CN106950199A - The golden octahedron preparation method of graphene composite nano material and the sensing chip based on it and its application - Google Patents
The golden octahedron preparation method of graphene composite nano material and the sensing chip based on it and its application Download PDFInfo
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- 238000004528 spin coating Methods 0.000 claims abstract description 12
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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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Abstract
The invention discloses a kind of preparation method of the octahedra graphene composite nano material of gold, comprise the following steps：(1) the octahedra nanostructured of gold is prepared：18~22mL ethylene glycol, 0.39~0.41mL polyethylene are added in 0.7~0.8mL 1M phosphoric acid, mixing, 0.015~0.02mL of addition 0.5M gold chloride, reacts 12~18 minutes at room temperature, 185~195 DEG C of 25~35min of reaction are kept again, produce golden octahedra nano-structured solution；(2) the octahedra graphene composite nano material of gold is prepared：The octahedra nano-structured solution of the gold prepared is diluted with 14~16ml alcohol, with ultrasonic machine ultrasound until solution solubility is adapted to spin coating, solution is spin-coated on above single-layer graphene using sol evenning machine.Also disclose sensing chip based on the octahedra graphene composite nano material of the gold and its preparation method and application.
Description
Technical field
The present invention relates to graphene composite material and its application field, and in particular to golden octahedron-graphene composite Nano
The preparation method of material and the sensing chip based on it and its application.
Background technology
Surface plasma body resonant vibration (Surface Plasmon Resonance, SPR) sensor is real-time, sensitive by its
The advantages of spending high, has been widely used in the fields such as life science, clinical diagnosis, drug screening, food security, environmental monitoring.With
The requirement more and more higher for environment measuring technology in society, real-time, quick, highly sensitive SPR sensorgram technology turns into weight
One main direction of studying of metal ion detection.
SPR is the evanescent wave produced when p-polarization light is totally reflected at glass and metal-graphite alkene nano-structural interfaces
The free electron of metal-graphite alkene nanostructured surface is triggered to produce surface plasma, and in surface plasma and evanescent wave ripple
A kind of covibration produced in the case of arrow identical.When occurring surface plasmon resonance, incident light energy almost all
Metal-graphite alkene nanostructured surface formation SPR is bound in, 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 nanostructured another side change
When, refractive index can be made to occur minor variations, the small value position of formant can produce skew.Therefore, it can according to minimum value position with
Relation between dielectric constant, measured matter is determined by measuring reflective light intensity.The sensing membrane of traditional spr sensor is usual
A thin layer of metal film, this planar structure result in its low specific surface area, the absorbent heavy metal ion of institute by
Limitation, so sensitivity is not high.
Optical fiber is made up 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 can conduct instrument as light.Transmission principle is the refraction and total reflection original according to light
Reason, when light is mapped to the angle of inner core and outer bed boundary more than the critical angle for producing total reflection, the impervious interface of light, all
Reflection.
Golden octahedron nanostructured, the corner angle at small size and many tips due to having, valence band and conduction band are separated, can formed not
Electron waves are stayed between energy level, with unique electrical and optical properties, have good electrochemical signals transmittability, by light
Easily cause surface plasma body resonant vibration under irradiation.
Graphene has the shape ratio (diameter/thickness ratio) of super large；Abundant surface group make its be used for as with nanometer
Material combines to form the backing material of composite, can be combined with the sensor information of various structures, realize different operating mechanism
Sensing function structure；With characteristics such as excellent conduction, absorption, corrosion-resistant, high temperature resistants.
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, generally has：It is ultraviolet can AAS (UV), atomic absorption method (AAS),
Atomic fluorescence method (AFS), inductively coupled plasma method (ICP), X fluorescence spectrum (XRF), Inductively coupled plasma-mass spectrometry
(ICP-MS), Anodic stripping etc..In these methods, a part of method sensitivity is high, the degree of accuracy is good, good selective,
Can with Direct Analysis sample, such as it is ultraviolet can AAS, X fluorescence spectrum method；Some method detection speeds are fast, and numerical value is accurate,
Such as Anodic stripping.But generally, otherwise existing method high cost, or detection reaction speed is slow, to trace heavy metal from
The reaction of son is not sensitive enough.
The content of the invention
Regarding the issue above, the present invention provides a kind of preparation of golden octahedron-graphene composite nano material
Method, comprises the following steps：
(1) the octahedra nanostructured of gold is prepared：By 18~22mL ethylene glycol, 0.39~0.41mL polyethylene add 0.7~
In 0.8mL 1M phosphoric acid, mixing, 0.015~0.02mL of addition 0.5M gold chloride reacts 12~18 minutes at room temperature,
185~195 DEG C of 25~35min of reaction are kept again, produce golden octahedra nano-structured solution；
(2) golden octahedron-graphene composite nano material is prepared：The octahedra nano-structured solution of the gold prepared is used 14
~16ml alcohol is diluted, and with ultrasonic machine ultrasound until solution solubility is adapted to spin coating, solution is spin-coated on into individual layer stone using sol evenning machine
Above black alkene.
The concentration of alcohol described in step (2) is 99.7%.
In step (2) during nano-structured solution octahedra using sol evenning machine spin coating gold, using the desk-top sol evenning machine of KW-4A types,
Spin speed is spin speed I, and spin-coating time is 1min.
Another object of the present invention is to provide a kind of sensing core based on golden octahedron-graphene composite nano material
Golden octahedron-graphene composite nano material that foregoing method is prepared is coated with piece, the sensing chip.
The preparation method of the foregoing sensing chip based on golden octahedron-graphene composite nano material, comprises the following steps：
Clean optical fiber, remove the pollutant of optical fiber surface, it is 10 that the vacuum in plated film, vacuum chamber is carried out in a vacuum chamber-4Pa, growth
Temperature is set as 280~320 DEG C, and sedimentation time is 45~55 minutes, and vacuum chamber is reduced into room temperature after having deposited, that is, made
It is coated with the sensing chip of golden octahedron-graphene composite nano material.
The preparation method of the foregoing sensing chip based on golden octahedron-graphene composite nano material selects blackbody chamber temperature
Sensor carries out plated film.
The another object that the present invention is solved is the application for providing foregoing sensing chip in spr sensor.
The beneficial effects of the invention are as follows：Using golden octahedra nanostructured and graphene film formation nano composite material,
With great specific surface area, excellent mechanical strength and pliability, good electrical and thermal conductivity performance, high transport efficiency and
Fabulous adsorptivity ability；This nano composite structure can avoid the generation of golden octahedron nanometer particle agglomeration, so that
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 and voidage of graphene film are protected
Hold, form gold-graphene composite nano material of 3D structures.
Graphene has very strong load capacity and good adsorptivity, and golden octahedron-graphene with stereochemical structure is multiple
Close structure to be combined together the high sensitivity of the high capacity rate of graphene, strong adsorptivity and golden octahedron nanometer particle, this is answered
Sensing chip prepared by condensation material can preferably absorb trace heavy metal ion, can amplify spr signal, its adsorption
The change of heavy metal ion slightly just can cause the change of body structure surface dielectric constant and refractive index, move SPR formants
Dynamic, it is obvious that unique photoelectric property moves SPR Feng Red, and heavy metal ion is detected to a greater extent, SPR is effectively enhanced with much money
Belong to trace detection ability and the sensitivity of ion detection sensor, can enzyme rapidly and sensitively detect trace in sewage with much money
Belong to ion, with ultralow detectable limit, have a good application prospect.
Brief description of the drawings
Fig. 1 is golden octahedra nano junction composition.
Fig. 2 is golden octahedron-graphene composite nano material illustraton of model.
Fig. 3 is the sensing letter of golden octahedron-graphene composite nano film of 100nm golden octahedra particle and 80nm
Number.
Fig. 4 is the SPR optical fibre sensor structure schematic diagrams of the present invention.
Fig. 5 is the sensing chip sensor mechanism schematic diagram of the present invention.
Fig. 6 is various concentrations Hg+The SPR peaks spectrogram that solution is obtained using inventive sensor.
Embodiment
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
First, golden octahedron-graphene composite nano material is prepared
Operate in accordance with the following steps：
(1) preparation of the octahedra nanostructured of gold
The octahedra nanostructured of gold is prepared with chemical method, first by 20mL ethylene glycol, 0.4mL polyethylene (Poly) adds
Enter the phosphoric acid (H that 0.8mL solubility is 1M3PO4) in, after mixing 2 minutes, the gold chloride that addition 0.02mL solubility is 0.5M
(HAuCl4), react 15min at room temperature, then keep in oil bath pan 195 DEG C of heating 30Min, during the course of the reaction, solution from
The colourless purple that is changed into is changed into brown again, finally obtains the octahedra nanostructured of gold.The octahedra nanostructured of obtained gold is big
It is small in 80~100nm, its structure is as shown in Figure 1.
(2) graphene film material is prepared
Graphene film material is provided by green intelligent research institute of the Chinese Academy of Sciences, and its number of plies majority is individual layer, thickness
In below 2nm, 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 strengthened with the SPR of 632nm laser excitation nano particles.
(3) prepared by golden octahedron-graphene composite nano material
The gold octahedron 15ml solubility prepared is diluted for 99.7% alcohol, it is ensured that golden octahedral liquid solution is in 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,
The golden octahedral liquid solution ultrasonic machine diluted is ultrasonic 20 minutes, observe under a scanning electron microscope, if solubility is adapted to rotation
Apply, solution is spin-coated on above single-layer graphene using the desk-top sol evenning machine of KW-4A types of Microelectronic Institute of the Chinese Academy of Sciences, selection rotation
Apply speed I, spin-coating time 1min, structural representation such as Fig. 2 institutes of the golden octahedron-graphene composite nano material prepared
Show.
2nd, sensing chip is prepared using golden octahedron-graphene composite nano material
According to the characteristic of material, from the head coating of black-body cavity temperature sensor.This experimental method is difficult pollution experiment
Material, meets golden octahedron-requirement of the graphene nano structure to the cleannes of environment.Before experiment, optical fiber surface is carried out
Polishing, first, ultrasonically treated pollutant to remove optical fiber surface etc. is carried out with deionized water to optical fiber surface.Coating process exists
Carried out in vacuum chamber, the vacuum 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 that vacuum chamber is reduced into room after the completion of plated film in vacuum deposition process
Temperature, is finally measured with AFM to coating film thickness, determines the film that thickness is 80nm-100nm.
3rd, sample detection
Sensor core is prepared with golden octahedron-graphene composite nano film of the octahedra particle of 100nm gold and 80nm
In piece, air dielectric, the SPR peaks of golden octahedra particle are measured at 722nm, the SPR peaks of golden octahedron-graphene nano film
At 670nm, as shown in Figure 3.The SPR peaks of golden octahedron-graphene composite nano film occur relative to golden octahedra particle
Blue shift, because the size variation of sensing chip causes refraction index changing, so as to cause SPR crests traversing.
The SPR fibre optical sensors of the golden octahedron-graphene composite nano material of the application of embodiment 2 and its application
First, the SPR fibre optical sensors of the golden octahedron-graphene composite nano material of application are built
Using the sensing chip for being coated with golden octahedron-graphene composite nano film prepared in embodiment 1, SPR is built
Fibre optical sensor, the SPR fibre optical sensors are made up of (its structural representation is as shown in Figure 4) following component：(1) light source group
Part --- wideband light source (HL-2000), wave-length coverage is in 350nm-1050nm, (2) optic path component --- 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 light path reflection, enhancing adsorptivity and photoelectric characteristic, (4) tank --- for containing detection sample, (5) connect
By component --- spectroanalysis instrument, computer.Except 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 the photoelectricity physical characteristic and chemical property, huge ratio using gold-graphene nano unique structure
Surface area and good adsorptivity, heavy metal ion in the solution can be adsorbed largely in gold-graphene nano body structure surface, drawn
The change of refractive index is played, formant minimum value position produces red shift or blue shift, and the sensor that the application is built has ultralow inspection
The limit is surveyed, the change in concentration of trace heavy metal ion is able to detect that.
2nd, 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 foregoing respectively
" the SPR fibre optical sensors of the golden octahedron-graphene composite nano material of application " built is detected, draws SPR peaks spectrum such as
Shown in Fig. 6.As seen from Figure 6, with Hg+Concentration increase, SPR gradually sends out in peak Red raw and moves, the SPR peaks of the aqueous solution in Fig. 6
At 678nm, 10ug/LHg+SPR Feng Red move 9.7nm, 30ug/L Hg+SPR Feng Red move 20.53nm, 50ug/L Hg+'s
SPR Feng Red move 30.34nm, and the SPR Feng Red of gold-graphene film sensing chip detection move obvious, Hg during to low concentration+With good
Good SPR response signals, test limit has reached 10ug/L.And the SPR Feng Red of traditional golden film chip detection move general in 2~8nm,
And it is weak to the SPR response signals of low concentration ion, it is impossible to detect 10ug/L, 30ug/L Hg+Solution, can only be detected
50ug/L Hg+Solution.Illustrate by the octahedra composite nanostructure of gold of graphene modified have very strong adsorption capacity and
Load capacity, the change to surrounding environment dielectric constant is very sensitive, and the increase that Gong Zhen Feng Red move distance improves heavy metal ion
The sensitivity of detection.
Work as Hg+When concentration is different, the dielectric constant of golden octahedron-graphene composite nano film sensing chip outer layer occurs
Change, with Hg+Concentration increase, the dielectric constant of sensing chip outer layer is also increased, and the increase of dielectric constant can cause
The red shift at SPR peaks.Meanwhile, detection of heavy metal ion prepared by this unique golden octahedron-graphene nano composite construction is passed
Sense chip, can replace traditional golden film sensing chip, with higher sensitivity.
Embodiment 3
(1) preparation of the octahedra nanostructured of gold
The octahedra nanostructured of gold, first by 18mL ethylene glycol, 0.39mL polyethylene (Poly) are prepared with chemical method
Add the phosphoric acid (H that 0.7mL solubility is 1M3PO4) in, after mixing 2 minutes, the gold chloride that addition 0.015mL solubility is 0.5M
(HAuCl4), react 12 minutes at room temperature, then kept for 185 DEG C heat 35 minutes, during the course of the reaction, solution in oil bath pan
It is changed into brown again from the colourless purple that is changed into, finally obtains the octahedra nanostructured of gold.The octahedra nanostructured of obtained gold
Size is in 100nm or so.
(2) prepared by golden octahedron-graphene nano structure
In the preparation process of golden octahedron-graphene nano structure, it is with 14ml solubility by the gold octahedron prepared
99.7% alcohol dilution, it is ensured that golden octahedral liquid solution observes that no large area reunion occurs under a scanning electron microscope,
It is but arrangement is uniformly dispersed, particle size is uniform, the golden octahedral liquid solution ultrasonic machine diluted is ultrasonic 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 types of Microelectronic Institute of 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
From the head coating of black-body cavity temperature sensor.Before experiment, optical fiber surface is polished, deionized water is used
Ultrasonically treated pollutant to remove optical fiber surface etc. is carried out to optical fiber surface.Coating process is carried out in a vacuum chamber, vacuum chamber
In vacuum 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 sunk
The product time is 55 minutes.Keep that vacuum chamber is reduced into room temperature after the completion of plated film in vacuum deposition process, finally use atomic force microscopy
Mirror is measured to coating film thickness, determines the film that thickness is 80nm-100nm.
Embodiment 4
(1) preparation of the octahedra nanostructured of gold
The octahedra nanostructured of gold, first by 22mL ethylene glycol, 0.41mL polyethylene (Poly) are prepared with chemical method
Add the phosphoric acid (H that 0.75mL solubility is 1M3PO4) in, after mixing 2 minutes, addition 0.018mL solubility is golden for 0.5M chlorine
Acid (HAuCl4), react 18 minutes at room temperature, then kept for 195 DEG C heat 25 minutes in oil bath pan, it is during the course of the reaction, molten
Liquid is changed into brown again from the colourless purple that is changed into, and finally obtains the octahedra nanostructured of gold.The octahedra nano junction of obtained gold
Structure size is in 100nm or so.
(2) prepared by golden octahedron-graphene nano structure
In the preparation process of golden octahedron-graphene nano structure, it is with 16ml solubility by the gold octahedron prepared
99.7% alcohol dilution, it is ensured that golden octahedral liquid solution observes that no large area reunion occurs under a scanning electron microscope,
It is but arrangement is uniformly dispersed, particle size is uniform, the golden octahedral liquid solution ultrasonic machine diluted is ultrasonic 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 types of Microelectronic Institute of 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
From the head coating of black-body cavity temperature sensor.Before experiment, optical fiber surface is polished, deionized water is used
Ultrasonically treated pollutant to remove optical fiber surface etc. is carried out to optical fiber surface.Coating process is carried out in a vacuum chamber, vacuum chamber
In vacuum 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 sunk
The product time is 55 minutes.Keep that vacuum chamber is reduced into room temperature after the completion of plated film in vacuum deposition process, finally use atomic force microscopy
Mirror is measured to coating film thickness, determines the film that thickness is 80nm-100nm.
Claims (7)
1. a kind of preparation method of golden octahedron-graphene composite nano material, it is characterised in that comprise the following steps：
(1) the octahedra nanostructured of gold is prepared：18~22mL ethylene glycol, 0.39~0.41mL polyethylene are added into 0.7~0.8mL
In 1M phosphoric acid, mixing, 0.015~0.02mL of addition 0.5M gold chloride reacts 12~18 minutes, then keep at room temperature
185~195 DEG C of 25~35min of reaction, produce golden octahedra nano-structured solution；
(2) golden octahedron-graphene composite nano material is prepared：By the octahedra nano-structured solution of gold prepared with 14~
16ml alcohol is diluted, and with ultrasonic machine ultrasound until solution solubility is adapted to spin coating, solution is spin-coated on into mono-layer graphite using sol evenning machine
Above alkene.
2. the preparation method of gold octahedron-graphene composite nano material as claimed in claim 1, it is characterised in that step
(2) concentration of alcohol described in is 99.7%.
3. the preparation method of gold octahedron-graphene composite nano material as claimed in claim 1, it is characterised in that step
(2) in during nano-structured solution octahedra using sol evenning machine spin coating gold, using the desk-top sol evenning machine of KW-4A types, spin speed is rotation
Speed I is applied, spin-coating time is 1min.
4. a kind of sensing chip based on golden octahedron-graphene composite nano material, it is characterised in that on the sensing chip
It is coated with golden octahedron-graphene composite nano material that the method described in claim 1 is prepared.
5. a kind of preparation method of the sensing chip based on golden octahedron-graphene composite nano material described in claim 4,
It is characterised in that it includes following steps：Clean optical fiber, remove the pollutant of optical fiber surface, plated film, vacuum are carried out in a vacuum chamber
Vacuum in room is 10-4Pa, growth temperature is set as 280~320 DEG C, and sedimentation time is 45~55 minutes, will after having deposited
Vacuum chamber is reduced to room temperature, that is, has made the sensing chip for being coated with golden octahedron-graphene composite nano material.
6. the preparation method of the sensing chip as claimed in claim 5 based on golden octahedron-graphene composite nano material, its
It is characterised by, plated film is carried out from black-body cavity temperature sensor.
7. application of the sensing chip described in claim 4 in spr sensor.
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