CN105954254A - Method for preparing surface-enhanced Raman substrate - Google Patents
Method for preparing surface-enhanced Raman substrate Download PDFInfo
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- CN105954254A CN105954254A CN201610264369.2A CN201610264369A CN105954254A CN 105954254 A CN105954254 A CN 105954254A CN 201610264369 A CN201610264369 A CN 201610264369A CN 105954254 A CN105954254 A CN 105954254A
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- titanium dioxide
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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Abstract
The invention relates to a method for synthesizing a gold-coated titanium dioxide surface-enhanced Raman substrate, and belongs to the field of environmental analysis. With yeast as a biological template, and with chloroauric acid and tetrabutyl titanate as precursors, porous gold-titanium dioxide is synthesized through mineralization. The material has three functions: (1) the material is used as a pollutant enrichment material, and is used for adsorbing pollutants onto the surface of the substrate; (2) the material is used as a surface-enhanced Raman active substrate, and gold on the substrate surface can enhance a Raman signal, so a Raman spectrogram of the pollutants are obtained; and (3) the material is used as a photocatalytic material, and titanium dioxide in the substrate can degrade the pollutants adsorbed on the surface under illumination conditions, so as to achieve recycling of the substrate.
Description
Technical field
The present invention relates to the synthetic method of a kind of gold cladding titanium dioxide surface enhanced Raman substrate, belong to environmental analysis field.
Technical background
Surface enhanced raman spectroscopy (SERS) is the special nanoscale effect of class that nano material represents, and has many excellences
Characteristic, including the fingerprint characteristic that can provide testing sample, it is achieved super sensitivity detection and the identification to object, and its detection
Time do not destroy sample, the detection used time is short, it is not necessary to sample is carried out complex process, therefore suffers from the attention in environmental monitoring field.
Along with the development of SERS technology, a large amount of nano materials needed for detection are inevitably released in environment.These people
Work nano material has high surface activity, has strong associativity to biomacromolecule, ecosystem exists potential accumulation simultaneously
Toxicity.Manufactured nanamaterials diffusion and the propagation extensity migrated determine it and can pollute organism and ecological environment, enter
And jeopardize human health.For solving this problem, scholar is had to propose the concept of " SERS substrate capable of circulation " in recent years.Research people
Member wraps up TiO with the noble metal granule that Template synthesis is novel2Or ZnO nano array, utilize SERS technology for detection object
After, by the photocatalysis performance of the materials such as titanium oxide, irradiate decline desorbing at ultraviolet light and invest the Organic substance of substrate, thus realize
The automatically cleaning of substrate.This new substrates embodies high sensitivity, high duplication, recyclability.
The research of " SERS substrate capable of circulation " at present is in the starting stage, there are some difficult points with not enough.Most important of which
Any is that conventional template preparation process is complicated, and synthetic yield is low.Along with nanotechnology, biotechnology and material science etc. are learned
Cross development is sent out by section, and this problem is expected to have been resolved.Compared with traditional physics and chemistry nanometer synthetic technology, nano biological
Synthetic technology cleaning, nontoxic, environmental friendliness, reaction condition gentleness is controlled, and is not required to add any reducing agent, combined coefficient
High.Bio-mimetic syntheses based on nano biological synthetic technology is according to biomineralization principle, imitates or utilize organism structure, function
And biochemical process, utilize natural principle to instruct the synthesis of special material, preparation to have unique microstructural inorganic material.Biological
Mineralization process can be divided into following several stages: the 1) structure of mineralising template: the most pre-organized one-tenth of organic macromolecule orderly, tool
Effigurate structure, forms an organized reaction microenvironment before biogenic deposit, divides outside cell membrane, syncytium, born of the same parents
The outer adipose membrane vesicle of organic matter, intracellular and the born of the same parents secreted etc. is all the pre-organized of natural organic macromolecule, and therefore biomineralization is the most usually sent out
Raw in these positions；2) organic and inorganic interfacial molecular recognition: by the template contral of organic interface, inorganic matter is at organic and inorganic circle
Nucleation at face；Molecular recognition is often by lattice geometric properties, stereoeffect identification and spatial symmetry, electrostatic effect, pole
The impact of the factor such as property and substrate pattern, the position of these controlling factors inorganic matter nucleation and the crystal formation of material, orientation and pattern；3)
Growth modulation: mineral mineralising occurs in the local domain structure skeleton that Organic substance is self-assembled into, and it is not only having of crystal growth
Effect center and to crystal three-dimensional growth play constraint and restriction effect；4) cell processing: under cell participates in, sub-
Unit biogenic mineral body can be assembled into the biogenic mineral material of higher structure, thus causes biogenic mineral material and artificial material to exist
Difference in performance.By said process, biomaterial self can provide template thus be controlled the pattern of product, raw
Organic macromolecule contained by thing material can interact in interface with inorganic matter ion, forms inorganic/organic complex, passes through
After the method for calcining or organic extraction removes Organic substance, inorganic material is made to have certain shape, size, orientation and structure.
Based on above research background, biomimetic synthesis technology is applied to the preparation of surface enhanced Raman substrate by the present invention.Utilize yeast
Bacterium is biological template, and with gold chloride, butyl titanate as presoma, mineralising has synthesized a kind of cavernous gold-titanium dioxide.This
Plant material and possess three functions: the pollutant in complex matrices, as the enrichment material of pollutant, are adsorbed onto substrate surface by (1)；
(2) as SERS active-substrate, the gold of substrate surface can strengthen Raman signal, thus obtains the Raman spectrogram of pollutant；
(3) as light degradation material, the pollutant being adsorbed in surface can be degraded under illumination condition by the titanium dioxide in substrate,
Realize the recycling of substrate, thus reduce materials synthesis cost.
Summary of the invention
In order to overcome the defect of prior art, present inventor has carried out further investigation repeatedly, thus completes the present invention.
Present invention biomineralization method has synthesized the surface enhanced Raman substrate of a Yeasts skeletal support, is proved by series of experiments
Sample preparation methods and target contaminant analysis method that the present invention uses are easy and simple to handle, and substrate can recycle.
The particular content of the present invention is illustrated by explained below:
(1) weigh 5g yeast powder to be placed in pyroreaction still inner bag, after cleaning with acetone, remove supernatant；
(2) glutaraldehyde of 500 μ L butyl titanate (TTIP) and 25mL 3% is mixed homogeneously, add step (1) high
In temperature reactor inner bag, and add the glutaraldehyde of 25mL 25%；
(3) in step (2) pyroreaction still inner bag, the gold chloride of 10mL 2% is added；
(4), after mix homogeneously, in vacuum drying oven, at 200 DEG C, react 12h, remove supernatant and obtain presoma；By forerunner
Body is placed in crucible, calcines 6h, i.e. obtain cellular gold-titanium dioxide substrate in Muffle furnace at 600 DEG C；
(5) weigh the solid substrate that 5mg step (4) obtains, be placed on silicon chip, the rhodamine 6G solution of 15 μ L is dripped
Being added to substrate surface, use Portable Raman spectrometer to carry out signals collecting, optical maser wavelength 785nm, sweep time, 5s, obtained
SERS spectrogram to rhodamine 6G；
(6) substrate after step (5) having mixed detection with rhodamine 6G is placed in quartz colorimetric utensil, ultraviolet lighting 10min,
With deionized water, substrate is rinsed 3 times, obtain the gold after automatically cleaning-titanium dioxide substrate, substrate is repeated step (5), obtains
The SERS spectrogram of rhodamine 6G.
Accompanying drawing explanation
Principal character below by the marginal data present invention:
Accompanying drawing 1 prepares the stereoscan photograph of gold-titanium dioxide substrate for the present invention, and substrate is cellular as can be seen from Figure.
Accompanying drawing 2 prepares the X-ray energy spectrum photo of gold-titanium dioxide substrate, as can be seen from Figure substrate surface gold and two for the present invention
The existence of titanium oxide.
Accompanying drawing 3 is the R6G SERS spectrogram in five cycle detection of gold-titanium dioxide surface, it can be seen that five cyclic processes
In SERS spectrogram, the feature peak-to-peak type of R6G, position, intensity are held essentially constant, and this fully demonstrates detection method
Feasibility.
Inventive embodiments
The present invention is illustrated further below by embodiment.
The preparation of embodiment 1 substrate: weigh 5g yeast powder and be placed in pyroreaction still inner bag, removes supernatant with acetone after cleaning
Liquid；The glutaraldehyde of 500 μ L TTIP with 25mL 3% is mixed homogeneously, adds in above-mentioned inner bag；It is sequentially added into 25mL 25%
The gold chloride of glutaraldehyde and 10mL 2%, after mix homogeneously, in vacuum drying oven, at 200 DEG C, react 12h, remove supernatant
Liquid obtains presoma；Presoma is placed in crucible, Muffle furnace is calcined at 600 DEG C 6h, i.e. obtains cellular gold-titanium dioxide
At the bottom of titanio.
The detection of embodiment 2R6G: weigh 5mg cellular gold-titanium dioxide substrate and be placed on silicon chip, by the Luo Dan of 15 μ L
Bright 6G solution is added drop-wise to substrate surface, uses Portable Raman spectrometer to carry out signals collecting, optical maser wavelength 785nm, scanning
Time 5s, obtains the SERS spectrogram of rhodamine 6G.
Embodiment 3 substrate automatically cleaning and recycling: the substrate after having mixed detection with rhodamine 6G is placed in quartz cuvette
In ware, ultraviolet lighting 10min, with deionized water, substrate is rinsed 3 times, obtain the gold after automatically cleaning-titanium dioxide substrate, will
The rhodamine 6G solution of 15 μ L is added dropwise to substrate surface, uses Portable Raman spectrometer to carry out signals collecting, optical maser wavelength
785nm, sweep time, 5s, obtained the SERS spectrogram of rhodamine 6G.
Claims (3)
1. a preparation method for surface enhanced Raman substrate, it is made up of following step:
(1) weigh 5g yeast powder to be placed in pyroreaction still inner bag, after cleaning with acetone, remove supernatant；
(2) glutaraldehyde of 500 μ L butyl titanate (TTIP) and 25mL 3% is mixed homogeneously, add step (1) high
In temperature reactor inner bag, and add the glutaraldehyde of 25mL 25%；
(3) in step (2) pyroreaction still inner bag, add the gold chloride of 10mL 2%, after mix homogeneously, do in vacuum
React 12h in dry case at 200 DEG C, remove supernatant and obtain presoma；
(4) step (3) presoma is placed in crucible, in Muffle furnace at 600 DEG C calcine 6h, i.e. obtain cellular gold-
Titanium dioxide substrate；
(5) gold-titanium dioxide substrate that step (4) obtains is placed on silicon chip, after mixing with rhodamine 6G, carries out Raman letter
Number gather；
(6) substrate after step (5) completing detection is placed in quartz colorimetric utensil, and ultraviolet lighting 10min uses deionized water
Substrate is rinsed 3 times, obtains the gold after automatically cleaning-titanium dioxide substrate, substrate is placed on silicon chip, mixes with rhodamine 6G
After carry out Raman signal collection.
The preparation method of a kind of surface enhanced Raman substrate the most as claimed in claim 1, in step (5), substrate consumption is 5mg.
The preparation method of a kind of surface enhanced Raman substrate the most as claimed in claim 1, the rhodamine 6G detection side in step (5)
Method is as follows: 15 μ L rhodamine 6G solution are added drop-wise to substrate surface, uses Portable Raman spectrometer to carry out signals collecting, swashs
Optical wavelength 785nm, sweep time 5s.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108675261A (en) * | 2018-06-01 | 2018-10-19 | 徐州医科大学 | The carbon fiber SERS base materials and its preparation method and application of gold-nano-piece modification |
| CN110813283A (en) * | 2019-12-06 | 2020-02-21 | 济南大学 | Titanium dioxide/gold/titanium dioxide photocatalyst and preparation method thereof |
| CN111257303A (en) * | 2020-04-22 | 2020-06-09 | 张维 | Detection method for detecting dioxin and polychlorinated biphenyl |
| CN113125484A (en) * | 2021-03-10 | 2021-07-16 | 西南科技大学 | Micro-nano layered space microbial mineralization and analysis method of action mechanism thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102759520A (en) * | 2012-05-14 | 2012-10-31 | 北京化工大学 | Preparation method of active radical with surface-enhanced Raman scattering (SERS) effect |
| CN102944544A (en) * | 2012-11-08 | 2013-02-27 | 清华大学 | Recycling surface-reinforced Raman scattering substrate as well as preparation method and application |
| CN103451610A (en) * | 2013-09-03 | 2013-12-18 | 华中农业大学 | Novel bionic surface-enhanced Raman spectrum base and preparation method thereof |
| CN103712972A (en) * | 2014-01-07 | 2014-04-09 | 厦门大学 | Preparation method for surface enhanced raman substrate |
| CN104357815A (en) * | 2014-09-24 | 2015-02-18 | 江苏大学 | Method for preparing self-cleaning type surface raman-enhanced substrate |
| CN104390950A (en) * | 2014-11-03 | 2015-03-04 | 华东理工大学 | High-efficiency photocatalytic renewable SERS (surface enhanced raman scattering) substrate based on mesoporous load Ag nanowire |
| CN105136774A (en) * | 2015-09-18 | 2015-12-09 | 中国科学院生态环境研究中心 | Quick analysis method for PBDEs (polybrominated diphenyl ethers) |
| US9279759B2 (en) * | 2012-05-01 | 2016-03-08 | University Of Maryland, College Park | Nanoparticle array with tunable nanoparticle size and separation |
-
2016
- 2016-04-26 CN CN201610264369.2A patent/CN105954254B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9279759B2 (en) * | 2012-05-01 | 2016-03-08 | University Of Maryland, College Park | Nanoparticle array with tunable nanoparticle size and separation |
| CN102759520A (en) * | 2012-05-14 | 2012-10-31 | 北京化工大学 | Preparation method of active radical with surface-enhanced Raman scattering (SERS) effect |
| CN102944544A (en) * | 2012-11-08 | 2013-02-27 | 清华大学 | Recycling surface-reinforced Raman scattering substrate as well as preparation method and application |
| CN103451610A (en) * | 2013-09-03 | 2013-12-18 | 华中农业大学 | Novel bionic surface-enhanced Raman spectrum base and preparation method thereof |
| CN103712972A (en) * | 2014-01-07 | 2014-04-09 | 厦门大学 | Preparation method for surface enhanced raman substrate |
| CN104357815A (en) * | 2014-09-24 | 2015-02-18 | 江苏大学 | Method for preparing self-cleaning type surface raman-enhanced substrate |
| CN104390950A (en) * | 2014-11-03 | 2015-03-04 | 华东理工大学 | High-efficiency photocatalytic renewable SERS (surface enhanced raman scattering) substrate based on mesoporous load Ag nanowire |
| CN105136774A (en) * | 2015-09-18 | 2015-12-09 | 中国科学院生态环境研究中心 | Quick analysis method for PBDEs (polybrominated diphenyl ethers) |
Non-Patent Citations (6)
| Title |
|---|
| JINGJING DU ET AL.: "Rapid in situ identification of arsenic species using a portable Fe3O4@Ag SERS sensor", 《CHEM. COMMUN.》 * |
| ZHENLI SUN ET AL.: "Multifunctional Fe3O4@SiO2-Au satellite structured SERS probe for charge selective detection of food dyes", 《ACS APPL. MATER. INTERFACES》 * |
| 于文文等: "环境水样中BDE-47的表面增强拉曼光谱定量定性分析", 《环境化学》 * |
| 刘文婧等: "表面增强拉曼光谱技术应用于环境污染物检测的研究进展", 《环境化学》 * |
| 温春叶: "石墨烯基复合物在追踪反应方面的应用", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 韩秀秀: "磷酸银/酵母纳米复合材料和纳米银的生物合成及其机理和性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108675261A (en) * | 2018-06-01 | 2018-10-19 | 徐州医科大学 | The carbon fiber SERS base materials and its preparation method and application of gold-nano-piece modification |
| CN108675261B (en) * | 2018-06-01 | 2019-12-27 | 徐州医科大学 | Gold nanosheet modified carbon fiber SERS substrate material and preparation method and application thereof |
| CN110813283A (en) * | 2019-12-06 | 2020-02-21 | 济南大学 | Titanium dioxide/gold/titanium dioxide photocatalyst and preparation method thereof |
| CN110813283B (en) * | 2019-12-06 | 2021-06-25 | 济南大学 | Titanium dioxide/gold/titanium dioxide photocatalyst and preparation method thereof |
| CN111257303A (en) * | 2020-04-22 | 2020-06-09 | 张维 | Detection method for detecting dioxin and polychlorinated biphenyl |
| CN113125484A (en) * | 2021-03-10 | 2021-07-16 | 西南科技大学 | Micro-nano layered space microbial mineralization and analysis method of action mechanism thereof |
| CN113125484B (en) * | 2021-03-10 | 2022-05-24 | 西南科技大学 | Micro-nano layered space microbial mineralization and analysis method of action mechanism thereof |
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