CN106290186A - 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 visualizing rapid mercury detection ion.It is with lucite emulsion as template, and sucrose and polypyrrole are carbon source, and sulphuric acid is catalyst, by primary reconstruction, be dried, carbonization obtains macropore carbon, then obtains porous carbon through base extraction；In porous carbon chitosan ultrasonic disperse solution, with sodium borohydride as reducing agent, by dropping AgNO3The Nano silver grain DHPC@CS AgNPs of preparation doping porous carbon.This particle preparation method is simple, and reaction condition is gentle, and dispersion stabilization is good, with Hg2+Coexist and there is high oxidation analog enzymatic activity, trace Hg in selectivity colorimetric detection Food and environment sample quick, sensitive, high can be used for2+.Detection method is visual, and instrument and equipment is simple, rapid sensitive, and selectivity is high, is suitable to laboratories popularization and application, can be widely used in trace Hg in food, environmental sample2+Visualization quickly analyze.
Description
Technical field
The invention belongs to field of material technology, relate to a kind of doping porous carbon Nano silver grain, be specifically related to one and hydrargyrum
Ion coexists and has the porous carbon silver-doped nanoparticle of high oxidation analogue enztme activity, may be directly applied to food, environmental sample
The visualization of middle trace amount mercury ion quickly detects.
Background technology
Hydrargyrum is a kind of widely used heavy metal, common mercury-vapour lamp, battery, mercurial thermometer, paint, pesticide, parasite killing
The raw materials of agent, dental amalgam, treatment scabies medicine and malignant boil etc. are the most mercurous.These products are in production process with after being finished
Deal with improperly, easily cause mercury pollution.Hydrargyrum seriously damages central nervous system, shows following symptom: tremble, psychoneural disease
Shape, toxic nephrosis and stomatitis.Additionally, the nervous system of people, immune system and digestive system also can be affected, seriously damage people
Pulmonary, kidney and brain.Therefore, of crucial importance to the detection of hydrargyrum in environment, food, animal and plant body, medicine.
The method of Mercury Determination typically 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, etc. electrochemistry, 2016,22 (1): 20-24；Zhang Lan, etc. Environmental Chemistry, 2013,32 (11):
2219-2222；Chen Shaohua, etc. 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 higher, is unsuitable for scene and laboratories pushes away
Wide application.
Colorimetric sensor can distinguish with naked eyes due to color change, it is not necessary to expensive instrument, has low cost, operation letter
Single, quick, highly sensitive, be suitable to the features such as field assay and favored, the novel colorimetric being based particularly on nano material passes
Sensor.The hydrargyrum colorimetric sensor based on nano material of report is more at present, the gold nano modified based on single stranded DNA such as Liu etc.
Particle is reunited in the presence of mercury ion, and the color of solution from red to blue, sets up a kind of side detecting trace mercury ion in water
Method, detection limit 250nM (Liu C W, et al.Chem.Commun., 2008,2242-2244), but the selectivity of method and spirit
Sensitivity is low, agents useful for same gold chloride, expensive.Li etc. are based on rich in the G-tetrad DNA enzymatic of T base and ferrous porphyrin
(hemin) coordination compound formed has the character of class horseradish peroxidase, can be catalyzed ABTS and H2O2Reaction generates aeruginous and produces
Thing, when system exists mercury ion, G-tetrad DNA enzymatic and mercury ion specific binding formation T-Hg2+-T rock-steady structure, causes
Ferrous porphyrin (hemin) cannot be catalyzed ABTS and aoxidize H2O2Thus realize to the colorimetric detection of hydrargyrum (Li T, et al.,
Chem.Commun., 2009,3551-3553), the selectivity of method is high, and rich in the G-tetrad DNA enzymatic of T base, preparation is multiple
Miscellaneous, cost is high.A kind of magnetic composite Au@Fe of Zhang et al. synthesis3O4@GO, this material is at Hg2+In the presence of can be catalyzed TMB
With H2O2Reaction generates blue product, Hg2+Detection limit reach 0.15nM (Zhang S, et al.Nanoscale, 2015,45 (7):
8495-8502), the method sensitivity and selectivity are high, but material used and reagent relate to gold chloride, Graphene, and cost is high,
Limit its popularization and application.For reducing cost, Annadhasan M et al. uses tyrosine to be 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. uses micro-in the alkaline solution of lignin
Wave radiation synthesis 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 based on nano manganese oxide the character of class horseradish peroxidase, TMB and H can be catalyzed2O2Reaction generation blue product, and paddy light
Ammonia Toplink stops nano manganese oxide catalysis TMB and H2O2Reaction makes blue disappearance, in the presence of mercury ion, because of mercury ion and paddy light
Ammonia peptide is coordinated, it is possible to recovers the catalysis activity of nano manganese oxide, makes solution blue restoration, thus build mercury ion detecting method,
Detection limit 80nM (Yang H, et al.Angew Chem Int Ed, 2009,48 (13): 2308.), but the method is the simplest
Just, insufficient sensitivity is high, and the H used in method2O2Instability, have impact on repeatability and the accuracy of result.Xu Xiufang is with lemon
Lemon acid trisodium is stabilizer, NaBO4Nano silver grain is prepared, the Nano silver grain of preparation energy in the presence of mercury ion for reducing agent
Dissolved oxygen oxidation TMB in catalytic solution generates blue product, establishes Trace Hg colorimetric detection method, and detection is limited to 28nM
(Xu Xiufang. nano material analogue enztme and analysis application [D] thereof. Jiangsu: Southern Yangtze University, 2014.), this method avoid instability
And the use of damaging hydrogen peroxide, but sensitivity and selectivity need to be improved further.
Summary of the invention
In order to solve the deficiencies in the prior art, it is an object of the invention to provide a kind of easy to be quick, sensitivity and selection
The doping porous carbon Nano silver grain of the visualization fast detection of trace mercury ion that property is high, the doping porous carbon nano grain of silver of invention
Sub-preparation method is simple, and dispersibility good stability coexists with mercury ion and has high oxidation enzymatic activity, can be widely used in food
Product, the quick detection of 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) is sequentially added into deionized water, methyl methacrylate and catalyst in 250mL three-neck flask, opens cooling water, logical
Nitrogen, stirring, water-bath 1～2h, obtain polymethyl methacrylate emulsion (PMMA).(2) add successively in PMMA emulsion
Enter sucrose and polypyrrole, stirring, add 1mL H2SO4, primary reconstruction reaction 20min.Products therefrom pours culture dish into, in
Drying baker is dried.Dry product is transferred to crucible be placed in tube furnace, fire 6h in a nitrogen atmosphere, then carbonization
3h, obtains macropore carbon.(3) macropore carbon being scattered in 5mL acetone, add 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, obtain porous carbon (DHPC).(4) chitosan (CS) is dissolved in 100mL 1% acetum, is subsequently adding
DHPC, ultrasonic disperse, filters, obtains the chitosan solution (DHPC@CS) of doping porous carbon.(5) by 0.02g NaBH4Add
DHPC@CS solution, stirs, is then slowly added dropwise 0.6mmol L-1AgNO3Solution, room temperature reaction, obtain the porous carbon that adulterates
Nano silver grain DHPC@CS-AgNPs.
The present invention first passes through Methyl Methacrylate Bulk Polymerization and prepares lucite emulsion (polymethyl methacrylate),
Again with lucite emulsion as template, sucrose and polypyrrole are carbon source, and sulphuric acid is catalyst, by primary reconstruction, dry, charcoal
Change and obtain macropore carbon, then obtain 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 being slowly added dropwise silver nitrate.This particle system
Preparation Method is simple, and reaction condition is gentle, and dispersion stabilization is good, with Hg2+Coexist and there is high oxidation analog enzymatic activity, can be used for fast
Fast, sensitive, optionally trace Hg in colorimetric detection Food and environment sample2+.Detection method is visual, and instrument and equipment is simple, soon
Speed is sensitive, and selectivity is high, is suitable to laboratories popularization and application, can be widely used in trace Hg in food, environmental sample2+'s
Visualization is quickly analyzed.
Doping porous carbon Nano silver grain of the present invention has the advantages that
(1) preparation method is simple, and reaction condition is gentle, and dispersion stabilization is good, and (Nano silver grain of doping porous carbon is in all
Even transparent solution state, places one week and will not precipitate, for catalytic reaction after one week, the light absorption value of its catalytic solution with
Light absorption value before one week is basically identical)；
(2) there is oxidase active, Hg2+In the presence of, catalysis activity high (Michaelis constant of oxidation TMB and maximum reaction speed
Degree is Km=0.0165mM, Vmax=4.6512x10-8M/s)；
(3) energy rapid sensitive, trace Hg in high selectivity 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 reaches 7.0 × 10-9mol/L)
(4) detection method is visually quick, simple to operate, facilitates popularization and application.
Accompanying drawing explanation
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 nanoparticle of the present invention.In figure, A is macropore carbon；B is macropore carbon
Porous carbon through base extraction gained.
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 doping porous carbon Nano silver grain of the present invention and mercury ion coexists (Hg2++DHPC@CS-AgNPs+
TMB) stability kinetics parametric measurement result figure.
Fig. 5 is that the Nano silver grain of doping porous carbon of the present invention is for colorimetric detection trace Hg2+Schematic diagram.
Fig. 6 is that doping porous carbon Nano silver grain of the present invention is for colorimetric detection trace Hg2+Selectivity result
Figure.
Fig. 7 is that doping porous carbon Nano silver grain of the present invention is for colorimetric detection trace Hg2+Canonical plotting.
Detailed description of the invention
Below by specific embodiment, the present invention is described further, but the present invention is not restricted 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 the rapid mercury detection ion described in the present embodiment
Showing, preparation method comprises the following steps:
(1) in 250mL three-neck flask, 100mL deionized water, 20mL methyl methacrylate and 0.04g mistake it are sequentially added into
Potassium sulfate, opens cooling water, leads to nitrogen, under 350r/min mechanical agitation, 90 DEG C of water-bath 1h, obtain polymethylacrylic acid
Methyl ester emulsions (PMMA).(2) in 20g PMMA emulsion, 0.5g sucrose and 0.1g polypyrrole it are sequentially added into, with 350r/min machinery
Stirring 15min, adds 1mL 0.5mol/L H2SO4, primary reconstruction reaction 15min.Products therefrom pours culture dish into, in 60
DEG C drying baker is dried 6h.Dry product is transferred to crucible be placed in tube furnace, in a nitrogen atmosphere 150 DEG C of fire 6h,
Then 900 DEG C of carbonization 3h, obtain macropore carbon.(3) 0.5g macropore carbon is scattered in 5mL acetone, adds 20mL 0.1g/mL KOH
Solution, magnetic agitation, 100 DEG C of water-baths are to forming paste mixture.Paste mixture is placed in tube furnace, protects at nitrogen
Lower 200 DEG C of activation.Activation products are washed with distilled water to neutrality, 70 DEG C of vacuum drying 24h, obtain porous carbon (DHPC).(4) will
0.1g chitosan (CS) is dissolved in 100mL 1% acetum, is subsequently adding 0.1g DHPC, ultrasonic disperse 4h, filters, obtains
The chitosan solution (DHPC@CS) of doping porous carbon.(5) by 0.02g NaBH4Add 60mL DHPC@CS solution, magnetic agitation
Mix homogeneously, is then slowly added dropwise 30mL 0.6mmol L-1AgNO3Solution, room temperature reaction 20h, obtain 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 the rapid mercury detection ion described in the present embodiment
Showing, preparation method comprises the following steps:
(1) in 250mL three-neck flask, 120mL deionized water, 20mL methyl methacrylate and 0.08g mistake it are sequentially added into
Potassium sulfate, opens cooling water, leads to nitrogen, under 500r/min mechanical agitation, 90 DEG C of water-bath 2h, obtain polymethylacrylic acid
Methyl ester emulsions (PMMA).(2) in 30g PMMA emulsion, 0.75g sucrose and 0.15g polypyrrole it are sequentially added into, with 350r/min machine
Tool stirring 20min, adds 1mL 1.0mol/L H2SO4, primary reconstruction reaction 20min.Products therefrom pours culture dish into, in
70 DEG C of drying baker are dried 8h.Dry product is transferred to crucible be placed in tube furnace, in a nitrogen atmosphere 200 DEG C of fire
6h, then 950 DEG C of carbonization 3h, obtain macropore carbon.(3) 1.0g macropore carbon is scattered in 10mL acetone, adds 40mL 0.2g/mL
KOH solution, magnetic agitation, 100 DEG C of water-baths are to forming paste mixture.Paste mixture is placed in tube furnace, at nitrogen
Protect lower 200 DEG C of activation.Activation products are washed with distilled water to neutrality, 80 DEG C of vacuum drying 20h, obtain porous carbon (DHPC).
(4) 0.05g chitosan (CS) is dissolved in 50mL 1% acetum, is subsequently adding 0.05g DHPC, ultrasonic disperse 4h, mistake
Filter, obtains the chitosan solution (DHPC@CS) of doping porous carbon.(5) by 0.02g NaBH4Add 70mL DHPC@CS solution,
Magnetic agitation mix homogeneously, is then slowly added dropwise 28mL 0.6mmol L-1AgNO3Solution, room temperature reaction 24h, is adulterated many
The Nano silver grain DHPC@CS-AgNPs of hole carbon.
Embodiment 3: the porous of porous carbon of the present invention (DHPC) nanoparticle.
Scanning electron microscope detects: porous carbon (DHPC) nanoparticle embodiment 1 prepared is carried out by scanning electron microscope
Observing, as in figure 2 it is shown, the macropore carbon prepared (Fig. 2 A) aperture is relatively big, pore size distribution is uniform；Gained after alkali liquor activation processing
Porous carbon (Fig. 2 B) smooth surface, aperture substantially diminishes, and has macropore, micropore and mesoporous, and based on micropore, specific surface area is big, warp
Calculated BET surface area is 840cm2/ g, total pore volume is 2.1cm3/g。
Embodiment 4: the DHPC@CS-AgNPs nanoparticle of the present invention oxidase active in the presence of mercury ion.
The DHPC@CS-AgNPs nanoparticle prepared by embodiment 1 is selected to carry out oxidase active test.
1mL 0.05mol L is added respectively in A, B, C color comparison tube-1NaAc-HAc buffer solution (pH=4.0) and
300μL 400mmol·L-1TMB solution, then in B, C color comparison tube, add 500 μ L 0.18mmol L respectively-1DHPC@
CS-AgNPs, adds 500 μ L10 the most respectively in A, C color comparison tube-6mol·L-1Hg2+, finally with ultra-pure water by A, B, C
Number color comparison tube is settled to 5mL, carries out uv scan after reacting 10 minutes in 40 DEG C of constant-temperature shaking incubators, result such as figure
3.Solution (the Hg of A color comparison tube2++ TMB) it is water white transparency, almost in straight line between 370nm to 800nm, Hg is described2 +Can not dissolved oxygen oxidation TMB colour developing in catalytic solution；The solution (DHPC@CS-AgNPs+TMB) of B color comparison tube presents nanometer
, there is the characteristic absorption peak of nanometer silver at about 400nm in the yellow of silver, shows that DHPC@CS-AgNPs can not be in catalytic solution
Dissolved oxygen oxidation TMB colour developing, catalysis activity is weak；Solution (the Hg of C color comparison tube2++ DHPC@CS-AgNPs+TMB) it is blue, say
Bright Hg2+Existence can promote DHPC@CS-AgNPs catalysis oxidation TMB colour developing, and the TMB after colour developing has feature at 370nm and 652nm
Absworption 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.
The DHPC@CS-AgNPs nanoparticle prepared by embodiment 1 is used to carry out following experiment.
Take 500 μ L 0.18mmol L-1DHPC@CS-AgNPs and 500 μ L 1 × 10-6mol·L-1Hg2+, add 300 μ L
The TMB solution of variable concentrations (100～500 μMs), adds 1mL 0.05mol L-1NaAc-HAc buffer solution (pH=4.0),
It is settled to 5mL with ultra-pure water, at 652nm wavelength, measures its ultraviolet absorptivity, the results are shown in Table 1.By table 1 measurement result, according to
Michaelis-Menten equation is with 1/cTMB1/V mapping is obtained the Lineweaver Burk curve of Fig. 4.Can be calculated by the linear equation of Fig. 4
Go out Hg2+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 affinity and the rate of catalysis reaction of TMB, has high oxidation analog enzymatic activity.
Table 1: the reaction rate of mensuration
Embodiment 6: DHPC@CS-AgNPs nanoparticle of the present invention is for the selectivity of colorimetric detection mercury ion.
The principle using the DHPC@CS-AgNPs nanoparticle colorimetric detection mercury ion prepared by embodiment 1 is shown in Fig. 5, real
Test step as follows.
Take 500 μ L 0.18mmol L-1DHPC@CS-AgNPs and 500 μ L 1 × 10-6mol·L-1Hg2+Colorimetric in 5ml
Guan Zhong, adds 300 μ L 400mmol L-1TMB solution, add 1mL 0.05mol L-1NaAc-HAc buffer solution (pH
=4.0), it is settled to 5mL with ultra-pure water, reacts 10 minutes in 40 DEG C of shaken cultivation casees, measure its absorbance at 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+Replace
Mercury ion, investigates the selectivity (see Fig. 6) of method.It was found that only mercury ion can make the aobvious blueness of system, at TMB characteristic wave
There is maximum absorption band at long 652nm, show that the nano silver particles of carbon doping has specific selectivity to the colorimetric detection of mercury ion.
Embodiment 7: DHPC@CS-AgNPs nanoparticle of the present invention is for the sensitivity of colorimetric detection mercury ion.
The principle using the DHPC@CS-AgNPs nanoparticle colorimetric detection mercury ion prepared by embodiment 1 is shown in Fig. 5, real
Test step as follows.
Take 500 μ L 0.18mmol L-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 color comparison tube of 5ml, add 300 μ L 400mmol L-1TMB solution, then add
Enter 1mL 0.05mol L-1NaAc-HAc buffer solution (pH=4.0), is settled to 5mL with ultra-pure water, at 40 DEG C of shaken cultivation casees
Middle reaction 10 minutes, measures its absorbance at 652nm.With the absorbance A that records to corresponding mercury ion concentration of standard solution c
(μmol·L-1) mapping (Fig. 7).Ion concentration of mercury is at 0.02～1 μm ol L-1In the range of be good linear relationship with A, line
Property regression equation is A=0.332c+0.085, correlation coefficient r2=0.995, detection limit (S/N=3) is 7nM, illustration method
Highly sensitive.
Embodiment 8: DHPC@CS-AgNPs nanoparticle of the present invention is applied to colorimetric detection Food and environment sample
Middle trace amount mercury ion.
The DHPC@CS-AgNPs nanoparticle prepared by embodiment 1 is used to carry out following experiment.
The process of fish sample: weigh 2.0g sample in counteracting tank, adds 5mL concentrated nitric acid, adds a cover and stand overnight, tighten lid
Son, places in microwave dissolver and clears up, and cooling is taken out, and slowly opens lid aerofluxus, with a small amount of milli-Q water bottle cap, clearing up
Ultrasonic 2min aerofluxus in ultrasonic water bath case placed by tank, digestion solution is moved to, in the volumetric flask of 25mL, be settled to scale.
The process of water sample: with the membrane filtration of 0.22 μm, use 0.05mol L-1NaAc_HAc buffer solution is adjusted to pH
=4, at 4 DEG C, cold preservation is standby.Take 500 μ L sample liquid to test according to 2.5 methods.
Take 500 μ L fish sample solutions or water sample in the color comparison tube of 5ml, be sequentially added into 500 μ L 0.18mmol L- 1DHPC@CS-AgNPs, 300 μ L 400mmol L-1TMB solution and 1mL 0.05mol L-1NaAc-HAc buffer solution (pH
=4.0), it is settled to 5mL with ultra-pure water, reacts 10 minutes in 40 DEG C of shaken cultivation casees, measure the sample solution suction at 652nm
Luminosity.The content of mercury ion in sample is calculated by the absorbance recorded.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.The method using the present invention, water sample, the flesh of fish and fish tail
In all 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%；Use GB/T 5009.17-2014 atomic fluorescence method, water sample does not detects mercury ion
Content, detects Trace Mercury ion in the flesh of fish and fish tail, and content is at 17.3～21.4 μ g kg-1, result that two kinds of methods record
Consistent, show that this method has high accuracy 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 does not detects.
Claims (10)
1. the doping porous carbon Nano silver grain visualizing rapid mercury detection ion, it is characterised in that described doping porous
Carbon Nano silver grain is DHPC@CS-AgNPs, through the following steps that prepare:
(1) in 250mL three-neck flask, it is sequentially added into deionized water, methyl methacrylate and catalyst, opens cooling water, logical
Nitrogen, stirring, water-bath 1～2h, obtain polymethyl methacrylate emulsion (PMMA)；
(2) in PMMA emulsion, sucrose and polypyrrole it are sequentially added into, stirring, add 1mL H2SO4, primary reconstruction reacts
20min；Products therefrom pours culture dish into, is dried in drying baker；Dry product is transferred to crucible be placed in tube furnace,
Fire 6h under nitrogen atmosphere, then carbonization 3h, obtain macropore carbon；
(3) macropore carbon being scattered in 5mL acetone, add 20mL KOH solution, stirring, water bath with thermostatic control reaction is to forming pulpous state mixing
Thing；Paste mixture is placed in tube furnace, under nitrogen protection high-temperature activation；Activation products are washed with distilled water to neutrality, very
Empty dry, obtain porous carbon i.e. DHPC；
(4) chitosan (CS) is dissolved in 100mL 1% acetum, is subsequently adding DHPC, ultrasonic disperse, filters, born
Carry the chitosan solution i.e. DHPC@CS of porous carbon；
(5) by 0.02g NaBH4Add DHPC@CS solution, stir, be then slowly added dropwise 0.6mmol L-1AgNO3Solution,
Room temperature reaction, obtains the Nano silver grain DHPC@CS-AgNPs of doping porous carbon.
Doping porous carbon Nano silver grain the most according to claim 1, it is characterised in that: in described step (1), described
The volume ratio of deionized water and methyl methacrylate is 5:1～6:1, and catalyst is potassium peroxydisulfate, azodiisobutyronitrile or mistake
Aoxidizing two carbonic acid cyclohexyls, consumption is 0.04～0.08g.
Doping porous carbon Nano silver grain the most according to claim 1, it is characterised in that: in described step (1), described
Alr mode is mechanical agitation, and mixing speed is 350～500r/min, and bath temperature is 90 DEG C.
Doping porous carbon Nano silver grain the most according to claim 1, it is characterised in that: in described step (2), PMMA breast
The mass ratio of liquid, sucrose and polypyrrole is 200:5:1, H2SO4Concentration be 0.5～1mol/L.
Doping porous carbon Nano silver grain the most according to claim 1, it is characterised in that: in described step (2), described
Alr mode is mechanical agitation, and mixing speed is 350～500r/min, and mixing time is 15～20min, baking temperature be 60～
70 DEG C, drying time is 6～8h, and fire temperature is 150～200 DEG C, and carbonization temperature is 900～950 DEG C.
Preparation method the most according to claim 1, it is characterised in that: in described step (3), macropore carbon mixes at acetone-KOH
The mass concentration that mass concentration is 20mg/mL, KOH closed in solution is 0.1～0.2g/mL, and the volume ratio of acetone and KOH is 1:
4。
Preparation method the most according to claim 1, it is characterised in that: in described step (3), described stirring is that magnetic force stirs
Mixing, bath temperature is 100 DEG C, and activation temperature is 200 DEG C, vacuum drying temperature be 70～80 DEG C, the vacuum drying time be 20～
24h。
Preparation method the most according to claim 1, it is characterised in that: in described step (4), described chitosan and porous
The mass concentration of carbon is 1mg/mL, and the ultrasonic disperse time is 4h.
Preparation method the most according to claim 1, it is characterised in that: in described step (5), described DHPC@CS solution
And AgNO3The volume ratio of solution is 2:1～2.5:1.
Preparation method the most according to claim 1, it is characterised in that: in described step (5), described alr mode is
Magnetic agitation, the room temperature reaction time is 20～24h.
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| CN113559880A (en) * | 2021-07-30 | 2021-10-29 | 曲阜师范大学 | Pd @ NiCo2O4Double-function nano mimic enzyme and preparation method and application thereof |
| 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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