CN108408778A - A kind of preparation method and application of molybdenum oxide - Google Patents
A kind of preparation method and application of molybdenum oxide Download PDFInfo
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- CN108408778A CN108408778A CN201810348576.5A CN201810348576A CN108408778A CN 108408778 A CN108408778 A CN 108408778A CN 201810348576 A CN201810348576 A CN 201810348576A CN 108408778 A CN108408778 A CN 108408778A
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- 229910000476 molybdenum oxide Inorganic materials 0.000 title claims abstract description 52
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims abstract description 20
- 239000006228 supernatant Substances 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 11
- 108010024636 Glutathione Proteins 0.000 claims abstract description 10
- 229960003180 glutathione Drugs 0.000 claims abstract description 10
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000004737 colorimetric analysis Methods 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000011088 calibration curve Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 23
- 150000001413 amino acids Chemical class 0.000 abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 238000001514 detection method Methods 0.000 abstract description 5
- 238000011017 operating method Methods 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 238000001139 pH measurement Methods 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 235000001014 amino acid Nutrition 0.000 description 9
- 229940024606 amino acid Drugs 0.000 description 9
- 239000007853 buffer solution Substances 0.000 description 9
- 229940043379 ammonium hydroxide Drugs 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- XPFJYKARVSSRHE-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].[Na+].OC(=O)CC(O)(C(O)=O)CC(O)=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XPFJYKARVSSRHE-UHFFFAOYSA-K 0.000 description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 3
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 description 3
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 3
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 description 3
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004475 Arginine Substances 0.000 description 2
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 2
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- 229920006221 acetate fiber Polymers 0.000 description 2
- 235000004279 alanine Nutrition 0.000 description 2
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 2
- 235000009582 asparagine Nutrition 0.000 description 2
- 229960001230 asparagine Drugs 0.000 description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
- MURGITYSBWUQTI-UHFFFAOYSA-N fluorescin Chemical compound OC(=O)C1=CC=CC=C1C1C2=CC=C(O)C=C2OC2=CC(O)=CC=C21 MURGITYSBWUQTI-UHFFFAOYSA-N 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 235000013922 glutamic acid Nutrition 0.000 description 2
- 239000004220 glutamic acid Substances 0.000 description 2
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- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
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- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- MWOROEBOHIXGTN-UHFFFAOYSA-N N[Mo]=O Chemical compound N[Mo]=O MWOROEBOHIXGTN-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 238000000502 dialysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
- G01N21/80—Indicating pH value
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N2021/6417—Spectrofluorimetric devices
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Plasma & Fusion (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a kind of preparation method and application of molybdenum oxide, the method is：Glutathione, molybdate and ammonium hydroxide are added in a kettle, is uniformly mixed, after mixed liquor hydro-thermal reaction, is centrifuged, obtains the supernatant containing molybdenum oxide；Molybdenum oxide prepared by the present invention can be used for measuring highly acid pH.Molybdenum oxide preparation method of the present invention is simple, molybdenum oxide nano material optical property obtained is stablized, detection method is environmentally protective, of low cost, whole process is not related to complicated chemical synthesis process and cumbersome operating procedure, common metal ion and amino acid not will produce interference to the measurement of pH.
Description
Technical field
The invention belongs to nano materials and analytical chemistry to be combined field, and in particular to a kind of preparation method of molybdenum oxide and
Using.
Background technology
It is well known that under strongly acidic conditions（pH<4）Most of biology is difficult existence.At the same time, in strong acidic condition
Under can grow some microorganisms, such as acidophil and helicobacter pylori, these bacteriums can cause the infection of threat to life.This
Outside, some enteropathogens（Such as Escherichia coli）It can also survive well under the acid condition of pH 2-4.Therefore, exploitation prison
Surveying the probe of highly acid pH is particularly important.
However most pH probes reported（Mainly organic fluorescence molecule and fluorescin）PH is mainly based upon to cause
The structure change of its functional group's carboxyl and hydroxyl is typically suitable for the pH ranges of 4-8 and 8-12.Because in strong acidic condition
Under, these pH probes functional groups will inactivate, and protein is also denaturalized.
In order to overcome the bottleneck of the above probe, the fluorescent molecular of some nitrogen-containing functional groups be exploited for replacing containing carboxyl and
The fluorescent molecular of hydroxyl, although this can measure the pH of highly acid, these fluorescent moleculars often refer to complicated synthesis
Process, which greatly limits its applications.
Invention content
For deficiencies of the prior art, the object of the present invention is to provide a kind of preparation method of molybdenum oxide, solutions
It is certainly currently used for measuring the problem of the fluorescent molecular synthesis complexity of highly acid pH.
The present invention also provides application of the molybdenum oxide of preparation in measuring acid pH.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of molybdenum oxide, specially：Glutathione, molybdate and ammonium hydroxide are added in a kettle, is uniformly mixed,
Mixed liquor is centrifuged after 150 ~ 250 DEG C of hydro-thermal reactions, obtains the supernatant containing molybdenum oxide.
The present invention uses hydro-thermal method one-step synthesis molybdenum oxide, the molybdenum oxide of synthesis to can be used as pH probes, in the above-mentioned methods,
Glutathione is reducing agent, and molybdate is precursor, provides molybdenum source, ammonium hydroxide provides alkaline environment, and molybdenum oxide surface can be made to modify
Amino, molybdenum oxide nano material is more stable after modifying amino, is applied to acid pH and detects, and is conducive to improve sensitivity and accurate
Property.
Preferably, the hydro-thermal reaction time is 34 ~ 46h.Time too short reaction is incomplete, time too long generation nano particle
Become larger.
Preferably, the mass ratio of ammonia is 1 ~ 1.5 in glutathione, molybdate and ammonium hydroxide:1:0.2~0.3.
Preferably, in mixed liquor molybdate a concentration of 0.015 ~ 0.02M.
Preferably, molybdate is sodium molybdate or ammonium molybdate.
Application the present invention also provides the molybdenum oxide prepared using the above method as pH probes in measuring acid pH.
Molybdenum oxide nano material prepared by the method for the present invention is under condition of acidic pH, with the reduction of pH, the six of surface
Valence molybdenum content reduces, and pentavalent molybdenum content increases, and increases to show molybdenum oxide nano material near-infrared visible absorbance peak, simultaneously
Fluorescence intensity reduces.Wherein, using ranging from the 1.0 ~ 6.0 of fluorescence spectrometry acid pH, the range of colorimetric method for determining pH is
1.0~4.5。
When using fluorescence spectrometry acid pH, pH and the standard curve of fluorescence intensity need to be established, and obtain regression equation,
The fluorescence intensity of acid solution to be measured is substituted into regression equation, you can quantitatively obtain the pH value of acid solution to be measured.Wherein
The method for building up of standard curve is existing conventional method, and the present invention provides following reference method：
（1）Prepare different pH value, concentration be 0.1mol/L citric acid-sodium citrate buffer solution；
（2）Pipette 0.1mL molybdenum oxide nano material original solutions（The supernatant centrifuged）In colorimetric cylinder, preparation is added
Buffer solution is settled to 5mL, is pipetted in part solution to fluorescence cuvette after mixing, in excitation wavelength 310nm, launch wavelength
At 395nm, fluorescence intensity is measured, is that ordinate draws standard curve using pH as abscissa, fluorescence intensity.
Wherein, 8 ~ 15min is mixed after constant volume, and molybdenum oxide nano material is made to be come into full contact with buffer solution.
It, can be by standard song in order to faster more directly judge the variation of pH in the change procedure for monitoring pH value of solution to be measured
Collimation method and colorimetric method are used in combination, and the variation range of pH is prejudged by colorimetric method, passes through calibration curve method Accurate Determining pH.
Wherein colorimetric method, the present invention provide following reference method：Acetate fiber paper is cut into the small side of 2 × 2cm sizes
Block is immersed in the original solution of molybdenum oxide nano material after 2min, and taking-up is placed in PVC board, is dried for use；Acidity to be measured is molten
Drop waits for 30min on filter paper drying, with molybdenum oxide nano material, observes its color change, and with standard color range pair
Than sxemiquantitative judges the pH value range of solution to be measured.
Compared with prior art, the present invention has the advantages that：
1. the molybdenum oxide nano material fluorescence probe used in detection method can preserve steadily in the long term, optical property is stablized；
2. detection method green and environmental protection, whole process are not involved with poisonous and harmful chemical reagent；It is of low cost, whole process
In the expensive chemical reagent and instrument that are not related to；Method is simple, and whole process is not involved with complicated chemistry and closes
At process and cumbersome operating procedure；
3. detection method high sensitivity, selectivity is good, testing result is accurate and reliable, common metal ion and amino acid are to pH's
Measurement not will produce interference；
4. fluorescence and colorimetric method are combined by the present invention, colorimetric anticipation, fluorescence Accurate Determining may be implemented.
Description of the drawings
Fig. 1 is fluorescence spectra of the molybdenum oxide nano material under condition of different pH in embodiment 1；
Fig. 2 is the fluorescence intensity that molybdenum oxide nano material acts under the conditions of pH 2.5 and 5.0 pH respectively with different metal ions
Figure.
Fig. 3 is that the fluorescence that molybdenum oxide nano material and different aminoacids act under the conditions of pH 2.5 and 5.0 pH respectively is strong
Degree figure.
Fig. 4 is the high power transmission electron microscope picture for the molybdenum oxide that embodiment 1 obtains.
Specific implementation mode
With reference to specific embodiment, invention is further described in detail.
One, the preparation of molybdenum oxide nano material
Embodiment 1
The method that the present embodiment prepares molybdenum oxide is as follows：
（1）Glutathione, sodium molybdate and ammonium hydroxide are added in a kettle, is uniformly mixed, in glutathione, sodium molybdate and ammonium hydroxide
The mass ratio of ammonia is 1.2:1:0.24, a concentration of 0.02M of sodium molybdate after mixing；
（2）Mixed liquor after mixing is heated to reaction 40h at 200 DEG C, passes through hydro-thermal method one-step synthesis molybdenum oxide；
（3）After centrifugation, the supernatant of the nano material containing molybdenum oxide is obtained.
The supernatant for the nano material containing molybdenum oxide that the method for the present invention obtains can be purified further, and method is：By supernatant
PH is adjusted to neutrality, is then dialysed using bag filter, removes impurity therein, obtains pure molybdenum oxide stoste.Fig. 4 is the present embodiment
The high power transmission electron microscope picture for the molybdenum oxide that supernatant obtains after dialysis purification, drying, average grain diameter is about 2.8nm.
Since the supernatant containing molybdenum oxide is for when measuring acid pH, the impurity such as ammonium hydroxide therein not to interfere with the survey of pH
Fixed, therefore, the present invention does not make further purification to the supernatant after centrifugation.
Embodiment 2
The method that the present embodiment prepares molybdenum oxide is as follows：
（1）It is added glutathione, ammonium molybdate and ammonium hydroxide in a kettle, the quality of ammonia in glutathione, ammonium molybdate and ammonium hydroxide
Than being 1.5:1:0.2, a concentration of 0.018M of ammonium molybdate after mixing are uniformly mixed；
（2）Mixed liquor after mixing is heated to reaction 45h at 250 DEG C, passes through hydro-thermal method one-step synthesis molybdenum oxide；
（3）After centrifugation, the supernatant of the nano material containing molybdenum oxide is obtained.
Two, the molybdenum oxide nano material of preparation is used for the measurement of acid pH
（One）Establish standard curve
The method for building up of standard curve is as follows：
（1）Prepare different pH value, concentration be 0.1mol/L citric acid-sodium citrate buffer solution, wherein pH value is respectively
1.0,1.2,1.4,1.6,1.8,2.0,2.2,2.4,2.6,2.8,3.0,3.2,3.4,3.6,3.8,4.0,4.2,4.4,4.6,
4.8,5.0,5.5,6.0；
（2）Pipette the molybdenum oxide nano material original solution of the preparation of 0.1mL embodiments 1（That is supernatant）It is corresponding to add in colorimetric cylinder
The buffer solution for entering above-mentioned preparation is settled to 5mL, is pipetted in part solution to fluorescence cuvette after mixing 10min, in excitation wavelength
At 310nm, launch wavelength 395nm, fluorescence intensity is measured, is that ordinate draws standard curve using pH as abscissa, fluorescence intensity
（As shown in Figure 1）.
According to the standard curve of foundation, regression equation, which is calculated, is：Y=365.40 + 162.02X.
（Two）The measurement of acid solution pH to be measured
The molybdenum oxide nano material original solution of the preparation of 0.1mL embodiments 1 is pipetted in colorimetric cylinder, acid solution to be measured is added
（Hydrochloric acid solution）, be settled to 5mL, after mixing 10min, pipette in part solution to fluorescence cuvette, excitation wavelength 310nm,
At launch wavelength 395nm, fluorescence intensity is measured, the fluorescence intensity measured is substituted into regression equation, acidity to be measured is calculated
The pH of solution is 3.50.
Above-mentioned acid solution to be measured is directly detected using pH meter, it is 3.52 and detection method to measure its pH
As a result it approaches.
In actual test, the situation of change of pH value of solution to be measured is monitored for convenience, and it is to be measured molten can to first pass through colorimetric method anticipation
The pH ranges of liquid, method are：Acetate fiber paper is cut into the blockage of 2 × 2cm sizes, is then immersed in molybdenum oxide nanometer material
In the original solution of material after 2min, taking-up is placed in PVC board, is dried for use；By different pH solution drop in it is drying, have molybdenum oxide
On the filter paper of nano material, 30min is waited for, observe its color change.Within the scope of pH 4.5-1.0, the color of filter paper is with pH's
Reduction gradually becomes navy blue from faint yellow.
According to the method described above, acid solution to be measured is dropped on the filter paper dried, passes through color contrast, you can sxemiquantitative is sentenced
The pH ranges of disconnected solution to be measured.
Three, the influence of metal ion and amino acid to test
Configure pH 5.0, a concentration of 0.1mol/L citric acid-sodium citrate buffer solutions；0.1 mL is pipetted in 30 colorimetric cylinders
Molybdenum oxide nano material original solution prepared by embodiment 1（Supernatant）With 4.8 mL citric acid-sodium citrate buffer solutions, then distinguish
It is corresponding that 0.1 mL H are added2O, the metal ion or amino acid of various concentration mixes 10min.Metal ion includes 0.1 mol/L
（It is not particularly illustrated, all indicates ultimate density）Na+ 、K+, 1 mmol/L Ca2+、Cd2+、Mn2+、Cr3+, 0.5 mmol/L Mg2 +、Zn2+、Ba2+、Pb2+、Co2+, 0.1 mmol/L Cu2+、Al3+, 0.01 mmol/L Ag+、Fe2+、Fe3+；Amino acid includes 0.1
Mol/L arginine（Arg）, glycine（Gly）, threonine（Thr）, leucine（Leu）, alanine（Ala）, histidine（His）、
Cysteine（Cys）, tyrosine（Tyr）, serine（Ser）, methionine（Met）, asparagine（Asn）, glutamic acid（Glu）；
0.1 mol/L glucose（Glc）.
Configure pH 2.5, a concentration of 0.1mol/L citric acid-sodium citrate buffer solutions；0.1 is pipetted in 30 colorimetric cylinders
Molybdenum oxide nano material original solution prepared by mL embodiments 1（Supernatant）With 4.8 mL citric acid-sodium citrate buffer solutions, then
It is separately added into 0.1 mL H2O, the metal ion or amino acid of various concentration mixes 10min.Metal ion includes 0.1 mol/L
（It is not particularly illustrated, all indicates ultimate density）Na+ 、K+, 1 mmol/L Ca2+、Cd2+、Mn2+、Cr3+, 0.5 mmol/L Mg2 +、Zn2+、Ba2+、Pb2+、Co2+, 0.1 mmol/LCu2+、Al3+, 0.01 mmol/L Ag+、Fe2+、Fe3+；Amino acid includes 0.1
Mol/L arginine, glycine, threonine, leucine, alanine, histidine, cysteine, tyrosine, serine, methionine,
Asparagine, glutamic acid；0.1 mol/L glucose.
It after above-mentioned solution mixing, takes part to correspond to respectively and is added into fluorescence cuvette, in 310 nm of excitation wavelength, transmitting
At 395 nm of wavelength, fluorescence intensity is measured, as a result as shown in Figures 2 and 3.
By Fig. 2 and Fig. 3 it is found that metal ion and amino acid to aoxidize Mo determination acid pH fluorescence intensity influence almost
It can ignore.As it can be seen that metal ion and amino acid not will produce interference to the measurement of acid pH of the present invention.
Finally illustrate, the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although with reference to compared with
Good embodiment describes the invention in detail, it will be understood by those of ordinary skill in the art that, it can be to the skill of the present invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the right of invention.
Claims (9)
1. a kind of preparation method of molybdenum oxide, which is characterized in that glutathione, molybdate and ammonium hydroxide are added in a kettle, mixes
It closes uniformly, mixed liquor is centrifuged after 150 ~ 250 DEG C of hydro-thermal reactions, obtains the supernatant containing molybdenum oxide.
2. the preparation method of molybdenum oxide according to claim 1, which is characterized in that the hydro-thermal reaction time is 34 ~ 46h.
3. the preparation method of molybdenum oxide according to claim 1, which is characterized in that glutathione, molybdate and ammonium hydroxide
The mass ratio of middle ammonia is 1 ~ 1.5:1:0.2~0.3.
4. the preparation method of molybdenum oxide according to claim 3, which is characterized in that molybdate is a concentration of in mixed liquor
0.015~0.02M。
5. the preparation method of molybdenum oxide according to claim 1, which is characterized in that molybdate is sodium molybdate or ammonium molybdate.
6. the application of molybdenum oxide prepared by any one of such as claim 1 to 5 the method in measuring acid pH.
7. application according to claim 6, which is characterized in that ranging from the 1.0 ~ 6.0 of the acid pH.
8. application according to claim 6, which is characterized in that it is ordinate to establish by abscissa, fluorescence intensity of pH
Standard curve, and regression equation is obtained, the fluorescence intensity of acid solution to be measured is substituted into regression equation, you can obtain to be measured
The pH value of acid solution.
9. application according to claim 8, which is characterized in that it is molten to measure acidity to be measured in conjunction with colorimetric method and calibration curve method
The pH value of liquid.
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| CN110713212A (en) * | 2019-11-19 | 2020-01-21 | 西南大学 | Preparation method of gamma-MnOOH nano rod and product thereof |
| CN111690406A (en) * | 2020-07-09 | 2020-09-22 | 长江师范学院 | Preparation method and application of optical property-adjustable molybdenum oxide quantum dots |
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| CN105366725A (en) * | 2014-08-29 | 2016-03-02 | 中国科学院大连化学物理研究所 | Method for hydro-thermally synthesizing MoS<2> nanoflower with sulfur-containing biological reagent as sulfur source |
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| CN105366725A (en) * | 2014-08-29 | 2016-03-02 | 中国科学院大连化学物理研究所 | Method for hydro-thermally synthesizing MoS<2> nanoflower with sulfur-containing biological reagent as sulfur source |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110713212A (en) * | 2019-11-19 | 2020-01-21 | 西南大学 | Preparation method of gamma-MnOOH nano rod and product thereof |
| CN111690406A (en) * | 2020-07-09 | 2020-09-22 | 长江师范学院 | Preparation method and application of optical property-adjustable molybdenum oxide quantum dots |
| CN111690406B (en) * | 2020-07-09 | 2022-12-23 | 长江师范学院 | Preparation method and application of optical property-adjustable molybdenum oxide quantum dots |
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