CN108593637B - Label color tape for detecting hydrogen and preparation method thereof - Google Patents
Label color tape for detecting hydrogen and preparation method thereof Download PDFInfo
- Publication number
- CN108593637B CN108593637B CN201810507741.7A CN201810507741A CN108593637B CN 108593637 B CN108593637 B CN 108593637B CN 201810507741 A CN201810507741 A CN 201810507741A CN 108593637 B CN108593637 B CN 108593637B
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- label
- noble metal
- parts
- sensitive material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- G01N21/783—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 for analysing gases
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention relates to the technical field of gas detection, in particular to a label color band for detecting hydrogen and a preparation method thereof. The preparation method comprises the following steps: and modifying noble metal quantum dots on the surface of the hydrogen sensitive material substrate by adopting an ultraviolet light reduction method to obtain the label ribbon for detecting hydrogen. According to the invention, the hydrogen sensitive material reacts with hydrogen to cause changes of optical signals such as emissivity, transmissivity, wavelength and the like, so that the corresponding hydrogen concentration in the environment is detected, and the noble metal quantum dots are modified on the surface of the hydrogen sensitive material by adopting an ultraviolet light reduction method, so that the sensitivity of the label ribbon to hydrogen is improved while the specific surface area of the sensitive layer is increased, and the hydrogen can be adsorbed more quickly and responded.
Description
Technical Field
The invention relates to the technical field of gas detection, in particular to a label color band for detecting hydrogen and a preparation method thereof.
Background
The energy crisis caused by the decrease of fossil energy such as petroleum and coal forces people to aim at renewable clean energy. Hydrogen energy is regarded as a renewable energy source with wide raw material sources, and the hydrogen gas is taken as a high-efficiency clean fuel and reducing gas and is widely applied to various fields such as metallurgy, petrifaction, medical treatment, medicine and the like. However, hydrogen has a low molecular weight and is colorless and odorless, resulting in its easy leakage and imperceptibility. Most of the hydrogen used in industrial production is high-concentration hydrogen, and the limit explosion concentration of the hydrogen in the air is low and the explosion power is high, so that great potential safety hazard is brought when the hydrogen is used, stored and transported. Therefore, people must realize the detection of hydrogen leakage rapidly, safely and reliably by means of highly sensitive detection equipment.
At present, most of commonly used hydrogen sensors are semiconductor type hydrogen sensors, and the sensors are usually externally connected with a current and electric signal processor according to the change of electric signals such as resistance or voltage and the like caused by hydrogen sensitive materials after meeting hydrogen, output signals can be distorted in places with electromagnetic interference, and if the electric spark is caused in a hydrogen atmosphere, the electric spark can be very dangerous. Therefore, the research on the visual hydrogen label color band with low cost and convenient use has important significance due to the problems of inconvenient carrying, low safety coefficient, high cost and the like of the current mainstream hydrogen sensor.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a label ribbon for detecting hydrogen, which adopts an ultraviolet light reduction method to uniformly modify noble metals on the surface of a nanowire, so as to enhance the response of the nanowire to hydrogen, so that the prepared label ribbon can change color in an environment with low hydrogen content, and thus, the visible detection of the hydrogen concentration is realized.
The second purpose of the invention is to provide a label ribbon for detecting hydrogen, which is prepared by the preparation method of the invention, can uniformly modify noble metal on the surface of a nanowire, improve the response speed to hydrogen, has high detection sensitivity, can detect hydrogen as low as 0.1%, has cycle reversibility, and can be reused.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a preparation method of a label ribbon for detecting hydrogen comprises the following steps:
and modifying noble metal quantum dots on the surface of the hydrogen sensitive material substrate by adopting an ultraviolet light reduction method to obtain the label ribbon for detecting hydrogen.
The invention detects the corresponding hydrogen concentration in the environment by utilizing the change of optical signals such as emissivity, transmissivity, wavelength and the like caused by the change of the reaction structure of the hydrogen sensitive material and the hydrogen. The conventional tungsten oxide, molybdenum oxide and vanadium pentoxide have long response time to hydrogen and narrow detection range, and cannot realize quick and visual detection of hydrogen. According to the invention, the ultraviolet light reduction method is adopted, noble metal quantum dots are modified on the surface of the hydrogen sensitive material, so that the sensitivity of the label color band to hydrogen is improved while the specific surface area is increased, and the hydrogen can be adsorbed and responded more quickly.
The noble metal quantum dots are modified by adopting an ultraviolet light reduction method, the reduction time is short, the reduction range is wide, the noble metal quantum dots can be uniformly modified on the surface of the hydrogen sensitive material, and the uniformity and the sensitivity of the label color band are improved.
Preferably, the noble metal includes one or more of Au, Ag, Ru, Rh, Pd, Os, Ir, and Pt. More preferably, the noble metal includes any one of Pd and Pt.
The Pd and Pt quantum dots have the advantages of volume effect, quantum effect and the like, have excellent catalytic effect on hydrogen, and can further improve the gasochromic characteristic of the label color band.
In addition, the Pd or Pt quantum dots can be uniformly modified on the surface of the base material by adopting an ultraviolet light reduction method, and the activity of the prepared label color band on hydrogen is improved, so that the response to the hydrogen is enhanced; and moreover, the ultraviolet light reduction method is adopted, so that the process is simple, the energy consumption is low, and the manufacturing process is pollution-free.
Preferably, the hydrogen sensitive material comprises one or more of molybdenum oxide, tungsten oxide and vanadium pentoxide. More preferably, the hydrogen sensitive material is molybdenum oxide. The substrate is preferably in the form of nanowires, and more preferably in the form of a nanowire paper.
Molybdenum oxide (MoO)3) The material is a wide-gap (3.2eV) transition metal oxide semiconductor material with stable chemical and physical properties, and has excellent gasochromic performance.
Preferably, the method for modifying the noble metal quantum dots on the surface of the hydrogen-sensitive material substrate by adopting the ultraviolet light reduction method comprises the following steps: the solution containing the noble metal compound is evenly dipped on the hydrogen sensitive material substrate and exposed under the ultraviolet light condition. More preferably, the ultraviolet light is 200-280nm ultraviolet light, more preferably 254nm ultraviolet light.
Preferably, when the surface of the hydrogen sensitive material substrate is modified with the Pd quantum dots, the exposure time is 0.5-2h, and preferably 1 h.
Preferably, when the Pt quantum dots are modified on the surface of the hydrogen sensitive material substrate, the exposure time is 4-6h, and preferably 5 h.
Preferably, the method for preparing the solution containing the noble metal compound includes: and dispersing the noble metal compound in a solvent, and stirring in the dark to obtain the solution containing the noble metal compound. More preferably, the noble metal compound includes any one of a Pd compound and a Pt compound. Further preferably, the solvent includes any one of methanol and acetone, preferably methanol. The mixture is preferably stirred for 12 to 48 hours, more preferably 20 to 30 hours, and still more preferably 24 hours in the absence of light.
Preferably, the Pd compound comprises palladium chloride.
Preferably, the Pt compound includes chloroplatinic acid.
The Pd or Pt quantum dots can be modified by adopting two compounds, namely palladium chloride or chloroplatinic acid, so that K, Na and other impurities are prevented from being introduced.
Preferably, the concentration of the noble metal compound in the solution containing the noble metal compound is 0.01 to 0.1mg/mL, preferably 0.03 to 0.08 mg/mL.
As in various embodiments, the concentration of the noble metal compound can be 0.01mg/mL, 0.02mg/mL, 0.03mg/mL, 0.0375mg/mL, 0.04mg/mL, 0.05mg/mL, 0.06mg/mL, 0.07mg/mL, 0.075mg/mL, 0.08mg/mL, and the like.
Preferably, the preparation method of the hydrogen-sensitive material substrate comprises the following steps:
(A) dissolving molybdate in water, adding concentrated nitric acid to obtain a precursor solution A, and reacting at the constant temperature of 200-300 ℃ for 48-120h to obtain a material B;
(B) and cleaning the material B to be neutral, stirring to obtain a dissolving pulp C, pouring into a mould, and drying at the constant temperature of 40-60 ℃ for 12-36h to obtain the molybdenum oxide nanowire paper substrate.
The molybdenum oxide nanowire paper substrate prepared by the method is treated by hydrothermal synthesis, a self-assembly technology and an ultra-long time, so that the crystallinity of the nanowire is better, the length of the nanowire is longer, self-assembly is easier to occur, and the uniformly-grown nanowire paper substrate is obtained.
Preferably, the parts by weight of the molybdate, the water and the concentrated nitric acid are respectively 1-4 parts, 10-50 parts and 2-10 parts. The molybdate is preferably sodium molybdate dihydrate, and the mass concentration of the concentrated nitric acid is 70 +/-2%, and the purity is more than 99%. More preferably, the parts by weight of the molybdate, the water and the concentrated nitric acid are 2-3 parts, 20-40 parts and 8-9 parts respectively.
As in the different embodiments, the parts by mass of molybdate may be 2 parts, 2.42 parts, 2.5 parts, 3 parts, etc.; the mass parts of the water can be 20 parts, 25 parts, 30 parts, 35 parts, 40 parts and the like; the mass parts of the concentrated nitric acid can be 8 parts, 8.25 parts, 8.5 parts, 8.75 parts, 9 parts and the like.
Preferably, the reaction temperature in the step (A) is 260 ℃, and the reaction time is 96 h.
Preferably, the drying temperature in the step (B) is 50 ℃, and the drying time is 24 hours.
The invention also provides the label color band for detecting hydrogen prepared by the preparation method of the label color band for detecting hydrogen.
According to the label ribbon for detecting hydrogen, noble metal quantum dots are uniformly modified on the surface of the nanowire, the response speed of the label ribbon to hydrogen is improved, the detection sensitivity is high, and hydrogen with the concentration as low as 0.1% can be detected.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method, the surface of the nanowire is uniformly decorated with precious metals by adopting an ultraviolet light reduction method, so that the response of the nanowire to hydrogen is enhanced, and the prepared label color band can be subjected to color change in an environment with low hydrogen content, so that the visual detection of the hydrogen concentration is realized;
(2) the preparation method has the advantages of simple process, low energy consumption, no pollution in the preparation process and suitability for large-scale production;
(3) the label color band prepared by the preparation method can uniformly modify noble metal on the surface of the nanowire, improve the response speed to hydrogen, has high detection sensitivity, and can detect hydrogen as low as 0.1%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a photo of a label ribbon for detecting hydrogen, which is obtained by modifying Pd quantum dots on molybdenum oxide nanowire paper according to embodiment 1 of the present invention;
fig. 2 is an XRD chart of a label color band for detecting hydrogen, which is obtained by modifying Pd quantum dots on molybdenum oxide nanowire paper according to embodiment 1 of the present invention;
fig. 3 is an SEM image of a label color band for detecting hydrogen gas obtained by modifying Pd quantum dots on a molybdenum oxide nanowire paper according to embodiment 1 of the present invention;
fig. 4 is a TEM image of a label ribbon for detecting hydrogen obtained by modifying Pd quantum dots on a molybdenum oxide nanowire paper according to embodiment 1 of the present invention;
fig. 5 is a photo of a label ribbon for detecting hydrogen gas, obtained by modifying Pt quantum dots on molybdenum oxide nanowire paper according to embodiment 2 of the present invention;
fig. 6 is an XRD chart of a label color band for detecting hydrogen gas obtained by modifying Pt quantum dots on molybdenum oxide nanowire paper according to embodiment 2 of the present invention;
fig. 7 is an SEM image of a label ribbon for detecting hydrogen gas obtained by modifying Pt quantum dots on a molybdenum oxide nanowire paper according to embodiment 2 of the present invention;
fig. 8 is a TEM image of a label ribbon for detecting hydrogen obtained by modifying Pt quantum dots on a molybdenum oxide nanowire paper according to embodiment 2 of the present invention;
FIG. 9 is a photograph of a real object of the pure molybdenum oxide nanowire paper provided in comparative example 1;
fig. 10 is an EDS energy spectrum of a label ribbon for detecting hydrogen obtained by modifying Pd quantum dots on a molybdenum oxide nanowire paper according to example 1 of the present invention;
fig. 11 is an EDS energy spectrum of a label ribbon for detecting hydrogen gas, which is obtained by modifying Pt quantum dots on molybdenum oxide nanowire fiber paper according to embodiment 2 of the present invention;
FIG. 12 is a graph of the transmittance of light at different wavelengths after reaction of the Pt modified label ribbons prepared at different exposure times with hydrogen;
fig. 13 is a physical photograph of a tag color band for detecting hydrogen obtained by modifying Pd quantum dots on molybdenum oxide nanowire paper according to embodiment 1 of the present invention, where the color of the nanowire paper changes with time under different hydrogen concentrations;
FIG. 14 is a photograph of a sample of pure molybdenum oxide nanowire paper provided in comparative example 1 showing the change in color of the nanowire paper with time at a hydrogen concentration of 1%;
fig. 15 is a time-dependent change curve of the reflectivity of the nanowire paper at different hydrogen concentrations of a tag color band for detecting hydrogen, which is obtained by modifying Pd quantum dots on molybdenum oxide nanowire paper according to embodiment 1 of the present invention;
fig. 16 is a time-dependent change curve of the reflectivity of the nanowire paper at different hydrogen concentrations of a tag color band for detecting hydrogen, which is obtained by modifying Pt quantum dots on molybdenum oxide nanowire paper according to embodiment 2 of the present invention;
fig. 17 is a cycle reversibility test chart of a label color band for detecting hydrogen, which is obtained by modifying Pd quantum dots on molybdenum oxide nanowire paper according to embodiment 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides a preparation method of a label color band for detecting hydrogen, which comprises the following steps:
and modifying noble metal quantum dots on the surface of the hydrogen sensitive material substrate by adopting an ultraviolet light reduction method to obtain the label ribbon for detecting hydrogen.
The invention detects the corresponding hydrogen concentration in the environment by utilizing the change of optical signals such as emissivity, transmissivity, wavelength and the like caused by the change of the reaction structure of the hydrogen sensitive material and the hydrogen. And by adopting an ultraviolet light reduction method, precious metal is modified on the surface of the hydrogen sensitive material, so that the sensitivity of the label ribbon to hydrogen is improved while the specific surface area of the sensitive layer is increased, and the hydrogen can be adsorbed and responded more quickly.
In a preferred embodiment of the invention, the noble metal comprises one or more of Au, Ag, Ru, Rh, Pd, Os, Ir and Pt. More preferably, the noble metal includes any one of Pd and Pt.
In a preferred embodiment of the present invention, the hydrogen sensitive material includes one or more of molybdenum oxide, tungsten oxide, and vanadium pentoxide. Preferably, the hydrogen sensitive material is molybdenum oxide. The substrate is preferably in the form of nanowires, and more preferably in the form of a nanowire paper.
In a preferred embodiment of the present invention, the method for modifying noble metal quantum dots on the surface of the hydrogen-sensitive material substrate by using an ultraviolet light reduction method comprises: the solution containing the noble metal compound is evenly dipped on the hydrogen sensitive material substrate and exposed under the ultraviolet light condition. More preferably, the ultraviolet light is 100-280nm ultraviolet light, more preferably 254nm ultraviolet light.
Preferably, when the surface of the hydrogen sensitive material substrate is modified with the Pd quantum dots, the exposure time is 0.5-2h, and preferably 1 h.
Preferably, when the Pt quantum dots are modified on the surface of the hydrogen sensitive material substrate, the exposure time is 4-6h, and preferably 5 h.
In a preferred embodiment of the present invention, the method for preparing the solution containing the noble metal compound includes: and dispersing the noble metal compound in a solvent, and stirring in the dark to obtain the solution containing the noble metal compound. More preferably, the noble metal compound includes any one of a Pd compound and a Pt compound. Further preferably, the solvent includes any one of methanol and acetone, preferably methanol. The mixture is preferably stirred for 12 to 48 hours, more preferably 20 to 30 hours, and still more preferably 24 hours in the absence of light.
In a preferred embodiment of the present invention, the Pd compound includes palladium chloride.
In a preferred embodiment of the present invention, the Pt compound includes chloroplatinic acid.
In a preferred embodiment of the present invention, the concentration of the noble metal compound in the solution containing the noble metal compound is 0.01 to 0.1mg/mL, preferably 0.03 to 0.08 mg/mL.
In a preferred embodiment of the present invention, the method for preparing the hydrogen-sensitive material substrate comprises:
(A) dissolving molybdate in water, adding concentrated nitric acid to obtain a precursor solution A, and reacting at the constant temperature of 200-300 ℃ for 48-120h to obtain a material B;
(B) and cleaning the material B to be neutral, stirring to obtain a dissolving pulp C, pouring into a mould, and drying at the constant temperature of 40-60 ℃ for 12-36h to obtain the molybdenum oxide nanowire paper substrate.
The molybdenum oxide nanowire paper substrate prepared by the method is treated by hydrothermal synthesis, a self-assembly technology and an ultra-long time, so that the crystallinity of the nanowire is better, the length of the nanowire is longer, self-assembly is easier to occur, and the uniformly-grown nanowire paper substrate is obtained.
In a preferred embodiment of the present invention, the reaction temperature in step (a) is preferably 260 ℃ and the reaction time is preferably 96 hours.
In a preferred embodiment of the present invention, the drying temperature in the step (B) is preferably 50 ℃, and the drying time is preferably 24 hours.
In a preferred embodiment of the invention, the parts by weight of the molybdate, the water and the concentrated nitric acid are respectively 1-4 parts, 10-50 parts and 2-10 parts. The molybdate is preferably sodium molybdate dihydrate, and the mass concentration of the concentrated nitric acid is 70 +/-2%, and the purity is more than 99%. More preferably, the parts by weight of the molybdate, the water and the concentrated nitric acid are 2-3 parts, 20-40 parts and 8-9 parts respectively.
The invention also provides the label color band for detecting hydrogen prepared by the preparation method of the label color band for detecting hydrogen.
According to the label ribbon for detecting hydrogen, the surface of the nanowire is uniformly modified with noble metal, so that the response speed of the sensor to hydrogen is improved, the detection sensitivity is high, and hydrogen with the concentration as low as 0.1% can be detected.
It should be noted that the hydrogen content is described in volume fraction in this document.
Example 1
The preparation method of the label ribbon for detecting hydrogen gas in the embodiment is as follows:
(1) dissolving 2.42g of sodium molybdate dihydrate in 30mL of deionized water, then dripping 6.25mL of concentrated nitric acid (the mass concentration is 70 +/-2%) into the solution, and continuously stirring the solution for 30min to obtain a precursor solution A; transferring the precursor solution A into a clean reaction kettle, placing the reaction kettle in a constant-temperature reaction box at 260 ℃, continuously reacting for 96 hours, and naturally cooling to room temperature to obtain a material B;
(2) washing the material B with deionized water to neutrality to remove MoO3After impurities, the MoO in the solution is removed3Mechanically stirring the nanowires for 24 hours to obtain a dissolving pulp C; pouring the dissolving pulp C into a mould, and drying at the constant temperature of 50 ℃ for 24h to obtain a molybdenum oxide nanowire paper substrate;
(4) 0.003g of PdCl2Pouring the powder into a clean container, adding 80mL of methanol, and magnetically stirring in a dark condition to obtain the PdCl-containing material2The solution of (1);
(5) taking out a proper amount of the solution obtained in the step (4) by using a rubber head dropper, and placing the solution in a small clean beaker; and (3) cutting the substrate obtained in the step (3) into small paper sheets of 1.5cm multiplied by 1.5cm, quickly and uniformly dipping the molybdenum oxide nanowire paper sheets with a clean forceps to obtain a solution in a small beaker, and then placing the small beaker under an ultraviolet lamp of 254nm for exposure for 1h to obtain the label ribbon which is modified with Pd on the molybdenum oxide nanowire paper and is used for detecting hydrogen.
The physical photograph, XRD chart, SEM chart and TEM chart of the label ribbon for detecting hydrogen obtained by modifying Pd quantum dots on the molybdenum oxide nanowire paper prepared in this example are respectively shown in fig. 1 to 4.
Example 2
The preparation method of the label ribbon for detecting hydrogen gas in the embodiment is as follows:
(1) dissolving 2.42g of sodium molybdate dihydrate in 30mL of deionized water, then dripping 6.25mL of concentrated nitric acid (the mass concentration is 70 +/-2%) into the solution, and continuously stirring the solution for 30min to obtain a precursor solution A; transferring the precursor solution A into a clean reaction kettle, placing the reaction kettle in a constant-temperature reaction box at 260 ℃, continuously reacting for 96 hours, and naturally cooling to room temperature to obtain a material B;
(2) washing the material B with deionized water to neutrality to remove MoO3After impurities, the MoO in the solution is removed3Mechanically stirring the nanowires for 24 hours to obtain a dissolving pulp C; pouring the dissolving pulp C into a mould, and drying at the constant temperature of 50 ℃ for 24h to obtain a molybdenum oxide nanowire paper substrate;
(4) pouring 0.006g of chloroplatinic acid powder into a clean container, adding 80mL of methanol, and magnetically stirring under the condition of keeping out of the sun to obtain a chloroplatinic acid-containing solution;
(5) taking out a proper amount of the solution obtained in the step (4) by using a rubber head dropper, and placing the solution in a small clean beaker; and (3) cutting the substrate obtained in the step (3) into small paper sheets of 1.5cm multiplied by 1.5cm, quickly and uniformly dipping the molybdenum oxide nanowire paper sheets with a clean forceps to obtain a solution in a small beaker, and then placing the small beaker under an ultraviolet lamp of 254nm for exposure for 5 hours to obtain the label ribbon which is modified with Pt on the molybdenum oxide nanowire paper and is used for detecting hydrogen.
The real photograph, XRD chart, SEM chart and TEM chart of the label ribbon for detecting hydrogen obtained by modifying Pt quantum dots on the molybdenum oxide nanowire paper prepared in this example are respectively shown in fig. 5 to 8.
Example 3
This example is substantially the same as example 2 except that the concentration of chloroplatinic acid was 0.08 mg/mL.
Example 4
This example is essentially the same as example 1 except that the concentration of palladium chloride is 0.03 mg/mL.
Example 5
This example is substantially the same as example 1 except that the molybdenum oxide nanowires were prepared using 2 parts by mass, 20 parts by mass and 8 parts by mass of molybdate, deionized water and concentrated nitric acid, respectively.
Example 6
This example is substantially the same as example 1 except that the molybdenum oxide nanowires were prepared using 3 parts by mass, 40 parts by mass and 9 parts by mass of molybdate, deionized water and concentrated nitric acid, respectively.
Example 7
This example is substantially the same as example 2 except that the uv exposure time is 1 h.
Example 8
This example is substantially the same as example 2 except that the uv exposure time was 3 hours. Comparative example 1
The photo of the pure molybdenum oxide nanowire paper without the noble metal modification is shown in fig. 9.
Experimental example 1
To further demonstrate the success of noble metal modification on the molybdenum oxide nanowire paper in the examples of the present invention, the prepared label ribbons were subjected to EDS spectroscopy analysis using examples 1 and 2 as examples, and the results are shown in fig. 10-11, which are EDS spectroscopy spectra of the label ribbons prepared in examples 1 and 2, respectively.
As can be seen from the figure, in examples 1 and 2 of the present invention, Pd and Pt were uniformly modified on the molybdenum oxide nanowire paper, respectively.
Experimental example 2
To further illustrate the effect of uv exposure time on the sensitivity of the label ribbon, using example 2, example 7 and example 8 and a set substantially the same as example 2 except that the exposure time is 0h, the test results are shown in fig. 12, which is the transmittance of Pt-modified label ribbons prepared at different exposure times to light of different wavelengths after reaction with hydrogen having a volume fraction of 5%, compared to the effect of exposure time on the sensitivity of hydrogen when noble metal quantum dots are modified by uv reduction.
As can be seen from the figure, the transmittance of the label color band with the exposure time of 5h for different wavelengths is significantly reduced, that is, the darker the color of the label color band, the more significant the detection effect.
Experimental example 3
In order to comparatively illustrate the sensitivity of the noble metal-modified molybdenum oxide nanowire paper and the pure molybdenum oxide nanowire paper prepared in the examples and the comparative examples of the present invention to hydrogen, the change of the color of the Pd-modified label ribbon molybdenum oxide nanowire paper with different hydrogen concentrations over time is tested by taking example 1 as an example. The specific operation is as follows: the label ribbons were placed in hydrogen atmosphere at certain concentrations (0.1%, 5%, and 100%) and photographed under the same conditions for certain times, and a physical photograph of the color of the nanowire paper in example 1 with different hydrogen concentrations as a function of time is shown in fig. 13.
As can be seen in fig. 13, at the same time, the color of the label ribbon darkens as the hydrogen gas volume fraction increases; the color of the label ribbon gradually darkens over time at the same volume fraction of hydrogen.
For comparison, the pure molybdenum oxide nanowire paper prepared in comparative example 1 is placed in an environment with a hydrogen volume fraction of 1%, and as can be seen from fig. 14, the color change is not obvious within 1min, further illustrating the high sensitivity of the label color band prepared in the invention to hydrogen.
To further illustrate the response of the noble metal-modified molybdenum oxide nanowire paper prepared in examples 1 and 2 of the present invention to hydrogen in hydrogen atmosphere with different concentrations, the time-dependent change of the reflectance of the nanowire paper with different hydrogen concentrations was measured, and the test results are shown in fig. 15-16, which are the time-dependent change curves of the reflectance of the fiber paper with different hydrogen concentrations for the molybdenum oxide nanowire paper of examples 1 and 2, respectively.
As can be seen from the figure, the label color band obtained by modifying noble metals such as Pd and Pt on the molybdenum oxide nanowire paper has gradually reduced reflectivity along with the increase of time under the condition of the same hydrogen concentration; at the same time, the reflectivity is gradually reduced along with the increase of the hydrogen concentration, and the hydrogen concentration can be detected as a standard working curve.
Experimental example 4
To further illustrate that the label ink ribbon of the present invention has excellent reversibility, taking example 1 as an example, after the label ink ribbon prepared in example 1 is used for hydrogen detection, the label ink ribbon is placed in an annealing furnace and annealed at 200 ℃ for 2 hours in an air atmosphere, and the nanowire paper of the label ink ribbon returns to the original color. And (3) performing reflectivity test on the label color bands before and after annealing under the same hydrogen concentration, repeating the reflectivity test for multiple times, and obtaining a test result shown in figure 17.
As can be seen from the figure, the color of the label ribbon can be recovered after the annealing treatment, the reflectance to the hydrogen atmosphere can be recovered, and the performance is almost unchanged after the multiple use, so that the label ribbon has excellent cycle reversibility.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A preparation method of a label color band for detecting hydrogen is characterized by comprising the following steps:
modifying noble metal quantum dots on the surface of the hydrogen sensitive material substrate by adopting an ultraviolet light reduction method to obtain the label ribbon for detecting hydrogen;
the ultraviolet light is 254nm ultraviolet light;
the hydrogen sensitive material is molybdenum oxide, and the base material is in the form of nanowire paper;
the preparation method of the hydrogen-sensitive material substrate comprises the following steps:
(A) dissolving molybdate in water, adding concentrated nitric acid to obtain a precursor solution A, and reacting at the constant temperature of 200-300 ℃ for 48-120h to obtain a material B;
(B) cleaning the material B to be neutral, stirring to obtain a dissolving pulp C, pouring the dissolving pulp C into a mould, and drying at the constant temperature of 40-60 ℃ for 12-36h to obtain a molybdenum oxide nanowire paper substrate;
the noble metal includes any one of Pd and Pt;
the method for modifying the noble metal quantum dots on the surface of the hydrogen sensitive material substrate by adopting an ultraviolet light reduction method comprises the following steps: uniformly dipping a solution containing a noble metal compound on a hydrogen-sensitive material substrate, and exposing under an ultraviolet light condition;
when the surface of the hydrogen sensitive material substrate is modified with Pd quantum dots, the exposure time is 0.5-2 h;
when Pt quantum dots are modified on the surface of the hydrogen sensitive material substrate, the exposure time is 4-6 h;
the concentration of the noble metal compound is 0.03-0.08 mg/mL;
the noble metal compound includes any one of palladium chloride and chloroplatinic acid;
the parts by weight of the molybdate, the water and the concentrated nitric acid are respectively 1-4 parts, 10-50 parts and 2-10 parts.
2. The method of preparing a label ribbon for detecting hydrogen gas according to claim 1, wherein the method of preparing the solution containing the noble metal compound comprises: and dispersing the noble metal compound in a solvent, and stirring in the dark to obtain the solution containing the noble metal compound.
3. The method of preparing a label ribbon for detecting hydrogen gas according to claim 2, wherein the solvent includes any one of methanol and acetone.
4. The method for preparing a label ribbon for detecting hydrogen according to claim 2, wherein the label ribbon is stirred for 12-48 hours in the absence of light.
5. The method for preparing a label color band for detecting hydrogen according to claim 4, wherein the label color band is stirred for 20-30 hours in the absence of light.
6. The method for preparing a label ribbon for detecting hydrogen gas according to claim 1, wherein in the step (A), the reaction is carried out at 260 ± 10 ℃ for 96 ± 5 h.
7. The method for preparing a label ribbon for detecting hydrogen gas according to claim 1, wherein in the step (B), the label ribbon is dried at a constant temperature of 50 ± 5 ℃ for 24 ± 4 h.
8. The method for preparing a label ribbon for detecting hydrogen gas according to claim 1, wherein the parts by mass of the molybdate, the water and the concentrated nitric acid are 2-3 parts, 20-40 parts and 8-9 parts, respectively.
9. A label ribbon for detecting hydrogen produced by the method of producing a label ribbon for detecting hydrogen of any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810507741.7A CN108593637B (en) | 2018-05-24 | 2018-05-24 | Label color tape for detecting hydrogen and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810507741.7A CN108593637B (en) | 2018-05-24 | 2018-05-24 | Label color tape for detecting hydrogen and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108593637A CN108593637A (en) | 2018-09-28 |
| CN108593637B true CN108593637B (en) | 2021-12-10 |
Family
ID=63629039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810507741.7A Active CN108593637B (en) | 2018-05-24 | 2018-05-24 | Label color tape for detecting hydrogen and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108593637B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110132502B (en) * | 2019-05-22 | 2021-05-25 | 北京航天试验技术研究所 | Active material capable of indicating existence of hydrogen through color change |
| CN113218936B (en) * | 2021-06-07 | 2021-09-10 | 江苏欣诺科催化剂有限公司 | Method for detecting purity of potassium osmate |
| CN115711713B (en) * | 2021-08-19 | 2023-09-12 | 中国石油化工股份有限公司 | Hydrogen leakage detection material and preparation method and application thereof |
| CN114570922B (en) * | 2022-03-17 | 2023-06-02 | 中国石油大学(华东) | Nanometer material capable of rapidly and repeatedly detecting hydrogen and preparation method thereof |
| CN114505058B (en) * | 2022-03-17 | 2023-06-20 | 中国石油大学(华东) | Metal organic framework material-assisted high-sensitivity hydrogen detection nano material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106198648A (en) * | 2016-09-14 | 2016-12-07 | 扬州大学 | A kind of preparation method of room-temperature hydrogen sensor |
| CN106517332A (en) * | 2016-10-26 | 2017-03-22 | 湖北大学 | Preparation method of Pd quantum dot modified molybdenum oxide nanofiber paper |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101734733B1 (en) * | 2015-12-30 | 2017-05-11 | 현대자동차주식회사 | Color changeable hydrogen sensor based on molybdenum oxide and method of manufacturing the same |
-
2018
- 2018-05-24 CN CN201810507741.7A patent/CN108593637B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106198648A (en) * | 2016-09-14 | 2016-12-07 | 扬州大学 | A kind of preparation method of room-temperature hydrogen sensor |
| CN106517332A (en) * | 2016-10-26 | 2017-03-22 | 湖北大学 | Preparation method of Pd quantum dot modified molybdenum oxide nanofiber paper |
Non-Patent Citations (2)
| Title |
|---|
| Kaori Nishizawa等.Low-temperature chemical fabrication of Pt-WO3 gasochromic switchable films using UV irradiation.《Solar Energy Materials and Solar Cells》.2017,第170卷 * |
| Rapid hydrogen sensing response and aging of α-MoO3 nanowires paper sensor;Xiantao Luo等;《International Journal of Hydrogen Energy》;20170210;第42卷(第12期);第8399-8401页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108593637A (en) | 2018-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108593637B (en) | Label color tape for detecting hydrogen and preparation method thereof | |
| Ramgir et al. | TiO2/ZnO heterostructure nanowire based NO2 sensor | |
| Mani et al. | A highly selective and wide range ammonia sensor—Nanostructured ZnO: Co thin film | |
| Shinde et al. | Synthesis of ZnO nanorods by spray pyrolysis for H2S gas sensor | |
| Wang et al. | V‐shaped tin oxide nanostructures featuring a broad photocurrent signal: an effective visible‐light‐driven photocatalyst | |
| Pawar et al. | Synthesis of multi-dimensional ZnO nanostructures in aqueous medium for the application of gas sensor | |
| Wang et al. | Controlled synthesis of Sn-based oxides via a hydrothermal method and their visible light photocatalytic performances | |
| Deng et al. | A novel ammonia gas sensors based on p-type delafossite AgAlO2 | |
| Mahmoudabadi et al. | Synthesis of Ag/TiO2 nanocomposite via plasma liquid interactions: Improved performance as photoanode in dye-sensitized solar cell | |
| KR101704122B1 (en) | Hydrogen detecting coloration sensor | |
| Shen et al. | Facile synthesis of Au–SnO 2 hybrid nanospheres with enhanced photoelectrochemical biosensing performance | |
| Liang et al. | Morphology-dependent photocatalytic and gas-sensing functions of three-dimensional TiO 2–ZnO nanoarchitectures | |
| Bai et al. | Synthesis of novel BiVO4/Cu2O heterojunctions for improving BiVO4 towards NO2 sensing properties | |
| KR20170027200A (en) | Chemochromic nanoparticles, method for manufacturing the same, and hydrogen sensor comprising the same | |
| Hoa et al. | An effective H 2 S sensor based on SnO 2 nanowires decorated with NiO nanoparticles by electron beam evaporation | |
| Devi et al. | SILAR-coated Mg-doped ZnO thin films for ammonia vapor sensing applications | |
| Pilliadugula et al. | Effect of pH dependent morphology on room temperature NH3 sensing performances of β-Ga2O3 | |
| Zhen et al. | Ultra-high response and low temperature NO2 sensor based on mesoporous SnO2 hierarchical microtubes synthesized by biotemplating process | |
| Jiang et al. | Preparation and gas-sensing performance of GO/SnO2/NiO gas-sensitive composite materials | |
| Xie et al. | Facile synthesis and superior ethyl acetate sensing performance of Au decorated ZnO flower-like architectures | |
| KR20130093306A (en) | Copper(ii) oxide nanonods coated with palladium, a preparation method thereof, and gas sensor using the same | |
| CN111562155B (en) | Detection method of sulfur ion concentration | |
| CN109916965A (en) | It is a kind of using FTO electro-conductive glass as the ZnO nano cluster gas sensor of electrode member | |
| Li et al. | A highly stable and sensitive ethanol sensor based on Ru-decorated 1D WO 3 nanowires | |
| Raj et al. | Improved ammonia vapor sensing properties of Al-doped ZnO nanoparticles prepared by sol-gel process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |