CN115219419A - LSPR hydrogen detection device based on palladium nano-ring array - Google Patents
LSPR hydrogen detection device based on palladium nano-ring array Download PDFInfo
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- CN115219419A CN115219419A CN202210569030.9A CN202210569030A CN115219419A CN 115219419 A CN115219419 A CN 115219419A CN 202210569030 A CN202210569030 A CN 202210569030A CN 115219419 A CN115219419 A CN 115219419A
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Abstract
The invention belongs to the technical field of hydrogen detection, and provides an LSPR hydrogen detection device based on a palladium nanoring array. The optical detection unit is used for transmitting light emitted by the light source to the optical probe through the optical fiber, so that the light is irradiated to the palladium nano ring array and the substrate in the sensing unit in parallel through the optical probe, the palladium nano ring array generates a local surface plasma resonance phenomenon, a strong resonance absorption peak appears on a spectrum, the transmitted light and the scattered light passing through the palladium nano ring array and the substrate are transmitted to the spectrophotometer through the optical fiber in the data recording and processing unit to measure a scattering or extinction spectrum, and the computer terminal performs data analysis processing on the resonance absorption peak in the spectrum measured by the spectrophotometer so as to realize hydrogen concentration detection. The invention has the advantages of no spark, no influence from electromagnetic interference, remote data reading and no influence from severe environment.
Description
Technical Field
The invention belongs to the technical field of hydrogen detection, and particularly relates to an LSPR hydrogen detection device based on a palladium nano-ring array.
Background
Hydrogen, as a new energy source that is pollution-free, renewable and sustainable, has been widely used in aerospace, fuel cells, medical applications, petroleum exploration, chemical processing, and other fields. However, hydrogen gas has a minimum molecular weight, is extremely diffusive and permeable, is colorless and odorless, is very easy to leak and is not easily perceived, and in addition, hydrogen gas has low ignition energy (0.018 mJ), high combustion heat (285.8 kJ/mol) and a wide explosive concentration range (4% -75%), making it a highly flammable and explosive hazardous gas. Therefore, the detection of hydrogen is of great significance to industrial manufacturing and safety of daily life.
At present, conventional hydrogen sensors based on electrochemical characteristics have been developed and widely used in various fields. The electrochemical hydrogen sensor is characterized in that hydrogen and a sensing electrode generate electrochemical reaction to cause charge transmission or change of electrical properties, so that the detection of the hydrogen concentration is realized. For example, chinese patent CN201110335970.3 discloses a three-electrode solid electrolyte hydrogen sensor and a hydrogen concentration measuring method using the same, by measuring electromotive force E between a first measuring electrode and a reference electrode 1 Electromotive force E between the second measuring electrode and the reference electrode 2 And calculating the ratio of the two electromotive forces, and further calculating to obtain the hydrogen concentration. However, such electrochemical hydrogen sensors have errors due to potential sparking, non-specific hydrogen selectivity, and even interference from ambient temperature. The hydrogen sensors in other applied patents have complex structures (such as CN201921101612.4, a solid electrolyte-based electrochemical hydrogen sensor) or adopt liquid electrolytes (such as CN202110400850.0, a hydrogen sensor and its application), and have the problems of leakage corrosion and the like, and the cost is high.
Therefore, in view of the shortcomings of the conventional electrochemical hydrogen sensor in safety and gas selectivity, it is an urgent need to invent a safe and sensitive hydrogen detection device capable of realizing hydrogen detection.
Disclosure of Invention
In order to solve the above problems, the present invention provides an LSPR (localized surface plasmon resonance) hydrogen detection apparatus based on a palladium nanoring array, which has the advantages of no spark generation, no electromagnetic interference, remote data reading, and no adverse environment effect.
The technical purpose of the invention is realized by the following technical scheme:
an LSPR hydrogen detection device based on a palladium nanoring array comprises an optical detection unit, a sensing unit and a data recording and processing unit.
The optical detection unit comprises a light source, an optical fiber and an optical probe; the sensing unit comprises a substrate, a palladium nano-ring array and a gas chamber with controllable gas components; the data recording and processing unit comprises a spectrophotometer, an optical probe, an optical fiber and a computer terminal.
In the sensing unit, a palladium nano ring array grows on a substrate, and the substrate is vertically placed in a gas chamber with controllable gas components; the front end and the rear end of the gas chamber with controllable gas components are provided with mounting holes for mounting optical probes, and the optical probes are oppositely arranged on two sides of the substrate; the side face of the gas chamber with controllable gas components is provided with an interface for introducing hydrogen to be detected.
In the optical detection unit, an optical probe is arranged in a mounting hole on one side, close to the palladium nano-ring array, of the gas chamber with controllable gas components, and a light source is connected with the optical probe through an optical fiber.
In the data recording and processing unit, the optical probe is arranged in a mounting hole on the gas chamber with controllable gas components, which is close to one side of the substrate, and the spectrophotometer is connected with the optical probe through an optical fiber; the computer terminal is connected with the spectrophotometer through an optical fiber.
Light emitted by a light source in the optical detection unit is transmitted to an optical probe through an optical fiber and is irradiated onto a palladium nano ring array and a substrate in the sensing unit in parallel through the optical probe, the palladium nano ring array generates a Local Surface Plasmon Resonance (LSPR) phenomenon, a strong resonance absorption peak appears on a spectrum, transmitted light and scattered light passing through the palladium nano ring array and the substrate are transmitted to a spectrophotometer through the optical probe in the data recording and processing unit through the optical fiber to measure a scattering or extinction spectrum, and a computer terminal performs data analysis processing on the resonance absorption peak in the spectrum measured by the spectrophotometer so as to realize hydrogen concentration detection.
Further, the light source spectrum range is 190 nm-2500 nm, and the light source is a halogen lamp, an LED lamp, a mercury lamp or a sodium lamp;
further, the optical fiber in the optical detection unit is a single-core optical fiber;
further, the substrate is a glass sheet;
further, the palladium nanoring array structure is a hexagonal periodic array structure;
further, the gas chamber with controllable gas components is filled with nitrogen and hydrogen.
The invention has the beneficial effects that:
1. the hydrogen detection method adopts the LSPR optical principle to detect the hydrogen, is not interfered by external factors such as environmental temperature, humidity and the like, and has extremely high stability;
2. the palladium nano ring array is pollution-free, the whole palladium nano ring array is in a hexagonal periodic array shape, compared with other nano array structures, the coupling strength of the hexagonal palladium nano ring array structure is higher, the gas sensitivity is improved, the rapid concentration measurement is realized, the measurement range is wide, and the palladium nano ring array only acts with hydrogen, cannot be interfered by other gases such as carbon monoxide, carbon dioxide and methane, and has high specificity;
3. the invention analyzes the resonance absorption peak in the spectrum measured by the spectrophotometer through the computer terminal, not only can realize the detection of hydrogen, but also can construct the numerical relation between the change of the characteristics of the position, the intensity, the line width and the like of the resonance absorption peak in the spectrum and the hydrogen concentration, thereby realizing the accurate detection of the hydrogen concentration;
4. the invention has simple structure, low cost, small volume, light weight and convenient carrying, can meet the requirements of laboratories, factories and the like on hydrogen detection and is convenient for popularization.
Drawings
Fig. 1 is a schematic diagram of the overall structure of an LSPR hydrogen detection device based on a palladium nanoring array.
Fig. 2 (a) -2 (c) are schematic diagrams of palladium nanoring arrays on glass sheets at different angles.
In the figure: 1, a light source; 2, an optical fiber a;3, an optical probe a;4, a palladium nanoring array; 5 a substrate; 6 gas chamber with controllable gas component; 7 an optical fiber b;8, a spectrophotometer; 9 a computer terminal; 10 glass sheets; 11 hexagonal palladium nanoring arrays; 12 individual palladium nanoring outer diameters; 13 single palladium nanoring inner diameter; 14 a single palladium nanoring thickness; 15, the distance between the centers of two adjacent palladium nanorings; 16 optical probe b.
Detailed Description
The following further describes the specific embodiments of the present invention with reference to the drawings and technical overturns.
The invention provides an LSPR hydrogen detection device based on a palladium nanoring array, which comprises an optical detection unit, a sensing unit and a data recording and processing unit, wherein the optical detection unit is used for detecting hydrogen in a hydrogen sensor; the optical detection unit comprises a light source 1, an optical fiber a2 and an optical probe a3; the sensing unit comprises a palladium nano ring array 4, a substrate 5 and a gas chamber 6 with controllable gas components; the data recording and processing unit comprises an optical probe b16, an optical fiber b7, a spectrophotometer 8 and a computer terminal 9. The method comprises the following specific steps:
the optical detection unit is used for transmitting light with different wavelengths emitted by the light source 1 to the optical probe a3 through the optical fiber a2 in the optical detection unit, so that the light is irradiated onto the palladium nano ring array 4 and the substrate 5 in parallel through the optical probe 3, when the frequency of incident photons is matched with the overall vibration frequency of positive ion core excited conduction electrons fixed in the palladium nano particle lattice on the palladium nano ring array 4, the palladium nano particles can generate strong absorption effect on photon energy, a phenomenon of Local Surface Plasmon Resonance (LSPR) can occur, at the wavelength of the resonance, the palladium nano particles can strongly absorb and scatter light, and a strong resonance absorption peak can occur on a spectrum. The wavelength at which LSPR occurs depends on the size and shape of the nanoparticleAnd material, but also on its surroundings, i.e. its dielectric properties. Thus, by tracking the LSPR wavelength, any change in the nanoparticle itself (by a change in the size shape or electronic properties of the material) or its surroundings (by a change in the properties of the surrounding dielectric) can be detected. The former sensing principle may be referred to as direct plasma sensing, and the latter may be referred to as indirect plasma sensing. The invention adopts direct plasma sensing and consists of hydride-forming metal nano-particle palladium. The palladium nanoring array 4 reacts with hydrogen in the gas chamber 6 with controllable gas components, and when hydrogen is absorbed into palladium nano metal lattices, palladium nanoparticles form PdH x And the palladium expands, and the dielectric constant of the metal palladium changes, so that the resonance absorption peak of the LSPR shifts, the optical probe b16 in the data recording and processing unit transmits the transmission light and the scattering light passing through the palladium nanoring array 4 and the substrate 5 to the spectrophotometer 8 through the optical fiber b7 to measure a scattering or extinction spectrum, and the computer terminal 9 detects the hydrogen concentration by analyzing the changes of the features such as the position, the intensity and the line width of the LSPR resonance absorption peak in the scattering or extinction spectrum measured by the spectrophotometer 8.
Further, the spectral range of the light source 1 in the optical detection unit is 190nm to 2500nm, the light source 1 is a halogen lamp, an LED lamp, a mercury lamp, or a sodium lamp, and the optical fiber a2 in the optical detection unit is a single-core optical fiber.
Furthermore, the substrate 5 is made of a glass sheet, and is used for integrally supporting the palladium nano-ring array 4 and facilitating transmission and scattering of incident light.
Further, the gas chamber 6 with controllable gas composition is filled with nitrogen and hydrogen, and the concentration of released hydrogen is precisely controlled by a flow controller.
Further, the computer terminal 9 constructs a numerical relationship between the change of the characteristic of the position, intensity, line width and the like of the resonance absorption peak in the spectrum and the hydrogen concentration by the change of the characteristic of the position, intensity, line width and the like of the resonance absorption peak in the spectrum measured by the spectrophotometer 8, thereby realizing the accurate detection of the hydrogen concentration.
Fig. 2 (a) -2 (c) are schematic diagrams of palladium nanoring arrays, the entire palladium nanoring array is formed by periodically arranging hexagonal palladium nanoring arrays 11 located above a glass sheet 10, the outer diameter 12 of a single palladium nanoring is 200nm, the inner diameter 13 of the single palladium nanoring is 150nm, the thickness 14 of the single palladium nanoring is 100nm, the central distance 15 between two adjacent palladium nanorings is 350nm, and the size of the entire palladium nanoring array is 50 μm × 50 μm.
In this embodiment, the preparation method of the palladium nanoring array includes:
firstly, selecting a glass sheet with the size of 1cm multiplied by 1cm, then sequentially washing the glass sheet for 10 minutes by using liquid detergent, deionized water, acetone and isopropanol, wherein the solution is pre-washed by the solution of the next step for each solution replacement, and blowing the glass sheet by using nitrogen after the solution replacement is finished;
spin-coating a layer of PMMA glue on a cleaned glass sheet by adopting a spin-coating process, uniformly coating the PMMA glue on the glass sheet at a low rotation speed of 400rpm for 9 seconds, uniformly coating the PMMA glue on the glass sheet at a high rotation speed of 3000rpm for 30 seconds, placing the glass sheet on a constant-temperature heating table at 150 ℃ for drying for 10 minutes to volatilize a solvent in a PMMA coating, and then cooling to normal temperature to prepare a substrate on which the photoresist is spin-coated;
controlling an electron beam to draw a palladium nanoring structure pattern to be exposed on the etching glue by a pattern generator;
and horizontally fixing a glass sheet coated with the electron beam etching glue PMMA on a workpiece table by using a copper sheet, and performing electron beam exposure after focusing and field calibration. The exposure area is controlled by NPGS, and the exposure parameters are set as follows: the exposure voltage is 30keV, the exposure current is 100pA, the exposure dose is 180fc, and then development is carried out in a developing solution for 60 seconds; using mixed solution prepared by methyl isobutyl ketone (MIBK) and Isopropanol (IPA) according to the volume ratio of 1:3 as developing solution, and fixing and cleaning for 20-30 seconds by using ionized water, alcohol or isopropanol solvent which does not dissolve the photoresist after the development is finished;
sputtering a layer of palladium on a sample for generating a photoetching pattern by adopting a magnetron sputtering process, and setting the sputtering environment to be a vacuum degree lower than 1.5 multiplied by 10 -4 Pa, and setting: sputtering power of 140W, sputtering pressure of 0.8Pa and sputtering time of 1.5 hours to obtain a glass sheet containing a palladium film;
and finally, putting the glass sheet deposited with the palladium film into an acetone solution, ultrasonically cleaning the glass sheet in an ultrasonic cleaner for 5 minutes to remove the PMMA layer, taking out the glass sheet, drying the glass sheet by using nitrogen, and then putting the glass sheet on a constant-temperature heating table at the temperature of 100 ℃ to dry the glass sheet for 3 minutes to obtain the regularly arranged palladium nano-ring array structure.
The LSPR hydrogen detection device based on the palladium nanoring array can be used for monitoring the hydrogen concentration of a cooling system or a power transformer of a nuclear power station and the like, and has wide application prospect in hydrogen safety detection in various fields of aerospace engineering, oil exploration, metallurgical oil refineries, cryogenic cooling, chemical processing, automobiles and the like.
Claims (10)
1. The LSPR hydrogen detection device based on the palladium nanoring array is characterized by comprising an optical detection unit, a sensing unit and a data recording and processing unit;
the optical detection unit comprises a light source, an optical fiber and an optical probe; the sensing unit comprises a substrate, a palladium nanoring array and a gas chamber with controllable gas components; the data recording and processing unit comprises a spectrophotometer, an optical probe, an optical fiber and a computer terminal;
in the sensing unit, a palladium nanoring array grows on a substrate, and the substrate is vertically placed in a gas chamber with controllable gas components; mounting holes are formed in the front end and the rear end of the gas chamber with controllable gas components and used for mounting optical probes, and the optical probes are oppositely arranged on the two sides of the substrate; the side surface of the gas chamber with controllable gas components is provided with an interface for introducing hydrogen to be detected;
in the optical detection unit, an optical probe is arranged in a mounting hole on the side, close to the palladium nanoring array, of the gas chamber with controllable gas components, and a light source is connected with the optical probe through an optical fiber;
in the data recording and processing unit, the optical probe is arranged in a mounting hole on one side, close to the substrate, of the gas chamber with controllable gas components, and the spectrophotometer is connected with the optical probe through an optical fiber; the computer terminal is connected with the spectrophotometer through an optical fiber;
light emitted by a light source in the optical detection unit is transmitted to the optical probe through an optical fiber and is irradiated onto the palladium nano ring array and the substrate in the sensing unit in parallel through the optical probe, the phenomenon of Local Surface Plasma Resonance (LSPR) occurs in the palladium nano ring array, a resonance absorption peak appears on a spectrum, transmitted light and scattered light passing through the palladium nano ring array and the substrate are transmitted to a spectrophotometer through the optical probe in the data recording and processing unit through the optical fiber to measure a scattering or extinction spectrum, and a computer terminal performs data analysis processing on the resonance absorption peak in the spectrum measured by the spectrophotometer so as to realize hydrogen concentration detection.
2. The LSPR hydrogen detection device based on palladium nanoring array according to claim 1, wherein the light source spectrum range is 190 nm-2500 nm, and the light source is halogen lamp, LED lamp, mercury lamp or sodium lamp.
3. An LSPR hydrogen gas detection device based on palladium nanoring array as claimed in claim 1 or 2, wherein said palladium nanoring array structure is hexagonal periodic array structure.
4. An LSPR hydrogen gas detection device based on palladium nanoring array according to claim 1 or 2, characterized in that the optical fiber in the optical detection unit is single core optical fiber.
5. An LSPR hydrogen gas detection device based on palladium nanoring array according to claim 3, wherein the optical fiber in the optical detection unit is single core optical fiber.
6. An LSPR hydrogen detection device based on palladium nanoring array according to claim 1, 2 or 5, characterized in that the substrate is a glass sheet.
7. The LSPR hydrogen detection device based on palladium nanoring array of claim 3, wherein the substrate is a glass sheet.
8. The LSPR hydrogen detection device based on palladium nanoring array of claim 4, wherein the substrate is a glass sheet.
9. An LSPR hydrogen detection device based on palladium nanoring array according to claim 1 or 2 or 5 or 7 or 8, characterized in that the gas chamber with controllable gas composition is filled with nitrogen and hydrogen.
10. An LSPR hydrogen detection device based on palladium nanoring array according to claim 3, characterized in that the gas chamber with controllable gas composition is filled with nitrogen and hydrogen.
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| DE102021127227A1 (en) | 2021-10-20 | 2023-04-20 | Endress+Hauser Conducta Gmbh+Co. Kg | Sensor for measuring a pH value |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102021127227A1 (en) | 2021-10-20 | 2023-04-20 | Endress+Hauser Conducta Gmbh+Co. Kg | Sensor for measuring a pH value |
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