CN106290186B - A kind of doping porous carbon Nano silver grain visualizing rapid mercury detection ion - Google Patents
A kind of doping porous carbon Nano silver grain visualizing rapid mercury detection ion Download PDFInfo
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Abstract
The present invention relates to a kind of doping porous carbon Nano silver grain DHPC@CS-AgNPs for visualizing rapid mercury detection ion.It is using organic glass lotion as template, and sucrose and polypyrrole are carbon source, and sulfuric acid is catalyst, obtains macropore carbon by primary reconstruction, drying, charing, then obtain porous carbon through base extraction；In porous carbon-chitosan ultrasonic disperse solution, using sodium borohydride as reducing agent, by the way that AgNO is added dropwise3The Nano silver grain DHPC@CS-AgNPs of preparation doping porous carbon.The particle preparation method is simple, and reaction condition is mild, and dispersion stabilization is good, with Hg2+It coexists with high oxidation analog enzymatic activity, trace Hg in quick, sensitive, highly selective colorimetric detection Food and environment sample can be used for2+.Detection method is visual, and instrument and equipment is simple, rapid sensitive, and selectivity is high, is suitable for laboratories and promotes and applies, and can be widely used in food, trace Hg in environmental sample2+Visualization quickly analyze.
Description
Technical field
The invention belongs to field of material technology, are related to a kind of doping porous carbon Nano silver grain, and in particular to a kind of and mercury
The doping Nano silver grain of the porous carbon with high oxidation analogue enztme activity coexists in ion, may be directly applied to food, environmental sample
The visualization of middle trace amount mercury ion quickly detects.
Background technique
Mercury is a kind of widely used heavy metal, common mercury-vapour lamp, battery, mercurial thermometer, paint, pesticide, desinsection
Agent, dental amalgam, the raw material etc. for the treatment of scabies drug and malignant sore are mercurous in various degree.These products are in production process and after being finished
It deals with improperly, easily causes mercury pollution.Mercury seriously damages central nervous system, shows following symptom: trembling, psychoneural disease
Shape, toxic nephropathy and stomatitis.In addition, also will affect the nervous system of people, immune system and digestive system, people is seriously damaged
Lung, kidney and brain.Therefore, of crucial importance to the detection of mercury in environment, food, animal and plant body, drug.
The method of Mercury Determination generally has electrochemical process, microwave auxiliary extraction-high performance liquid chromatography-inductance even summation etc.
Ion mass spectrometry, atomic fluorescence spectrometry etc. (B Kuswandi, et al.Analytica ChimicaActa, 2007,591
(2):208-213；Qiu Tianyu waits electrochemistry, 2016,22 (1): 20-24；Zhang Lan waits Environmental Chemistry, 2013,32 (11):
2219-2222；Chen Shaohua waits leather science and engineering, 2016,26 (1): 69-72.).These method detection limits are low, but analyze
Time is long, needs complicated sample pre-treatments, and instrument is expensive, and cost is relatively high, and discomfort is pushed away with laboratories on site
Wide application.
Colorimetric sensor does not need expensive instrument since color change can be distinguished visually, has at low cost, operation letter
Single, quickly, high sensitivity is favored the features such as suitable for field assay, and the novel colorimetric for being based particularly on nano material passes
Sensor.The mercury colorimetric sensor based on nano material reported at present is more, the gold nano modified such as Liu et al. based on single stranded DNA
Particle is reunited in the presence of mercury ion, and the color of solution from red to blue, establishes a kind of side for detecting trace mercury ion in water
Method, detection limit 250nM (Liu C W, et al.Chem.Commun., 2008,2242-2244), but the selectivity and spirit of method
Sensitivity is low, agents useful for same gold chloride, expensive.Li et al. is based on the G- tetrad DNA enzymatic and PORPHYRIN IRON for being rich in T base
(hemin) complex formed has the property of class horseradish peroxidase, can be catalyzed ABTS and H2O2Reaction generates blue-green and produces
Object, when there are mercury ion, G- tetrad DNA enzymatic and mercury ions to specifically bind to form T-Hg in system2+- T rock-steady structure, causes
PORPHYRIN IRON (hemin) can not be catalyzed ABTS oxidation H2O2To realize to the colorimetric detection of mercury (Li T, et al.,
Chem.Commun., 2009,3551-3553), the selectivity of method is high, the G- tetrad DNA enzymatic rich in T base, and preparation is multiple
It is miscellaneous, it is at high cost.Zhang et al. synthesizes a kind of magnetic composite Au@Fe3O4@GO, the material is in Hg2+In the presence of can be catalyzed TMB
With H2O2Reaction generates blue product, Hg2+Detection limit up to 0.15nM (Zhang S, et al.Nanoscale, 2015,45 (7):
8495-8502), this method sensitivity and selectivity are high, but material and reagent used is related to gold chloride, graphene, at high cost,
Limit its popularization and application.To reduce cost, Annadhasan M et al. uses tyrosine for stabilizer and reducing agent, synthesis
Nano silver grain, colorimetric detection mercury ion, detection limit 16nM (Annadhasan M, et al.ACS Sustainable
Chemistry&Engineering,2014,2(4):887-896.)；Shen Z etc. is in the alkaline solution of lignin using micro-
Wave radiation synthesizes Nano silver grain, colorimetric detection mercury ion, detection limit 23nM (Shen Z, et al.ACS Applied
Materials&Interfaces, 2014,6 (18): 16147-16155.), but the selectivity of above method is not high enough.Yang etc.
There is the property of class horseradish peroxidase based on nano manganese oxide, TMB and H can be catalyzed2O2Reaction generation blue product, and Gu Guang
Ammonia peptide can prevent nano manganese oxide from being catalyzed TMB and H2O2Reaction makes blue disappearance, in the presence of mercury ion, because of mercury ion and Gu Guang
The coordination of ammonia peptide, can restore the catalytic activity of nano manganese oxide, make solution blue restoration, so that mercury ion detecting method is constructed,
(Yang H, et al.Angew Chem Int Ed, 2009,48 (13): 2308.), but this method is not simple enough by detection limit 80nM
Just, sensitivity is not high enough, and H used in method2O2It is unstable, affect the reproducibility and accuracy of result.Xu Xiufang is with lemon
Lemon acid trisodium is stabilizer, NaBO4Nano silver grain, the Nano silver grain of preparation energy in the presence of mercury ion are prepared for reducing agent
Dissolved oxygen oxidation TMB in catalytic solution generates blue product, establishes Trace Hg colorimetric detection method, detection is limited to 28nM
(Xu Xiufang nano material analogue enztme and its analysis are using the Jiangsu [D]: Southern Yangtze University, 2014.), this method avoid unstable
And the use of damaging hydrogen peroxide, but sensitivity and selectivity need to be further increased.
Summary of the invention
In order to solve the deficiencies in the prior art, the purpose of the present invention is to provide a kind of easy to be quick, sensitivity and selections
The doping porous carbon Nano silver grain of the high visualization fast detection of trace mercury ion of property, the doping porous carbon nano grain of silver of invention
Sub- preparation method is simple, and dispersed stability is good, coexists with mercury ion with high oxidation enzymatic activity, can be widely used in food
The quick detection of product, Trace Amount of Mercury in Environmental Samples ion.
The Nano silver grain DHPC@CS-AgNPs of doping porous carbon of the present invention, through the following steps that prepare
: (1) deionized water, methyl methacrylate and catalyst in 250mL three-neck flask are sequentially added, cooling water is opened, is led to
Nitrogen, stirring, 1~2h of water-bath obtain polymethyl methacrylate lotion (PMMA).(2) successively add in PMMA lotion
Enter sucrose and polypyrrole, stirs, add 1mL H2SO4, primary reconstruction reaction 20min.Products therefrom pours into culture dish, in
It is dry in drying box.Dry product is transferred to crucible to be placed in tube furnace, in a nitrogen atmosphere baking 6h, then be carbonized
3h obtains macropore carbon.(3) 5mL acetone being dispersed by macropore carbon, being added 20mL KOH solution, stirring, water-bath is to forming slurry
Shape mixture.Paste mixture is placed in tube furnace, under nitrogen protection high-temperature activation.During activation products are washed with distilled water to
Property, vacuum drying obtains porous carbon (DHPC).(4) chitosan (CS) is dissolved in 1% acetum of 100mL, is then added
DHPC, ultrasonic disperse, filtering obtain the chitosan solution (DHPC@CS) of doping porous carbon.(5) by 0.02g NaBH4It is added
DHPC@CS solution, stirs evenly, 0.6mmolL is then slowly added dropwise-1AgNO3Solution, room temperature reaction obtain doping porous carbon
Nano silver grain DHPC@CS-AgNPs.
The present invention first passes through Methyl Methacrylate Bulk Polymerization and prepares organic glass lotion (polymethyl methacrylate),
Again using organic glass lotion as template, sucrose and polypyrrole are carbon source, and sulfuric acid is catalyst, passes through primary reconstruction, drying, charcoal
Change obtains macropore carbon, then obtains porous carbon through base extraction；Then by porous carbon ultrasonic disperse in chitosan solution, with hydroboration
Sodium is reducing agent, obtains the Nano silver grain DHPC@CS-AgNPs of doping porous carbon by the way that silver nitrate is slowly added dropwise.The particle system
Preparation Method is simple, and reaction condition is mild, and dispersion stabilization is good, with Hg2+It coexists with high oxidation analog enzymatic activity, can be used for fast
Fast, sensitive, selectively trace Hg in colorimetric detection Food and environment sample2+.Detection method is visual, and instrument and equipment is simple, fastly
Speed is sensitive, and selectivity is high, is suitable for laboratories and promotes and applies, and can be widely used in food, trace Hg in environmental sample2+'s
Visualization quickly analysis.
Doping porous carbon Nano silver grain of the present invention has the advantages that
(1) preparation method is simple, and reaction condition is mild, and dispersion stabilization is good, and (Nano silver grain of doping porous carbon is in equal
Even transparent solution state, placing will not precipitate for one week, after a week for being catalyzed reaction, the light absorption value of catalytic solution with
Light absorption value before one week is almost the same)；
(2) there is oxidase active, Hg2+In the presence of, catalytic activity high (Michaelis constant of oxidation TMB and maximum reaction speed
Degree is Km=0.0165mM, Vmax=4.6512x10-8M/s)；
(3) can rapid sensitive, trace Hg in highly selective colorimetric detection Food and environment sample2+(the silver of doping porous carbon
Nanoparticle only coexists with mercury ion, just has oxidation analog enzymatic activity, and detection limit is up to 7.0 × 10-9mol/L)
(4) detection method is visually quick, easy to operate, facilitates popularization and application.
Detailed description of the invention
Fig. 1 is the preparation principle figure of doping porous carbon Nano silver grain of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of porous carbon nano-particles of the present invention.In figure, A is macropore carbon；B is macropore carbon
Through the resulting porous carbon of base extraction.
Fig. 3 is the oxidase active experimental result picture of doping porous carbon Nano silver grain of the present invention.In figure, A is bent
Line is Hg2++TMB；B curve is DHPC@CS-AgNPs+TMB；C curve is Hg2++DHPC@CS-AgNPs+TMB。
Fig. 4 is that (Hg coexists in doping porous carbon Nano silver grain of the present invention and mercury ion2++DHPC@CS-AgNPs+
TMB stability kinetics parametric measurement result figure).
Fig. 5 is the Nano silver grain of doping porous carbon of the present invention for colorimetric detection trace Hg2+Schematic diagram.
Fig. 6 is doping porous carbon Nano silver grain of the present invention for colorimetric detection trace Hg2+Selectivity result
Figure.
Fig. 7 is doping porous carbon Nano silver grain of the present invention for colorimetric detection trace Hg2+Canonical plotting.
Specific embodiment
Below by specific embodiment, the present invention is described further, but the present invention is not limited to these embodiments.
Embodiment 1: the preparation of the doping porous carbon Nano silver grain of rapid mercury detection ion of the present invention.
Preparation principle figure such as Fig. 1 institute of the doping porous carbon Nano silver grain of rapid mercury detection ion described in the present embodiment
Show, preparation method the following steps are included:
(1) 100mL deionized water, 20mL methyl methacrylate and 0.04g mistake are sequentially added in 250mL three-neck flask
Potassium sulfate opens cooling water, leads to nitrogen, under 350r/min mechanical stirring, 90 DEG C of water-bath 1h obtain polymethylacrylic acid
Methyl ester emulsions (PMMA).(2) 0.5g sucrose and 0.1g polypyrrole are sequentially added in 20g PMMA lotion, with 350r/min machinery
15min is stirred, 1mL 0.5mol/L H is added2SO4, primary reconstruction reaction 15min.Products therefrom pours into culture dish, in 60
Dry 6h in DEG C drying box.Dry product is transferred to crucible to be placed in tube furnace, in a nitrogen atmosphere 150 DEG C of baking 6h,
Then 900 DEG C of charing 3h, obtain macropore carbon.(3) 5mL acetone is dispersed by 0.5g macropore carbon, 20mL 0.1g/mL KOH is added
Solution, magnetic agitation, 100 DEG C of water-baths are to forming paste mixture.Paste mixture is placed in tube furnace, in nitrogen protection
Lower 200 DEG C of activation.Activation products are washed with distilled water to neutrality, and 70 DEG C of vacuum drying for 24 hours, obtain porous carbon (DHPC).(4) will
0.1g chitosan (CS) is dissolved in 1% acetum of 100mL, and 0.1g DHPC, ultrasonic disperse 4h is then added, and filtering obtains
Adulterate the chitosan solution (DHPC@CS) of porous carbon.(5) by 0.02g NaBH460mL DHPC@CS solution, magnetic agitation is added
It is uniformly mixed, 30mL 0.6mmolL is then slowly added dropwise-1AgNO3Solution reacts at room temperature 20h, obtains the silver of doping porous carbon
Nanoparticle DHPC@CS-AgNPs.
Embodiment 2: the preparation of the doping porous carbon Nano silver grain of rapid mercury detection ion of the present invention.
Preparation principle figure such as Fig. 1 institute of the doping porous carbon Nano silver grain of rapid mercury detection ion described in the present embodiment
Show, preparation method the following steps are included:
(1) 120mL deionized water, 20mL methyl methacrylate and 0.08g mistake are sequentially added in 250mL three-neck flask
Potassium sulfate opens cooling water, leads to nitrogen, under 500r/min mechanical stirring, 90 DEG C of water-bath 2h obtain polymethylacrylic acid
Methyl ester emulsions (PMMA).(2) 0.75g sucrose and 0.15g polypyrrole are sequentially added in 30g PMMA lotion, with 350r/min machine
Tool stirs 20min, adds 1mL 1.0mol/L H2SO4, primary reconstruction reaction 20min.Products therefrom pours into culture dish, in
Dry 8h in 70 DEG C of drying boxes.Dry product is transferred to crucible to be placed in tube furnace, in a nitrogen atmosphere 200 DEG C of baking
6h, then 950 DEG C of charing 3h, obtain macropore carbon.(3) 10mL acetone is dispersed by 1.0g macropore carbon, 40mL 0.2g/mL is added
KOH solution, magnetic agitation, 100 DEG C of water-baths are to forming paste mixture.Paste mixture is placed in tube furnace, in nitrogen
Protect lower 200 DEG C of activation.Activation products are washed with distilled water to neutrality, and 80 DEG C of vacuum drying 20h obtain porous carbon (DHPC).
(4) 0.05g chitosan (CS) is dissolved in 1% acetum of 50mL, 0.05g DHPC, ultrasonic disperse 4h, mistake is then added
Filter obtains the chitosan solution (DHPC@CS) of doping porous carbon.(5) by 0.02g NaBH470mL DHPC@CS solution is added,
Magnetic agitation is uniformly mixed, and 28mL 0.6mmolL is then slowly added dropwise-1AgNO3Solution, room temperature reaction for 24 hours, it is more to obtain doping
The Nano silver grain DHPC@CS-AgNPs of hole carbon.
Embodiment 3: the porosity of porous carbon (DHPC) nanoparticle of the present invention.
Scanning electron microscope detection: porous carbon (DHPC) nanoparticle that embodiment 1 is prepared is carried out by scanning electron microscope
Observation, as shown in Fig. 2, the aperture macropore carbon (Fig. 2A) being prepared is larger, pore size distribution is uniform；The gained after lye is activated
The surface porous carbon (Fig. 2 B) is smooth, and aperture obviously becomes smaller, and has macropore, micropore and mesoporous, based on micropore, large specific surface area, and warp
The BET surface area being calculated is 840cm2/ g, total pore volume 2.1cm3/g。
Embodiment 4: oxidase active of the DHPC@CS-AgNPs nanoparticle of the present invention in the presence of mercury ion.
DHPC@CS-AgNPs nanoparticle prepared by selection example 1 carries out oxidase active test.
1mL 0.05molL is added into A, B, C colorimetric cylinder respectively-1NaAc-HAc buffer solution (pH=4.0) and
300μL 400mmol·L-1TMB solution, then 500 μ L 0.18mmolL are added into B, C colorimetric cylinder respectively-1DHPC@
Then 500 μ L10 are added in CS-AgNPs into A, C colorimetric cylinder respectively again-6mol·L-1Hg2+, finally with ultrapure water by A, B, C
Number colorimetric cylinder is settled to 5mL, reacts in 40 DEG C of constant-temperature shaking incubators and carries out uv scan after ten minutes, as a result as schemed
3.Solution (the Hg of A colorimetric cylinder2++ TMB) be it is colorless and transparent, between 370nm to 800nm almost be in straight line, illustrate Hg2 +The dissolved oxygen oxidation TMB colour developing being unable in catalytic solution；Nanometer is presented in the solution (DHPC@CS-AgNPs+TMB) of B colorimetric cylinder
, there is the characteristic absorption peak of nano silver in 400nm or so, shows that DHPC@CS-AgNPs is unable in catalytic solution in the yellow of silver
Dissolved oxygen aoxidizes TMB colour developing, and catalytic activity is weak；Solution (the Hg of C colorimetric cylinder2++ DHPC@CS-AgNPs+TMB) it is blue, it says
Bright Hg2+In the presence of DHPC@CS-AgNPs catalysis oxidation TMB can be promoted to develop the color, the TMB after colour developing has feature at 370nm and 652nm
Absorption peak illustrates Hg2++ DHPC@CS-AgNPs has oxidation analog enzymatic activity.
Embodiment 5: Hg of the present invention2+The kinetic parameter of+DHPC@CS-AgNPs oxidation analog enzyme.
Following experiment is carried out using DHPC@CS-AgNPs nanoparticle prepared by embodiment 1.
Take 500 μ L 0.18mmolL-1DHPC@CS-AgNPs and 500 μ L 1 × 10-6mol·L-1Hg2+, 300 μ L are added
The TMB solution of various concentration (100~500 μM), adds 1mL 0.05molL-1NaAc-HAc buffer solution (pH=4.0),
It is settled to 5mL with ultrapure water, its ultraviolet absorptivity is measured at 652nm wavelength, the results are shown in Table 1.By 1 measurement result of table, according to
Michaelis-Menten equation is with 1/cTMB1/V is mapped to obtain the Lineweaver-Burk curve of Fig. 4.It can be calculated by the linear equation of Fig. 4
Hg out2+The Michaelis constant K of+DHPC@CS-AgNPs oxidation analog enzymem=0.0165mM, Vmax=4.65 × 10-8M/s illustrates Hg2 ++ DHPC@CS-AgNPs is high to the affinity and rate of catalysis reaction of TMB, has high oxidation analog enzymatic activity.
Table 1: the reaction rate of measurement
Embodiment 6: DHPC@CS-AgNPs nanoparticle of the present invention is used for the selectivity of colorimetric detection mercury ion.
Principle using DHPC@CS-AgNPs nanoparticle colorimetric detection mercury ion prepared by embodiment 1 is shown in Fig. 5, real
Test that steps are as follows.
Take 500 μ L 0.18mmolL-1DHPC@CS-AgNPs and 500 μ L 1 × 10-6mol·L-1Hg2+In the colorimetric of 5ml
300 μ L 400mmolL are added in Guan Zhong-1TMB solution, add 1mL 0.05molL-1NaAc-HAc buffer solution (pH
=4.0) it, is settled to 5mL with ultrapure water, is reacted 10 minutes in 40 DEG C of shaken cultivation casees, measures it in the absorbance of 652nm.
Respectively with the Cu of same concentration in above-mentioned experiment2+、Fe2+、Zn2+、Pb2+、Cd2+、Mn2+With 500 times of Ca2+、Mg2+、K+、Na+Instead of
Mercury ion investigates the selectivity of method (see Fig. 6).As a result, it has been found that only mercury ion can make the aobvious blue of system, in TMB characteristic wave
There is maximum absorption band at long 652nm, shows that the nano silver particles of carbon doping have specific selectivity to the colorimetric detection of mercury ion.
Embodiment 7: DHPC@CS-AgNPs nanoparticle of the present invention is used for the sensitivity of colorimetric detection mercury ion.
Principle using DHPC@CS-AgNPs nanoparticle colorimetric detection mercury ion prepared by embodiment 1 is shown in Fig. 5, real
Test that steps are as follows.
Take 500 μ L 0.18mmolL-1DHPC@CS-AgNPs and 500 μ L concentration are respectively 0.02,0.05,0.2,0.5,1
μmol·L-1Mercury ion standard solution in the colorimetric cylinder of 5ml, be added 300 μ L 400mmolL-1TMB solution, then plus
Enter 1mL 0.05molL-1NaAc-HAc buffer solution (pH=4.0), is settled to 5mL with ultrapure water, in 40 DEG C of shaken cultivation casees
Middle reaction 10 minutes, measures it in the absorbance of 652nm.With the absorbance A that measures to corresponding mercury ion concentration of standard solution c
(μmol·L-1) mapping (Fig. 7).Ion concentration of mercury is in 0.02~1 μm of olL-1With A in good linear relationship, line in range
Property regression equation be A=0.332c+0.085, correlation coefficient r2=0.995, detection limit (S/N=3) is 7nM, illustration method
High sensitivity.
Embodiment 8: DHPC@CS-AgNPs nanoparticle of the present invention is applied to colorimetric detection Food and environment sample
Middle trace amount mercury ion.
Following experiment is carried out using DHPC@CS-AgNPs nanoparticle prepared by embodiment 1.
The processing of fish sample: weighing 2.0g sample in counteracting tank, and 5mL concentrated nitric acid is added, and capping is stood overnight, and tightens lid
Son is placed and is cleared up in microwave dissolver, cooling to take out, and slowly opens lid exhaust, with a small amount of milli-Q water bottle cap, clearing up
Tank places ultrasound 2min exhaust in ultrasonic water bath case, and digestion solution is moved in the volumetric flask of 25mL, scale is settled to.
The processing of water sample: with 0.22 μm of membrane filtration, 0.05molL is used-1NaAc_HAc buffer solution is adjusted to pH
=4, it is refrigerated at 4 DEG C spare.500 μ L sample liquids are taken to be tested according to 2.5 methods.
It takes 500 μ L fish sample solution or water sample in the colorimetric cylinder of 5ml, sequentially adds 500 μ L 0.18mmolL- 1DHPC@CS-AgNPs, 300 μ L 400mmolL-1TMB solution and 1mL 0.05molL-1NaAc-HAc buffer solution (pH
=4.0) it, is settled to 5mL with ultrapure water, is reacted 10 minutes in 40 DEG C of shaken cultivation casees, suction of the measurement sample solution in 652nm
Luminosity.The content of mercury ion in sample is calculated by the absorbance measured.Fish sample solution and water sample sample use GB/T simultaneously
5009.17-2014 atomic fluorescence method carries out control experiment, the results are shown in Table 2.Using method of the invention, water sample, the flesh of fish and fish tail
In do not detect the content of mercury ion, the recovery of standard addition of water sample, the flesh of fish and fish tail sample is 91.6%~103%, relatively
Standard deviation is 2.6%~6.7%；Using GB/T 5009.17-2014 atomic fluorescence method, mercury ion is not detected in water sample
Micro mercury ion is detected in content, the flesh of fish and fish tail, content is in 17.3~21.4 μ gkg-1, result that two methods measure
It is consistent, show that this method has high exactness and accuracy, can apply to the detection of Trace Hg in actual sample.
Table 2: mercury ion assay result (n=3) in water sample and fish sample
"-" expression is not detected.
Claims (10)
1. a kind of doping porous carbon Nano silver grain for visualizing rapid mercury detection ion, which is characterized in that the doping is porous
Carbon Nano silver grain is DHPC@CS-AgNPs, through the following steps that prepare:
(1) deionized water, methyl methacrylate and catalyst are sequentially added in 250mL three-neck flask, opens cooling water, are led to
Nitrogen, stirring, 1~2h of water-bath obtain polymethyl methacrylate (PMMA) lotion；
(2) sucrose and polypyrrole are sequentially added in PMMA lotion, are stirred, are added 1mL H2SO4, primary reconstruction reaction
20min；Products therefrom pours into culture dish, dry in drying box；Dry product is transferred to crucible to be placed in tube furnace,
Baking 6h under nitrogen atmosphere, then carbonizes 3h, obtains macropore carbon；
(3) 5mL acetone is dispersed by macropore carbon, 20mL KOH solution, stirring is added, water bath with thermostatic control is reacted to formation pulpous state mixing
Object；Paste mixture is placed in tube furnace, under nitrogen protection high-temperature activation；Activation products are washed with distilled water to neutrality, very
Sky is dry, obtains porous carbon i.e. DHPC；
(4) chitosan (CS) is dissolved in 1% acetum of 100mL, DHPC, ultrasonic disperse is then added, filtering is born
Carry chitosan solution, that is, DHPC@CS of porous carbon；
(5) by 0.02g NaBH4DHPC@CS solution is added, stirs evenly, 0.6mmolL is then slowly added dropwise-1AgNO3Solution,
Room temperature reaction obtains the Nano silver grain DHPC@CS-AgNPs of doping porous carbon.
2. doping porous carbon Nano silver grain according to claim 1, it is characterised in that: described in the step (1)
Deionized water and the volume ratio of methyl methacrylate are 5:1~6:1, and catalyst is potassium peroxydisulfate, azodiisobutyronitrile or mistake
Two carbonic acid cyclohexyls are aoxidized, dosage is 0.04~0.08g.
3. doping porous carbon Nano silver grain according to claim 1, it is characterised in that: described in the step (1)
Stirring is mechanical stirring, and mixing speed is 350~500r/min, and bath temperature is 90 DEG C.
4. doping porous carbon Nano silver grain according to claim 1, it is characterised in that: in the step (2), PMMA cream
The mass ratio of liquid, sucrose and polypyrrole is 200:5:1, H2SO4Concentration be 0.5~1mol/L.
5. doping porous carbon Nano silver grain according to claim 1, it is characterised in that: described in the step (2)
Stirring is mechanical stirring, and mixing speed is 350~500r/min, and mixing time is 15~20min, and drying temperature is 60~70
DEG C, drying time is 6~8h, and baking temperature is 150~200 DEG C, and carbonization temperature is 900~950 DEG C.
6. doping porous carbon Nano silver grain according to claim 1, it is characterised in that: in the step (3), macropore carbon
Mass concentration in acetone-KOH mixed solution is 20mg/mL, and the mass concentration of KOH is 0.1~0.2g/mL, acetone and KOH
Volume ratio be 1:4.
7. doping porous carbon Nano silver grain according to claim 1, it is characterised in that: described in the step (3)
Stirring is magnetic agitation, and bath temperature is 100 DEG C, and activation temperature is 200 DEG C, and vacuum drying temperature is 70~80 DEG C, and vacuum is dry
The dry time be 20~for 24 hours.
8. doping porous carbon Nano silver grain according to claim 1, it is characterised in that: described in the step (4)
The mass concentration of chitosan and porous carbon is 1mg/mL, and the ultrasonic disperse time is 4h.
9. doping porous carbon Nano silver grain according to claim 1, it is characterised in that: described in the step (5)
DHPC@CS solution and AgNO3The volume ratio of solution is 2:1~2.5:1.
10. doping porous carbon Nano silver grain according to claim 1, it is characterised in that: described in the step (5)
Stirring be magnetic agitation, room temperature reaction the time be 20~for 24 hours.
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| CN113125407B (en) * | 2020-01-16 | 2024-05-03 | 武汉市农业科学院 | Cr (chromium)6+Ion rapid detection method |
| CN111842923B (en) * | 2020-07-14 | 2022-11-29 | 西安工程大学 | Preparation method of silver nanowire/biomass porous carbon electromagnetic wave absorption material |
| CN112697781B (en) * | 2020-11-26 | 2023-01-31 | 南京师范大学 | Visual Hg 2+ Preparation method of detection material, detection material prepared by preparation method and application of detection material |
| CN113559880B (en) * | 2021-07-30 | 2023-09-01 | 曲阜师范大学 | Pd@NiCo 2 O 4 Double-function nano imitation enzyme and preparation method and application thereof |
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| CN103855366A (en) * | 2012-11-28 | 2014-06-11 | 中国科学院大连化学物理研究所 | Nitrogen-doped porous carbon material for lithium-air battery positive electrode |
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