CN104569091A - Method for preparing air-sensitive sensing material of nano-graphene-supported palladium - Google Patents
Method for preparing air-sensitive sensing material of nano-graphene-supported palladium Download PDFInfo
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- CN104569091A CN104569091A CN201510005823.8A CN201510005823A CN104569091A CN 104569091 A CN104569091 A CN 104569091A CN 201510005823 A CN201510005823 A CN 201510005823A CN 104569091 A CN104569091 A CN 104569091A
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Abstract
The invention relates to a method for preparing an air-sensitive sensing material of nano-graphene-supported palladium. The method comprises the following steps: dispersing graphene in an organic solution, and performing ultrasonic treatment; adding palladium chloride into the organic solution to obtain a mixed solution I; adding sodium borohydride into the obtained solution I, mixing and then standing; carrying out centrifugal separation; and drying in a vacuum furnace to obtain the required material. The method is low in raw material price, simple in process, stable in material shape, high in CO gas detection sensitivity and excellent in selectivity. The material can be made into an electrode, an Agilent 34410A Digit multimeter is adopted for detecting CO gas, and the result shows that the sensitivity is relatively high. The material of the nano structure has the relatively high sensitivity on CO, greatly improves the measurement lower limit of a CO gas sensor, and can reach the ppb level.
Description
Technical field
The invention belongs to electrochemical gas sensor technical field, relate to a kind of gas sensing materials and chemical preparation process thereof of nano-graphene supported palladium.This gas sensitive preparation technology is simple, and the structure and morphology of material is stablized, and high to CO gas detect susceptibility, selectivity is good.
Background technology
Electrochemical gas sensor belongs to the one of gas sensor, is also the most widely used gas sensor in the market.The air-sensitive performance of electrochemical gas sensor depends mainly on the susceptibility of sensitive electrode material to object gas, so prepare the target place that the sensitive electrode material having a high response to object gas is numerous studies personnel.
Since the research of Japanese Scientists due to Graphene aspect has obtained since the Nobel Prize, the research of Graphene is gone after like a flock of ducks.Graphene is the bi-dimensional cellular shape crystalline network formed by carbon hexatomic ring, only has the thickness of a carbon atom, is a kind of two-dimensional material truly.The structure of Graphene uniqueness makes it have the process based prediction model of some excellences, such as intensity is very large, pliability is very strong, electric conductivity is fabulous, electron mobility is very large, Young modulus is also larger, and this just makes Graphene have high using value in nano electron device, supercomputer, solar cell, transparency electrode etc.University Of Suzhou patent Wang Yan is gorgeous waits people's (patent No.: 201310680689) disclose a kind of gas sensor based on redox graphene and preparation method thereof, by large scale graphene oxide dispersion is assembled in amidized electrode surface, and adopt the graphene oxide of liquid reducer to assembling to carry out in-situ reducing, thus obtaining redox graphene gas sensor, the redox graphene gas sensor prepared by method of the present invention has excellent sensing capabilities to ammonia molecule.And the noble metals such as Pt/Pd/Ag and compound thereof play remarkable effect in the preparation process of gas sensor, obviously element function can be improved.Noble metal effectively can increase catalytic performance, by noble metal or it is compound doped in Gas-sensitive Functional Materials, can improve the sensitivity of sensor, selectivity to gas.So be widely used in the field such as sensor, catalyzer.Etc. report a kind of gas sensor for detecting CO and oxygen in waste gas, working electrode and auxiliary electrode are all alloy platinum material (Sensors and Actuators B, 2000,70:25).The people such as Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences Wang Yu river disclose a kind of preparation method of full Buddhist sulfonic acid ion exchange membrane electrode, and use colloid Au, Pt material makes electrochemical gas sensor (patent No. ZL 00126531.8) as catalyst material.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of preparation method of gas sensing materials of nano-graphene supported palladium, utilizing the catalytic activity of noble metal, the high electric conductivity in conjunction with grapheme material makes the electrode material of electrochemical gas sensor.
A preparation method for the gas sensing materials of nano-graphene supported palladium, is characterized in that, comprises the following steps:
(1) join in organic solvent by Graphene, the ultrasonic disperse that stirs again obtains precursor solution A;
(2) take palladium bichloride to join in solution A and to stir;
(3) take boron hydracid sodium to join in above-mentioned solution and to stir, maintain and stir, then leave standstill;
(4) by centrifugal for the powder of step (3), washing;
(5) to the centrifugal product of step (4) dry in a vacuum furnace, obtain the gas sensing materials of nano-graphene supported palladium.
Described in step (1), Graphene addition is 15 ~ 25 milligrams, and described organic solvent is 1-Methyl-2-Pyrrolidone (NMP).
The ultrasonic disperse time described in step (1) is 1 ~ 3 hour.
Palladium bichloride addition described in step (2) is 0.15 ~ 0.25 gram.
The addition of boron hydracid sodium described in step (3) is 0.06 ~ 0.08 gram, and described mixing time is 6 ~ 8 hours, and described time of repose is 1 ~ 3 hour.
Described in step (4), washing spends deionized water, adopts hydro-extractor precipitation after each washing.
In vacuum drying oven described in step (5), baking temperature is 50 ~ 70 DEG C, finger, and the time is 10 ~ 14 hours.
This material is made into electrode, and adopt Agilent Agilent 34410A Digit multimeter to detect CO gas, result shows to have higher sensitivity.The material of this nanostructured, has higher sensitivity to CO, and the measurement lower limit of raising CO gas sensor by a relatively large margin, can reach ppb level level.
Beneficial effect of the present invention:
(1) the graphene-supported palladium catalyst nano material prepared of the present invention, is conducive to gas absorption, significantly can scheme the vapor sensitivity promoting material;
(2) the graphene-supported palladium catalyst material prepared by the present invention, has very high sensitivity to CO gas, solves the problem that general gas flow transducer sensitivity is lower, resolution is poor;
(3) present invention process route is simple, easy and simple to handle, is easy to suitability for industrialized production, can be used for the making of high-performance CO electrochemical gas sensor.
Accompanying drawing explanation
The SEM picture of the graphene-supported palladium of Fig. 1 prepared by embodiment 2.
The TEM picture of the graphene-supported palladium of Fig. 2 prepared by embodiment 2.
The air-sensitive performance figure of the graphene-supported palladium of Fig. 3 prepared by embodiment 2.
Embodiment
embodiment 1:
(1) join in organic solvent by the Graphene of 25 milligrams, the ultrasonic disperse that stirs again obtains precursor solution A in 3 hours;
(2) palladium bichloride taking 0.25 gram to join in solution A and stirs;
(3) the boron hydracid sodium taking 0.08 gram to join in above-mentioned solution and stirs, and maintains stirring 8 time, then leaves standstill 3 hours;
(4) by centrifugal for the powder of step (3), washing;
(5) to the centrifugal product of step (4) at 50 DEG C dry 14 hours in a vacuum furnace, the gas sensing materials of nano-graphene supported palladium is obtained.
This material is made into electrode, and adopt Agilent Agilent 34410A Digit multimeter to detect CO gas, response signal is converted to magnitude of voltage by software and exports.
embodiment 2:
(1) join in organic solvent by the Graphene of 15 milligrams, the ultrasonic disperse that stirs again obtains precursor solution A in 2 hours;
(2) palladium bichloride taking 0.15 gram to join in solution A and stirs;
(3) the boron hydracid sodium taking 0.06 gram to join in above-mentioned solution and stirs, and maintains stirring 6 time, then leaves standstill 1 hour;
(4) by centrifugal for the powder of step (3), washing;
(5) to the centrifugal product of step (4) at 70 DEG C dry 10 hours in a vacuum furnace, the gas sensing materials of nano-graphene supported palladium is obtained.
Fig. 1 is the SEM figure of the sensitive material that the present embodiment makes, and catalyzer is divided into two-phase as can be seen from Fig., is mutually entrained in together, and bulk multi-hole.Fig. 2 is the TEM photo of sensitive material prepared by the present embodiment, and as can be seen from photo, the nano Pd particle grain diameter of preparation is less, is substantially less than 10 nanometers, is dispersed on Graphene on chip.Fig. 3 is the air-sensitive performance test done the gas sensitive of preparation, and measurement lower limit reaches 500ppb level, shows that air-sensitive performance is excellent.
This material is made into electrode, and adopt the response of Agilent Agilent 34410A Digit multimeter test to CO gas, result is converted to magnitude of voltage by software and exports.
embodiment 3;
(1) join in organic solvent by the Graphene of 20 milligrams, the ultrasonic disperse that stirs again obtains precursor solution A in 1 hour;
(2) palladium bichloride taking 0.1739 gram to join in solution A and stirs;
(3) the boron hydracid sodium taking 0.0757 gram to join in above-mentioned solution and stirs, and maintains stirring 7 hours, then leaves standstill 2 hours;
(4) by centrifugal for the powder of step (3), washing;
(5) to the centrifugal product of step (4) at 60 DEG C dry 12 hours in a vacuum furnace, the gas sensing materials of nano-graphene supported palladium is obtained.
This material is made into electrode, and adopt the response of Agilent Agilent 34410A Digit multimeter test to CO gas, result is converted to magnitude of voltage by software and exports.
embodiment 4:
(1) join in organic solvent by the Graphene of 23 milligrams, the ultrasonic disperse that stirs again obtains precursor solution A in 2 hours;
(2) palladium bichloride taking 0.21 gram to join in solution A and stirs;
(3) the boron hydracid sodium taking 0.07 gram to join in above-mentioned solution and stirs, and maintains stirring 7 time, then leaves standstill 2 hours;
(4) by centrifugal for the powder of step (3), washing;
(5) to the centrifugal product of step (4) at 70 DEG C dry 13 hours in a vacuum furnace, the gas sensing materials of nano-graphene supported palladium is obtained.
This material is made into electrode, and adopt the response of Agilent Agilent 34410A Digit multimeter test to CO gas, result is converted to magnitude of voltage by software and exports.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiment and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art are according to announcement of the present invention, and the improvement made for the present invention and amendment all should within protection scope of the present invention.
Claims (7)
1. a preparation method for the gas sensing materials of nano-graphene supported palladium, is characterized in that, comprises the following steps:
(1) join in organic solvent by Graphene, the ultrasonic disperse that stirs again obtains precursor solution A;
(2) take palladium bichloride to join in solution A and to stir;
(3) take boron hydracid sodium to join in above-mentioned solution and to stir, maintain and stir, then leave standstill;
(4) by centrifugal for the powder of step (3), washing;
(5) to the centrifugal product of step (4) dry in a vacuum furnace, obtain the gas sensing materials of nano-graphene supported palladium.
2. the preparation method of the gas sensing materials of a kind of nano-graphene supported palladium according to claim 1, is characterized in that, described in step (1), Graphene addition is 15 ~ 25 milligrams, and described organic solvent is 1-Methyl-2-Pyrrolidone (NMP).
3. the preparation method of the gas sensing materials of a kind of nano-graphene supported palladium according to claim 1, is characterized in that, the ultrasonic disperse time described in step (1) is 1 ~ 3 hour.
4. the preparation method of the gas sensing materials of a kind of nano-graphene supported palladium according to claim 1, is characterized in that, the palladium bichloride addition described in step (2) is 0.15 ~ 0.25 gram.
5. the preparation method of the gas sensing materials of a kind of nano-graphene supported palladium according to claim 1, it is characterized in that, the addition of boron hydracid sodium described in step (3) is 0.06 ~ 0.08 gram, and described mixing time is 6 ~ 8 hours, and described time of repose is 1 ~ 3 hour.
6. the preparation method of the gas sensing materials of a kind of nano-graphene supported palladium according to claim 1, is characterized in that, described in step (4), washing spends deionized water, adopts hydro-extractor precipitation after each washing.
7. the preparation method of the gas sensing materials of a kind of nano-graphene supported palladium according to claim 1, is characterized in that, in the vacuum drying oven described in step (5), baking temperature is 50 ~ 70 DEG C, finger, and the time is 10 ~ 14 hours.
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Cited By (2)
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| CN109103467A (en) * | 2018-08-17 | 2018-12-28 | 北京师范大学 | A kind of preparation method and application of the graphene-based metallic catalyst of electrochemical stripping |
| CN109557138A (en) * | 2018-10-25 | 2019-04-02 | 北京镭硼科技有限责任公司 | A kind of graphene-based gas sensing materials of Metal Palladium load and preparation and application |
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Application publication date: 20150429 |