CN106865522B - A kind of three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material and application - Google Patents
A kind of three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material and application Download PDFInfo
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- CN106865522B CN106865522B CN201710044533.3A CN201710044533A CN106865522B CN 106865522 B CN106865522 B CN 106865522B CN 201710044533 A CN201710044533 A CN 201710044533A CN 106865522 B CN106865522 B CN 106865522B
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- 239000006260 foam Substances 0.000 title claims abstract description 91
- 239000003610 charcoal Substances 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 43
- 229940005654 nitrite ion Drugs 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 18
- 239000007832 Na2SO4 Substances 0.000 claims abstract description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 11
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 7
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 238000001816 cooling Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 13
- 238000001514 detection method Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 6
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 239000008363 phosphate buffer Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 108010061951 Methemoglobin Proteins 0.000 description 2
- -1 NO is being added3- Chemical class 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 210000004211 gastric acid Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material and application, preparation method includes: that melamine sponge is placed in the environment full of protective gas and calcines 1~3 hour with 800~1000 DEG C to which three-dimensional foam charcoal be made；Three-dimensional foam charcoal is placed in nitric acid and reacts 1~4 hour three-dimensional foam charcoal to which functionalization be made with 100~150 DEG C；By FeCl3、Na2SO4And the three-dimensional foam charcoal of functionalization mixes, and reacts 2~8 hours under conditions of being placed in 100~150 DEG C, it is then cooling, wash and dry, then be placed in full of being calcined 2~5 hours in protective gas environment with 400~500 DEG C.Using the three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material directly as the working electrode detected to water body Nitrite ion.The present invention can not only carry out quick, efficient and selective enumeration method to the nitrite ion in water body, and avoid the complex process that tradition prepares electrode.
Description
Technical field
The present invention relates to pollutant monitoring technical field in water body more particularly to a kind of three-dimensional foam charcoal/di-iron trioxides
Nanometer stick array composite material and application.
Background technique
Nitrite is the chemical substance being widely present in natural environment, especially in food, such as: grain, vegetable
Dish, meat and fish all contain a certain amount of nitrite.Nitrite is commonly called as industrial salt, is white powder, soluble easily in water,
Other than industrial use, nitrite is used in food production as food additives.Excessive edible nitrite can make blood
Low Ferri-hemoglobin in liquid is oxidized to ferrihemoglobin, loses the ability of transport oxygen and histanoxia is caused to be damaged, together
When nitrite be ingested in stomach after, generation strong carcinogen can react with protein breakdown products secondary amine under gastric acid effect
Matter nitrosamine, therefore the nitrite in water body detect particularly necessary.
Currently, the method that the nitrite in water body is detected specifically include that spectrophotometry, the chromatography of ions,
Chemoluminescence method, Raman spectroscopy, electrochemical analysis method etc., major part detection method therein require accurate instrument,
The sample preparation technology of complicated test program and profession, this largely hinders their practical application；But it is therein
Electrochemical analysis method has many advantages, such as that simple easy to operate, instrument, rapid sensitive, selectivity are high, therefore utilizes electrochemical credit
Analysis method carries out detection to the nitrite in water body and is paid attention to deeply.In existing electrochemical analysis method, tradition preparation electricity
Pole method complexity is cumbersome, and binder used in electrode itself hinders the charge transfer effciency of electrode surface significantly, this
Reduce the detection efficiency to Nitrite.
Summary of the invention
For above-mentioned shortcoming in the prior art, the present invention provides a kind of three-dimensional foam charcoal/di-iron trioxides to receive
Rice stick array composite material and application can not only carry out quick, efficient and selectivity to the nitrite ion in water body and examine
It surveys, and avoids the complex process that tradition prepares electrode.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material, preparation method includes the following steps:
Step A, melamine sponge is placed in the environment full of protective gas, and with 800~1000 DEG C of calcinings 1~3
Hour, so that three-dimensional foam charcoal be made；
Step B, three-dimensional foam charcoal obtained in step A is placed in nitric acid, and is reacted 1~4 hour with 100~150 DEG C,
To which the three-dimensional foam charcoal of functionalization be made；
Step C, by FeCl3、Na2SO4And this three of the three-dimensional foam charcoal of functionalization obtained is blended in one in step B
It rises, reacts 2~8 hours, then cool to room temperature, and washed and dried, then set under conditions of being placed in 100~150 DEG C
It in the environment full of protective gas, is calcined 2~5 hours with 400~500 DEG C, so that three-dimensional foam charcoal/di-iron trioxide be made
Nanometer stick array composite material.
Preferably, in stepb, three-dimensional foam charcoal obtained in step A is placed in the nitric acid that concentration is 3mol/L, and
It is reacted 1 hour with 120 DEG C, so that the three-dimensional foam charcoal of functionalization be made.
Preferably, in step C, by FeCl3、Na2SO4And in step B functionalization obtained three-dimensional foam charcoal this three
Person mixes, and reacts 6 hours, then cools to room temperature, and washed and dried under conditions of being placed in 120 DEG C, then
It is placed in the environment full of protective gas, is calcined 2 hours with 450 DEG C, so that three-dimensional foam charcoal/di-iron trioxide nanometer rods be made
Array composite material.
Preferably, the FeCl3Dosage be 1.5mmol, the Na2SO4Dosage be 1.5mmol.
Using the charcoal of three-dimensional foam described in technical solution/di-iron trioxide nanometer stick array composite material directly as right
The working electrode that water body Nitrite ion is detected.
As seen from the above technical solution provided by the invention, three-dimensional foam charcoal/di-iron trioxide provided by the invention
Nanometer stick array composite material is by hydro-thermal method to FeCl3、Na2SO4It is handled, and is passed through with the three-dimensional foam charcoal of functionalization
The final di-iron trioxide obtained in the growth of three-dimensional foam carbon surface after supercooling, washing, drying and further heat treatment
Nanometer stick array；The three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material can be used as detection nitrite ion
Working electrode, without using binder, and to the nitrite ion concentration in water body have the wider range of linearity, compared with
Low detection limit and good selectivity, therefore three-dimensional foam provided by the present invention charcoal/di-iron trioxide nanometer stick array
Composite material can not only carry out quick, efficient and selective enumeration method to the nitrite ion in water body, and avoid biography
Controlling for electrode complex process.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill in field, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is that three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material prepared by the embodiment of the present invention 1 is swept
Retouch electromicroscopic photograph.
Fig. 2 is three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material X prepared by the embodiment of the present invention 1
X ray diffraction map.
Fig. 3 is three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material drawing prepared by the embodiment of the present invention 1
Graceful spectrogram.
Fig. 4 is three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material light prepared by the embodiment of the present invention 1
Electron spectrum.
Fig. 5 is three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material prepared by the embodiment of the present invention 1 to not
With the cyclic voltammetry curve figure of the nitrite ion of concentration and the linear relationship of nitrite ion concentration and oxidation peak current
Figure.
Fig. 6 is three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material prepared by the embodiment of the present invention 1 to not
With the current-time curvel figure of the nitrite ion of concentration and the linear relationship chart of nitrite ion concentration and current strength.
Fig. 7 is three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material prepared by the embodiment of the present invention 1 to not
With the current-time curvel figure of ion.
Specific embodiment
With reference to the attached drawing in the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete
Ground description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this
The embodiment of invention, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, belongs to protection scope of the present invention.
Three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material of the invention and application are retouched in detail below
It states.
A kind of three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material, preparation method includes the following steps:
Step A, melamine sponge is placed in full of protective gas (protective gas is nitrogen or rare gas)
It in environment, and is calcined 1~3 hour with 800~1000 DEG C, so that three-dimensional foam charcoal be made.
Specifically, melamine sponge is preferably disposed in the tube furnace full of nitrogen or rare gas, and is forged with 900 DEG C
It burns 2 hours, so that three-dimensional foam charcoal be made.
Step B, three-dimensional foam charcoal obtained in step A is placed in dust technology, and small with 100~150 DEG C of reactions 1~4
When, so that the three-dimensional foam charcoal of functionalization be made.
Specifically, three-dimensional foam charcoal obtained in step A is preferably placed in the reaction kettle for filling that concentration is 3mol/L nitric acid
In, and reacted 1 hour with 120 DEG C, so that the three-dimensional foam charcoal of functionalization be made.
Step C, by FeCl3、Na2SO4And this three of the three-dimensional foam charcoal of functionalization obtained is blended in one in step B
It rises, reacts 2~8 hours, then cool to room temperature, and washed and dried, then set under conditions of being placed in 100~150 DEG C
It is small with 400~500 DEG C of calcinings 2~5 in the environment full of protective gas (protective gas is nitrogen or rare gas)
When, to can be prepared by three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material.
Specifically, by FeCl3、Na2SO4And this three of the three-dimensional foam charcoal of functionalization obtained is blended in one in step B
It rises, reacts 6 hours, then cool to room temperature, and washed and dried, then be placed in full of nitrogen under conditions of being placed in 120 DEG C
It in the tube furnace of gas or rare gas, is calcined 2 hours with 450 DEG C, so that three-dimensional foam charcoal/di-iron trioxide nanometer rods battle array be made
Column composite material.In practical applications, 1.5mmol FeCl can be taken3·6H2O and 1.5mmol Na2SO4It is dissolved in deionized water
In, then the three-dimensional foam charcoal of functionalization obtained in step B is placed in one, is persistently stirred 60 minutes, then by the mixing
Object is transferred in autoclave, is reacted 6 hours under conditions of 120 DEG C；To be cooled to room temperature after the reaction was completed, taking-up is obtained
The product obtained sufficiently washs, and to remove surface physical attachment object, then place the product in place is dried under the conditions of 60 DEG C
Then dry product is placed in nitrogen or the tube furnace of rare gas protection, is calcined 2 hours with 450 DEG C by reason, thus
Three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material is made.
Further, by adopting the above technical scheme described in three-dimensional foam charcoal/di-iron trioxide nanometer stick array it is compound
Material can be directly as the working electrode detected to water body Nitrite ion.
To sum up, the embodiment of the present invention can not only carry out quick, efficient and choosing to the nitrite ion in water body
The detection of selecting property, and avoid the complex process that tradition prepares electrode.
In order to more clearly from show technical solution provided by the present invention and generated technical effect, below with tool
Body embodiment be provided for the embodiments of the invention three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material and application into
Row detailed description.
Embodiment 1
A kind of three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material, preparation method includes the following steps:
Step a, it will be placed in the tube furnace of nitrogen protection having a size of 0.5cm × 3cm × 9cm melamine sponge, and
It is calcined 2 hours with 900 DEG C, so that the three-dimensional foam charcoal of black be made.
Step b, three-dimensional foam charcoal obtained in step a is placed in the autoclave for filling that concentration is 3mol/L nitric acid
In, and reacted 1 hour with 120 DEG C, so that the three-dimensional foam charcoal of functionalization be made.
Step c, 1.5mmol FeCl is taken3·6H2O and 1.5mmol Na2SO4It is dissolved in deionized water, it then will be having a size of
The three-dimensional foam charcoal of functionalization obtained is placed in one in 0.25cm × 1.5cm × 3cm step b, persistently stirs 60 minutes, so
The mixture is transferred in the autoclave of 50mL afterwards, is reacted 6 hours under conditions of 120 DEG C；To cold after the reaction was completed
But it to room temperature, takes out product obtained and sufficiently washs, to remove surface physical attachment object, then place the product in 60 DEG C
Under the conditions of be dried, then dry product is placed in the tube furnace of nitrogen protection, with 450 DEG C calcine 2 hours, from
And it can be prepared by three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material.
Specifically, to the charcoal of three-dimensional foam prepared by the embodiment of the present invention 1/di-iron trioxide nanometer stick array composite material
Microstructure observing, constituent analysis and Electrochemical Detection nitrite ion effect test are carried out, to obtain following result:
(1) to three-dimensional foam charcoal obtained in the step a of the embodiment of the present invention 1 and most using scanning electron microscope
The three-dimensional foam charcoal prepared eventually/di-iron trioxide nanometer stick array composite material carries out observation shooting, to obtain as shown in Figure 1
Scanning electron microscopic picture；Wherein, Fig. 1 a is the scanning electron microscope of three-dimensional foam charcoal obtained in the step a of the embodiment of the present invention 1
Picture；Fig. 1 b, Fig. 1 c and Fig. 1 d are respectively the charcoal of three-dimensional foam prepared by the embodiment of the present invention 1/di-iron trioxide nanometer rods battle array
Scanning electron microscopic picture of the column composite material in different magnification ratios.By Fig. 1 a it can be seen that the step a of the embodiment of the present invention 1
In obtained three-dimensional foam charcoal be tridimensional network, and its surface is smooth；By Fig. 1 b, Fig. 1 c and Fig. 1 d it can be seen that originally
In the charcoal of three-dimensional foam prepared by inventive embodiments 1/di-iron trioxide nanometer stick array composite material, three-dimensional foam carbon surface becomes
It is coarse, be uniformly dispersed with di-iron trioxide nanometer stick array.
(2) ingredient point is carried out to final product obtained in the step c of the embodiment of the present invention 1 using X-ray diffractometer
Analysis, to obtain X ray diffracting spectrum as shown in Figure 2；Wherein, the ordinate of Fig. 2 is intensity, and abscissa is 2 θ (i.e. diffraction
Angle, unit are degree).As seen from Figure 2: final product prepared by the step c of the embodiment of the present invention 1 be located at 21.1 °,
33.1 °, 35.6 °, 40.8 °, 49.4 °, 54.0 °, 62.4 ° and 63.9 ° of diffraction maximum can be with the di-iron trioxide of bloodstone phase
(0 1 2), (1 0 4), (1 1 0), (1 1 3), (0 2 4), (1 1 6), (2 1 4) and (3 0 0) crystal face one it is a pair of
It answers, this shows that the product of three-dimensional foam carbon surface is di-iron trioxide.
(3) using Raman spectrum to the charcoal of three-dimensional foam prepared by the embodiment of the present invention 1/di-iron trioxide nanometer stick array
The structure of composite material is further analyzed, to obtain Raman spectrogram as shown in Figure 3.As seen from Figure 3: being located at
1353 and 1553cm-1Two characteristic peaks belong to the peak D and the peak G of three-dimensional foam charcoal, and be located at 217,280 and 397cm-1Three
A characteristic peak belongs to the A of Fe-O1g(217cm-1) and Eg(280and 397cm-1) vibration mode.
(4) using x-ray photoelectron spectroscopy to the surface of final product obtained in the step c of the embodiment of the present invention 1
It constitutes and element valence is analyzed, to obtain x-ray photoelectron spectroscopy figure as shown in Figure 4.As seen from Figure 4: position
In 297.8,411.8, the peak of 546.8and 710.7eV be belonging respectively to C 1s, N 1s, O 1s and Fe 2p, this shows the present invention
Contain C, N, Fe, tetra- kinds of elements of O in obtained final product in the step c of embodiment 1.
(5) on CHI760E electrochemical workstation, using three-dimensional foam charcoal prepared by the embodiment of the present invention 1/tri- oxidations
Two iron nanometer stick array composite materials are as working electrode, using saturated calomel electrode as reference electrode, using platinum electrode
It is 0.1mol/L phosphate buffer as electrolyte using the concentration that pH value is 7 then at room temperature as to electrode
Solution is continually fed into nitrogen, and under conditions of being stirred continuously, and the nitrous acid that different amounts of concentration is 1mol/L is added thereto
Sodium solution detects the nitrite ion in water body using cyclic voltammetry (sweep speed be 50mv/s), thus obtain as
The linear relationship chart of cyclic voltammetry curve figure shown in fig. 5 and nitrite ion concentration and oxidation peak current；Wherein, Fig. 5 a is
Nitrous of the charcoal of three-dimensional foam prepared by the embodiment of the present invention 1/di-iron trioxide nanometer stick array composite material to various concentration
The cyclic voltammetry curve figure of acid ion, Fig. 5 b are three-dimensional foam charcoal/di-iron trioxide nanometer prepared by the embodiment of the present invention 1
The nitrite ion concentration of stick array composite material and the linear relationship chart of oxidation peak current.From Fig. 5 a and Fig. 5 b: with
The addition of nitrite ion, current potential be about at 0.85V appearance one spike potential, i.e. the oxidation of nitrite ion
Peak；In addition, oxidation peak current increases with the increase of the concentration of nitrite ion, and peak current and nitrite ion
Concentration is in a linear relationship, linear equation Ipa(μ A)=32.36+0.076C (μM), R2=0.998.
(6) on CHI760E electrochemical workstation, using three-dimensional foam charcoal prepared by the embodiment of the present invention 1/tri- oxidations
Two iron nanometer stick array composite materials are as working electrode, using saturated calomel electrode as reference electrode, using platinum electrode
It is 0.1mol/L phosphate buffer as electrolyte using the concentration that pH value is 7 then at room temperature as to electrode
Solution is continually fed into nitrogen, and under conditions of being stirred continuously, and the nitrous acid that different amounts of concentration is 1mol/L is added thereto
Sodium solution, using current-time curvel method (oxidizing potential 0.85V) to the range of linearity of the nitrite ion in water body into
Row measurement, and limited by the concentration linear relationship of electrochemical signals and the nitrite ion being added to calculate its detection, from
And obtain the linear relationship chart of current-time curvel figure as shown in FIG. 6 and nitrite ion concentration and current strength；Wherein,
Fig. 6 a is three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material prepared by the embodiment of the present invention 1 to various concentration
Nitrite ion current-time curvel figure, Fig. 6 b is the oxidation of three-dimensional foam charcoal/tri- prepared by the embodiment of the present invention 1 two
The nitrite ion concentration of iron nanometer stick array composite material and the linear relationship chart of current strength.It can by Fig. 6 a and Fig. 6 b
Know: the charcoal of three-dimensional foam prepared by the embodiment of the present invention 1/di-iron trioxide nanometer stick array composite material is in nitrite ion
In the range of concentration is 0.5 μM~1000 μM, nitrite ion concentration and current strength are in good linear relationship (R2=
0.998), linear equation Ipa(μ A)=0.016C (μM)+5.524, detection are limited to 0.12 μM.
It (7) is to utilize current-time curvel method (oxidation electricity in 0.1mol/L phosphate buffer in the concentration that pH value is 7
Position is 0.85V) to the charcoal of three-dimensional foam prepared by the embodiment of the present invention 1/di-iron trioxide nanometer stick array composite material conduct
The selectivity for detecting the working electrode of nitrite ion is tested, to obtain 1 institute of the embodiment of the present invention as shown in Figure 7
Current-time curvel figure of the three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material of preparation to different ions.By Fig. 7
Known to: other interfering ions (such as NO is being added3-、CH3COO-、CO3 2-、SO4 2-、Zn2+、Cl-、K+、Mg2+And Ca2+) when, electric current is not
It is added and changes with it, but NO is once added2-, electric current increases in a short period of time, this shows the embodiment of the present invention 1
Working electrode of the prepared three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material as detection nitrite ion
It has good selectivity.
To sum up, three-dimensional foam charcoal prepared by the embodiment of the present invention 1/di-iron trioxide nanometer stick array composite material
In the working electrode as detection nitrite ion, the nitrite ion concentration in water body is shown wider linear
Range, lower detection limit and good selectivity, therefore the embodiment of the present invention can not only be to the nitrite anions in water body
Ion carries out quick, efficient and selective enumeration method, and avoids the complex process that tradition prepares electrode.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (5)
1. a kind of three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material, which is characterized in that preparation method include with
Lower step:
Step A, melamine sponge is placed in the environment full of protective gas, and is calcined 1~3 hour with 800~1000 DEG C,
To which three-dimensional foam charcoal be made；
Step B, three-dimensional foam charcoal obtained in step A is placed in the autoclave for filling nitric acid, and with 100~150 DEG C
Reaction 1~4 hour, so that the three-dimensional foam charcoal of functionalization be made；
Step C, by FeCl3、Na2SO4And this three of the three-dimensional foam charcoal of functionalization obtained mixes in step B, and
It is placed in autoclave under conditions of 100~150 DEG C and reacts 2~8 hours, then cool to room temperature, and washed and done
It is dry, then be placed in the environment full of protective gas, it is calcined 2~5 hours with 400~500 DEG C, so that three-dimensional foam charcoal/tri- be made
Aoxidize two iron nanometer stick array composite materials.
2. three-dimensional foam charcoal according to claim 1/di-iron trioxide nanometer stick array composite material, which is characterized in that
In stepb, three-dimensional foam charcoal obtained in step A is placed in the nitric acid that concentration is 3mol/L, and small with 120 DEG C of reactions 1
When, so that the three-dimensional foam charcoal of functionalization be made.
3. three-dimensional foam charcoal according to claim 1 or 2/di-iron trioxide nanometer stick array composite material, feature exist
In in step C, by FeCl3、Na2SO4And this three of the three-dimensional foam charcoal of functionalization obtained is blended in one in step B
It rises, reacts 6 hours, then cool to room temperature, and washed and dried under conditions of being placed in 120 DEG C, then be placed in full of guarantor
It protects in the environment of gas, is calcined 2 hours with 450 DEG C, so that three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite wood be made
Material.
4. three-dimensional foam charcoal according to claim 3/di-iron trioxide nanometer stick array composite material, which is characterized in that
The FeCl3Dosage be 1.5mmol, the Na2SO4Dosage be 1.5mmol.
5. straight using three-dimensional foam charcoal/di-iron trioxide nanometer stick array composite material described in any one of Claims 1-4
It connects as the working electrode detected to water body Nitrite ion.
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| CN106179213A (en) * | 2016-07-25 | 2016-12-07 | 浙江沁园水处理科技有限公司 | A kind of nanometer α Fe2o3the preparation method and applications of modified activated carbon |
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| CN106179213A (en) * | 2016-07-25 | 2016-12-07 | 浙江沁园水处理科技有限公司 | A kind of nanometer α Fe2o3the preparation method and applications of modified activated carbon |
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