CN109932351A - A kind of TiO2The preparation method of/ZnO heterojunction semiconductor SERS active-substrate - Google Patents
A kind of TiO2The preparation method of/ZnO heterojunction semiconductor SERS active-substrate Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000243 solution Substances 0.000 claims abstract description 47
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 45
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- 238000001514 detection method Methods 0.000 abstract description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract description 2
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Abstract
A kind of TiO2The preparation method of/ZnO heterojunction semiconductor SERS active-substrate, it is related to the preparation method of SERS active-substrate.It is to solve existing TiO2/ ZnO heterojunction semiconductor preparation method is complicated, as SERS substrate when the low technical problem of activity.This method: solution of tetrabutyl titanate is instilled in ethyl alcohol, water and concentrated nitric acid mixed liquor and prepares colloidal sol, then through hydro-thermal and roasting, obtains TiO2Nanoparticle；By TiO2Nanoparticle is added to Zn (NO3)2.6H2In O aqueous solution, NaOH aqueous solution and promotor are added, stirring, sedimentation, drying, roasting obtain TiO2The novel SERS active-substrate of/ZnO heterojunction semiconductor.It reaches 1 × 10 to the concentration limit of 4- mercaptopyridine‑9M can be used for surface-enhanced Raman detection field.
Description
Technical field
The present invention relates to the preparation methods of SERS active-substrate.
Background technique
Surface enhanced Raman scattering (Surface-enhanced Raman Scattering, SERS) effect is due to dividing
The species such as son absorption or very close to when the surface of certain nanostructure (i.e. so-called SERS active-substrate), Raman
Signal strength has the phenomenon that significantly increasing compared to its bulk mole.SERS is since it is with high sensitivity, highly selective, high
Accuracy, quickly, non-destructive testing the advantages that, pass through applied to many fields, especially in environmental catalysis, chemistry and bio-sensing
Device, Surface Science and material science etc. have outstanding behaviours.The generation of SERS, which depends on, has the active substrate of SERS, SERS
Active substrate experienced from metal material to semiconductor material, again to the development course of metal/semiconductor composite material, about
The preparation of SERS active-substrate and the research for enhancing mechanism are always hot spot concerned by people.
Wide band gap semiconducter nano material (TiO2, ZnO etc.) have stable chemical performance, acid-fast alkali-proof it is good, to biology
Body is nontoxic and has many advantages, such as good biocompatibility, is widely used in the fields such as environmental protection, photocatalysis.Exactly by
Excellent properties and extensive use in wide band gap semiconducter nano material, the SERS based on wide band gap semiconducter just gradually cause people
Extensive concern, but be still in the primary stage currently based on the SERS of semiconductor research, substrate forms are more single, SERS
Enhancing ability is significantly smaller than noble metal substrate.Therefore, the high-performance semiconductor base SERS active-substrate of Development of Novel has important
Theoretical and practical significance.
Semiconductor is mostly derived from the electric charge transfer between semiconductor base and molecule to the SERS enhancing of binding molecule and contributes,
The special surface property of semiconductor base is also relied on simultaneously, therefore is improved the charge transfer effciency between substrate and molecule, mentioned
The specific surfaces enhancing Raman active of high substrate may be the effective of Development of Novel high-performance semiconductor base SERS active-substrate
One of approach.
Semiconductor heterostructure is usually to be made of two or more different materials, they respectively have different band gaps.By
In forming heterojunction structure, the change of electronic state and surface property, so that the surface and interface performance generation of heterojunction structure is bright
Aobvious change, it is thus possible to excellent optical physics or photochemical properties can be brought.Currently, about TiO2The research of/ZnO heterojunction
It is limited only to some fields such as photocatalysis.588-593 pages of " nanoscale " (Nanoscale) the 5th phase in 2013 is upper disclosed
A kind of article " efficient TiO2@ZnO n-p-n hetero-junctions nano-rod photo-catalyst " (A Highly efficient TiO2@ZnO
N-p-n heterojunction nanorod photocatalyst) in use P25TiO2In conjunction with ZnO, form heterogeneous
Material is tied, and as photochemical catalyst in the research of photocatalytic activity.On the one hand this method needs in the synthesis process
PH value is controlled, P25TiO is on the other hand used2It is suspended in it on synthetic ZnO nanorod by hydro-thermal method, due to different
The asynchronous synthesis of matter knot and its Component units, therefore the hetero-junctions that this method obtains is unfavorable for forming good interfacial effect,
Activity is poor when as SERS substrate." British royal chemistry can be in progress " (RSC Adv.) is the 8064-8070 of the 8th phase in 2018
Article " ZnO@TiO disclosed in page2The thermal decomposition method of nano tube hetero-junction structure film prepares and its photocatalysis performance "
(Preparation of ZnO@TiO2nanotubes heterostructured film by thermal
Decomposition and their photocatalytic performances) use thermal decomposition method to be prepared for ZnO@
TiO2Nano tube hetero-junction film, while being used for the research of photocatalysis performance.But this method synthesis condition is more complicated, needs
Zinc acetate is added to TiO2In nanotube, harsh preparation process brings very big difficulty to the preparation of sample.
Up to the present, by TiO2/ ZnO heterojunction semiconductor not yet appears in the newspapers as the research of SERS substrate.Also,
The TiO reported in photocatalysis field at present2The preparation method of/ZnO heterojunction does not have specificity contribution to SERS effect, obtains
Large-sized nanometer rods (or pipe) and its interface cohesion mode be unsuitable for the application in the field SERS.
Summary of the invention
The present invention is to solve existing TiO2/ ZnO heterojunction semiconductor preparation method is complicated, it is living when SERS substrate to be used as
The low technical problem of property, and a kind of TiO is provided2The preparation method of the novel SERS active-substrate of/ZnO heterojunction semiconductor.
TiO of the invention2The preparation method of/ZnO heterojunction semiconductor SERS active-substrate, sequentially includes the following steps:
One, butyl titanate and absolute ethyl alcohol and stirring are uniformly mixed for 1:1 by volume, obtain solution A；
Two, by volume (5~7): (5~7): 1 is uniformly mixed ethyl alcohol, water and concentrated nitric acid, obtains solution B；By solution A
It is added dropwise in solution B, after completion of dropwise addition, stirs 100~120min, obtain colloidal sol；
Three, colloidal sol is transferred in water heating kettle, is put into 6~7h of hydro-thermal reaction at 155~165 DEG C of baking oven, naturally cools to
Room temperature after outwelling waste liquid, obtained hydrothermal product is put into baking oven at 75~80 DEG C and dries 6~7h, after natural cooling, then
Grind into powder obtains predecessor；
Four, predecessor is placed in Muffle furnace, is warming up to 450~460 DEG C of 2~3h of roasting, obtains TiO2Nanoparticle；
Five, NaOH aqueous solution is prepared, solution I is denoted as；
Six, Zn (NO is prepared3)2.6H2O aqueous solution is denoted as solution II；Again by TiO2Nanoparticle is added in solution II,
Wherein TiO2With Zn (NO3)2.6H2The molar ratio of O is (1~1.2): 1；It stirs evenly, obtains suspension；
Seven, under agitation, solution I is added in suspension and is stirred evenly, is then added at one time promotor,
30~40min is settled after stirring 50~70min, after removing supernatant, oven drying, then grind into powder is put into, obtains heterogeneous
Tie predecessor；Wherein promotor is NH4HCO3, wherein NH4HCO3With Zn (NO3)2.6H2The mass ratio of O is 1:(2~3), or
Promotor is NH4HCO3With the combination of laureth sodium sulfovinate, wherein NH4HCO3With Zn (NO3)2.6H2The mass ratio of O is
1:(2~3), laureth sodium sulfovinate and Zn (NO3)2.6H2The molar ratio of O is (1~1.6): 200；
Eight, hetero-junctions predecessor is placed in Muffle furnace, is warming up to 400~410 DEG C of 2~3h of roasting, obtains TiO2/ZnO
Heterojunction semiconductor SERS active-substrate.
Further, in step 2, speed when solution A is added dropwise in solution B is to instill within 2~3 seconds 1 drop；
Further, in step 5, the concentration of NaOH aqueous solution is 0.02~0.03g/mL；
Further, in step 6, Zn (NO3)2.6H2The concentration of O aqueous solution is 0.02~0.04g/mL；
Further, in step 7, Zn (NO in the quality of NaOH and suspension in solution I3)2.6H2The mass ratio of O is
1:(2~4)；
Further, in step 7, the drying is dry 19~20h at 75~80 DEG C.
The present invention is prepared for a kind of TiO using seasoning2/ ZnO heterojunction, this method is simple, cost of material is low, nontoxic nothing
It is harmful, environmental-friendly.It joined promotor, accelerant N H when preparing hetero-junctions4HCO3, so that TiO2With Zn2+Ion is in molecular water
Uniform TiO is generated on the basis of flat mixing2/ ZnO heterojunction structure；NH4HCO3Promotion is combined with laureth sodium sulfovinate
Agent not only can be generating uniform TiO on the basis of molecular level mixes2/ ZnO heterojunction structure, while laureth
Sodium sulfovinate can control the generating rate and its interface performance of hetero-junctions, so that the hetero-junctions formed has higher specificity
SERS effect.
Due to TiO prepared by the present invention2/ ZnO heterojunction has the SERS effect of specificity, therefore SERS with higher
Activity.4- mercaptopyridine (4-MPY) probe molecule is in TiO of the invention2In/ZnO heterojunction substrate, concentration limit can
Reach 1 × 10-9M, this is highest detection sensitivity in the semiconductor base reported at present.TiO of the invention2/ ZnO heterojunction
The range of SERS technology and semiconductor SERS active-substrate is expanded.
Detailed description of the invention
Fig. 1 is TiO prepared by embodiment 12/ ZnO heterojunction semiconductor SERS active-substrate, comparative test 1 prepare pure
Anatase TiO2ZnO nanoparticle, the unfired predecessor system of comparative test 3 prepared by nanoparticle, comparative test 2
Standby TiO2The enhancing Raman spectrogram of/ZnO heterojunction semiconductor；
Fig. 2 is the TiO that embodiment 1 is prepared under the conditions of 400 DEG C2/ ZnO heterojunction semiconductor SERS active-substrate and implementation
The TiO that example 2 is prepared under the conditions of 450 DEG C, 500 DEG C, 550 DEG C respectively2The enhancing Raman spectrogram of/ZnO heterojunction semiconductor；
Fig. 3 is embodiment 1 in TiO2With Zn (NO3)2.6H2The TiO that the molar ratio of O is prepared under conditions of being 1:12/ ZnO half
Conductor hetero-junctions SERS active-substrate and embodiment 3 are in TiO2With Zn (NO3)2.6H2The molar ratio of O is 2:1,3:1,4:1,5:1
Under the conditions of the TiO for preparing2The enhancing Raman spectrogram of/ZnO heterojunction semiconductor；
Fig. 4 is the TiO that various concentration 4- mercaptopyridine (4-MPY) ethanol solution is adsorbed on the preparation of embodiment 12/ ZnO is partly led
Enhancing Raman spectrogram in bulk heterojunction SERS active-substrate；
Fig. 5 is TiO prepared by embodiment 12Prepared by/ZnO heterojunction semiconductor SERS active-substrate and embodiment 4 partly leads
The enhancing Raman spectrogram of bulk heterojunction SERS active-substrate.
Specific embodiment
Beneficial effects of the present invention are verified with the following examples:
Embodiment 1: the TiO of the present embodiment2The preparation method of/ZnO heterojunction semiconductor SERS active-substrate, by following step
It is rapid to carry out:
One, 15mL butyl titanate is added in 15mL dehydrated alcohol, stirs 10min, obtains solution A；
Two, the concentrated nitric acid that 15mL dehydrated alcohol, 15mL water and 3mL mass percentage concentration are 65% is mixed, stirring
10min obtains solution B；Under agitation, solution A is added dropwise in solution B, control rate of addition was added dropwise in 2-3 seconds/drop
After, 120min is stirred, pale yellow transparent colloidal sol is obtained；
Three, colloidal sol is transferred in water heating kettle, is put into hydro-thermal reaction 6h at 160 DEG C of baking oven, cooled to room temperature is outwelled
After waste liquid, obtained hydrothermal product is put into baking oven at 80 DEG C and dries 6h, after natural cooling, then grind into powder, it obtains
Predecessor；
Four, predecessor is placed in Muffle furnace, is warming up to 450 DEG C of roasting 2h, obtains TiO2Nanoparticle；
Five, it weighs 1.6g NaOH to be dissolved in 80mL deionized water, obtains NaOH aqueous solution, be denoted as solution I；
Six, 5.9498g Zn (NO is weighed3)2.6H2O is dissolved in 200mL deionized water, is denoted as solution II；Again by 1.5973g
TiO2Nanoparticle is added in solution II, TiO2With Zn (NO3)2.6H2The molar ratio of O is 1:1；It stirs evenly, is suspended
Liquid；
Seven, under agitation, solution I is added in suspension and is stirred evenly, is then added at one time 2.4g
NH4HCO3, the laureth sodium sulfovinate aqueous solution that 5mL concentration is 0.02mol/L is added, is settled after stirring 60min
30min after removing supernatant, is put into 80 DEG C of baking oven dry 20h, then grind into powder, obtains hetero-junctions predecessor；
Eight, hetero-junctions predecessor is placed in Muffle furnace, is warming up to 400 DEG C of roasting 2h, obtains TiO2/ ZnO semiconductor is different
Matter knot SERS active-substrate.
Comparative test 1: pure anatase TiO is prepared2Nanoparticle is with comparing, and specific preparation step is as follows: first
15mL butyl titanate is added in 15mL dehydrated alcohol and stirs 10min, obtains solution of tetrabutyl titanate, is denoted as solution A；It will
The concentrated nitric acid that 15mL dehydrated alcohol, 15mL water and 3mL mass percentage concentration are 65% mixes, and stirs 10min, obtains solution B；?
Under stirring condition, solution A is slowly dropped in solution B and is hydrolyzed, keeps rate of addition 2-3 seconds/drop, after completion of dropwise addition,
Continue to stir 2h, obtains pale yellow transparent colloidal sol；Then obtained colloidal sol is transferred in water heating kettle, is put into 160 DEG C of baking oven
Lower hydro-thermal reaction 6h, cooled to room temperature after outwelling waste liquid, will obtain hydrothermal product and evenly spread in surface plate, by table
Face ware, which is put into baking oven at 80 DEG C, dries 6h, after natural cooling, is put into grind into powder in mortar and obtains predecessor；By forerunner
Object roasts 2h at 450 DEG C to get pure anatase TiO is arrived2Nanoparticle.
Comparative test 2: for preparation ZnO nanoparticle with comparing, specific preparation step is as follows: it is molten to weigh 1.6g NaOH
In 80mL deionized water, NaOH solution is obtained；Weigh 5.9498g Zn (NO3)2.6H2O is dissolved in 200mL deionized water, is obtained
To Zn (NO3)2Solution；Under agitation, obtained NaOH solution is instilled into Zn (NO3)2In solution, rate of addition 2-3 is kept
Second/drop after completion of dropwise addition, settles 30min after stirring 60min, pours out supernatant, obtain white suspension；Suspension is put into
In baking oven at 80 DEG C dry 19h, after natural cooling, grind into powder obtains predecessor；Predecessor is placed in Muffle furnace again
2h is roasted at 400 DEG C to get ZnO nanoparticle is arrived.
Comparative test 3: this comparative test omits step 4 unlike the first embodiment, i.e., is not fired predecessor；Step
In rapid six, predecessor is substituted into TiO2Nanoparticle is operated；It is other same as Example 1, obtain TiO2/ ZnO semiconductor is different
Matter knot.
TiO prepared by embodiment 12/ ZnO heterojunction semiconductor SERS active-substrate, comparative test 1 are prepared pure sharp
Titanium ore TiO2The TiO of ZnO nanoparticle, the preparation of comparative test 3 prepared by nanoparticle, comparative test 22/ ZnO heterogeneous semiconductor
It is 1 × 10 that knot is distributed to 8mL concentration respectively-3In 4- mercaptopyridine (4-MPY) ethanol solution of M, magnetic agitation 6h at room temperature.So
Afterwards, mixture 9500 revolutions per seconds of centrifuge are put into be centrifuged 12 minutes, later with being centrifuged after ethanol washing, repetitive operation 2 times.From
So to get the material for arriving probe molecule 4-MPY surface modification after drying.Using HORIBA LabRam ARAMIS type Raman spectrum
Instrument, the wavelength of excitation light source are 633nm, carry out Raman spectrum test, obtained enhancing Raman spectrogram is as shown in Figure 1, from Fig. 1
In as can be seen that embodiment 1 prepare TiO2The performance of/ZnO heterojunction semiconductor SERS active-substrate is significantly better than TiO2、ZnO
Itself；The TiO calcined through 450 DEG C2The SERS performance of the hetero-junctions of formation is better than predecessor, i.e., unfired TiO2It is formed
TiO2/ ZnO heterojunction.This illustrates stable TiO2Skeleton is conducive to being successfully formed for hetero-junctions, and has excellent table, interface
Performance, using the TiO of 450 DEG C of calcined states2It is to form high performance Ti O2The key of/ZnO heterojunction semiconductor SERS substrate.
Embodiment 2: the TiO of the present embodiment2The preparation method and embodiment 1 of/ZnO heterojunction semiconductor SERS active-substrate
The difference is that the maturing temperature in step 8 is respectively 450 DEG C, 500 DEG C, 550 DEG C；It is other same as Example 1.
The TiO that embodiment 1 is prepared under the conditions of 400 DEG C2/ ZnO heterojunction semiconductor SERS active-substrate and embodiment 2
The TiO prepared under the conditions of 450 DEG C, 500 DEG C, 550 DEG C respectively2/ ZnO heterojunction semiconductor be distributed to respectively 8mL concentration be 1 ×
10-3In 4- mercaptopyridine (4-MPY) ethanol solution of M, magnetic agitation 6h at room temperature.Then, mixture is put into centrifuge
9500 revolutions per seconds are centrifuged 12 minutes, later with being centrifuged after ethanol washing, repetitive operation 2 times.Divide after natural drying to get to probe
The material of sub- 4-MPY surface modification.Using HORIBA LabRam ARAMIS type Raman spectrometer, the wavelength of excitation light source is
633nm carries out Raman spectrum test, and obtained enhancing Raman spectrogram is as shown in Fig. 2, it will be clear that working as from figure
TiO2When the maturing temperature of/ZnO heterojunction in step 8 is 400 DEG C, with the TiO prepared under other maturing temperatures2/ ZnO phase
Than SERS enhances ability highest.This is because due to as temperature increases, the reduction of hetero-junctions formation efficiency leads to surface
It is reduced in combination with site, so that the SERS performance of prepared substrate is affected, 400~410 DEG C of maturing temperatures that the present invention selects,
Good SERS activity is obtained.
Embodiment 3: the TiO of the present embodiment2The preparation method and embodiment 1 of/ZnO heterojunction semiconductor SERS active-substrate
The difference is that in step 6, TiO2With Zn (NO3)2.6H2The molar ratio of O is 2:1,3:1,4:1,5:1；It is other with 1 phase of embodiment
Together.
By embodiment 1 in TiO2With Zn (NO3)2.6H2The TiO that the molar ratio of O obtains under conditions of being 1:12/ ZnO semiconductor
Hetero-junctions SERS active-substrate and embodiment 3 are in TiO2With Zn (NO3)2.6H2The molar ratio of O is 2:1,3:1,4:1,5:1 condition
The TiO of lower preparation2It is 1 × 10 that/ZnO heterojunction semiconductor is distributed to 8mL concentration respectively-34- mercaptopyridine (4-MPY) ethyl alcohol of M
In solution, magnetic agitation 6h at room temperature.Then, mixture is put into 9500 revolutions per seconds of centrifuge to be centrifuged 12 minutes, uses ethyl alcohol later
It is centrifuged after washing, repetitive operation 2 times.The material of probe molecule 4-MPY surface modification is arrived after natural drying.Using
HORIBA LabRam ARAMIS type Raman spectrometer, the wavelength of excitation light source are 633nm, carry out Raman spectrum test, obtain
Enhancing Raman spectrogram as shown in figure 3, it can be seen from the figure that the enhancing for the heterojunction semiconductor that different composition ratio obtains
Degree is different, wherein 4-MPY Molecular Adsorption is in TiO2With Zn (NO3)2.6H2The TiO that the molar ratio of O is prepared when being 1:12/ ZnO half
Maximum SERS enhancing is shown in conductor hetero-junctions SERS active-substrate.This is attributed to addition TiO2The amount mistake of nanoparticle
It is more, inhibiting effect can be generated to the formation of hetero-junctions.The TiO that the present invention selects2With Zn (NO3)2 .6H2The molar ratio of O be (1~
1.2): 1 TiO prepared2The SERS signal of probe molecule can be improved in/zno-based bottom.
TiO prepared by 20mg embodiment 12/ ZnO heterojunction semiconductor SERS active-substrate is distributed to 8mL concentration respectively
It is 1 × 10-3、1×10-4、1×10-5、1×10-6、1×10-7、1×10-8、1×10-9With 1 × 10-104- mercaptopyridine (the 4- of M
MPY) in ethanol solution, magnetic agitation 6h at room temperature.Then, mixture 9500 revolutions per seconds of centrifuge are put into be centrifuged 12 minutes, it
Afterwards with being centrifuged after ethanol washing, repetitive operation 2 times.The TiO of probe molecule 4-MPY surface modification is arrived after natural drying2/
ZnO heterojunction material.Using HORIBA LabRam ARAMIS type Raman spectrometer, the wavelength of excitation light source is 633nm,
Obtained Raman spectrogram is as shown in Figure 4.From fig. 4, it can be seen that TiO2The minimum detection limit of/ZnO heterojunction SERS substrate reaches
To 10-9M.It follows that this novel TiO2The detectability of/ZnO heterojunction semiconductor SERS active-substrate is higher than general
Logical TiO2, and it is better than common zno-based bottom.Therefore, this novel TiO2/ ZnO heterojunction semiconductor shows as SERS substrate
Excellent SERS performance.
Embodiment 4: the TiO of the present embodiment2The preparation method and embodiment 1 of/ZnO heterojunction semiconductor SERS active-substrate
Unlike: the operation of step 7 is as follows: under agitation, solution I is added in suspension and stirred evenly, then one
2.4g NH is added in secondary property4HCO3, 30min is settled after stirring 60min, after removing supernatant, is put into oven drying, then pulverize
End obtains hetero-junctions predecessor；It is other same as Example 1.Obtain TiO2/ ZnO heterojunction semiconductor SERS active-substrate.
TiO prepared by embodiment 12TiO prepared by/ZnO surface-enhanced Raman scattering activity substrate and embodiment 42/ZnO
It is 1 × 10 that heterojunction semiconductor SERS active-substrate is distributed to 8mL concentration respectively-34- mercaptopyridine (4-MPY) ethanol solution of M
In, magnetic agitation 6h at room temperature.Then, mixture is put into 9500 revolutions per seconds of centrifuge to be centrifuged 12 minutes, uses ethanol washing later
After be centrifuged, repetitive operation 2 times.The material of probe molecule 4-MPY surface modification is arrived after natural drying.Using HORIBA
LabRam ARAMIS type Raman spectrometer, the wavelength of excitation light source are 633nm, carry out Raman spectrum test, obtained enhancing is drawn
Graceful spectrogram is as shown in Figure 5.As shown in Figure 5, with NH4HCO3The compound accelerant combined with laureth sodium sulfovinate obtains
TiO2The SERS performance at/zno-based bottom is than single NH4HCO3Promotor has further raising.Laruyl alcohol is poly- in preparation process
Ether sodium sulfovinate, which can control the generating rate of hetero-junctions and obtain, has the interface characteristics of specificity contribution to SERS effect
Can, make the heterojunction structure to be formed that there is higher SERS activity to probe molecule.
Claims (8)
1. a kind of TiO2The preparation method of/ZnO heterojunction semiconductor SERS active-substrate, it is characterised in that this method presses following step
It is rapid to carry out:
One, butyl titanate and absolute ethyl alcohol and stirring are uniformly mixed for 1:1 by volume, obtain solution A；
Two, by volume (5~7): (5~7): 1 is uniformly mixed ethyl alcohol, water and concentrated nitric acid, obtains solution B；Solution A is instilled
Into solution B, after completion of dropwise addition, 100~120min is stirred, colloidal sol is obtained；
Three, colloidal sol is transferred in water heating kettle, is put into 6~7h of hydro-thermal reaction at 155~165 DEG C of baking oven, cooled to room temperature,
After outwelling waste liquid, obtained hydrothermal product is put into baking oven at 75~80 DEG C and dries 6~7h, after natural cooling, then ground
At powder, predecessor is obtained；
Four, predecessor is placed in Muffle furnace, is warming up to 450~460 DEG C of 2~3h of roasting, obtains TiO2Nanoparticle；
Five, NaOH aqueous solution is prepared, solution I is denoted as；
Six, Zn (NO is prepared3)2.6H2O aqueous solution is denoted as solution II；Again by TiO2Nanoparticle is added in solution II, wherein
TiO2With Zn (NO3)2.6H2The molar ratio of O is (1~1.2): 1；It stirs evenly, obtains suspension；
Seven, under agitation, solution I is added in suspension and is stirred evenly, is then added at one time promotor, is stirred
30~40min is settled after 50~70min, after removing supernatant, oven drying, then grind into powder is put into, before obtaining hetero-junctions
Drive object；Wherein promotor is NH4HCO3, wherein NH4HCO3With Zn (NO3)2.6H2The mass ratio of O is 1:(2~3), or promote
Agent is NH4HCO3With the combination of laureth sodium sulfovinate, wherein NH4HCO3With Zn (NO3)2.6H2The mass ratio of O is 1:(2
~3), laureth sodium sulfovinate and Zn (NO3)2.6H2The molar ratio of O is (1~1.6): 200；
Eight, hetero-junctions predecessor is placed in Muffle furnace, is warming up to 400~410 DEG C of 2~3h of roasting, obtains TiO2The surface /ZnO increases
Strong Raman scattering active substrate.
2. a kind of TiO according to claim 12The preparation method of/ZnO heterojunction semiconductor SERS active-substrate, feature
It is in step 2, speed when solution A is added dropwise in solution B is to instill within 2~3 seconds 1 drop.
3. a kind of TiO according to claim 1 or 22The preparation method of/ZnO heterojunction semiconductor SERS active-substrate,
It is characterized in that in step 5, the concentration of NaOH aqueous solution is 0.02~0.03g/mL.
4. a kind of TiO according to claim 1 or 22The preparation method of/ZnO heterojunction semiconductor SERS active-substrate,
It is characterized in that in step 6, Zn (NO3)2.6H2The concentration of O aqueous solution is 0.02~0.04g/mL.
5. a kind of TiO according to claim 1 or 22The preparation method of/ZnO heterojunction semiconductor SERS active-substrate,
It is characterized in that in step 7, Zn (NO in the quality of NaOH and suspension in solution I3)2.6H2The mass ratio of O is 1:(2~4).
6. a kind of TiO according to claim 1 or 22The preparation method of/ZnO heterojunction semiconductor SERS active-substrate,
It is characterized in that in step 7, the drying is dry 19~20h at 75~80 DEG C.
7. the TiO prepared by method described in claim 12/ ZnO heterojunction semiconductor SERS active-substrate.
8.TiO2Application of/ZnO the heterojunction semiconductor as SERS active-substrate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113567414A (en) * | 2021-07-02 | 2021-10-29 | 合肥工业大学 | ZIF 8-derived semiconductor heterojunction-silver SERS substrate and preparation method and application thereof |
| CN116408127A (en) * | 2023-04-26 | 2023-07-11 | 吉林大学 | Multiphase nano composite photocatalyst, preparation method and application |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5518419A (en) * | 1978-07-25 | 1980-02-08 | Shin Etsu Chem Co Ltd | Manufacture of molded foamed silicone resin article |
| CN1865936A (en) * | 2006-05-10 | 2006-11-22 | 吉林大学 | SERS detection method employing nano semiconductor material as substrate |
| CN102505128A (en) * | 2011-12-23 | 2012-06-20 | 西北有色金属研究院 | Method for directly preparing porous metal product by molten salt electrolysis |
| CN102706857A (en) * | 2012-07-02 | 2012-10-03 | 中国科学院合肥物质科学研究院 | Preparation method of multifunctional surface enhanced raman scattering (SERS) substrate |
| CN103673866A (en) * | 2013-12-13 | 2014-03-26 | 山东大学 | Method for determining strain of under-grid barrier layer of GaN heterojunction field effect transistor |
| CN104945957A (en) * | 2015-06-29 | 2015-09-30 | 镇江纳微新材料科技有限公司 | Graphene-base all-band ultraviolet shielding material and preparation method thereof |
| CN108330525A (en) * | 2018-01-31 | 2018-07-27 | 南京工业大学 | Preparation method of titanium oxide porous membrane SERS substrate |
| US20180340174A1 (en) * | 2014-11-11 | 2018-11-29 | Nanocore Aps | Method for identification of molecules with desired characteristics |
-
2019
- 2019-03-15 CN CN201910196490.XA patent/CN109932351B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5518419A (en) * | 1978-07-25 | 1980-02-08 | Shin Etsu Chem Co Ltd | Manufacture of molded foamed silicone resin article |
| CN1865936A (en) * | 2006-05-10 | 2006-11-22 | 吉林大学 | SERS detection method employing nano semiconductor material as substrate |
| CN102505128A (en) * | 2011-12-23 | 2012-06-20 | 西北有色金属研究院 | Method for directly preparing porous metal product by molten salt electrolysis |
| CN102706857A (en) * | 2012-07-02 | 2012-10-03 | 中国科学院合肥物质科学研究院 | Preparation method of multifunctional surface enhanced raman scattering (SERS) substrate |
| CN103673866A (en) * | 2013-12-13 | 2014-03-26 | 山东大学 | Method for determining strain of under-grid barrier layer of GaN heterojunction field effect transistor |
| US20180340174A1 (en) * | 2014-11-11 | 2018-11-29 | Nanocore Aps | Method for identification of molecules with desired characteristics |
| CN104945957A (en) * | 2015-06-29 | 2015-09-30 | 镇江纳微新材料科技有限公司 | Graphene-base all-band ultraviolet shielding material and preparation method thereof |
| CN108330525A (en) * | 2018-01-31 | 2018-07-27 | 南京工业大学 | Preparation method of titanium oxide porous membrane SERS substrate |
Non-Patent Citations (3)
| Title |
|---|
| XIAOLEI WANG ET AL: "An enhanced degree of charge transfer in dye-sensitized solar cells with a ZnO-TiO2/N3/Ag structure as revealed by surface-enhanced Raman scattering", 《THE ROYAL SOCIETY OF CHEMISTRY》 * |
| 时光 等，: "碳酸氢铵法制备氧化锌及 NiO/ZnO-Al2O3脱硫性能的研究", 《应用化工》 * |
| 杨立滨: "几种基于半导体涉及电荷转移的SERS及其增强机制研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113567414A (en) * | 2021-07-02 | 2021-10-29 | 合肥工业大学 | ZIF 8-derived semiconductor heterojunction-silver SERS substrate and preparation method and application thereof |
| CN116408127A (en) * | 2023-04-26 | 2023-07-11 | 吉林大学 | Multiphase nano composite photocatalyst, preparation method and application |
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