CN107478635A - A kind of MOF noble metals composite S ERS substrates and preparation method thereof - Google Patents
A kind of MOF noble metals composite S ERS substrates and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to MOF noble metal nano field of compound material, and in particular to a kind of MOF noble metals composite S ERS substrates and preparation method thereof.In alcoholic solution, by electrostatic interaction, the noble metal nano particles of the positively charged of CTAB modifications are carried on MOF material surfaces, form MOF noble metal nano composite S ERS substrates.It is compared to growth in situ method, noble metal nano particles are loaded to MOF surfaces by the present invention by electrostatic interaction, while the high porosity of MOF materials, specific surface area and excellent adsorption capacity is kept, the controllable precise of the patterns of MOF surface metal nano-particles, size and density can be achieved, a large amount of Raman active sites are prepared, and then further effectively improve composite substrate SERS performances.MOF AuNPs composite S ERS substrates prepared by the present invention, possess the double action of adsorption and enrichment and Raman enhancing, without surface modification, direct, highly sensitive detection equimolecular to fluoranthene can be achieved.
Description
Technical field
The present invention relates to MOF- noble metal nano field of compound material, and in particular to a kind of MOF- noble metals composite S ERS bases
Bottom and preparation method thereof.
Background technology
SERS technology is a kind of hypersensitive, lossless molecular detection technology, is widely used in chemical biography
The field such as sense, biomedicine, environmental pollution analyte detection.Nowadays, the high SERS of high sensitivity, favorable reproducibility, stability is prepared
Substrate, it is still the significant challenge that people face to realize quick, the directly highly sensitive detection to environmental organic pollutant.It is more
Cyclophane Hydrocarbon Organic, a kind of oil combustion product, and conventional precious metal SERS substrate surface adsorptivities are poor, it is difficult to reach local
Surface plasma resonance area, SERS effects are weak.It is at present to use surface modification more --- the method for introducing sulfydryl, capture and absorption point
Son, experimentation are complicated.
MOF materials compared with conventional porous materials, have regular as a kind of novel organic-inorganic hybrid porous material
Pore passage structure, specific surface area, high porosity and the surface chemical property adjustability of super large, in recent years catalysis, Chemical Decomposition,
The field such as selective absorption and medicament transport has huge potential using value.Particularly led in SERS
Domain, MOF porous materials and noble metal nanometer material is mutually compound, using the features such as MOF materials are bigger than surface, porosity is high, have
Effect combines the excellent adsorption and enrichment abilities and noble metal nano particles local surface plasma resonance property of MOF, is remarkably improved
The sensitivity of SERS detections and reproducibility.Li Gongke (Analyst. 2015,140,8165-8171) report one
Detection molecules can be largely enriched to gold nano by kind Au@MIL-100 (Fe) core-shell nano composite construction, MOF materials as shell
Core surface, to the test limit as little as 8 × 10 of malachite green molecule-9mol/L.But such method is difficult to prepare particle gap
Substantial amounts of avtive spot.Li Yuanfang are using the method for in-situ reducing respectively at MIL-101 (Fe)（Anal.Chem.
2015, 87, 12177-12182）With MIL-101 (Cr) (RSC Adv. 2016,6,79805-79810) MOF material tables
Face loads Nano silver grain, is successfully prepared the AgNPs/MOF composite S ERS substrates of excellent performance.But utilize in-situ reducing
Method can not accurately control the size of metal nanoparticle, pattern and attachment density, and pass through growth in situ method institute
The metal nanoparticle of preparation/impurity such as MOF composites, metallic precursor is easily remained in MOF ducts, causes MOF materials
Material porosity, specific surface area are decreased obviously, and substantially reduce the spirit that MOF materials detect to the adsorption capacity and SERS of detection molecules
Sensitivity and signal reproducibility.
MOF- noble metal composite S ERS substrates prepared by the present invention, by electrostatic interaction, by CTAB（Cetyl trimethyl
Ammonium bromide）The golden nanometer particle of modification（AuNPs）It is supported on MIL-101（Cr）Surface, utilize the great specific surface area of MOF materials
And high porosity, realize the effective absorption and enrichment to testing molecule.By accurately adjust pattern, the size of golden nanometer particle with
And load density, Raman active site between a large amount of particle gaps is prepared, further regulates and controls the SERS performances of composite substrate, realizes and draws
The very big enhancing of graceful detection signal.
The content of the invention
The present invention is prepared for a kind of MOF-AuNPs composite Ss ERS of metal-organic framework materials area load golden nanometer particle
Substrate is detected, effective combination of MOF and metal nanoparticle is realized by electrostatic interaction.The compound particle combines
MOF material specific surface areas are big, porosity is high, effectively can adsorb and be enriched with testing molecule and surface that golden nanometer particle is excellent etc.
Ionic nature, sensitivity of the composite S ERS substrates to organic contamination analyte detection is significantly improved, solves current multiring aromatic hydrocarbon
Organic matter and conventional precious metal material binding ability are weak, the problem of detection signal difference, are successfully realized organic to multiring aromatic hydrocarbon
Quick, direct, the highly sensitive SERS detections of thing.
The present invention is achieved by the following technical solutions：A kind of MOF- noble metal nanos composite S ERS substrates, it is molten in alcohol
In liquid, by electrostatic interaction, the noble metal nano particles of the positively charged of CTAB modifications are carried on MOF material surfaces, formed
MOF- noble metal nano composite S ERS substrates.
MOF particle surfaces contain a large amount of unsatuated metal sites, and in alcoholic solution, these unsatuated metal sites are easily supplied
Electron group occupies, so that MOF is in elecrtonegativity.And it is in positive electricity in the solution by the CTAB noble metal nano particles coated
Property, electrostatic attraction can be produced with electronegative MOF, so that both are combined together by electrostatic interaction.Ultimately form
The MOF- noble metal nano composite S ERS substrates of area load noble metal nano particles.
As the further improvement of MOF- noble metal nanos composite S ERS substrate technical schemes of the present invention, described noble metal
Nano-particle is golden nanometer particle, Nano silver grain or gold and silver nanometer nuclear shell nano-structure.
As the further improvement of MOF- noble metal nanos composite S ERS substrate technical schemes of the present invention, described MOF materials
Expect for MIL-101 (Fe), MIL-101 (Cr) or MIL-100 (Fe).
Invention further provides a kind of preparation method of MOF- noble metal nanos composite S ERS substrates, including following step
Suddenly：
(1) AuNPs preparation：2-4 DEG C of sodium borohydride solution is quickly adding into tetra chlorauric acid and CTAB mixed solution
In, 1 min is stirred vigorously, 1 h is stood at room temperature, obtains gold seeds；
CTAB, tetra chlorauric acid, ascorbic acid are added sequentially in ultra-pure water, configuration growth solution is stand-by；Gold seeds is diluted
After be added in growth solution and stir 1min, stand 6 h at room temperature, obtain AuNPs；Product is centrifuged, after milli-Q water 2 times
Disperse in methyl alcohol, to form AuNPs dispersion liquids；
(2) prepared by MOF-AuNPs compound particles：MOF materials are mixed rapidly with AuNPs dispersion liquids, stir 1min, at room temperature
1h is stood, obtains the MOF-AuNPs composite S ERS substrates of area load golden nanometer particle.
The preparation method of the present invention is simple, and efficiently, repetitive rate is high, and reaction condition is gentle.For novel nano composite S ERS bases
The design at bottom provides realistic plan with preparation.
During concrete operations, when gold seeds dispersion liquid volume is bigger in growth solution（That is concentration is higher, addition more
It is more）When, obtained AuNPs particle diameters are smaller, and pattern levels off to spherical；Got over conversely, working as gold seeds dispersion liquid volume in growth solution
Hour, obtained AuNPs particle diameters are bigger, and pattern levels off to faceted particles.In AuNPs dispersion liquids, AuNPs and MOF materials
Ratio determines the density of MOF-AuNPs composite S ERS substrate surface load gold nano particles, and when ratio is higher, load density is got over
Greatly；When ratio is lower, load density is smaller.Above-mentioned golden nanometer particle size, pattern and load density essence provided by the invention
True adjustable mechanism, is equally applicable to the preparation of other MOF- noble metal nano composite S ERS substrates.
As the further improvement of preparation method technical scheme of the present invention, described MOF materials be MIL-101 (Fe),
MIL-101 (Cr) or MIL-100 (Fe).
Further, the invention provides a kind of any of the above-described MOF- noble metal nanos composite S ERS substrates and above-mentioned
The MOF- noble metal nano composite S ERS bases that a kind of one preparation method of MOF- noble metal nanos composite S ERS substrates prepares
Application of the bottom in polycyclic aromatic hydrocarbon type organic is detected.
Specifically, the polycyclic aromatic hydrocarbon type organic is fluoranthene or naphthalene, phenanthrene etc..
Compared with prior art, the MOF-AuNPs composite S ERS substrates being prepared by electrostatic interaction have such as
The advantages of lower and beneficial effect：
（1）Growth in situ method is compared to, noble metal nano particles are loaded to MOF tables by the present invention by electrostatic interaction
Face, the controllable precise of the patterns of MOF surface metal nano-particles, size and density can be achieved, prepare a large amount of Raman active positions
Point, and then further effectively improve composite substrate SERS performances.
（2）Pass through the MOF- metal nanoparticle composite S ERS substrates, metallic precursor etc. prepared by growth in situ method
Impurity is easily remained in MOF ducts, is caused MOF materials porosity, specific surface area to be decreased obviously, is substantially reduced MOF materials pair
The sensitivity of adsorption capacity and the SERS detection of detection molecules and signal reproducibility.And the MOF- prepared by the present invention
AuNPs composite S ERS substrates, two kinds of particles are first respectively synthesized, then are combined both by electrostatic interaction, do not influence MOF
Absorption property of the material to detection molecules.
（3）Efficiently solve polycyclic aromatic hydrocarbon and conventional precious metal substrate adsorptivity is poor, SERS responds the problem of low.More cyclophanes
Hydrocarbon Organic and noble metal nano particles binding ability are weak, SERS detection difficults, for example introduce sulfydryl using surface modification more
Deng.MOF-AuNPs composite S ERS substrates prepared by the present invention, possess the double action of adsorption and enrichment and Raman enhancing, without
Surface modification, direct, highly sensitive detection equimolecular to fluoranthene can be achieved.
Brief description of the drawings
Fig. 1 is different-grain diameter（Average diameter）The MOF-AuNPs composite S ERS substrate SEM pictures of golden nanometer particle load.
(a) 48 nm（Embodiment 7）, (b) 54 nm（Embodiment 6）, (c) 66 nm（Embodiment 5）, (d) 84 nm（Embodiment 4）,
Scale is 100nm.
Fig. 2 is the MOF-AuNPs of different loads density（66 nm）Composite S ERS substrate SEM pictures.MIL-101 dispersion liquids
With AuNPs dispersion liquid volumes than being respectively (a) 1:1（Embodiment 5）, (b) 1:2（Embodiment 8）, (c) 1:3（Embodiment 9）, mark
Chi is 400nm.
Fig. 3 is various concentrations R6G in MOF-AuNPs (66nm, MIL-101 (Cr) methanol dispersion liquids:AuNPs dispersing liquids
Product ratio 1：2) the Raman signal figure in composite S ERS substrates.In figure numerical digit 1 to 6 respectively it is corresponding be various concentrations R6G.
Fig. 4 is various concentrations fluoranthene in MOF-AuNPs (66 nm, MIL-101 (Cr) methanol dispersion liquids:AuNPs dispersion liquids
Volume ratio 1：2) the Raman signal figure in composite S ERS substrates.It is the glimmering of various concentrations that numerical digit 1 to 6 is corresponding respectively in figure
Anthracene.
Embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only it is part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, ordinary skill
The every other embodiment that personnel are obtained under the premise of creative work is not made, belongs to the scope of protection of the invention.
For clearer explanation MOF- noble metal nanos composite S ERS substrates of the present invention, the present invention is in detail below
Describe the preparation method of MOF-AuNPs composite S ERS substrates.Using the material rate of the preparation method, concentration and process conditions system
The standby SERS substrates obtained, relative to other preparation methods, the detection to polycyclic aromatic hydrocarbon type organic is sensitiveer.
The preparation method of described MOF-AuNPs composite S ERS substrates, comprises the following steps：
1. MIL-101 preparation：By 5mmol chromic nitrate nonahydrate, hydrofluoric acid, terephthalic acid (TPA) and 24mL deionized water
It is added in reactor, at 220 DEG C after constant temperature 12h, 150 DEG C is gradually cooled in 1h, room temperature is slowly dropped in 12h.By product
Centrifuge, obtain MIL-101 (Cr) powder.1 mg MIL-101 (Cr) powder is dispersed in 10 mL methanol, obtained dense
Spend MIL-101 (Cr) methanol dispersion liquid for 0.1 mg/mL.
(1) AuNPs preparation：It is using seed mediated growth method that 2-4 DEG C sodium borohydride (0.01M, 0.6mL) solution is rapid
It is added in tetra chlorauric acid (0.01M, 0.25mL) and CTAB (0.1M, 7.5mL) mixed solution, is stirred vigorously 1min, room temperature
Lower standing 1h, obtains gold seeds.
By CTAB (0.1M, 6.4mL), tetra chlorauric acid (0.01M, 6.8mL), ascorbic acid (0.1M, 3.8mL) sequentially adds
Into 32mL ultra-pure waters, growth solution is configured.Take the μ L of 15 μ L ~ 40 to be added in growth solution after gold seeds is diluted into 10 times to stir
1min, 6h is stood at room temperature, obtain average grain diameter 48nm ~ 84nm AuNPs nano-particles.Product is centrifuged, milli-Q water 2
It is dispersed in after secondary in 8mL methanol, obtains AuNPs dispersion liquids.
(2) prepared by MOF-AuNPs compound particles：By MIL-101 (Cr) methanol dispersion liquids and different-grain diameter AuNPs dispersion liquids
According to volume ratio 1：3~1：1 rapid mixing, is stirred vigorously 1min, stands 1h at room temperature, obtain area load different-grain diameter, difference
The MOF-AuNPs composite S ERS substrates of density.
In above-mentioned preparation method, the stir speed (S.S.) of used " being stirred vigorously " is 800r/min, used " to stir
Mix " stir speed (S.S.) be 350r/min.
Preferably, step（1）MIL-101 (Cr) powder that middle product obtains after centrifuging, with 60 DEG C of ethanol and N, N-
Dimethylformamide（DMF）Solution cleans.Again by the immersion of above-mentioned product in ethanol, flow back 6 hours, fully remove in duct not
The residue of reaction.150 DEG C of vacuum drying 12h, fully remove the unsatuated metal site residual water molecules of MOF material surfaces.
Specifically, step（2）In, gold seeds takes the μ L of 15 μ L ~ 40 to be added in growth solution after diluting 10 times, obtain grain
Footpath 48nm ~ 84nm AuNPs.Wherein preferred gold seeds addition is 20 μ L, and when addition is 20 μ L, AuNPs particle diameter is
66nm。
Further, step（3）By MIL-101 (Cr) methanol dispersion liquids and different-grain diameter AuNPs dispersion liquids according to volume
Than 1：3 ~1：1 rapid mixing, wherein preferred volume ratio are 1：2.
MOF-AuNPs composite Ss ERS substrates of the present invention are described in detail below in conjunction with the accompanying drawings
Embodiment 1：
The preparation of gold seeds, its step are：
2-4 DEG C of sodium borohydride (0.01M, 0.6mL) solution is quickly adding into tetra chlorauric acid (0.01M, 0.25mL) and CTAB
In the mixed solution of (0.1M, 7.5mL), 1min is stirred vigorously, stands 1h at room temperature, obtains gold seeds（8.35 mL）.
Embodiment 2：
The preparation of gold seeds growth solution, its step are：
By CTAB (0.1M, 6.4mL), tetra chlorauric acid (0.01M, 6.8mL), ascorbic acid (0.1M, 3.8mL) is added sequentially to 32
In mL ultra-pure waters, gold seeds growth solution is configured to（49 mL）.
Embodiment 3：
MIL-101 (Cr) preparation：
5mmol chromic nitrate nonahydrate, hydrofluoric acid, terephthalic acid (TPA) and 24mL deionized water are added to 100mL reactions
In kettle, at 220 DEG C after constant temperature 12h, 150 DEG C are gradually cooled in 1h, room temperature is slowly dropped in 12h.Product is centrifuged, used
60 DEG C of ethanol and DMF solution cleaning.Again by the immersion of above-mentioned product in ethanol, flow back 6 hours, 150 DEG C of vacuum drying 12h, obtain
To MIL-101 (Cr) powder.1 mgMIL-101 (Cr) powder is dispersed in 10mL methanol, it is 0.1mg/mL's to obtain concentration
MIL-101 (Cr) methanol dispersion liquid.
Embodiment 4：
A kind of preparation method of MOF-AuNPs composite Ss ERS substrates, its step are：
After the gold seeds obtained in embodiment 1 is diluted into 10 times, take 15 μ L to be added in the growth solution of the preparation of embodiment 2 and stir
1min, 6h is stood at room temperature.Obtain the AuNPs that average grain diameter is about 84nm.Product is centrifuged, with after milli-Q water 2 times points
It is dispersed in 8 mL methanol solution.
MIL-101 (Cr) dispersion liquids and average grain diameter that embodiment 3 is obtained are 84 nm AuNPs dispersion liquids by body
Product is than being 1：1 rapid mixing, is stirred vigorously 1min, stands 1h at room temperature, obtain MOF-AuNPs composite S ERS base dispersion liquids.
Such as accompanying drawing 1d.
Embodiment 5：
A kind of preparation method of MOF-AuNPs composite Ss ERS substrates, its step are：
After the gold seeds obtained in embodiment 1 is diluted into 10 times, take 20 μ L to be added in the growth solution of the preparation of embodiment 2 and stir
1min is mixed, stands 6 h at room temperature, obtains the AuNPs that average grain diameter is about 66 nm.Product is centrifuged, with after milli-Q water points
It is dispersed in 8 mL methanol solution.
MIL-101 (Cr) dispersion liquids and average grain diameter that embodiment 3 is obtained are 66 nm AuNPs dispersion liquids by body
Product is than being 1：1 rapid mixing, is stirred vigorously 1min, stands 1h at room temperature, obtain MOF-AuNPs composite S ERS base dispersion liquids.
Such as accompanying drawing 1c and 2a.
Embodiment 6：
A kind of preparation method of MOF-AuNPs composite Ss ERS substrates, its step are：
After the gold seeds obtained in embodiment 1 is diluted into 10 times, take 30 μ L to be added in the growth solution of the preparation of embodiment 2 and stir
1min is mixed, stands 6 h at room temperature, obtains the AuNPs that average grain diameter is about 54 nm.Product is centrifuged, with after milli-Q water points
It is dispersed in 8 mL methanol solution.
MIL-101 (Cr) dispersion liquids and average grain diameter that embodiment 3 is obtained are 54 nm AuNPs dispersion liquids by body
Product is than being 1：1 rapid mixing, is stirred vigorously 1min, stands 1h at room temperature, obtain MOF-AuNPs composite S ERS base dispersion liquids.
Such as accompanying drawing 1b.
Embodiment 7：
A kind of preparation method of MOF-AuNPs composite Ss ERS substrates, its step are：
After the gold seeds obtained in embodiment 1 is diluted into 10 times, take 40 μ L to be added in the growth solution of the preparation of embodiment 2 and stir
1min is mixed, stands 6 h at room temperature.Obtain the AuNPs that average grain diameter is about 48 nm.Product is centrifuged, with after milli-Q water points
It is dispersed in 8 mL methanol solution.
MIL-101 (Cr) dispersion liquids and average grain diameter that embodiment 3 is obtained are 48 nm AuNPs dispersion liquids by body
Product is than being 1：1 rapid mixing, is stirred vigorously 1min, stands 1h at room temperature, obtain MOF-AuNPs composite S ERS base dispersion liquids.
Such as a of accompanying drawing 1.
Embodiment 8：
A kind of preparation method of MOF-AuNPs composite Ss ERS substrates, its step are：
The AuNPs that MIL-101 (Cr) dispersion liquids that embodiment 3 is obtained are 66 nm with the particle diameter obtained in embodiment 5 disperses
Liquid is 1 by volume：2 rapid mixing, are stirred vigorously 1 min, stand 1h at room temperature, obtain MOF-AuNPs composite S ERS substrates
Dispersion liquid.Such as accompanying drawing 2b.
Embodiment 9：
A kind of preparation method of MOF-AuNPs composite Ss ERS substrates, its step are：
The AuNPs that MIL-101 (Cr) dispersion liquids that embodiment 3 is obtained are 66 nm with the particle diameter obtained in embodiment 5 disperses
Liquid is 1 by volume：3 rapid mixing, are stirred vigorously 1min, stand 1h at room temperature, obtain MOF-AuNPs composite S ERS substrates point
Dispersion liquid.Such as accompanying drawing 2c.
Embodiment 10：
A kind of MOF-AuNPs composite Ss ERS substrates detect bioprobe molecule rhodamine 6G, and its detecting step is：Take 0.5mL not
With concentration R6G solution to be detected in 1mL centrifuge tubes, the MOF-AuNPs composite Ss ERS that 0.5mL embodiments 8 are obtained is added
Base dispersion liquid, turned upside down, make it well mixed.After standing 40 min, 4000 rpm centrifugations, 0.8mL supernatant liquids are taken out.
It is remaining solid-liquid part is ultrasonic 3 seconds so that the MOF-AuNPs compound particles for having adsorbed R6G molecules disperse again.Draw L points of 15 μ
Dispersion liquid is on silicon chip.Raman detection is carried out after methanol volatilization.Raman detection optical maser wavelength is 532nm, power 3mW, is integrated
Time is 10s.Such as accompanying drawing 3.Certainly, other preparation methods are passed through（Material rate, concentration and process conditions are different）Obtain
MOF- noble metal nano composite S ERS substrates can also realize the detection of bioprobe molecule rhodamine 6G by above-mentioned detection method.
Embodiment 11：
A kind of MOF-AuNPs composite Ss ERS substrates detection polycyclic aromatic hydrocarbon type organic-fluoranthene molecule, its detecting step are：
0.5mL various concentrations fluoranthene solution to be detected is taken to add what 0.5mL embodiments 8 were obtained in 1mL centrifuge tubes
MOF-AuNPs composite S ERS base dispersion liquids, turned upside down, make it well mixed.After standing 40min, 4000rpm centrifugations, take
Go out 0.8mL supernatant liquids.It is remaining solid-liquid part is ultrasonic 3 seconds so as to have adsorbed the MOF-Au compound particles of fluoranthene molecule again
It is scattered.15 μ L dispersion liquids are drawn on silicon chip.Raman detection is carried out after methanol volatilization.Raman detection optical maser wavelength is 532nm,
Power is 3mW, time of integration 10s.Such as accompanying drawing 4.Certainly, other preparation methods are passed through（Material rate, concentration and process conditions
It is different）The MOF- noble metal nano composite S ERS substrates of acquisition also can realize that multiring aromatic hydrocarbon is organic by above-mentioned detection method
The detection of thing-fluoranthene molecule.
Claims (7)
1. a kind of MOF- noble metal nanos composite S ERS substrates, it is characterised in that, will by electrostatic interaction in alcoholic solution
The noble metal nano particles of the positively charged of CTAB modifications are carried on MOF material surfaces, form MOF- noble metal nano composite Ss ERS
Substrate.
A kind of 2. MOF- noble metal nanos composite S ERS substrates according to claim 1, it is characterised in that your described gold
Category nano-particle is golden nanometer particle, Nano silver grain or gold and silver nanometer nuclear shell nano-structure.
A kind of 3. MOF- noble metal nanos composite S ERS substrates according to claim 1, it is characterised in that described MOF
Material is MIL-101 (Fe), MIL-101 (Cr) or MIL-100 (Fe).
4. a kind of preparation method of MOF- noble metal nanos composite S ERS substrates, it is characterised in that comprise the following steps：
(1) AuNPs preparation：2-4 DEG C of sodium borohydride solution is quickly adding into tetra chlorauric acid and CTAB mixed solution
In, 1 min is stirred vigorously, 1 h is stood at room temperature, obtains gold seeds；
CTAB, tetra chlorauric acid, ascorbic acid are added sequentially in ultra-pure water, configuration growth solution is stand-by；Gold seeds is diluted
After be added in growth solution and stir 1min, stand 6 h at room temperature, obtain AuNPs；Product is centrifuged, divided after milli-Q water
Dissipate in methyl alcohol, form AuNPs dispersion liquids；
(2) prepared by MOF-AuNPs compound particles：MOF materials are mixed rapidly with AuNPs dispersion liquids, stir 1min, at room temperature
1h is stood, obtains the MOF-AuNPs composite S ERS substrates of area load golden nanometer particle.
A kind of 5. preparation method of MOF- noble metal nanos composite S ERS substrates according to claim 4, it is characterised in that
Described MOF materials are MIL-101 (Fe), MIL-101 (Cr) or MIL-100 (Fe).
6. a kind of the MOF- noble metal nanos composite S ERS substrates and right described in claims 1 to 3 any claim will
Ask what the preparation methods of MOF- noble metal nanos composite S ERS substrates described in 4 to 5 any claims a kind of prepared
Application of the MOF- noble metal nanos composite S ERS substrates in polycyclic aromatic hydrocarbon type organic is detected.
7. application according to claim 6, it is characterised in that the polycyclic aromatic hydrocarbon type organic is fluoranthene or naphthalene, phenanthrene.
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| CN201710486565.9A CN107478635B (en) | 2017-06-23 | 2017-06-23 | MOF-noble metal composite SERS substrate and preparation method thereof |
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| CN108195903A (en) * | 2017-12-25 | 2018-06-22 | 济南大学 | A kind of preparation method of electrochemical sensing material to arsenic detection |
| CN108414494A (en) * | 2018-01-24 | 2018-08-17 | 中国工程物理研究院化工材料研究所 | For the MOFs@precious metal surfaces enhancing Raman scattering substrate of trace harmful toxic matter detection, preparation method and application |
| CN108918855A (en) * | 2018-07-31 | 2018-11-30 | 济南大学 | A kind of preparation method and application based on signal " on-off " type Electrochemiluminescsensor sensor that AgNCs is illuminator |
| CN108982466A (en) * | 2018-06-06 | 2018-12-11 | 上海应用技术大学 | A method of for antibiotic field quick detection in Amoxicillin in water body |
| CN109119253A (en) * | 2018-09-12 | 2019-01-01 | 安徽大学 | Composition metal-organic framework materials, metal composite oxide-organic framework materials and preparation method and application |
| CN110054791A (en) * | 2019-06-04 | 2019-07-26 | 中国工程物理研究院化工材料研究所 | MOFs- noble metal ordered composite material and its preparation method and application |
| WO2019205364A1 (en) * | 2018-04-28 | 2019-10-31 | 厦门斯贝克科技有限责任公司 | Enhanced raman detection method using satellite structure |
| CN110646400A (en) * | 2019-10-08 | 2020-01-03 | 吉林师范大学 | PS/Ag/ZIF-8 composite structure surface enhanced Raman scattering active substrate and preparation method thereof |
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| CN112649413A (en) * | 2020-11-03 | 2021-04-13 | 中山大学 | Nano-gold-MOF composite flexible SERS film substrate and preparation method and application thereof |
| CN112730375A (en) * | 2020-12-16 | 2021-04-30 | 厦门大学 | Method for detecting VOC gas by using MOF-coated gold nanoparticles through enhanced Raman spectroscopy |
| CN112798571A (en) * | 2020-12-29 | 2021-05-14 | 中国检验检疫科学研究院 | Preparation method of SERS substrate, SERS substrate and application of SERS substrate |
| CN112986215A (en) * | 2021-04-20 | 2021-06-18 | 江南大学 | Method for detecting benzoic acid in milk based on surface enhanced Raman spectroscopy |
| CN113138185A (en) * | 2021-04-28 | 2021-07-20 | 江南大学 | Method for detecting sodium thiocyanate in milk by using SERS (surface enhanced Raman Scattering) technology based on MOF (metal-organic framework) |
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| CN113933283A (en) * | 2021-09-28 | 2022-01-14 | 中山大学 | Composite SERS substrate and preparation method and application thereof |
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| CN108195903B (en) * | 2017-12-25 | 2019-07-02 | 济南大学 | A kind of preparation method of the electrochemical sensing material of pair of arsenic detection |
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| CN109119253B (en) * | 2018-09-12 | 2020-06-02 | 安徽大学 | Composite metal-organic framework material, composite metal oxide-organic framework material, preparation method and application |
| CN110054791A (en) * | 2019-06-04 | 2019-07-26 | 中国工程物理研究院化工材料研究所 | MOFs- noble metal ordered composite material and its preparation method and application |
| CN110054791B (en) * | 2019-06-04 | 2021-06-22 | 中国工程物理研究院化工材料研究所 | MOFs-noble metal ordered composite material and preparation method and application thereof |
| CN110646400A (en) * | 2019-10-08 | 2020-01-03 | 吉林师范大学 | PS/Ag/ZIF-8 composite structure surface enhanced Raman scattering active substrate and preparation method thereof |
| CN110687098B (en) * | 2019-10-30 | 2020-09-08 | 江南大学 | Preparation method of nano-silver SERS substrate based on polyurethane |
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| CN112649413A (en) * | 2020-11-03 | 2021-04-13 | 中山大学 | Nano-gold-MOF composite flexible SERS film substrate and preparation method and application thereof |
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| WO2022142109A1 (en) * | 2020-12-29 | 2022-07-07 | 中国检验检疫科学研究院 | Preparation method for sers substrate, sers substrate, and application |
| CN112986215A (en) * | 2021-04-20 | 2021-06-18 | 江南大学 | Method for detecting benzoic acid in milk based on surface enhanced Raman spectroscopy |
| CN112986215B (en) * | 2021-04-20 | 2022-08-02 | 江南大学 | Method for detecting benzoic acid in milk based on surface enhanced Raman spectroscopy |
| CN113138185A (en) * | 2021-04-28 | 2021-07-20 | 江南大学 | Method for detecting sodium thiocyanate in milk by using SERS (surface enhanced Raman Scattering) technology based on MOF (metal-organic framework) |
| CN113603894A (en) * | 2021-07-23 | 2021-11-05 | 上海应用技术大学 | Ag-MOF/AuNRs nano composite material and preparation and application thereof |
| CN113603894B (en) * | 2021-07-23 | 2022-08-16 | 上海应用技术大学 | Ag-MOF/AuNRs nano composite material and preparation and application thereof |
| CN113484304A (en) * | 2021-07-28 | 2021-10-08 | 上海应用技术大学 | AuNP/UiO-68 composite material and preparation method and application thereof |
| CN113624730A (en) * | 2021-08-26 | 2021-11-09 | 军事科学院军事医学研究院环境医学与作业医学研究所 | Application of precious metal-doped metal organic framework composite material in detection of tetrodotoxin and detection method of tetrodotoxin |
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| CN113933283A (en) * | 2021-09-28 | 2022-01-14 | 中山大学 | Composite SERS substrate and preparation method and application thereof |
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