wherein TiO of N doping2As research hotspot, attract most attention.
Atomic layer deposition（Atomic layer deposition, ALD）It is to be occurred in substrate surface based on gaseous precursor
A kind of novel thin film deposition technique of Chemisorption ensure that the large area of deposition is uniform from restricted with self-saturation
Property, three-dimensional conformability and film thickness exact controllability.In recent years, ALD is shown in fields such as semiconductor, new energy, photocatalysis
Wide application prospect especially shows advantage outstanding in terms of Surface Modification of Nanosized Materials.
Existing at present based on ALD technique is to use ammonia as nitrogen source to the mode of titanium dioxide nitrating, is introduced into
To ALD deposition TiO2Technique in realize the incorporation of nitrogen, but the effect is unsatisfactory for nitrating.On the other hand, photocatalytic degradation is anti-
The skin effect of powder should be depended on, therefore it is most important to carry out N doping modification to the surface of titanium dioxide.
Invention content
Technical problem to be solved by the invention is to provide a kind of nitrogen-doped modified to titania powder progress surface
Method, and then obtain a kind of efficient visible light catalyst of N surface-modified titanium dioxides nano particle.
The system of the visible light catalyst of surface nitrogen modifying titanium dioxide nano particle of the present invention based on ALD technique
Preparation Method comprising following steps：
1) titania powder is transferred to ALD reative cells, the depositional packages of ultra-thin TiAlN thin film is carried out to its surface, wrapped
The parameter for wrapping up in TiAlN thin film is：
Reaction chamber temperature：100-500oC；
Reaction source：Titanium source：Titanium tetrachloride（TiCl4）, four dimethylamino titaniums（Ti(NMe2)4,TDMAT）Or isopropyl titanate
（Ti(OiPr)4）；Nitrogen source：Ammonia or ammonia plasmas；
Carrier gas：Titanium source uses high pure nitrogen or argon gas（5N）As carrier gas, flow is 50-200 sccm；Nitrogen source uses
High-purity argon gas（5N）As carrier gas, flow is 50-200 sccm；
Ammonia pulse parameter：Flow is 10-200 sccm；
Ammonia plasmas parameter：Flow is 10-200 sccm, and plasma power is 100-3000 W.
Pulse and scavenging period：Titanium source pulse is 0.1-10 s；High Purity Nitrogen is all and then used after each inorganic source pulse
Gas cleans 2-60 s；Nitrogen source pulse is 5-60s, and then cleans 2-60 s with high pure nitrogen, washes out byproduct of reaction and residual
Reaction source；
2）Repeat step 1）Ultra-thin TiN until requiring thickness in titania powder surface deposition forms ultra-thin N doping
Titanium dioxide surface layer.
Above-mentioned steps 1）The titania powder can be commercialized titania powder P25.Titanium dioxide P25 is
The hydroxyl group of a kind of nano level white powder, surface makes it have hydrophily, and the product does not have any pigment feature.
The average grain diameter of basic granules is about 21nm, the size and 4g/cm of particle3Density make it have 50m2The special surface of/g.
Titanium dioxide P25 belongs to mixed crystal type, and the weight ratio of anatase and rutile is about 71/29, since two kinds of mixing up of structure increase
TiO2Intracell defect concentration increases the concentration of carrier, so that electronics, number of cavities is increased, makes it have stronger
Capture is in TiO2The solution components on surface（Water, oxygen, organic matter）Ability.
The present invention provides a kind of surface nitrogen method of modifying of titania nanoparticles, utilize technique for atomic layer deposition reality
Now to the depositional packages of titania nanoparticles very thin TiAlN thin film, achieve the effect that surface is nitrogen-doped modified.Use this
Method can carry out effective N doping to P25 powder surface, due to being only the ultra-thin TiN packets for carrying out several nanometers to surface
Modification is wrapped up in, few using raw material, experimental period is short, and visible light catalytic performance significantly increases.Pure P25 under visible light 30 minutes it is several
Without degradation methyl orange, and ALD technique is only used only, ultra-thin TiN is carried out to surface（Only ~ 2.3 nm）Wrap up it is modified, 30 points
Visible light greatly improves the degradation rate of methyl orange in clock, has reached 91%.This method is simple and practicable, and performance improvement is notable, greatly
Improve utilization rate of the business P25 powder to visible light.
Description of the drawings
Fig. 1, P25 powder and surface PEALD deposit the XRD spectrum of the P25 powder of different recurring numbers；
Fig. 2, P25 powder（a）With surface PEALD depositions 20（b）、50（c）With 100（d）Recycle the SEM of the P25 powder of TiN
Photo；
Fig. 3, P25（a）With the P25 of 50 cycle TiN of surface PEALD depositions（b）TEM figure；
Fig. 4, pure P25 powder and surface PEALD deposited (ahv) of the P25 powder of different recurring number TiN2- hv curves are quasi-
Close result；
The P25 that Fig. 5, pure P25, surface PEALD deposit different recurring number TiN is catalyst, it is seen that photocatalytic degradation methyl
The time graph of orange；
The P25 samples of 50 cycle TiN of Fig. 6, surface PEALD deposition reuse Photocatalytic Degradation of Methyl Orange three times
Rate；
The P25 samples of 50 cycle TiN of Fig. 7, surface A LD or PEALD deposition degrade under visible light methyl orange time it is bent
Line.
Specific implementation mode
Using embodiment below, the invention will be further described
Embodiment 1：
Use commercialized titania powder（P25）As carrier, ALD reactions are directly transferred to by powder sample tank
Room, using plasma enhance atomic layer deposition（PEALD）, the TiN depositional packages of 20,50 and 100 cycles are carried out to its surface.
Specific deposition parameter is as follows：Growth temperature is 360oC；Use titanium tetrachloride（TiCl4）With ammonia plasmas respectively as titanium
Source and nitrogen source；The high-purity argon gas of the high pure nitrogen and 50 sccm that use 150 sccm respectively is as carrier gas；Growing loop parameter is
0.1s TiCl4-4s N2- 21.5s ammonia plasmas -6s N2Cleaning；The flow of ammonia is 150 sccm, plasma power
For 2500 W.
Fig. 1 is the XRD spectrum for the P25 powder that P25 powder and surface PEALD deposit different recurring numbers, it is seen that all samples
It all shows similar diffraction maximum, corresponds to the titanium dioxide of Anatase.By calculating the lattice it can be found that all samples
Parameter is similar, and particle size is in 19 nm or so.Fig. 2 is the P25 powder that P25 powder and surface PEALD deposit different recurring numbers
SEM photograph, it can be seen that business P25 powder is the cluster reunited by small grains and formed, and tiny crystal grain is in 10-25 nm
Between, it substantially coincide with XRD Diffraction Calculations data.Showing after depositing different recurring number TiN, powder size does not have significant change, but
It is the agglomerate phenomenon for some micron dimensions occurred.Thus there is no the crystal knots for changing P25 powder for the deposition of a small amount of TiN in surface
Structure and crystallite dimension.By Fig. 3（a）TEM photos can be seen that the nanocrystalline crystallinity of pure P25 is good, and crystallite dimension is about on the left sides 20 nm
It is right；After 50 cycle TiN of surface deposition, there are a disordered layer or chaotic areas for P25 nanocrystal surfaces regional area（At b figure arrows）,
About 2 nm are thick, enter TiO with surface N doping2Lattice is related, but other regions still have good crystallinity.By powder
Uv-visible absorption spectroscopy figure can calculate the band gap of each sample, as shown in figure 4, pure TiO2（P25）Band gap be 3.32
EV, the micro N in surface adulterate TiO2Between 3.34-3.38 eV, band gap does not change the band gap of powder sample substantially.
It is degraded under visible light methyl orange using pure P25 and surface TiN the P25 powder being modified, the xenon lamp of 300W is used to make
For visible light source, ultraviolet portion (λ is filtered off with filter plate<Visible light 420nm) is obtained, leads to recirculated cooling water to keep its temperature
It is constant at 25 DEG C ± 0.5 DEG C, the distance of reaction solution identity distance light source is about 10 centimetres or so.Fig. 5 is heavy for pure P25 and surface PEALD
The time graph of the P25 of the different recurring number TiN of product catalytic degradation methyl oranges under visible light, it is found that pure P25 powder is can
Light-exposed lower basic without activity, methyl orange is not degraded substantially after 2 hours.After the N doping vario-properties of the surfaces P25, photocatalysis drop
Solution rate significantly becomes larger, and surface deposited the P25 samples of 20 cycle TiN, and the degradation rate of 2 h is increased to 58%, surface deposition
The P25 samples of 50 cycle TiN, 2 h photocatalytic activities are 85%, and surface deposited the P25 samples of 100 cycle TiN, light
Catalytic degradation efficiency highest reaches 97% after 2 h.
Embodiment 2：
Use commercialized titania powder（P25）As carrier, using plasma enhances atomic layer deposition
（PEALD）360oThe TiN of 50 cycles is deposited under C on the surfaces P25.Titanium tetrachloride and ammonia plasmas as titanium source and
Nitrogen source, carrier gas are respectively the high-purity argon gas of the high pure nitrogen and 50 sccm of 150 sccm；Growth loop parameter is 0.1s
TiCl4-4sN2- 21.5s ammonia plasmas -6sN2Cleaning；The flow of ammonia is 150 sccm, plasma power 2500
W。
Using the methyl orange solution for 4 mg/L of P25 powder degradation that above-mentioned surface is modified, every 100 mL methyl orange solutions make
With 100 mg P25 powder.2 h of irradiation catalysis under visible light, measure the degradation rate of methyl orange, then centrifuge solution
Separation recycles P25 powder, in box-annealing furnace 350oIt anneals under C two hours, the methyl orange of removal catalyst surface absorption,
The photo-catalytic degradation of methyl-orange under similarity condition again.So in triplicate, structure is as shown in Figure 6, it is found that by returning twice
The photochemical catalyst after utilizing is received compared with use for the first time, degradation efficiency is basically unchanged.Illustrate the surfaces PEALD N doping vario-properties
P25 photochemical catalysts, catalytic activity are stablized, can be repeatedly used.
Embodiment 3：
Use commercialized titania powder（P25）As carrier, using plasma enhances atomic layer deposition
（PEALD）360oThe TiN of 50 cycles is deposited under C on the surfaces P25.In order to enhance wrapping properties of the TiN to titanium dioxide granule
Can, extend the titanium tetrachloride burst length to 2s, other parameters such as embodiment 1.
Using the methyl orange solution for 4 mg/L of P25 powder degradation that above-mentioned surface is modified, every 100 mL methyl orange solutions make
With 100 mg P25 powder, this P25 sample degrade under visible light methyl orange time graph it is as shown in Figure 7.It can be found that prolonging
TiCl is grown4After the time of pulse, the P25 powder that surface N is modified greatly improves the catalytic effect of methyl orange, 2 h photocatalysis
Degradation rate is up to 94%.
Embodiment 4：
It is limited to incomplete package of the plasma to high-aspect-ratio material, TiN's is carried out to P25 using hot ALD patterns
Package.Growth temperature at this time is 400oC, using titanium tetrachloride and ammonia as titanium source and nitrogen source, carrier gas is respectively 150
The high-purity argon gas of the high pure nitrogen of sccm and 150 sccm；Growth loop parameter is 2 s TiCl4-4s N2- 21.5s ammonias-
6sN2The flow of cleaning, ammonia is 150 sccm.The TiN that 50 cycles are equally carried out to P25 is wrapped up.
The P25 powder of hot ALD modifications is as shown in Figure 7 to the catalytic degradation effect of methyl orange, it is found that uses hot ALD instead
After pattern, the catalytic effect for the P25 powder that surface N is modified further increases, and the photocatalytic activity of 0.5 h just reaches 91%, 1h
Methyl orange is completely broken down substantially afterwards.Therefore, the pattern of hot ALD is either used at high temperature by extending the burst length,
The surface modification to P25 powder can be enhanced, greatly improve the photocatalysis effect of P25 powder.
Embodiment 5：
Method in the present embodiment and embodiment 4 the difference is that, growth temperature 300oC is made using isopropyl titanate
For titanium source, the burst length of titanium tetrachloride and ammonia is increased to 30s, and scavenging period increases to 60s, and other parameters are then complete
Unanimously.The time of further extended pulse can promote the depositional packages to P25 powder surface.
Embodiment 6：
Method in the present embodiment and embodiment 1 the difference is that, growth temperature 200oC uses TDMAT conducts instead
Titanium source, TDMAT and nitrogen source burst length are increased to 60 s, and scavenging period is 60s, and other parameters are then completely the same.Deng from
Daughter enhancing atomic layer deposition can make reaction carry out at a lower temperature, and the fully long burst length is to realize to P25
The good package of powder.
There are many concrete application approach of the present invention, the above is only a preferred embodiment of the present invention, it is noted that for
For those skilled in the art, without departing from the principle of the present invention, it can also make several improvements, this
A little improve also should be regarded as protection scope of the present invention.
Claims (2)
1. a kind of preparation method of the visible light catalyst of the surface nitrogen modifying titanium dioxide nano particle based on ALD technique,
It is characterized in that including the following steps：
1) titania powder is transferred to ALD reative cells, the depositional packages of ultra-thin TiAlN thin film is carried out to its surface, wrap up TiN
The parameter of film is：
Reaction chamber temperature：100-500oC；
Reaction source：Titanium source：Titanium tetrachloride, four（Dimethylamino）Titanium or isopropyl titanate；Nitrogen source：Ammonia or ammonia plasmas；
Carrier gas：Titanium source uses high pure nitrogen or argon gas as carrier gas, and flow is 50-200 sccm；Nitrogen source uses high-purity argon gas
As carrier gas, flow is 50-200 sccm；
Ammonia pulse parameter：Flow is 10-200 sccm；
Ammonia plasmas parameter：Flow is 10-200 sccm, and plasma power is 100-3000 W；
Pulse and scavenging period：Titanium source pulse is 0.1-10 s；It is all and then clear with high pure nitrogen after each inorganic source pulse
Wash 2-60 s；Nitrogen source pulse be 5-60s, and then clean 2-60 s with high pure nitrogen, wash out byproduct of reaction and it is remaining instead
Ying Yuan；
2）Repeat step 1）Ultra-thin TiN until requiring thickness in titania powder surface deposition forms ultra-thin N doping dioxy
Change titanium superficial layer.
2. the visible light catalytic of the surface nitrogen modifying titanium dioxide nano particle according to claim 1 based on ALD technique
The preparation method of agent, it is characterised in that step 1）The titania powder is titania powder P25.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610582290.4A CN106268903B (en) | 2016-07-22 | 2016-07-22 | A kind of preparation method of the visible light catalyst of the surface nitrogen modifying titanium dioxide nano particle based on ALD technique |
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| CN201610582290.4A CN106268903B (en) | 2016-07-22 | 2016-07-22 | A kind of preparation method of the visible light catalyst of the surface nitrogen modifying titanium dioxide nano particle based on ALD technique |
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| CN106268903A CN106268903A (en) | 2017-01-04 |
| CN106268903B true CN106268903B (en) | 2018-08-24 |
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