CN113155904A - High-sensitivity hydrogen sensor for air environment and preparation method thereof - Google Patents
High-sensitivity hydrogen sensor for air environment and preparation method thereof Download PDFInfo
- Publication number
- CN113155904A CN113155904A CN202110144024.4A CN202110144024A CN113155904A CN 113155904 A CN113155904 A CN 113155904A CN 202110144024 A CN202110144024 A CN 202110144024A CN 113155904 A CN113155904 A CN 113155904A
- Authority
- CN
- China
- Prior art keywords
- sealed cavity
- hydrogen
- hydrogen sensor
- palladium
- conductive
- 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.)
- Granted
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (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 Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention discloses a high-sensitivity hydrogen sensor used in an air environment and a preparation method thereof, wherein the high-sensitivity hydrogen sensor comprises a drying unit, a sensing unit and an external circuit; the sensing unit comprises a sealed cavity and a sensing assembly arranged in the sealed cavity, the sensing assembly comprises an insulating substrate arranged at the bottom of the sealed cavity, a palladium cluster film arranged on the upper surface of the insulating substrate and two conductive microelectrodes arranged at two ends of the palladium cluster film, two wiring terminals are arranged on the sealed cavity, one ends of the wiring terminals in the sealed cavity are connected with the conductive microelectrodes through leads, and one ends of the wiring terminals outside the sealed cavity are connected with an external circuit through leads; the sealed cavity is communicated with the drying unit, and the drying unit is provided with an air inlet. The invention adopts the seepage conductive film composed of palladium clusters, can sense and monitor the change of the hydrogen concentration in the air in real time, has the advantages of high sensitivity and short response time, and does not need heating and pre-separation of hydrogen in the operation process.
Description
Technical Field
The invention relates to the field of sensors, in particular to a high-sensitivity hydrogen sensor used in an air environment and a preparation method thereof.
Background
The hydrogen has the advantages of high calorific value, no pollution, convenient production and the like, is a novel energy resource and is concerned by people, and in addition, the hydrogen has wide application in the fields of industrial and agricultural production, medical treatment, scientific research and the like. However, since hydrogen is colorless, odorless, flammable and explosive, the presence of hydrogen in the environment cannot be sensed at all by human perception systems alone. Therefore, the safe use of hydrogen becomes the final elbow brake for large-scale popularization and use of hydrogen energy. A reliable hydrogen sensing and alarming device is developed, effective safety guarantee is provided for hydrogen utilization and hydrogen-related industries, and the most effective way for solving the toggle is provided.
Materials capable of responding to hydrogen, such as metallic palladium and oxides of some metals, are not lacking in nature. Based on the hydrogen sensitive materials, people design different sensing structures, and develop various hydrogen sensing alarm devices by means of measurement means such as electricity, electrochemistry, catalytic combustion, optics and the like. Among them, the hydrogen sensor using a palladium thin film as a sensing device is most commonly used. For example, the publication No. CN105510400B of "a hydrogen sensor based on a carbon nanotube and palladium composite film" disclosed in the chinese patent document sequentially includes, from inside to outside, a P-type silicon substrate, a carbon nanotube, a metal palladium film and two metal electrodes, wherein the carbon nanotube is uniformly arranged in a longitudinal and a transverse direction, and the two metal electrodes are both strip-shaped and are symmetrically arranged on the upper surface of the metal palladium film. However, such sensors have long response times and low resolution; the electrochemical sensor which is used for introducing hydrogen into an electrochemical solution and measuring an electrochemical reaction signal of the hydrogen through the reference electrode can only maintain a very narrow measurement range although the response time can be effectively shortened; in addition, when part of the metal oxide is used as a hydrogen sensitive material, hydrogen reacts with oxygen on the surface of the material to change the impedance property of the material, but the reaction needs external heating; similarly, hydrogen sensors measured by a catalytic combustion method need to work in a high-temperature environment of 200-300 ℃, certain risks exist in the use process, and the hydrogen sensors have the defect of poor selectivity; in addition, many other types of hydrogen sensors have a response capability only to pure hydrogen, and when the sensors are in an air environment, the interference of other gases in the air cannot be eliminated, so that the hydrogen needs to be separated from the air in advance for subsequent quantitative measurement of the sensors.
Generally, the existing hydrogen sensing technology has the defects of long response time, narrow measurement range, poor selectivity, poor interference resistance and the like, and the sensing and alarming requirements on various occasions of hydrogen consumption, hydrogen involvement and hydrogen monitoring are difficult to meet.
Disclosure of Invention
The invention aims to overcome the defects of long response time, narrow measurement range, poor selectivity, poor anti-interference and the like of a hydrogen sensing technology in the prior art and the problem that the sensing alarm requirement of various hydrogen using, hydrogen relating and hydrogen monitoring occasions is difficult to meet.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-sensitivity hydrogen sensor used in air environment comprises a drying unit, a sensing unit and an external circuit; the sensing unit comprises a sealed cavity and a sensing assembly arranged in the sealed cavity, the sensing assembly comprises an insulating substrate arranged at the bottom of the sealed cavity, a palladium cluster film arranged on the upper surface of the insulating substrate and two conductive microelectrodes arranged at two ends of the palladium cluster film, two wiring terminals are arranged on the sealed cavity, one ends of the wiring terminals are positioned in the sealed cavity, one ends of the wiring terminals are positioned outside the sealed cavity, one ends of the wiring terminals in the sealed cavity are connected with the conductive microelectrodes through leads, and one ends of the wiring terminals outside the sealed cavity are connected with an external circuit through leads; the sealed cavity is communicated with the drying unit, and an air inlet is formed in the drying unit.
Preferably, the material of the insulating substrate is selected from flexible or rigid insulating materials, and the stable resistivity of the insulating substrate is more than or equal to 109Omega.m; the flexible insulating material is selected from one of polyimide, polydimethylsiloxane and polyethylene terephthalate; the rigid insulating material is selected from one of quartz, glass, ruby, sapphire, resin, and a single crystal silicon wafer with a silicon oxide insulating layer.
Preferably, the shape of the conductive microelectrode is an interdigital electrode or a spiral electrode, the thickness of the conductive microelectrode is 50 nm-10 μm, and the distance between the two conductive microelectrodes is 2-100 μm.
Preferably, the material of the conductive microelectrode is one selected from gold, silver, copper, iron, aluminum and indium tin oxide.
Preferably, the diameter distribution of the palladium clusters in the palladium cluster thin film is 1 to 10nm, and the average nearest neighbor distance between the palladium clusters is 0.5 to 5 nm.
Preferably, the coverage of the palladium cluster thin film is 30 to 95%, and the resistance of the palladium cluster thin film is 50k Ω to 1G Ω.
Preferably, the external circuit comprises a power supply connected through a lead, an electric signal measuring device and a programmable and visual output device which can convert the measured electric signal into a hydrogen concentration signal and visually output and display the hydrogen concentration signal.
Preferably, the drying unit comprises a drying tank body and a drying agent arranged in the drying tank body, the drying tank body is provided with a plurality of air inlets, and the drying tank body is communicated with the sealed cavity.
The invention also provides a preparation method of the hydrogen sensor, which comprises the following steps:
(1) preparing an insulating substrate;
(2) printing a conductive microelectrode on the surface of the insulating substrate;
(3) depositing a palladium cluster film between the conductive microelectrodes;
(4) placing the insulating substrate on which the palladium cluster film is deposited in a sealed cavity, connecting the conductive microelectrode with one end of the wiring terminal in the sealed cavity by using a lead respectively, and connecting one end of the wiring terminal outside the sealed cavity with an external circuit by using the lead;
(5) assembling a drying unit to enable the drying unit to be communicated with the sealed cavity to obtain the assembled hydrogen sensor;
(6) placing the assembled hydrogen sensor in hydrogen environments with different concentrations, recording the macroscopic resistance change of the palladium cluster film in the hydrogen environments with different concentrations through an external circuit, fitting the response relation, and inputting the macroscopic resistance change into the external circuit to finish the calibration of the hydrogen sensor;
(7) and placing the calibrated hydrogen sensor in an air environment to be measured, and measuring the hydrogen concentration through an external circuit.
Preferably, the palladium cluster thin film in the step (3) is deposited by adopting a method of nano printing, physical vapor deposition, chemical vapor deposition or block self-assembly.
The hydrogen sensor adopts the seepage conductive film consisting of small-size palladium clusters, the transmission mode of electrons among the clusters in the palladium cluster film is quantized tunneling jump, the tunneling probability and the intrinsic property of a tunnel junction among the clusters show an exponential decay relation, and the intrinsic property of the tunnel junction is directly determined by parameters such as a potential barrier filling material, a potential barrier dielectric constant, a potential barrier geometric dimension and the like, so the macro resistance of the cluster film is very sensitive to the weak change of the type and the component of the filling material among the clusters. For example, filling a certain insulating substance (such as pure water) between clusters can greatly change the resistance of the cluster thin film. Therefore, the hydrogen sensor manufactured by adopting the palladium cluster film as the sensitive element is placed in an air environment mixed with hydrogen, mixed gas diffuses into the sealed cavity in the sensing unit through the drying unit, and the drying unit can absorb original water vapor in the mixed gas, so that interference on subsequent detection is avoided. As shown in fig. 2, after the mixed gas diffuses into the sealed cavity, hydrogen molecules and oxygen molecules are adsorbed on the surface of the palladium cluster, at this time, a bias voltage is applied to two sides of the conductive microelectrode by a power supply in an external circuit, palladium cluster d electrons in the film are excited to a higher energy level under the action of the bias voltage, the hydrogen molecules and the oxygen molecules are easily dissociated into active hydrogen atoms and active oxygen atoms respectively, then the hydrogen molecules and the oxygen molecules are catalytically synthesized into water molecules, the generated water molecules belong to purified water, and are enriched on the surface of the palladium cluster and filled between the clusters, so that tunneling impedance of electron transmission is enhanced, and the macro resistance of the palladium cluster film is increased. Therefore, the resistance change of the palladium cluster film is monitored in real time through an electric signal measuring device in an external circuit, and the change of the hydrogen concentration in the air environment can be sensed.
The hydrogen sensor can sense and monitor the change of the hydrogen concentration in the air in real time, has the advantages of high sensitivity and short response time, does not need heating in the operation process, does not need to separate the hydrogen in advance, can be directly applied to the air environment, and is suitable for various occasions of using hydrogen, involving hydrogen and monitoring hydrogen.
Therefore, the invention has the following beneficial effects:
(1) the hydrogen concentration change in the air can be sensed and monitored in real time, the hydrogen concentration monitoring system has the advantages of high sensitivity and short response time, and provides safe and reliable guarantee for hydrogen utilization, hydrogen involvement and hydrogen monitoring industries and places;
(2) the sensor core device adopts a high-impedance palladium cluster film, and the device has low power consumption and is in the micro-nano watt level;
(3) the palladium cluster film does not generate a large amount of joule heat during electric conduction, and the sensor does not need to be heated during working, so that potential safety hazards caused by high temperature are avoided;
(4) can directly work in the air environment without the operation procedures of gas pre-separation and the like.
Drawings
FIG. 1 is a schematic diagram of a hydrogen sensor according to the present invention;
in the figure: 1 a sealed cavity, 2 an insulating substrate, 3 palladium cluster films, 4 conductive microelectrodes, 5 wiring terminals, 6 external circuits and 7 a drying unit;
FIG. 2 is a basic operation diagram of the hydrogen sensor of the present invention;
FIG. 3 is a graph showing the real-time variation of the resistance of the palladium cluster thin film in example 1 during deposition;
FIG. 4 is a transmission electron micrograph of a palladium cluster thin film in example 1;
FIG. 5 is a graph showing the real-time change of the resistance of the hydrogen sensor in example 1 in response to hydrogen of different concentrations;
FIG. 6 is a calibration curve of the hydrogen sensor in example 1;
FIG. 7 is a graph showing the change in resistance of the hydrogen sensor in example 1 in response to an unknown concentration of hydrogen;
FIG. 8 is a calibration curve of the hydrogen sensor in example 2;
fig. 9 is a calibration curve of the hydrogen sensor in example 3.
Detailed Description
The invention is further described with reference to the following detailed description and accompanying drawings.
In the present invention, all equipment and materials are commercially available or commonly used in the art, and the methods used in the present invention are conventional in the art unless otherwise specified.
As shown in fig. 1, a highly sensitive hydrogen sensor for use in an air environment includes a drying unit 7, a sensing unit, and an external circuit 6.
The sensing unit comprises a sealed cavity 1 and a sensing assembly arranged in the sealed cavity, wherein the sensing assembly comprises an insulating substrate 2 arranged at the bottom of the sealed cavity, a palladium cluster film 3 arranged on the upper surface of the insulating substrate and two conductive microelectrodes 4 arranged at two ends of the palladium cluster film. The left side wall of the sealed cavity is provided with two wiring terminals 5, one end of each wiring terminal is located in the sealed cavity, one end of each wiring terminal is located outside the sealed cavity, one end of each wiring terminal in the sealed cavity is connected with the conductive microelectrode through a wire, one end of each wiring terminal outside the sealed cavity is connected with an external circuit through a wire, and the external circuit comprises a power supply, an electric signal measuring device and a programmable and visual output device, wherein the power supply, the electric signal measuring device and the programmable and visual output device are connected through wires, and the programmable and visual output device can convert measured electric signals into hydrogen concentration signals and visually output and display the hydrogen concentration signals.
The right side wall of the sealed cavity is provided with a connecting through hole, the drying unit comprises a stainless steel drying tank body and a silica gel drying agent arranged in the drying tank body, the drying tank body is provided with an installation part matched with the connecting through hole in the sealed cavity, the installation part is clamped in the connecting through hole, the drying tank body is arranged on the side wall outside the sealed cavity and the surface of the installation part in the sealed cavity is provided with a plurality of air inlets with the diameter of 1 mm, and the drying tank body is communicated with the sealed cavity through the air inlets in the installation part.
Example 1:
a preparation method of the high-sensitivity hydrogen sensor comprises the following steps:
(1) preparing an insulating substrate: selecting flat-surface epoxy resin covered with polyimide as insulating substrate with stable resistivity of 1019Ω·m；
(2) Printing a conductive microelectrode on the surface of an insulating substrate: coating a layer of thin adhesive on the surface of an insulating substrate, adhering a layer of copper foil with the thickness of 15 mu m on the surface of the insulating substrate to ensure that an electrode conducting layer is stably attached to the surface of the insulating substrate, and manufacturing an interdigital electrode with the gap of 100 mu m as a conducting microelectrode by adopting a mask corrosion method;
(3) depositing a palladium cluster film between the conductive microelectrodes: generating a stable palladium cluster beam by adopting a magnetron plasma gas gathering method, depositing the stable palladium cluster beam into gaps of the interdigital conductive microelectrodes, measuring the resistance among the conductive microelectrodes in real time in the deposition process, and stopping deposition until the palladium cluster film resistance reaches a preset value, wherein the preset value is 1 MOmega; the evolution curve of the palladium cluster film resistance along with the deposition time is shown in fig. 3, the photomicrograph of the palladium cluster film is shown in fig. 4, the average cluster particle size is 5nm, the average nearest neighbor distance between palladium clusters is 1nm, and the coverage rate of the palladium cluster film is 44.56%;
(4) placing the insulating substrate on which the palladium cluster film is deposited in a sealed cavity, connecting the conductive microelectrode with one end of the wiring terminal in the sealed cavity by using a lead, and connecting one end of the wiring terminal outside the sealed cavity with an external circuit by using the lead, so as to realize real-time monitoring of the palladium cluster film macro-resistance by the external circuit; during connection, two ends of an enameled wire with the diameter of 50 micrometers are respectively welded at the inner end of the wiring terminal cavity and the pin of the interdigital conductive microelectrode in the sealed cavity; connecting an external circuit and the outer end of the terminal cavity by utilizing a BNC-to-alligator clamp cable outside the sealed cavity;
(5) assembling a drying unit, namely clamping the mounting part of the drying tank body in a connecting through hole on the side wall of the sealed cavity, so that the drying unit is communicated with the sealed cavity to obtain the assembled hydrogen sensor;
(6) the assembled hydrogen sensor is sequentially placed in an air environment with hydrogen concentrations of 1000ppm, 2000ppm, 3000ppm, 5000ppm, 10000ppm and 12000ppm, the resistance change of the palladium cluster film is measured in real time through an electric signal measuring device in an external circuit, as shown in fig. 5, the resistance average value under different hydrogen concentrations is taken as a response resistance value, and the resistance average value of the palladium cluster film before each section of hydrogen response is taken as a common resistance value, and the relative resistance change is obtained according to calculation:
corresponding to different hydrogen concentrations one by one, drawing a calibration curve, as shown in fig. 6, and fitting a polynomial to obtain a calibration relation as follows: hydrogen concentration 1.43 × 106X (relative resistance change)2+20253 × relative resistance change
Inputting the hydrogen sensor into a programmable and visual output device in an external circuit to finish the calibration of the hydrogen sensor;
(7) placing the calibrated hydrogen sensor in an air environment to be measured, and reading the hydrogen concentration through a programmable and visual output device in an external circuit; the resistance change of the palladium cluster thin film is shown in fig. 7, the relative resistance change is about 0.065797, the response starts within about 1 second, the response equilibrium is reached within about 10 seconds, and the hydrogen concentration in the current environment is displayed and read from the programmable and visual output device to be about 8000 ppm.
Example 2:
when the palladium cluster thin film is deposited in the step (3) of the embodiment 2, the preset resistance value is 50k Ω, and the coverage rate of the palladium cluster thin film is 85%; the average cluster particle size was 7nm, the average nearest neighbor distance between palladium clusters was 0.5nm, and the rest was the same as in example 1.
Example 3:
when the palladium cluster thin film is deposited in the step (3) of example 3, the preset resistance value is 15M Ω, and the coverage rate of the palladium cluster thin film is 34%; the average cluster diameter was 9nm, the average nearest neighbor distance between palladium clusters was 3nm, and the rest was the same as in example 1.
The results of fitting curves shown in fig. 8 and 9 were obtained after testing the sensitivity of the hydrogen sensors in example 2 and example 3.
Wherein the response curve fitting formula of the hydrogen sensor prepared in example 2 is:
hydrogen concentration 2.95 × 105X (relative resistance change)2-5769 x relative resistance change.
Example 3 the response curve fitting equation for the prepared hydrogen sensor was:
hydrogen concentration 15011 × (relative resistance change)2+11576 × relative resistance change.
The differences in sensitivity of examples 1 to 3 demonstrate that the coverage of the palladium cluster thin film, the average cluster particle size, and the average nearest neighbor distance between palladium clusters have an effect on the sensitivity of the sensor.
Claims (10)
1. A high-sensitivity hydrogen sensor used in air environment is characterized by comprising a drying unit (7), a sensing unit and an external circuit (6); the sensing unit comprises a sealed cavity (1) and a sensing assembly arranged in the sealed cavity, the sensing assembly comprises an insulating substrate (2) arranged at the bottom of the sealed cavity, a palladium cluster film (3) arranged on the upper surface of the insulating substrate and two conductive microelectrodes (4) arranged at two ends of the palladium cluster film, two wiring terminals (5) are arranged on the sealed cavity, one ends of the wiring terminals are positioned in the sealed cavity, one ends of the wiring terminals are positioned outside the sealed cavity, one ends of the wiring terminals in the sealed cavity are connected with the conductive microelectrodes through leads, and one ends of the wiring terminals outside the sealed cavity are connected with an external circuit through leads; the sealed cavity is communicated with the drying unit, and an air inlet is formed in the drying unit.
2. The high-sensitivity hydrogen sensor for use in air environment as claimed in claim 1, wherein the insulating substrate is made of a flexible or rigid insulating material, and has a stable resistivity of 10 or more9Omega, m; the flexible insulating material is selected from one of polyimide, polydimethylsiloxane and polyethylene terephthalate; the rigid insulating material is selected from one of quartz, glass, ruby, sapphire, resin, and a single crystal silicon wafer with a silicon oxide insulating layer.
3. The high-sensitivity hydrogen sensor for the air environment as claimed in claim 1, wherein the conductive microelectrode is an interdigital electrode or a spiral electrode, the thickness of the conductive microelectrode is 50nm to 10 μm, and the distance between two conductive microelectrodes is 2 to 100 μm.
4. The high-sensitivity hydrogen sensor for the air environment according to claim 1 or 4, wherein the material of the conductive microelectrode is one selected from gold, silver, copper, iron, aluminum and indium tin oxide.
5. The hydrogen sensor according to claim 1, wherein the diameter distribution of the palladium clusters in the palladium cluster thin film is 1-10 nm, and the average nearest neighbor distance between the palladium clusters is 0.5-5 nm.
6. The hydrogen sensor according to claim 1 or 6, wherein the palladium cluster thin film has a coverage rate of 30-95%, and a resistance of 50kΩ -1G Ω.
7. The hydrogen sensor as claimed in claim 1, wherein the external circuit comprises a power supply, an electrical signal measuring device and a programmable and visual output device, wherein the power supply, the electrical signal measuring device and the programmable and visual output device are connected through wires, and the programmable and visual output device can convert the measured electrical signal into a hydrogen concentration signal and visually output and display the hydrogen concentration signal.
8. The hydrogen sensor for the air environment as claimed in claim 1, wherein the drying unit comprises a drying tank body and a drying agent arranged in the drying tank body, the drying tank body is provided with a plurality of air inlets, and the drying tank body is communicated with the sealed cavity.
9. A method for producing a hydrogen sensor according to any one of claims 1 to 8, comprising the steps of:
(1) preparing an insulating substrate;
(2) printing a conductive microelectrode on the surface of the insulating substrate;
(3) depositing a palladium cluster film between the conductive microelectrodes;
(4) placing the insulating substrate on which the palladium cluster film is deposited in a sealed cavity, connecting the conductive microelectrode with one end of the wiring terminal in the sealed cavity by using a lead respectively, and connecting one end of the wiring terminal outside the sealed cavity with an external circuit by using the lead;
(5) assembling a drying unit to enable the drying unit to be communicated with the sealed cavity to obtain the assembled hydrogen sensor;
(6) placing the assembled hydrogen sensor in hydrogen environments with different concentrations, recording the macroscopic resistance change of the palladium cluster film in the hydrogen environments with different concentrations through an external circuit, fitting the response relation, and inputting the macroscopic resistance change into the external circuit to finish the calibration of the hydrogen sensor;
(7) and placing the calibrated hydrogen sensor in an air environment to be measured, and measuring the hydrogen concentration through an external circuit.
10. The hydrogen sensor for air environment of claim 1, wherein the palladium cluster thin film in step (3) is deposited by nano printing, physical vapor deposition, chemical vapor deposition or block self-assembly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110144024.4A CN113155904B (en) | 2021-02-02 | 2021-02-02 | High-sensitivity hydrogen sensor used in air environment and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110144024.4A CN113155904B (en) | 2021-02-02 | 2021-02-02 | High-sensitivity hydrogen sensor used in air environment and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113155904A true CN113155904A (en) | 2021-07-23 |
| CN113155904B CN113155904B (en) | 2023-06-20 |
Family
ID=76879195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110144024.4A Active CN113155904B (en) | 2021-02-02 | 2021-02-02 | High-sensitivity hydrogen sensor used in air environment and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113155904B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114113236A (en) * | 2021-11-10 | 2022-03-01 | 北京惠朗时代科技有限公司 | Hydrogen concentration measurement sensor and measurement system |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5394735A (en) * | 1993-12-20 | 1995-03-07 | National Science Council | Gas sensor |
| US20030079999A1 (en) * | 2001-07-20 | 2003-05-01 | The Regents Of The University Of California | Hydrogen gas sensor |
| US20040113216A1 (en) * | 2002-12-06 | 2004-06-17 | National Cheng Kung University | Semiconductor diode capable of detecting hydrogen at high temperatures |
| US20050258051A1 (en) * | 2004-04-28 | 2005-11-24 | Alps Electric Co., Ltd. | Hydrogen sensor and method for detecting hydrogen |
| US20060112756A1 (en) * | 2004-12-01 | 2006-06-01 | The University Of Chicago | Ultrafast and ultrasensitive hydrogen sensors based on self-assembly monolayer promoted 2-dimensional palladium nanoclusters |
| WO2006121349A1 (en) * | 2005-05-09 | 2006-11-16 | Nano Cluster Devices Limited | Hydrogen sensors and fabrication methods |
| WO2007117156A1 (en) * | 2006-04-07 | 2007-10-18 | Nano Cluster Devices Limited | Temperature modulated hydrogen sensing |
| CN101482528A (en) * | 2009-01-23 | 2009-07-15 | 南京大学 | Production method for integrated concentrated nano-particle monolayer film hydrogen sensor |
| CN101501480A (en) * | 2005-08-03 | 2009-08-05 | 毫微-专卖股份有限公司 | Continuous-range hydrogen sensors |
| US20100005853A1 (en) * | 2005-08-03 | 2010-01-14 | Nano-Proprietary, Inc. | Continuous Range Hydrogen Sensor |
| EP2175265A1 (en) * | 2008-10-08 | 2010-04-14 | IEE International Electronics & Engineering S.A.R.L. | Hydrogen sensor and production method thereof |
| CN102313761A (en) * | 2011-07-11 | 2012-01-11 | 西安交通大学 | Array gas-sensitive sensor structure for detection of hydrogen |
| US20120085145A1 (en) * | 2010-10-08 | 2012-04-12 | Zhili Xiao | Sensors and devices containing ultra-small nanowire arrays |
| US20140326615A1 (en) * | 2013-05-01 | 2014-11-06 | Board Of Trustees Of Northern Illinois University | Hydrogen sensor |
| CN110702743A (en) * | 2019-10-16 | 2020-01-17 | 南京大学 | Nano electromechanical hydrogen sensor and preparation method thereof |
-
2021
- 2021-02-02 CN CN202110144024.4A patent/CN113155904B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5394735A (en) * | 1993-12-20 | 1995-03-07 | National Science Council | Gas sensor |
| US20030079999A1 (en) * | 2001-07-20 | 2003-05-01 | The Regents Of The University Of California | Hydrogen gas sensor |
| US20040113216A1 (en) * | 2002-12-06 | 2004-06-17 | National Cheng Kung University | Semiconductor diode capable of detecting hydrogen at high temperatures |
| US20050258051A1 (en) * | 2004-04-28 | 2005-11-24 | Alps Electric Co., Ltd. | Hydrogen sensor and method for detecting hydrogen |
| US20060112756A1 (en) * | 2004-12-01 | 2006-06-01 | The University Of Chicago | Ultrafast and ultrasensitive hydrogen sensors based on self-assembly monolayer promoted 2-dimensional palladium nanoclusters |
| WO2006121349A1 (en) * | 2005-05-09 | 2006-11-16 | Nano Cluster Devices Limited | Hydrogen sensors and fabrication methods |
| US20100005853A1 (en) * | 2005-08-03 | 2010-01-14 | Nano-Proprietary, Inc. | Continuous Range Hydrogen Sensor |
| CN101501480A (en) * | 2005-08-03 | 2009-08-05 | 毫微-专卖股份有限公司 | Continuous-range hydrogen sensors |
| WO2007117156A1 (en) * | 2006-04-07 | 2007-10-18 | Nano Cluster Devices Limited | Temperature modulated hydrogen sensing |
| EP2175265A1 (en) * | 2008-10-08 | 2010-04-14 | IEE International Electronics & Engineering S.A.R.L. | Hydrogen sensor and production method thereof |
| CN101482528A (en) * | 2009-01-23 | 2009-07-15 | 南京大学 | Production method for integrated concentrated nano-particle monolayer film hydrogen sensor |
| US20120085145A1 (en) * | 2010-10-08 | 2012-04-12 | Zhili Xiao | Sensors and devices containing ultra-small nanowire arrays |
| CN102313761A (en) * | 2011-07-11 | 2012-01-11 | 西安交通大学 | Array gas-sensitive sensor structure for detection of hydrogen |
| US20140326615A1 (en) * | 2013-05-01 | 2014-11-06 | Board Of Trustees Of Northern Illinois University | Hydrogen sensor |
| CN110702743A (en) * | 2019-10-16 | 2020-01-17 | 南京大学 | Nano electromechanical hydrogen sensor and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| JOSHI,RAKESH K., ET AL.: "Pd nanoparticles and thin films for room temperature hydrogen sensor", 《NANOSCALE RESEARCH LETTERS》 * |
| M KRISHNA KUMAR, ET AL.: "Structural, morphological and hydrogen sensing studies on pulsed laser deposited nanostructured palladium thin films", 《JOURNAL OF PHYSICS D: APPLIED PHYSICS》 * |
| N. NAKAMURA, ET AL.: "Hydrogen-gas sensing at low concentrations using extremely narrow gap palladium nanoclusters prepared by resistive spectroscopy", 《JOURNAL OF APPLIED PHYSICS》 * |
| NAKAMURA, N. ET AL.: "Precise control of hydrogen response of semicontinuous palladium film using piezoelectric resonance method" * |
| XIE, B. ET AL.: "Pd Nanoparticle Film on a Polymer Substrate for Transparent and Flexible Hydrogen Sensor" * |
| 谢波: "钯纳米粒子密集阵列量子输运性质的调控与氢传感器的性能优化", 《中国博士学位论文全文数据库（电子期刊） 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114113236A (en) * | 2021-11-10 | 2022-03-01 | 北京惠朗时代科技有限公司 | Hydrogen concentration measurement sensor and measurement system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113155904B (en) | 2023-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104749223B (en) | A kind of hydrogen gas sensor monitored on-line for oil-filled transformer density of hydrogen and its application method | |
| KR101110532B1 (en) | Method and apparatus for sensing hydrogen gas | |
| Aroutiounian et al. | Thin-film SnO 2 and ZnO detectors of hydrogen peroxide vapors | |
| US20060251543A1 (en) | Miniaturized gas sensors featuring electrical breakdown in the vicinity of carbon nanotube tips | |
| CN101477076A (en) | Sensor apparatus for measuring and detecting acetylene and hydrogen dissolved in a fluid | |
| CN103975236A (en) | Lead-free oxygen sensor | |
| CN113155904B (en) | High-sensitivity hydrogen sensor used in air environment and preparation method thereof | |
| Lashkov et al. | The Ti wire functionalized with inherent TiO2 nanotubes by anodization as one-electrode gas sensor: A proof-of-concept study | |
| CN204479506U (en) | A kind of hydrogen gas sensor for oil-filled transformer density of hydrogen on-line monitoring | |
| CN112611788A (en) | Semiconductor hydrogen sulfide gas sensor | |
| Aroutiounian et al. | Nanostructured sensors for detection of hydrogen peroxide vapours | |
| CN101458220B (en) | Multi-sensor by utilizing platinum and palladium doped SO2 film and method for making same | |
| JPH0675048B2 (en) | Conductivity probe for use in the presence of high intensity nuclear radiation | |
| CN113465838A (en) | Hydrogen sensor for leakage detection and preparation method of sensitive element thereof | |
| RU196523U1 (en) | GAS-SENSITIVE SENSOR BASED ON CARBON NANOSTRUCTURES | |
| JP2006513403A5 (en) | ||
| KR20120126977A (en) | CNT-based three electrode system, fabrication of the same and electrochemical biosensor using the same | |
| KUSAKABE et al. | Charge transfer rate in liquid-solid and gas-liquid-solid fluidized bed electrodes | |
| WO2014199287A1 (en) | Hydrogen gas sensor and method for fabrication thereof | |
| CN109612920B (en) | Atmospheric corrosion monitoring method for metal component | |
| JPS6290529A (en) | Method for detecting gas and gas sensor | |
| US5589085A (en) | Process of manufacturing a detecting unit for an electrolytic cell with thin film electrodes | |
| CN216770934U (en) | Hydrogen sensor for leakage detection | |
| JP2003344341A (en) | Gas detector | |
| RU2814054C1 (en) | Gas analytical multisensor chip based on phosphorylated graphene and method for its manufacture |
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 |