CN106950199B - The preparation method of golden octahedron-graphene composite nano material and sensing chip and its application based on it - Google Patents
The preparation method of golden octahedron-graphene composite nano material and sensing chip and its application based on it Download PDFInfo
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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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/55—Specular reflectivity
- G01N21/552—Attenuated total reflection
- G01N21/553—Attenuated total reflection and using surface plasmons
- G01N21/554—Attenuated total reflection and using surface plasmons detecting the surface plasmon resonance of nanostructured metals, e.g. localised surface plasmon resonance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82—NANOTECHNOLOGY
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Abstract
The invention discloses a kind of preparation methods of golden octahedron-graphene composite nano material, include the following steps: the octahedra nanostructure of (1) preparation gold: 18~22mL ethylene glycol, 0.39~0.41mL polyethylene are added in the phosphoric acid of 0.7~0.8mL 1M, mixing, add the gold chloride of 0.015~0.02mL 0.5M, it reacts 12~18 minutes at room temperature, keep 185~195 DEG C of 25~35min of reaction to get golden octahedra nano-structured solution again；(2) it prepares golden octahedron-graphene composite nano material: the octahedra nano-structured solution 14~16ml alcohol of the gold prepared is diluted, with ultrasonic machine ultrasound until the suitable spin coating of solution solubility, solution is spin-coated on above single-layer graphene using sol evenning machine.It also discloses based on gold octahedron-graphene composite nano material sensing chip and its preparation method and application.
Description
Technical field
The present invention relates to graphene composite material and its application fields, and in particular to golden octahedron-graphene composite Nano
The preparation method of material and sensing chip and its application based on it.
Background technique
Surface plasma body resonant vibration (Surface Plasmon Resonance, SPR) sensor is real-time, sensitive by its
The advantages that high is spent, the fields such as life science, clinical diagnosis, drug screening, food safety, environmental monitoring have been widely used in.With
Requirement for environment measuring technology is higher and higher in society, real-time, quick, highly sensitive SPR sensorgram technology, which has become, attaches most importance to
One main direction of studying of metal ion detection.
SPR is the evanescent wave generated when p-polarization light is totally reflected at glass and metal-graphite alkene nano-structural interfaces
The free electron for causing metal-graphite alkene nanostructured surface generates surface plasma, and in surface plasma and evanescent wave wave
Swear a kind of covibration generated in identical situation.When surface plasmon resonance occurs, incident laser energy almost all
It is bound in metal-graphite alkene nanostructured surface and forms SPR, the energy of reflected light declines suddenly, occurs in reflectance spectrum anti-
Minimum of intensity is penetrated, formant is formed.When the dielectric constant and thickness of metal-graphite alkene nanostructure another side change
When, it can make refractive index that minor change occur, the small value position of formant can generate offset.Therefore, can according to minimum value position with
Relationship between dielectric constant determines measured matter by measurement reflective light intensity.The sensing membrane of traditional spr sensor is usual
A thin layer of metal film, this planar structure results in its low specific surface area, the absorbent heavy metal ion of institute by
Limitation, so sensitivity is not high.
Optical fiber is made of the different glass of two layers of refractive index or plastics.Internal layer is light inner core, and diameter is at several microns to several
Ten microns, 0.1~0.2mm of diameter of outer layer, it can be used as light conduction tool.Transmission principle is former according to the refraction and total reflection of light
Reason, when light is mapped to the angle of inner core and outer bed boundary greater than the critical angle for generating total reflection, the impervious interface of light, all
Reflection.
Golden octahedron nanostructure, due to there is the corner angle of small size and multi-stylus end, valence band and conduction band are separated, be will form not
Electron waves are stayed between energy level, there are unique electrical and optical properties, have good electrochemical signals transmittability, by light
Surface plasma body resonant vibration is easily caused under irradiation.
Graphene has the shape ratio (diameter/thickness ratio) of super large；Surface group abundant make its be used for as with nanometer
Material combines the backing material for forming composite material, can realize different operating mechanism in conjunction with the sensor information of various structures
Sensing function structure；With the characteristics such as excellent conduction, absorption, corrosion-resistant, high temperature resistant.
Golden octahedron-graphene nano structure, due to unique photoelectricity physical characteristic and chemical property, good point
Property, huge specific surface area and good adsorptivity are dissipated, has very big advantage in trace heavy metal ion detection.
Existing detection of heavy metal ion method, usually has: it is ultraviolet can spectrophotometry (UV), atomic absorption method (AAS),
Atomic fluorescence method (AFS), inductively coupled plasma body method (ICP), X fluorescence spectrum (XRF), Inductively coupled plasma-mass spectrometry
(ICP-MS), Anodic stripping etc..In these methods, a part of method high sensitivity, accuracy be good, good selective,
Sample can directly be analyzed, such as it is ultraviolet can spectrophotometry, X fluorescence spectrum method；Some methods detection speed is fast, and numerical value is accurate,
Such as Anodic stripping.But generally, existing method otherwise it is at high cost or detection reaction speed it is slow, to trace heavy metal from
The reaction of son is not sensitive enough.
Summary of the invention
Regarding the issue above, the present invention provides a kind of preparation of gold octahedron-graphene composite nano material
Method includes the following steps:
(1) the octahedra nanostructure of preparation gold: 18~22mL ethylene glycol, 0.39~0.41mL polyethylene are added 0.7~
In the phosphoric acid of 0.8mL 1M, the gold chloride of 0.015~0.02mL 0.5M is added in mixing, reacts 12~18 minutes at room temperature,
Keep 185~195 DEG C of 25~35min of reaction to get golden octahedra nano-structured solution again；
(2) golden octahedron-graphene composite nano material is prepared: by the octahedra nano-structured solution of the gold prepared with 14
Solution is spin-coated on single layer stone using sol evenning machine with ultrasonic machine ultrasound until the suitable spin coating of solution solubility by the dilution of~16ml alcohol
Above black alkene.
The concentration of alcohol described in step (2) is 99.7%.
In step (2) when nano-structured solution octahedra using sol evenning machine spin coating gold, using the desk-top sol evenning machine of KW-4A type,
Spin speed is spin speed I, spin-coating time 1min.
Another object of the present invention is to provide a kind of sensing cores based on golden octahedron-graphene composite nano material
Piece is coated with golden octahedron-graphene composite nano material that method above-mentioned is prepared on the sensing chip.
The preparation method of the aforementioned sensing chip based on golden octahedron-graphene composite nano material, includes the following steps:
The pollutant for cleaning optical fiber, removing optical fiber surface, carries out plated film in a vacuum chamber, and the vacuum degree in vacuum chamber is 10-4Pa, growth
Temperature is set as 280~320 DEG C, and sedimentation time is 45~55 minutes, and vacuum chamber is reduced to room temperature after having deposited, that is, is made
It is coated with the sensing chip of golden octahedron-graphene composite nano material.
The preparation method of the aforementioned sensing chip based on golden octahedron-graphene composite nano material selects blackbody chamber temperature
Sensor carries out plated film.
The another object of solution of the present invention is to provide application of the aforementioned sensing chip in spr sensor.
The beneficial effects of the present invention are: nanocomposite is formed using the octahedra nanostructure of gold and graphene film,
With great specific surface area, excellent mechanical strength and flexibility, good electrical and thermal conductivity performance, high transport efficiency and
Fabulous adsorptivity ability；This nano composite structure can be avoided the generation of golden octahedron nanometer particle agglomeration, thus
Big surface area and active site are kept, there is high adsorption capacity to pollutant；It concurrently there are the golden octahedral in two-dimensional graphene
Body nano particle can effectively prevent the polymerization of graphene, so that the high-specific surface area of graphene film and voidage are protected
It holds, forms gold-graphene composite nano material of 3D structure.
Graphene has very strong load capacity and good adsorptivity, and golden octahedron-graphene with stereochemical structure is multiple
It closes structure to be combined together the high sensitivity of the high load rate of graphene, strong adsorptivity and golden octahedron nanometer particle, this is multiple
The sensing chip of condensation material preparation can better absorbing trace heavy metal ion, spr signal can be amplified, adsorption
The pico- change of heavy metal ion can cause the variation of body structure surface dielectric constant and refractive index, move SPR formant
Dynamic, unique photoelectric property keeps the red shift of the peak SPR obvious, detects heavy metal ion to a greater extent, effectively enhances a SPR huge sum of money
The trace detection ability and sensitivity for belonging to ion detection sensor can rapidly and sensitively detect out the trace huge sum of money in sewage
Belong to ion, there is ultralow detectable limit, have a good application prospect.
Detailed description of the invention
Fig. 1 is golden octahedra nano junction composition.
Fig. 2 is golden octahedron-graphene composite nano material illustraton of model.
Fig. 3 is the octahedra particle of gold of 100nm and golden octahedron-graphene composite nano film sensing letter of 80nm
Number.
Fig. 4 is SPR optical fibre sensor structure schematic diagram of the invention.
Fig. 5 is sensing chip sensor mechanism schematic diagram of the invention.
Fig. 6 is various concentration Hg+The peak the SPR spectrogram that solution is obtained using inventive sensor.
Specific embodiment
Below with reference to embodiment, the invention will be further described, but not thereby limiting the invention.
Embodiment 1 prepares golden octahedron-graphene composite nano material and prepares sensing chip using the structure
One, golden octahedron-graphene composite nano material is prepared
It operates in accordance with the following steps:
(1) preparation of the octahedra nanostructure of gold
The octahedra nanostructure of gold is prepared with chemical method, first by the ethylene glycol of 20mL, the polyethylene (Poly) of 0.4mL adds
Enter the phosphoric acid (H that 0.8mL solubility is 1M3PO4) in, after being mixed 2 minutes, add the gold chloride that 0.02mL solubility is 0.5M
(HAuCl4), react 15min at room temperature, then in oil bath pan keep 195 DEG C of heating 30Min, during the reaction, solution from
The colourless purple that becomes becomes brown again, finally obtains the octahedra nanostructure of gold.The octahedra nanostructure of obtained gold is big
It is small in 80~100nm, structure is as shown in Figure 1.
(2) prepare graphene film material
Graphene film material is provided by green intelligent research institute, the Chinese Academy of Sciences, and number of plies majority is single layer, thickness
In 2nm hereinafter, size is in 200~500nm, 0.5~3um of diameter.Its Raman signal is characterized with Raman spectrometer, in deposition Jenner
After rice grain, the Raman signal of its single-layer graphene can be enhanced with the SPR of 632nm laser excitation nano particle.
(3) golden octahedron-graphene composite nano material preparation
The octahedra alcohol for being 99.7% with 15ml solubility of the gold prepared is diluted, guarantee fund's octahedral liquid solution is scanning
Observed under electron microscope is reunited to no large area to be occurred, but arrangement as shown in Figure 1 is uniformly dispersed, particle size is uniform,
It observes, the golden octahedral liquid solution ultrasonic machine diluted ultrasound 20 minutes if solubility is suitble to revolve under a scanning electron microscope
It applies, solution is spin-coated on above single-layer graphene using the desk-top sol evenning machine of KW-4A type of Microelectronic Institute, the Chinese Academy of Sciences, selection rotation
Apply speed I, spin-coating time 1min, the structural schematic diagram such as Fig. 2 institute for the golden octahedron-graphene composite nano material being prepared
Show.
Two, sensing chip is prepared using golden octahedron-graphene composite nano material
According to the characteristic of material, the head coating of black-body cavity temperature sensor is selected.The experiment not easy to pollute of this experimental method
Material meets golden octahedron-requirement of the graphene nano structure to the cleannes of environment.Before experiment, optical fiber surface is carried out
Polishing, firstly, being ultrasonically treated to optical fiber surface with deionized water to remove pollutant of optical fiber surface etc..Coating process exists
It is carried out in vacuum chamber, the vacuum degree in vacuum chamber reaches 10-4Pa is passed through oxygen in a vacuum chamber.Growth temperature in vacuum chamber
It is set as 300 DEG C.This process sedimentation time is 50 minutes.Keep plated film that vacuum chamber is reduced to room after the completion in vacuum deposition process
Temperature finally measures coating film thickness with atomic force microscope, determines the film with a thickness of 80nm-100nm.
Three, sample detection
Sensor core is prepared with golden octahedron-graphene composite nano film of the octahedra particle of the gold of 100nm and 80nm
Piece in air dielectric, measures the peak SPR of golden octahedra particle at 722nm, golden octahedron-graphene nano film peak SPR
At 670nm, as shown in Figure 3.Golden octahedron-graphene composite nano film peak SPR occurs relative to golden octahedra particle
Blue shift, this is because the size variation of sensing chip leads to refraction index changing, it is so as to cause SPR wave crest traversing.
The SPR fibre optical sensor of the golden octahedron-graphene composite nano material of the application of embodiment 2 and its application
One, the SPR fibre optical sensor of the golden octahedron-graphene composite nano material of building application
It is coated with golden octahedron-graphene composite nano film sensing chip using what is prepared in embodiment 1, constructs SPR
Fibre optical sensor, the SPR fibre optical sensor is by forming (its structural schematic diagram is as shown in Figure 4): (1) light source group with lower component
Part --- wideband light source (HL-2000), wave-length coverage is in 350nm-1050nm, (2) optic path component --- it is used for transmission light
The optical fiber of signal, (3) SPR sensorgram chip --- what is prepared in embodiment 1 is coated with golden octahedron-graphene composite nano film
Sensing chip, for optical path reflection, enhancing adsorptivity and photoelectric characteristic, (4) sink --- for containing test sample, (5) are connect
By component --- spectroanalysis instrument, computer.In addition to component (3) SPR sensorgram chip, remaining component is same as the prior art.SPR
The sensor mechanism of sensing chip is as shown in Figure 5.
Sensing process is to utilize gold-graphene nano unique structure photoelectricity physical characteristic and chemical property, huge ratio
Surface area and good adsorptivity, heavy metal ion in the solution can largely be adsorbed on gold-graphene nano body structure surface, draw
The variation of refractive index is played, formant minimum value position generates red shift or blue shift, and the sensor of the application building has ultralow inspection
The limit is surveyed, is able to detect that the concentration variation of trace heavy metal ion.
Two, concentration of heavy metal ion is detected
At room temperature, it is equipped with the Hg that concentration is 10ug/L, 30ug/L, 50ug/L+Solution takes 1ml solution to utilize aforementioned respectively
" the SPR fibre optical sensor of the golden octahedron-graphene composite nano material of application " of building is detected, and obtains the peak SPR spectrum such as
Shown in Fig. 6.As seen from Figure 6, with Hg+Concentration increase, red shift gradually occurs for the peak SPR, the peak SPR of aqueous solution in Fig. 6
At 678nm, 10ug/LHg+The red shift of the peak SPR 9.7nm, 30ug/L Hg+The red shift of the peak SPR 20.53nm, 50ug/L Hg+'s
The peak SPR red shift 30.34nm, the gold-graphene film sensing chip detection peak SPR red shift is obvious, Hg when to low concentration+With good
Good SPR response signal, detection limit have reached 10ug/L.And the peak the SPR red shift of traditional golden film chip detection is generally in 2~8nm,
And it is weak to the SPR response signal of low concentration ion, it cannot detect the Hg of 10ug/L, 30ug/L+Solution can only detect
The Hg of 50ug/L+Solution.Illustrate to have by the octahedra composite nanostructure of gold of graphene modified very strong adsorption capacity and
Load capacity, very sensitive to the variation of ambient enviroment dielectric constant, the increase of formant red shift distance improves heavy metal ion
The sensitivity of detection.
Work as Hg+When concentration difference, golden octahedron-graphene composite nano film sensing chip outer layer dielectric constant occurs
Variation, with Hg+Concentration increases, and the dielectric constant of sensing chip outer layer also increases, and the increase of dielectric constant will lead to
The red shift at the peak SPR.Meanwhile this unique golden octahedron-graphene nano composite construction preparation detection of heavy metal ion passes
Sense chip can replace traditional golden film sensing chip, have higher sensitivity.
Embodiment 3
(1) preparation of the octahedra nanostructure of gold
The octahedra nanostructure of gold is prepared with chemical method, first by the ethylene glycol of 18mL, the polyethylene (Poly) of 0.39mL
Phosphoric acid (the H that 0.7mL solubility is 1M is added3PO4) in, after being mixed 2 minutes, add the gold chloride that 0.015mL solubility is 0.5M
(HAuCl4), it reacts 12 minutes at room temperature, then kept for 185 DEG C heat 35 minutes, during the reaction, solution in oil bath pan
Become brown again from the colourless purple that becomes, finally obtains the octahedra nanostructure of gold.The octahedra nanostructure of obtained gold
Size is in 100nm or so.
(2) golden octahedron-graphene nano structure preparation
In golden octahedron-graphene nano structure preparation process, it is with 14ml solubility by the gold octahedron prepared
99.7% alcohol dilution, guarantee fund's octahedral liquid solution observe that no large area reunion occurs under a scanning electron microscope,
But arrangement is uniformly dispersed, particle size is uniform, by the golden octahedral liquid solution ultrasonic machine diluted ultrasound 20 minutes, with scanning
Electron microscope observation determines the solubility of solution if appropriate for spin coating graphene.After the completion of the allotment of solution solubility, sol evenning machine is used
Solution is spin-coated on above single-layer graphene.Solution is revolved using the desk-top sol evenning machine of KW-4A type of Microelectronic Institute, the Chinese Academy of Sciences
It is coated in above single-layer graphene, selects spin speed I, spin-coating time 1min.
(3) sensing chip is prepared using golden octahedron-graphene composite nano material
Select the head coating of black-body cavity temperature sensor.Before experiment, optical fiber surface is polished, uses deionized water
Optical fiber surface is ultrasonically treated to remove pollutant of optical fiber surface etc..Coating process carries out in a vacuum chamber, vacuum chamber
In vacuum degree reach 10-4Pa is passed through oxygen in a vacuum chamber.Growth temperature in vacuum chamber is set as 320 DEG C.This process is heavy
The product time is 55 minutes.It keeps plated film that vacuum chamber is reduced to room temperature after the completion in vacuum deposition process, finally uses atomic force microscopy
Mirror measures coating film thickness, determines the film with a thickness of 80nm-100nm.
Embodiment 4
(1) preparation of the octahedra nanostructure of gold
The octahedra nanostructure of gold is prepared with chemical method, first by the ethylene glycol of 22mL, the polyethylene (Poly) of 0.41mL
Phosphoric acid (the H that 0.75mL solubility is 1M is added3PO4) in, after being mixed 2 minutes, the chlorine that addition 0.018mL solubility is 0.5M is golden
Acid (HAuCl4), it reacts 18 minutes at room temperature, then kept for 195 DEG C heat 25 minutes in oil bath pan, it is during the reaction, molten
Liquid becomes brown from the colourless purple that becomes again, finally obtains the octahedra nanostructure of gold.The octahedra nano junction of obtained gold
Structure size is in 100nm or so.
(2) golden octahedron-graphene nano structure preparation
In golden octahedron-graphene nano structure preparation process, it is with 16ml solubility by the gold octahedron prepared
99.7% alcohol dilution, guarantee fund's octahedral liquid solution observe that no large area reunion occurs under a scanning electron microscope,
But arrangement is uniformly dispersed, particle size is uniform, by the golden octahedral liquid solution ultrasonic machine diluted ultrasound 20 minutes, with scanning
Electron microscope observation determines the solubility of solution if appropriate for spin coating graphene.After the completion of the allotment of solution solubility, sol evenning machine is used
Solution is spin-coated on above single-layer graphene.Solution is revolved using the desk-top sol evenning machine of KW-4A type of Microelectronic Institute, the Chinese Academy of Sciences
It is coated in above single-layer graphene, selects spin speed I, spin-coating time 1min.
(3) sensing chip is prepared using golden octahedron-graphene composite nano material
Select the head coating of black-body cavity temperature sensor.Before experiment, optical fiber surface is polished, uses deionized water
Optical fiber surface is ultrasonically treated to remove pollutant of optical fiber surface etc..Coating process carries out in a vacuum chamber, vacuum chamber
In vacuum degree reach 10-4Pa is passed through oxygen in a vacuum chamber.Growth temperature in vacuum chamber is set as 280 DEG C.This process is heavy
The product time is 55 minutes.It keeps plated film that vacuum chamber is reduced to room temperature after the completion in vacuum deposition process, finally uses atomic force microscopy
Mirror measures coating film thickness, determines the film with a thickness of 80nm-100nm.
Claims (3)
1. a kind of spr sensor is in Hg+Application in detection, which is characterized in that be coated with gold on the sensing chip of spr sensor
Octahedron-graphene composite nano material, concrete operation step are as follows: cleaning optical fiber, the pollutant for removing optical fiber surface, in vacuum
Plated film is carried out in room, the vacuum in vacuum chamber is 10-4Pa, growth temperature are set as 280-320 DEG C, and sedimentation time is 45-55 points
Vacuum chamber is cooled down room temperature after the completion of deposition, that is, has made the sensing for being coated with golden octahedron-graphene composite nano material by clock
Chip；
Wherein the preparation method of the golden octahedron-graphene composite nano material includes the following steps: that (1) preparation gold is octahedra
Nanostructure: 18~22mL ethylene glycol, 0.39~0.41mL polyethylene are added in the phosphoric acid of 0.7~0.8mL 1M, and mixing adds
Add the gold chloride of 0.015~0.02mL 0.5M, at room temperature react 12~18 minutes, then keep 185~195 DEG C reaction 25~
35min is to get golden octahedra nano-structured solution；(2) golden octahedron-graphene composite nano material is prepared: by what is prepared
Golden octahedron nano-structured solution is diluted with 14~16ml alcohol, with ultrasonic machine ultrasound until solution solubility is suitble to spin coating, use
Solution is spin-coated on above single-layer graphene by sol evenning machine.
2. spr sensor is in Hg according to claim 1+Application in detection, it is characterised in that: the concentration of alcohol is
99.7%.
3. spr sensor is in Hg according to claim 1+Application in detection, it is characterised in that: use sol evenning machine spin coating gold
When octahedra nano-structured solution, using the desk-top sol evenning machine of KW-4A type, spin speed is spin speed I, and spin-coating time is
1min。
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| CN104384524A (en) * | 2014-11-19 | 2015-03-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing flake graphite single/multiple load precious metal nano particles |
| CN106018376A (en) * | 2016-04-29 | 2016-10-12 | 中国科学院合肥物质科学研究院 | Hydrogel@gold nanocomposite and preparation method and application thereof |
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