CN108375569A - A kind of preparation method of phthalocyanine/graphene composite sensing material for cyanide ion identification - Google Patents
A kind of preparation method of phthalocyanine/graphene composite sensing material for cyanide ion identification Download PDFInfo
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- CN108375569A CN108375569A CN201810131848.6A CN201810131848A CN108375569A CN 108375569 A CN108375569 A CN 108375569A CN 201810131848 A CN201810131848 A CN 201810131848A CN 108375569 A CN108375569 A CN 108375569A
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- G—PHYSICS
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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
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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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
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
Abstract
The invention discloses a kind of preparation methods of phthalocyanine/graphene composite sensing material for cyanide ion identification, belong to sensing material field.The composite sensing material is self-assembly of with phthalocyanine derivates by π pi bonds stacking by graphene；Preparation method includes：(1) graphene oxide is restored；(2) preparation of phthalocyanine derivates；(3) room temperature 10 60min of ultrasound in graphene solution are added in the phthalocyanine derivates for dissolving organic solvent, obtain black suspension, centrifuge washing, and vacuum drying obtains black powder, as phthalocyanine derivates/graphene composite sensing material.Above-mentioned phthalocyanine derivates/graphene composite material is equably assembled on filter paper, the use of polyvinyl alcohol is filmogen uniform coating, obtains test paper.The present invention has simple, quick, cheap advantage, while obtained composite sensing material has the characteristics that high sensitivity, can be detected to 1~100 μM of cyanide ion.
Description
Technical field
The invention belongs to sensing material fields, and in particular to a kind of phthalocyanine/graphene for cyanide ion identification is compound
The preparation method of sensing material.
Background technology
With the quickening of human industryization process, problem of environmental pollution is also increasingly severe.The natural environment of human survival,
Air environment, water resource and land resource receive unprecedented destruction, seriously threaten own existence and the development of the mankind.
Currently, people pollute pay attention to day by day for heavy metal ion, but not enough concern anion contaminations and other small molecules
Close object pollution.And damage of these pollutants to the health and development of the mankind, just with the continuous expansion of its application field, and
The Natural Circulation of ecological environment, increasingly sharpens.Among numerous anion, cyanide is that toxicity is most strong, reaction is most fast
One of noxious material, the half lethal dose in human body are 1.0mg/kg.After human body sucks cyanide, the blood of human body is influenced whether
Pipe, vision, a variety of human organs such as nervous system.Cyanide is a kind of substance for being easy to be absorbed by the body, it can pass through
Number of ways enters human body, such as the sucking of mouth, respiratory tract or the infiltration of skin, keeps respiratory failure lethal.So it also becomes
Judge the index whether environment pollutes.However, due to cyanide metallurgy, mining, plating, dyestuff, synthetic fibers and
Extensive use in the industry productions such as resin is the indispensable raw material of industry.The World Health Organization (WHO) regulation, drinking water
The concentration of middle cryanide ion has to be lower than 1.9 μM, and excessive cyanide ion, which can cause to vomit, twitch, lose will eventually leads to extremely
It dies.It after such substance enters blood circulation, is combined with the iron ion of the cytochrome oxidase in blood, it is thin to generate cyaniding high ferro
Born of the same parents' chromo-oxidase, iron ion lose the ability for transmitting electronics, make breathing chain interruption, cell death by suffocation.Since cyanide exists
Solubility in lipoid is bigger, so central nervous system is first subjected to harm, especially respiratory center is more sensitive, breathing
Failure is the main reason for cyanide acute poisoning is lethal.Therefore, the identification of cyanide ion and detection are in life science and ring
The fields such as border science have great importance.
The researchers such as Yasuhiro (Yasuhiro S, Shigehiro S, Kenji M.ACS
Appl.Mater.Interfaces,2011,3(12):4649-4656) design synthetic copolymer (NIPAM-co-CS) is in room temperature
Under the conditions of fluoroscopic examination cyanide ion, this copolymer can accurately detect a concentration of 0.5 μM of cyanide ion or more.In recent years,
(Yasuhiro S, Masaya N, Naoto H, et al.Anal.Chem., 2016,88 (13) such as Yasuhiro:6805-
6811) report coumarin derivative by nucleophilic addition loop coil open loop quick, intuitive fluorescence identifying cyanide ion.Zahra etc.
(Zahra S,Bahram H,Mojtaba S.ACS Appl.Mater.Interfaces,2016,8(24):15177-15188)
Highly sensitive nanogold/CuPc composite sensing material is synthesized, a concentration of 7~350 μM of open hole detection cyanide ion are capable of.
Identification of the right graphene/phthalocyanine composite sensing material for cyanide ion does not have been reported that.
Invention content
The invention aims to solve the problems, such as that single metal phthalocyanine recognition capability is poor, and provide it is a kind of for cyanogen root from
The preparation method of phthalocyanine/graphene composite sensing material of son identification, it is easy to operate to this method, it is of low cost, it can improve
Composite material identifies the ability of cyanide ion.
To achieve the goals above, the present invention is achieved by the following technical programs.
A kind of preparation method of phthalocyanine/graphene composite sensing material for cyanide ion identification of the present invention, including such as
Lower step：
(1) by the concentrated sulfuric acid of 23~92ml, 1~4g graphite powders and 0.5~2g sodium nitrate stirs 10 in 0~3 DEG C~
30min, 3~12g potassium permanganate are slowly added to, and keep temperature of reaction system to be less than 20 DEG C, 2 are stirred to react under the conditions of ice-water bath
~4h, reaction solution are blackish green suspension；30~60min is reacted under the conditions of 35 DEG C, is then slowly added to distilled water and is controlled
Temperature is no more than 100 DEG C, with a large amount of distilled water dilute reaction solution and addition 5~15ml 30~50% after 15~45min
H2O2Solution, reaction solution gradually become glassy yellow suspension；It is washed with distilled water and dilute hydrochloric acid, BaCl is used in combination2Solution detects, directly
To filtrate without SO42-, graphene oxide is obtained after drying；The graphene oxide of 100~300mg is dispersed in 100~300ml to steam
In distilled water, 30~60min of ultrasonic disperse forms finely dispersed yellowish-brown turbid；85~250 μ L hydrazine hydrate solutions are added dropwise, make
Reaction solution pH9~11 are adjusted with ammonium hydroxide, 1~3h is reacted under the conditions of 85~95 DEG C of oil baths；Graphene is obtained after filtration washing.
(2) by pyromellitic dianhydride, urea, chlorate, after catalyst ammonium molybdate is fully ground, 5~10min is heated, is obtained
To the intermediate product of black, with 2~6M salt acid soak 12~for 24 hours, filtering, a large amount of hot water wash filter cakes；This intermediate product is added
Enter in the NaOH aqueous solutions that mass fraction is 5~20%, under the conditions of 75~95 DEG C, 6~12h of heating stirring；After reaction,
Mixture is filtered, filtrate salt acid for adjusting pH to 2~4；It centrifuges, obtains phthalocyanine derivates；
The molar ratio of the pyromellitic dianhydride, urea and chlorate is 1:10~20:2~3.
(3) graphene dispersion for preparing 5~20mg steps (1) is in 50~150ml organic solvents, 0.5~2h of ultrasound,
Make graphene uniform is good to be dispersed in solvent, phthalocyanine derivates prepared by 5~10 μM of steps (2) be added into dispersion liquid,
And 0.5~2h of ultrasonic disperse, 10~40min of standing obtain phthalocyanine/graphene composite sensing material at room temperature.
Further, the chlorate described in step (2) is copper chloride or zinc chloride.
Further, the organic solvent described in step (3) is dimethyl sulfone (DMSO).
The phthalocyanine obtained invention also provides above-mentioned preparation method/graphene composite sensing material for cyanogen root from
Application in son identification, specifically：5~10mg phthalocyanine derivates/graphene solution is equably assembled on filter paper, height is used
Polymers is filmogen uniform coating, obtains test paper.
Further, the high polymer is polyvinyl alcohol.
Compared with prior art, the present invention has the following technical effects：
1, the present invention is become using inorganic material graphene excellent electric conductivity and chemical stability by the periodicity of structure
Change and form composite material with phthalocyanine, that realizes organic/inorganic materials has complementary functions, optimizes and cooperate with enhancing.
2, phthalocyanine of the present invention/graphene composite sensing material passes through pi-pi bond heap by graphene and phthalocyanine derivates
Folded to be self-assembly of, preparation method is simple, of low cost.
3, phthalocyanine derivates/graphene composite sensing material prepared by the present invention substantially increases the recognition performance of phthalocyanine,
1~100 μM of cyanide ion can be detected.
Description of the drawings
Fig. 1 is the transmission electron microscope picture for the graphene that the embodiment of the present invention 1 is prepared；
As seen from the figure, it removes to obtain the graphene of single layer by electronation, scale is nanoscale.
Fig. 2 is that eight carboxyl CuPcs/graphene composite sensing material prepared by the embodiment of the present invention 2 identifies CN-Red shift becomes
Change figure (wherein：Ordinate 1~6 respectively represents 16.25 × 10-1mol/L、1.25×10-2mol/L、2.5×10-3mol/L、5×
10-4mol/L、1×10-5mol/L、2×10-6mol/L)；
As seen from the figure, eight carboxyl CuPcs/graphene complex is added in the cyanide ion solution of various concentration, it is purple
Outer absorption peak is moved to high wave, and different degrees of " red shift " phenomenon occurs；Wherein to 1 × 10-5The cyanide ion solution of mol/L is known
Not significantly.
Fig. 3 is that eight carboxyl zinc phthalocyanines/graphene composite sensing material prepared by the embodiment of the present invention 3 identifies CN-Red shift becomes
Change figure (wherein：Ordinate 1~6 respectively represents 16.25 × 10-1mol/L、1.25×10-2mol/L、2.5×10-3mol/L、5×
10-4mol/L、1×10-5mol/L、2×10-6mol/L)；
As seen from the figure, eight carboxyl zinc phthalocyanines/graphene complex is added in the cyanide ion solution of various concentration, it is purple
Outer absorption peak is moved to high wave, and different degrees of " red shift " phenomenon occurs；Wherein to 5 × 10-4The cyanide ion solution of mol/L is known
Not significantly.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.
Embodiment 1
By the concentrated sulfuric acid of 43ml, 2g graphite powders and 1g sodium nitrate stir 15min in 0~3 DEG C, and 6g potassium permanganate slowly adds
Enter, temperature of reaction system is kept to be less than 20 DEG C, 3h is stirred to react under the conditions of ice-water bath, reaction solution is blackish green suspension；In
42min is reacted under the conditions of 35 DEG C, be then slowly added to distilled water and controls temperature no more than 100 DEG C, is steamed with a large amount of after 35min
Distilled water dilute reaction solution and the H that 10ml 40% is added2O2Solution, reaction solution gradually become glassy yellow suspension；With distilled water and
For several times, BaCl is used in combination in 2% dilute hydrochloric acid washing2Solution detects, until filtrate is without SO42-, graphene oxide is obtained after drying.It will
The graphene oxide of 150mg is dispersed in 100ml distilled water, ultrasonic disperse 35min, forms finely dispersed yellowish-brown turbid；
100 μ L hydrazine hydrate solutions are added dropwise, adjusts reaction solution pH ≈ 10 using ammonium hydroxide, reacts 2h under the conditions of 90 DEG C of oil baths；Filtration washing
Graphene is obtained, transmission electron microscope picture is as shown in Figure 1.
Embodiment 2
Pyromellitic dianhydride, urea, the Copper dichloride dihydrate (1 of certain mol proportion:15:2), catalyst ammonium molybdate is fully ground
After mill, 5min is heated, the intermediate product of black is obtained, with 6M salt acid soak 12h, filtering, a large amount of hot water wash filter cake.It will be in this
Between product be added 20% (mass fraction) NaOH aqueous solutions in, under the conditions of 95 DEG C, heating stirring 12h, in hydrolytic process
NaOH aqueous solutions need to suitably be added.After reaction, mixture is filtered, the filtrate salt acid for adjusting pH value 4 of 12M.Centrifugation
Separation, obtains eight carboxyl CuPc of final product.By 5mg graphene dispersions in 50ml organic solvents, ultrasonic 0.5h makes graphite
Alkene is uniformly good to be dispersed in solvent, and 5 μM of eight carboxyl CuPc, and ultrasonic disperse 0.5h at room temperature are added into dispersion liquid,
10min is stood, phthalocyanine/graphene composite sensing material is obtained.Concentration difference is added into eight carboxyl CuPcs/graphene solution
It is 6.25 × 10-1mol/L,1.25×10-2mol/L,2.5×10-3mol/L,5×10-4mol/L,1×10-5mol/L,2×10-6The cyanide ion solution of mol/L, measures the uv-visible absorption spectra of its system, as shown in Figure 2.
Embodiment 3
Pyromellitic dianhydride, urea, the zinc chloride (1 of certain mol proportion:15:2) after, catalyst ammonium molybdate is fully ground,
5min is heated, the intermediate product of black is obtained, with 6M salt acid soak 12h, filtering, a large amount of hot water wash filter cake.By this intermediate production
Object is added in the NaOH aqueous solutions of 20% (mass fraction), and under the conditions of 95 DEG C, heating stirring 12h needs to fit in hydrolytic process
When adding NaOH aqueous solutions.After reaction, mixture is filtered, the filtrate salt acid for adjusting pH value 4 of 12M.It centrifuges,
Obtain eight carboxyl zinc phthalocyanine of final product.By 5mg graphene dispersions in 50ml organic solvents, ultrasonic 0.5h keeps graphene equal
It is even it is good be dispersed in solvent, 5 μM of eight carboxyl zinc phthalocyanine is added into dispersion liquid, and ultrasonic disperse 0.5h at room temperature is stood
10min obtains phthalocyanine/graphene composite sensing material.Concentration is added into eight carboxyl CuPcs/graphene solution is respectively
6.25×10-1mol/L,1.25×10-2mol/L,2.5×10-3mol/L,5×10-4mol/L,1×10-5mol/L,2×10- 6The cyanide ion solution of mol/L, measures the uv-visible absorption spectra of its system, as shown in Figure 3.
Claims (5)
1. a kind of preparation method of phthalocyanine/graphene composite sensing material for cyanide ion identification, it is characterised in that including
Following steps：
(1) by the concentrated sulfuric acid of 23~92ml, 1~4g graphite powders and 0.5~2g sodium nitrate stir 10~30min in 0~3 DEG C, and 3
~12g potassium permanganate is slowly added to, and is kept temperature of reaction system to be less than 20 DEG C, 2~4h is stirred to react under the conditions of ice-water bath, instead
It is blackish green suspension to answer liquid；30~60min is reacted under the conditions of 35 DEG C, is then slowly added to distilled water and controls temperature not surpass
100 DEG C are crossed, with a large amount of distilled water dilute reaction solution and the H of addition 5~15ml 30~50% after 15~45min2O2Solution, instead
Liquid is answered to gradually become glassy yellow suspension；It is washed with distilled water and dilute hydrochloric acid, BaCl is used in combination2Solution detect, until filtrate without
SO42-, graphene oxide is obtained after drying；The graphene oxide of 100~300mg is dispersed in 100~300ml distilled water, is surpassed
Sound disperses 30~60min, forms finely dispersed yellowish-brown turbid；85~250 μ L hydrazine hydrate solutions are added dropwise, are adjusted using ammonium hydroxide
1~3h is reacted in reaction solution pH9~11 under the conditions of 85~95 DEG C of oil baths；Graphene is obtained after filtration washing；
(2) by pyromellitic dianhydride, urea, chlorate, after catalyst ammonium molybdate is fully ground, 5~10min is heated, is obtained black
The intermediate product of color, with 2~6M salt acid soak 12~for 24 hours, filtering, a large amount of hot water wash filter cakes；Matter is added in this intermediate product
It measures in the NaOH aqueous solutions that score is 5~20%, under the conditions of 75~95 DEG C, 6~12h of heating stirring；After reaction, it mixes
Object is filtered, filtrate salt acid for adjusting pH to 2~4；It centrifuges, obtains phthalocyanine derivates；
The molar ratio of the pyromellitic dianhydride, urea and chlorate is 1:10~20:2~3；
(3) for the graphene dispersion for preparing 5~20mg steps (1) in 50~150ml organic solvents, 0.5~2h of ultrasound makes stone
Black alkene is uniformly good to be dispersed in solvent, and phthalocyanine derivates prepared by 5~10 μM of steps (2), and room are added into dispersion liquid
Lower 0.5~the 2h of ultrasonic disperse of temperature, stands 10~40min, obtains phthalocyanine/graphene composite sensing material.
2. the preparation method for phthalocyanine/graphene composite sensing material of cyanide ion identification as described in claim 1,
It is characterized in that, the chlorate described in step (2) is copper chloride or zinc chloride.
3. the preparation method for phthalocyanine/graphene composite sensing material of cyanide ion identification as described in claim 1,
It is characterized in that, the organic solvent described in step (3) is dimethyl sulfone.
4. the phthalocyanine that preparation method as described in claim 1 obtains/graphene composite sensing material is identified for cyanide ion
In application, which is characterized in that 5~10mg phthalocyanine derivates/graphene solution is equably assembled on filter paper, it is poly- using height
Object is filmogen uniform coating, obtains test paper.
5. the phthalocyanine that preparation method as claimed in claim 4 obtains/graphene composite sensing material is identified for cyanide ion
In application, which is characterized in that the high polymer be polyvinyl alcohol.
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| CN110632128A (en) * | 2019-09-29 | 2019-12-31 | 浙江大学 | Preparation method and application method of graphene material resistance type gas sensing array |
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