CN110455888A - A kind of electrode material of nickel foam self-supporting, preparation method and its purposes in detection phosphoric acid hydrogen radical ion - Google Patents
A kind of electrode material of nickel foam self-supporting, preparation method and its purposes in detection phosphoric acid hydrogen radical ion Download PDFInfo
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- CN110455888A CN110455888A CN201910644370.1A CN201910644370A CN110455888A CN 110455888 A CN110455888 A CN 110455888A CN 201910644370 A CN201910644370 A CN 201910644370A CN 110455888 A CN110455888 A CN 110455888A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000001514 detection method Methods 0.000 title claims abstract description 58
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 43
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000006260 foam Substances 0.000 title claims abstract description 41
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 21
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 title claims abstract description 19
- 239000007772 electrode material Substances 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 239000002135 nanosheet Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 238000002848 electrochemical method Methods 0.000 claims description 4
- 229910001412 inorganic anion Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 150000001449 anionic compounds Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 26
- 239000011574 phosphorus Substances 0.000 abstract description 26
- 239000002351 wastewater Substances 0.000 abstract description 16
- 150000002500 ions Chemical class 0.000 abstract description 11
- 229910000480 nickel oxide Inorganic materials 0.000 abstract description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 5
- 238000011897 real-time detection Methods 0.000 abstract description 5
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 abstract description 4
- 150000002815 nickel Chemical class 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 230000002452 interceptive effect Effects 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 4
- 238000000970 chrono-amperometry Methods 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 241000195493 Cryptophyta Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- -1 phosphate radical Chemical class 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 150000005837 radical ions Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- WZOZCAZYAWIWQO-UHFFFAOYSA-N [Ni].[Ni]=O Chemical compound [Ni].[Ni]=O WZOZCAZYAWIWQO-UHFFFAOYSA-N 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000004295 detection of phosphate ion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007812 electrochemical assay Methods 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003891 environmental analysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000004401 flow injection analysis Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000000120 microwave digestion Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 238000012353 t test Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- 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
-
- 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
Abstract
The present invention design it is a kind of convenient and efficient, sensitive and accurate and inexpensive, can phosphoric acid hydrogen radical ion (HPO in real-time detection phosphorus-containing wastewater4 2‑) concentration sensing detection system.The invention belongs to sensing detection, water process and low temperature electrocatalytic fields.The sensing detection system that the present invention designs is one kind using modified nickel foam as self-supporting working electrode, and silver-colored silver chlorate (3 moles of KCl) is reference electrode, and carbon-point is the three-electrode system to electrode.The present invention is through one step hydro thermal method, form a kind of foam nickel sheet of the hydronium(ion) nickel oxide of area load form uniform (nano-sheet and three-dimensional flower-shaped), to detect the concentration of phosphoric acid hydrogen radical ion in phosphorus-containing wastewater, and show superpower stability and accuracy.
Description
Technical field
The present invention relates to a kind of sensing detection system that can be used for phosphoric acid hydrogen radical ion concentration in real-time detection phosphorus-containing wastewater,
Belong to sensing detection, water process and low temperature electrocatalytic field.
Background technique
Nitrogen and phosphorus are class plant growth necessary elements of swimming, and phosphorus is the most critical factor for limiting its growth, because
Even if many seaweed can maintain the demand of own growth but by the nitrogen in fixed atmosphere in phosphorous lower fresh water
P elements can not be obtained by other means.Also, the bioavailability of phosphorus is also to directly affect global primary productivity
Horizontal key factor.However, excessive phosphorus will cause water eutrophication again, cause algae or other planktons
Mass propagation in turn results in the decline of algae, planktonic organism and aqueous bio so that the dissolved oxygen content in water substantially reduces
Even become extinct.Because containing NO3-N and NO2-N in eutrophic water, people and animals' long-term drinking also brings along many diseases.Mesh
Before, China even the whole world because of phosphorus content it is excessively high caused by water pollution be subjected to national governments and the extensive pass of the masses
Note.Therefore, the inevitable concern and interest that can also cause more scientific research persons of the measurement of phosphorus content in water.
In natural water or sewage, phosphorus mainly exists in the form of phosphate.The content of general Phosphorus In Natural Water is not high,
But with industrialized continuous development, phosphorus content is often beyond country in trade effluent (such as chemical fertilizer, pesticide, washing, Metallurgical Factory)
Water standard.Therefore, strict inspection and control phosphorus in trade effluent content be only effectively control environmental pollution important channel.
Currently, for the detection of phosphate radical in water quality, there is numerous methods, such as ammonium molybdate spectrophotometric method, Reduction with Stannous Chloride molybdenum blue
Method, Flow Injection Analysis and Microwave Digestion etc..But such method preparation of reagents heavy workload, measurement is complex for operation step, examines
The defects of survey period is long, and operating cost is high, and disturbing factor is more has closely been unable to satisfy fast and convenient in environmental monitoring work now
With the demand of real-time online.
In recent years, electrochemical assay is because it has highly sensitive and selectivity, the wide range of linearity, response time short, long
Time stability and repeatedly using property, and the advantages that being easily achieved real-time online detection and automation control, exist
Environmental analysis and scientific research sphere of learning are widely applied and are furtherd investigate.Especially can self-supporting Electrochemical Detection system
To miniaturization in next step, Portable belt, low cost integrated detector part research and development with great research significance and exploitation
Prospect.
Summary of the invention
The object of the present invention is to provide it is a kind of can self-supporting, area load nano-sheet and three-dimensional flower-shaped hydrated hydroxide
Change the foam nickel electrode piece of nickel, to the concentration of phosphoric acid hydrogen radical ion in real-time detection phosphorus-containing wastewater, the present invention also provides this
The preparation method of kind self-supporting foam nickel electrode piece.The present invention using nickel foam after processing as can self-supporting working electrode
And with carbon-point (to electrode), the three-electrode system that silver-colored silver chlorate (reference electrode) forms forms one kind to detect phosphoric acid in solution
The sensing detection device system of hydrogen radical ion concentration, which is characterized in that the modification of one step hydro thermal method is so that foam nickel surface is formed
Two kinds of (nano-sheet and three-dimensional flower-shaped) form uniform hydronium(ion) nickel oxide, so that the selectivity of this electrode slice is than unsupported
The selectivity of the foam nickel electrode piece of hydronium(ion) nickel oxide is stronger, and biggish specific surface area also substantially increases sensing detection
Sensitivity and detection range.Also, it can be kept away again using the nickel foam after modifying itself as electrode slice (self-supporting electrode slice)
Exempt from many unfavorable factor bring interference, is also very beneficial for the further promotion of its detection performance.Most of all, of the invention
The three-electrode system of design is very suitable to facilitate the developmental research of small and exquisite, real-time online integrated detector part.
The first aspect of the invention provides:
A kind of electrode material of nickel foam self-supporting is that have nickel hydroxide in its area load using nickel foam as carrier.
In one embodiment, the nickel hydroxide is nano-sheet or three-dimensional flower-shaped.
In one embodiment, nickel foam porosity > 95%, with a thickness of 1 mm, purity >=99.97%, aperture 200-500
μm。
The second aspect of the invention provides:
The preparation method of the electrode material of nickel foam self-supporting includes the following steps: the table by hydrothermal synthesis method in nickel foam
Face generates nickel hydroxide.
In one embodiment, include the following steps:
Prepare containing nickel chloride, urea, ammonium chloride solution, add nickel foam in the solution, carry out hydrothermal synthesis；
After synthetic reaction, nickel foam after washing, obtains the electrode material of nickel foam self-supporting.
In one embodiment, nickel chloride, urea, ammonium chloride weight ratio be: 0.4-0.8:0.15-0.55:0.01-
0.03。
In one embodiment, 100-160 DEG C of the temperature of hydrothermal synthesis, time are 2-10h.
The third aspect of the invention provides:
Purposes of the electrode material of nickel foam self-supporting in electrochemical method detection water in phosphoric acid hydrogen radical ion.
In one embodiment, the detection is using three-electrode system.
In one embodiment, the electrode material of nickel foam self-supporting is as working electrode, and silver-silver chloride is as reference
Electrode, carbon-point are used as to electrode.
The fourth aspect of the invention provides:
Nickel hydroxide is for improving the purposes in foamed nickel electrode material detection water in the performance of phosphoric acid hydrogen radical ion.
In one embodiment, the detection refers to that electrochemical method detects.
In one embodiment, nickel hydroxide is used to improve the current signal strength in detection.
In one embodiment, nickel hydroxide is for improving the detection range of linearity.
In one embodiment, nickel hydroxide is used to reduce the response time in detection process.
In one embodiment, nickel hydroxide is used to improve the anti-interference ability of detection process.
In one embodiment, the anti-interference ability refers to the ability of anti-inorganic anion interference.
In one embodiment, the inorganic anion is selected from NO3 -、SO4 2-、Cl-、HCO3 -Or CH3COO-In
It is one or more of.
Beneficial effect
The present invention detects practical phosphorus-containing wastewater (in Jiangsu Province petroleum catalyst and pesticide research phosphorus-containing wastewater), sends out
Its existing repeatability can be up to 108% ± 10 and 144% ± 23.7 respectively.Therefore, it is considered herein that from operating procedure, performance detection,
The various aspects such as preparation cost, environmental protection consider, it is found that it is a kind of more portable integrated this detection architecture is very suitable to be made into
Sensing detection device has preferable practical application value applied to the Concentration Testing of phosphoric acid hydrogen radical ion in practical phosphorus-containing wastewater.
Detailed description of the invention
Fig. 1 be respectively in the embodiment of the present invention 1 3D-Ni HH/NF amplify NF(b in 1000 times (regions a) and comparative example 1
Region) 200 times of electron microscope of amplification.
Fig. 2 is centrifugal sediment and 3D-Ni HH/NF X-ray through hydro-thermal method upper suspension in the embodiment of the present invention 1
Diffraction curve figure.
Fig. 3 is NF electrode slice in 3D-Ni HH/NF electrode slice in the embodiment of the present invention 2 and comparative example 1 in the NaOH of pH=11
Contain or not contain 1 mM HPO4 2-CV test curve figure in solution.
Fig. 4 is the NF electrode slice (area b in 3D-Ni HH/NF electrode slice (region a) in the embodiment of the present invention 2 and comparative example 1
Domain) to HPO4 2-I-t test curve figure
Fig. 5 is right for NF electrode slice (region b) in 3D-Ni HH/NF electrode slice (region a) in the embodiment of the present invention 2 and comparative example 1
HPO4 2-I-C Linear Fit Chart.
Fig. 6 is 3D-Ni HH/NF electrode slice in the embodiment of the present invention 3 to HPO4 2-The I-t of anti-interference detection schemes.
Fig. 7 is NF electrode slice in 3D-Ni HH/NF electrode slice in the embodiment of the present invention 4 and comparative example 1 to HPO4 2-Stablize
Property test I-t figure.
Specific embodiment
The present invention design it is a kind of convenient and efficient, sensitive and accurate and inexpensive, can phosphoric acid in real-time detection phosphorus-containing wastewater
Hydrogen radical ion (HPO4 2-) concentration sensing detection system.The invention belongs to sensing detection, water process and low temperature electrocatalytic fields.
The sensing detection system that the present invention designs is one kind using modified nickel foam as self-supporting working electrode, (3 moles of silver-colored silver chlorate
It KCl) is reference electrode, carbon-point is the three-electrode system to electrode.The present invention is that it is negative to form a kind of surface through one step hydro thermal method
The foam nickel sheet for carrying the hydronium(ion) nickel oxide of form uniform (nano-sheet and three-dimensional flower-shaped), to detect phosphoric acid in phosphorus-containing wastewater
The concentration of hydrogen radical ion, and show superpower stability and accuracy.The present invention is to practical phosphorus-containing wastewater (stone in Jiangsu Province
Oily catalyst and pesticide research phosphorus-containing wastewater) detected, it is found that its repeatability can be up to 108% ± 10 and 144% respectively
±23.7.Compared with studying more cobalt-based electrode material, the cost and toxicity of nickel foam are also lower, more friendly to environment
It is good.Therefore, the present invention considers from various aspects such as operating procedure, detection performance, operating cost and environmental protections, finds this detection
System is very suitable to be made into a kind of more compact, portable integrated sensing detection device, is applied to phosphoric acid in practical phosphorus-containing wastewater
The real-time detection of hydrogen radical ion concentration has superpower practical application value.
1 one step hydro thermal method of embodiment prepares the foam of area load nano-sheet and three-dimensional flower-shaped hydronium(ion) nickel oxide
Nickel sheet
First by 2.5-3.5 mMs of NiCl2·6H2O, 0.25-0.35 grams of urea and 0.015-0.02 grams of NH4F adds
Enter in the water heating kettle that 100 milliliters are stirred evenly and be transferred in 60-80 milliliters of water, then by the similar foam of the size of wash clean
Nickel sheet (1.2*1.2 centimetres) is put into kettle, 120 degree hydro-thermal 6 hours, then natural cooling.Precipitating, water is collected by centrifugation in upper solution
Nickel sheet after heat is clean with deionized water repeated flushing, then surface can be obtained through 60 degree of oven dryings and be loaded with nano-sheet and flower
The composite foam nickel electrode (3D-Ni HH/NF being labeled as, shown in the region a as shown in figure 1) of valve microspheroidal hydronium(ion) nickel oxide.
The foam nickel electrode piece of the unsupported hydronium(ion) nickel oxide of reference examples 1
In addition to the similar foam nickel sheet (1.2*1.2 centimetres) of the size of wash clean to be put into 60 milliliters of pure water and be transferred to
In 100 milliliters of water heating kettle, other steps are identical as the preparation step of embodiment 1 (to be labeled as NF, the region b institute as shown in figure 1
Show).
SEM and XRD characterization
It will be seen from figure 1 that the material being prepared in embodiment 1 is nano-sheet or three in the Surface Creation of nickel foam
Tie up flower-shaped nickel hydroxide.Fig. 2 is the XRD spectrum of the above material, it can be seen from the figure that due to after hydrothermal synthesis
The intensity at the surface nickel simple substance peak of electrode is excessively high, and other peaks are not easy to show；Therefore, by the suspension after hydrothermal synthesis
Liquid precipitate is detected, and can show the characteristic peak of nickel hydroxide, and then is confirmed and be also capable of forming hydrogen on the surface of electrode
The modification of nickel oxide.
Detection to phosphoric acid hydrogen radical ion
Using NF in 3D-Ni HH/NF in embodiment 1 and reference examples 1 as can self-supporting working electrode, carbon-point is used as to electrode,
Silver-colored silver chlorate (3.5 moles of KCl) places the NaOH(of pH=10 as the three-electrode system that reference electrode forms or includes 1 mM
HPO4 2-) in electrolyte, 0.1V s-1Sweep speed carry out cyclic voltammetry (CV) test.Its result is as shown in fig. 3, it was found that 3D-Ni
HH/NF current signal ratio NF at 1 V is high, is especially containing 1 mM HPO4 2-Solution in current signal reach most
By force, show 3D-Ni HH/NF really and HPO4 2-Electrochemical reaction occurs and generates current signal.
Carry out detection limit, the range of linearity, sensitivity and the determination of response time.
3D-Ni HH/NF and NF electrode slice is put into the NaOH electrolyte of PH=10 respectively, with magnetic stirring apparatus by solution
With the revolving speed agitating solution of 300 rpm, the HPO of different volumes various concentration was just injected rapidly into solution at interval of 30 seconds4 2-It is molten
Liquid.Using chrono-amperometric (I-t) method observation operating current with HPO4 2-The variation that concentration changes.Such detection method is all constant
Voltage carries out under conditions of being 1 V, and the results of property (as shown in Figure 4 and Figure 5) of I-C is calculated according to the test result of I-t.Hair
Existing detection performance of the 3D-Ni HH/NF than NF is good, and specific data are as shown in table 1.
Table 1
In addition, above testing result in the prior art to HPO4 2-The sensor performance comparison detected, such as following table institute
Show:
Bibliography
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As can be seen that electrode material provided by the invention compared with the existing technology in detection of the chronoamperometry to hydrogen phosphate
For method, have the extremely low response time, the broader range of linearity, and sensitivity and detection limit in terms of, also with it is existing
Technology is in same level.
Detection to phosphoric acid hydrogen radical ion interference free performance
By 3D-Ni HH/NF in 3D-Ni HH/NF in embodiment 1 and comparative example 1 be self-supporting working electrode to hydrogen phosphate
The detection of ion interference free performance.
With it is above identical to the detection method of phosphoric acid hydrogen radical ion, equally detect 3D-Ni respectively using chronoamperometry
HH/NF was injected separately into 1 mmoles at 400,500,600,700,800,900,1000 seconds to the anti-interference ability of interfering substance
Your HPO4 2-、NO3 -、SO4 2-、Cl-、HCO3 -、CH3COO-、HPO4 2-, the variation of electric current is observed, finds the curent change of chaff interferent
Opposite HPO4 2-It is very small, show 3D-Ni HH/NF electrode slice to HPO4 2-The anti-interference ability of detection is very strong.Fig. 6 is this
3D-Ni HH/NF electrode slice is to HPO in inventive embodiments 34 2-The I-t of anti-interference detection schemes；The region a in figure is shown
It joined influence of the different interfering ions later to curent change, the region b in figure, it is shown that before interfering ion is added
Current changing rate on every kind of electrode afterwards, it can be seen from the figure that the addition for every kind of interfering ion, 3D-Ni HH/NF
Foam nickel electrode is all significantly less than to current changing rate, variation numerical value is as shown in the table:
As can be seen that the electrode that have passed through after nickel hydroxide modification shows the ability that preferably anti-ion is dry, especially
HCO3 -Ion, 3D-Ni HH/NF only has 1.1% to current changing rate, and NH has reached 3.8% to current changing rate.
To the stability of phosphoric acid hydrogen radical ion detection
In embodiment 1 in 3D-Ni HH/NF and comparative example 1 3D-Ni HH/NF be self-supporting working electrode to hydrogen phosphate from
The Detection of Stability of son.
With it is above identical to the detection method of phosphoric acid hydrogen radical ion, equally using chronoamperometry detect 3D-Ni HH/
NF electrode slice probably injected 5 mMs of HPO to the anti-interference ability of interfering substance at 300 seconds or so into solution4 2-, see
Examine the variation of electric current, find 3D-Ni HH/NF(23.5 hours) stability be almost NF(6.5 hours) 4 times, illustrate 3D-
The stability of Ni HH/NF is greatly improved.Current curve is as shown in Figure 7.
Detection to true phosphorus-containing wastewater
Detection by the 3D-Ni HH/NF in embodiment 1 to phosphate anion in practical phosphorus-containing wastewater, with above to phosphoric acid hydrogen
The detection method of radical ion is identical, equally using chronoamperometry detection 3D-Ni HH/NF electrode slice to true phosphorus-containing wastewater,
Such as petroleum catalyst (HPO in Jiangsu Province4 2-Concentration is 80.1 ppm) and pesticide research institute (HPO4 2-Concentration is 34.1 ppm)
Phosphorus-containing wastewater is detected, and 1 milliliter of authentic sample solution is taken to be added in 10 milliliters of the NaOH electrolyte of pH=10, observation electricity
The variation of stream and HPO is calculated according to I-C fit line equation4 2-Concentration.It was found that repeatability can be up to 108% ± 10 He respectively
144%±23.7。
3D-Ni HH/NF electrode slice is to HPO as can be seen from the above table4 2-High accuracy detection.
Claims (10)
1. a kind of electrode material of nickel foam self-supporting, which is characterized in that be to have using nickel foam as carrier in its area load
Nickel hydroxide.
2. the electrode material of nickel foam self-supporting according to claim 1, which is characterized in that in one embodiment,
The nickel hydroxide is nano-sheet or three-dimensional flower-shaped；Nickel foam porosity > 95%, 200-500 μm of aperture.
3. the preparation method of the electrode material of nickel foam self-supporting described in claim 1, which is characterized in that including walking as follows
It is rapid: by hydrothermal synthesis method nickel foam Surface Creation nickel hydroxide.
4. the preparation method according to claim 4, which is characterized in that in one embodiment, include the following steps: to match
Make containing nickel chloride, urea, ammonium chloride solution, add nickel foam in the solution, carry out hydrothermal synthesis；Synthetic reaction terminates
Afterwards, nickel foam after washing, obtains the electrode material of nickel foam self-supporting；Nickel chloride, urea, ammonium chloride weight ratio be:
0.4-0.8:0.15-0.55:0.01-0.03；100-160 DEG C of the temperature of hydrothermal synthesis, time are 2-10h.
5. the electrode material of nickel foam self-supporting described in claim 1 is in electrochemical method detection water in phosphoric acid hydrogen radical ion
Purposes.
6. purposes according to claim 8, which is characterized in that the detection is using three-electrode system；In a reality
It applies in mode, the electrode material of nickel foam self-supporting is as working electrode, and silver-silver chloride is as reference electrode, carbon-point conduct pair
Electrode.
7. nickel hydroxide is for improving the purposes in foamed nickel electrode material detection water in the performance of phosphoric acid hydrogen radical ion.
8. purposes according to claim 11, which is characterized in that the detection refers to that electrochemical method detects, and root
According to the purposes described in claim 12, which is characterized in that nickel hydroxide is used to improve the current signal strength in detecting, for mentioning
The high detection range of linearity, for reducing the response time in detection process or the anti-interference ability for improving detection process.
9. purposes according to claim 8, which is characterized in that the anti-interference ability refers to anti-inorganic anion interference
Ability.
10. purposes according to claim 9, which is characterized in that the inorganic anion is selected from NO3 -、SO4 2-、Cl-、
HCO3 -Or CH3COO-One or more of.
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