CN110194487A - A kind of Dispersion on surface has the monoatomic composite material and preparation method of platinum, gas sensitive - Google Patents
A kind of Dispersion on surface has the monoatomic composite material and preparation method of platinum, gas sensitive Download PDFInfo
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- CN110194487A CN110194487A CN201810171561.6A CN201810171561A CN110194487A CN 110194487 A CN110194487 A CN 110194487A CN 201810171561 A CN201810171561 A CN 201810171561A CN 110194487 A CN110194487 A CN 110194487A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
Abstract
The present invention provides one kind to be compounded with monoatomic composite material, including the defective tungsten oxide material in surface and is compounded in the monatomic of the tungsten oxide material surface.The monatomic Mouding of platinum on the tungsten oxide base material of manufacturing defect, is brought excellent sensitivity and selectivity by the present invention, can be will test lower limit and be reached ppb rank.Provided by the invention to be compounded with monoatomic composite material, gas sensitive obtained shows superior response performance and selectivity, and fast response time in detecting to acetone gas, high sensitivity, thermal stability is good, and preparation method is also simple and easy, yield is high, cheap.Present invention firstly provides monatomic material is used for gas sensitive detection, this synthetic method will provide a kind of new direction and strategy for chemical sensor, can promote the development in monatomic air-sensitive direction.
Description
This application claims in the submission of on February 27th, 2018 Patent Office of the People's Republic of China, application No. is 201810161263.9, invention
The Chinese patent application of entitled " a kind of Dispersion on surface have the monoatomic composite material and preparation method of platinum, gas sensitive "
Priority, entire contents are hereby incorporated by reference in the application.
Technical field
The invention belongs to chemical sensing material technical fields, are related to one kind and are compounded with monoatomic composite material and its preparation
Method, gas sensitive more particularly to a kind of Dispersion on surface have the monoatomic composite material and preparation method of platinum, gas sensitive.
Background technique
With the development of modern industry with science and technology progress, serious ecological environmental pollution, especially various pernicious gases
Pollution, be also accompanied, such as nitrogen oxide, sulfur oxide and volatile organic compounds (VOCs).So to this
A little gases are quickly and accurately detected and are particularly important, and with the improvement of living standards and health care, food industry,
The fast development of energy technology, space technology etc., which quickly and accurately detects gas, also proposed more, higher requirement.Cause
This, sensor is widely used to the energy, traffic, peace as receiving information and translate the information into the devices of visual signals
The fields such as inspection, chemical industry, biomedicine, national defence.Among these, gas sensor be it is a kind of can be by the related letter of gaseous species and its concentration
Breath is converted into the device of electric signal.According to these electric signals can obtain under test gas related information in the environment, from
And it can be detected, be alarmed.And gas sensitive is then the core of gas sensor, its flow of research drastically influences gas
The development and application of sensor.
Gas sensitive refers to after a certain material adsorbs certain gas, the changed one kind of the resistivity of the material
Functional material.Initially find that metal oxide has gas sensitive effect, when contacting gas, resistivity is with gaseous species and concentration
Variation and change, come into being from this gas sensitive concept.With the development of science and technology, the development experience of gas sensitive
From small molecule inorganic matter to conductive polymer polymer, from homogenous material to composite material, it is nano combined etc. from being simply doped to
Stage, correlative study are also more and more deep.It was largely ground for monitoring the sensor of toxic and harmful gas in environment in recent years
Study carefully, among these mainly metal oxide semiconductor gas sensor and optical sensor, to H2S、CO、NOx、NH3, volatilization
The monitoring of the toxic and harmful gas such as property organic compound (VOCs).
But the inherent defect of these sensors, such as it is complicated for operation, testing cost is expensive etc., limit its application model
It encloses.Currently, people require gas sensor that can be used for the real-time monitoring of various toxic and harmful gas and to atmosphere pollution, industry
The detection of exhaust gas, thus more stringent requirements are proposed to gas sensor.Oxide is as most widely used at present air-sensitive material
Material, cheap and stability is preferable, is generally used for industrial environment gas detection.But the problem of due to detection limit, it is difficult at present
To realize that the characteristic molecular to trace generates response.
Therefore, a kind of material preferably how is found, gas sensitive can be used as, there is response to trace characteristic molecular
Property, it has also become many forward-looking researchers widely one of focus of attention in field.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide one kind be compounded with monoatomic composite material and its
Preparation method, gas sensitive, especially a kind of Dispersion on surface have the monoatomic composite material of platinum, Dispersion on surface provided by the invention
Have a monoatomic tungsten oxide material of platinum, gas sensitive obtained shown in being detected to acetone gas superior response performance and
Selectivity, and preparation method is simple, thermal stability is good, and yield is high, cheap.
Be compounded with monoatomic composite material the present invention provides one kind, including the defective tungsten oxide material in surface and
It is compounded in the monatomic of the tungsten oxide material surface.
Preferably, it is described it is monatomic for platinum it is monatomic;
The monoatomic load capacity is 0.5~2.5 ‰.
Preferably, the platinum is monatomic in the form of monodispersed, is supported on the tungsten oxide material surface;
The platinum it is monatomic it is monatomic with platinum between metallic bond interconnected is not present.
Preferably, the tungsten oxide material is sheet tungsten oxide material;
The tungsten oxide material with a thickness of 10~60nm;
The piece diameter of the tungsten oxide material is 100~300nm;
The color of the composite material is blue.
The present invention provides a kind of preparation methods for being compounded with monoatomic composite material, comprising the following steps:
A after) closing tungsten source solution and acid-mixed, using washing, gel intermediate is obtained;
B gel intermediate, water and the intercalator for) obtaining above-mentioned steps carry out aging, using post-processing and annealing
After processing, tungsten oxide nanometer material is obtained;
C) under conditions of hydrogen or hydrogen mixed gas, hot place is carried out to the tungsten oxide nanometer material that above-mentioned steps obtain
Reason, obtains the defective tungsten oxide nanometer material in surface;
D the defective tungsten oxide nanometer material in surface that above-mentioned steps obtain and monatomic source solution are mixed again), passed through
It crosses and post-processes again, then under conditions of hydrogen or hydrogen mixed gas, after being restored, obtain being compounded with monoatomic compound
Material.
Preferably, tungsten source solution include sodium tungstate solution, wolframic acid potassium solution, ammonium tungstate solution, tungstate lithium solution and
One of secondary tungsten acid ammonium solution is a variety of;
The acid includes one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and hydrobromic acid or a variety of;
The molar ratio of the tungsten source and the acid is 1:(5~20);
The washing is repeatedly washing.
Preferably, the step B) specifically:
B1 it after) being dispersed gel intermediate and water that above-mentioned steps obtain, adds intercalator and carries out aging, obtain
To suspension;
B2) suspension for obtaining above-mentioned steps obtains tungsten oxide nanometer material after post treatment and after annealing;
The intercalator includes one of oxalic acid, citric acid, acetic acid, salicylic acid and glutamic acid or a variety of;
The water and the mass ratio in the tungsten source are (5~20): 1;
The intercalator and the mass ratio in the tungsten source are (0.1~1): 1.
Preferably, the temperature of the aging is 25~80 DEG C;
The time of the aging is 6~30h;
The post-processing includes one of separation, washing and drying or a variety of;
The temperature of the annealing is 200~500 DEG C;
The time of the annealing is 3~30h.
Preferably, the temperature of the heat treatment is 300~600 DEG C;
The time of the heat treatment is 10~100min;
The monatomic source includes platinum salt;
The platinum salt includes one of potassium chloroplatinate, platinic sodium chloride, chloroplatinic acid and ammonium chloroplatinate or a variety of;
The mass ratio of the monatomic source and the defective tungsten oxide nanometer material in the surface is (0.01~0.15): 1;
The temperature of the reduction is 100~400 DEG C;
The time of the reduction is 10~100min.
The present invention provides a kind of gas sensitive, including composite material described in above-mentioned technical proposal any one or above-mentioned
Composite material prepared by preparation method described in technical solution any one.
Be compounded with monoatomic composite material the present invention provides one kind, including the defective tungsten oxide material in surface and
It is compounded in the monatomic of the tungsten oxide material surface.Compared with prior art, the present invention is grasped for existing gas sensor
Make complicated, testing cost valuableness problem, and oxide is due to the problem of detecting limit, it is difficult to realize the characteristic molecular to trace
Generate the defect of response.The present invention starts with from nano material doping vario-property direction, promotes the responsiveness of oxide.Further inventive
Using the nano material technology of monatomic rank, by monatomic Mouding on base material, each atom all can serve as to live
Property center, thus manufacture composite material have very strong activity.Meanwhile monatomic on base material of Mouding can be to part
React insensitive, and it is very sensitive to certain reactions, and then bring highly selective.
The present invention by the monatomic Mouding of platinum on the tungsten oxide base material of manufacturing defect, bring excellent sensitivity and
Selectivity, can will test lower limit and reach ppb rank.And the platinum carrying capacity needed in synthesis is extremely low (thousand classifications), manufactures gas
Sample required for quick element is also considerably less (several milligrams), so can't substantially mention because of introducing expensive platinum
Rise cost.It is provided by the invention to be compounded with monoatomic composite material, gas sensitive obtained table in detecting to acetone gas
Reveal superior response performance and selectivity, and preparation method is simple, thermal stability is good, and yield is high, cheap.This hair
Monatomic material is used for gas sensitive detection by bright be put forward for the first time, and this synthetic method will provide chemical sensor a kind of new
Direction and strategy.
The experimental results showed that the gas sensitive of platinum single atomic dispersion provided by the invention can be kept at 300~350 DEG C
Good stability and good response to acetone gas.Test has been loaded the monoatomic tungsten oxide of platinum than pure zirconia
Tungsten is well very much.At 350 DEG C, there is very high sensitivity to the acetone of 5ppm, the response time only needs 8 seconds.To 5ppm
Acetone carries out short time retest, and discovery reproducibility is good;Meanwhile under 0.1ppm acetone, it may have good response.Together
When acetone is had good selectivity, and cheap, stability is good, fast response time, high sensitivity, can promote list
The development in atom air-sensitive direction.
Detailed description of the invention
Fig. 1 is the surface of the tungsten oxide of the preparation of the embodiment of the present invention 1, surface defective tungsten oxide and platinum single atomic dispersion
The sample photo of defective tungsten oxide;
Fig. 2 is the stereoscan photograph of tungsten oxide prepared by the embodiment of the present invention 1;
Fig. 3 is the stereoscan photograph of the defective tungsten oxide in surface prepared by the embodiment of the present invention 1;
Fig. 4 is that the scanning electron microscope of the defective tungsten oxide in surface of platinum single atomic dispersion prepared by the embodiment of the present invention 1 is shone
Piece;
Fig. 5 is that the spherical aberration Electronic Speculum of the defective tungsten oxide in surface of platinum single atomic dispersion prepared by the embodiment of the present invention 1 is shone
Piece;
Fig. 6 is reproduction linearity curve of the gas sensor to 5ppm acetone gas sensitive signal of the preparation of the embodiment of the present invention 1;
Fig. 7 is detection curve of the gas sensor to 0.1ppm acetone air-sensitive of the preparation of the embodiment of the present invention 1;
Fig. 8 is tungsten oxide, defect tungsten oxide and the defective oxidation composite tungsten material of the monatomic load of platinum to 5ppm third
The air-sensitive response diagram of comparative sample under ketone.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze pure or atomic layer deposition
The purity requirement of field routine.
All raw materials of the present invention and technical process, the trade mark or abbreviation belong to this field routine trade mark or abbreviation, each
The trade mark or referred to as in the field of its associated uses be it is explicit, those skilled in the art according to the trade mark, abbreviation and
Corresponding purposes can be commercially available from city's mid-sales or conventional method is prepared, or be realized using corresponding equipment.
Be compounded with monoatomic composite material the present invention provides one kind, including the defective tungsten oxide material in surface and
It is compounded in the monatomic of the tungsten oxide material surface.
Present invention definition defective to the surface is not particularly limited, and has with surface well known to those skilled in the art
The usual definition of the oxide of defect, those skilled in the art can according to actual needs, product requirement and quality want
It asks and is selected and adjusted.
The defective tungsten oxide material in the surface is not particularly limited in the present invention, with well known to those skilled in the art
The defective oxide material in surface, those skilled in the art can according to actual needs, product requirement and quality want
It asks and is selected and adjusted, the color of tungsten oxide material is yellow in the present invention, and the defective tungsten oxide material in the surface
Color be blue.
The form of the defective tungsten oxide material in the surface is not particularly limited in the present invention, with those skilled in the art
The conventional form of the well known defective oxide material in surface, those skilled in the art can according to actual needs, produce
Product require and quality requirement is selected and adjusted, and the present invention is further to promote the performance of final products, and the surface has
The form of the tungsten oxide material of defect is preferably flaky material, more preferably nano-scale two-dimensional sheet tungsten oxide material.
The size of the defective tungsten oxide material in the surface is not particularly limited in the present invention, with those skilled in the art
The stock size of the well known defective oxide material of Nanoscale Surface, those skilled in the art can be according to practical need
It wants, product requirement and quality requirement are selected and adjusted, performance of the present invention for further promotion final products, the table
The thickness of the defective tungsten oxide material in face is preferably 10~60nm, more preferably 20~50nm, more preferably 30~40nm.Institute
The piece diameter for stating tungsten oxide material is preferably 100~300nm, and more preferably 120~280nm, more preferably 150~250nm are more excellent
It is selected as 180~220nm.
The monoatomic definition is not particularly limited in the present invention, with monatomic nanometer well known to those skilled in the art
The usual definition of material, those skilled in the art can according to actual needs, product requirement and quality requirement select
It selects and adjusts.
The specific choice of the monatomic material is not particularly limited in the present invention, and those skilled in the art can be according to reality
Border needs, product requirement and quality requirement are selected and adjusted, and monatomic preferably platinum of the present invention is monatomic, i.e. platinum
Element.
The compound definition is not particularly limited in the present invention, determines so that routine well known to those skilled in the art is compound
Justice, those skilled in the art can according to the actual application, product requirement and quality requirement select and adjust,
The present invention is to be further ensured that the performance of product, it is described it is compound preferably include load, insertion, growth, cladding, doping, absorption and
Key even one of or it is a variety of, more preferably load, be embedded in, growth, doping, absorption or key connect, most preferably load, specifically may be used
Think dispersion load.
The monoatomic load capacity is not particularly limited in the present invention, with such product well known to those skilled in the art
Conventional load amount, those skilled in the art can according to the actual application, product requirement and quality requirement select
It selects and adjusts, the present invention is to be further ensured that the performance of product, and the monoatomic load capacity is preferably 0.5~2.5 ‰, more excellent
It is selected as 0.8~2.2 ‰, more preferably 1.0~2.0 ‰, more preferably 1.2~1.8 ‰.
The micromorphology of the composite material is not particularly limited in the present invention, with well known to those skilled in the art such
Product routine micromorphology, those skilled in the art can according to the actual application, product requirement and quality requirement
It is selected and is adjusted, the present invention is to be further ensured that the performance of product, and the platinum is monatomic in the form of monodispersed, is supported on
The defective tungsten oxide material surface in surface, i.e. platinum are monatomic evenly dispersed to be distributed on the base material of tungsten oxide.This
Invent the platinum it is monatomic it is monatomic with platinum between there is no metallic bonds interconnected, i.e. Pt-Pt metallic bond, so can be in
Existing monatomic state.
Composite material of the present invention is monatomic to be evenly distributed on the defective tungsten oxide table in surface after monatomic multiple load
In the defective bit in face, whether the present invention is all distributed by monatomic distribution or part without spy the defective bit on tungsten oxide surface
It is not restricted, those skilled in the art can according to the actual application, product requirement and quality requirement select and adjust
It is whole, the preferred lower load capacity of the present invention for being compounded with monoatomic composite material, thus most of defect all there is also.
The present invention also provides a kind of preparation methods for being compounded with monoatomic composite material, comprising the following steps:
A after) closing tungsten source solution and acid-mixed, using washing, gel intermediate is obtained;
B gel intermediate, water and the intercalator for) obtaining above-mentioned steps carry out aging, using post-processing and annealing
After processing, tungsten oxide nanometer material is obtained;
C) under conditions of hydrogen or hydrogen mixed gas, hot place is carried out to the tungsten oxide nanometer material that above-mentioned steps obtain
Reason, obtains the defective tungsten oxide nanometer material in surface;
D the defective tungsten oxide nanometer material in surface that above-mentioned steps obtain and monatomic source solution are mixed again), passed through
It crosses and post-processes again, then under conditions of hydrogen or hydrogen mixed gas, after being restored, obtain being compounded with monoatomic compound
Material.
Selection and requirement of the present invention to monoatomic composite material is compounded in above-mentioned preparation method, and it is corresponding excellent
Principle is selected, with the aforementioned selection and requirement for being compounded with corresponding parameter in monoatomic composite material, and corresponding preferred original
It can then be corresponded to, this is no longer going to repeat them.
After the present invention first closes tungsten source solution and acid-mixed, using washing, gel intermediate is obtained.
The selection in the tungsten source is not particularly limited in the present invention, is used for such material with well known to those skilled in the art
The tungsten source of preparation, those skilled in the art can select according to practical condition, product requirement and quality requirement
It selects and adjusts, tungsten source of the present invention is preferably soluble tungsten source, more preferably soluble tungstate salt, and tungsten source solution is preferred
Including one of sodium tungstate solution, wolframic acid potassium solution, ammonium tungstate solution, tungstate lithium solution and secondary tungsten acid ammonium solution or a variety of,
More preferably sodium tungstate solution, wolframic acid potassium solution, ammonium tungstate solution, tungstate lithium solution or secondary tungsten acid ammonium solution, most preferably tungsten
Acid sodium solution.The specific concentration of tungsten source solution is not particularly limited in the present invention, and those skilled in the art can be according to reality
The border condition of production, product requirement and quality requirement are selected and are adjusted.
The selection of the acid is not particularly limited in the present invention, is used for such material system with well known to those skilled in the art
Standby common acid, those skilled in the art can select according to practical condition, product requirement and quality requirement
Select and adjust, acid of the present invention is preferably strong acid, more preferably inorganic acid, can specifically include hydrochloric acid, nitric acid, sulfuric acid,
One of phosphoric acid and hydrobromic acid are a variety of, or are hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or hydrobromic acid, most preferably hydrochloric acid.
The tungsten source and sour additional proportion is not particularly limited in the present invention, is used for this with well known to those skilled in the art
The conventional ratio of class material preparation, those skilled in the art can be according to practical condition, product requirement and quality
It is required that being selected and being adjusted, the present invention is to improve the performance of final products, and the tungsten source and the molar ratio of the acid are preferably
1:(5~20), more preferably 1:(7.5~17.5), more preferably 1:(10~15).
The step of present invention is to the washing and parameter are not particularly limited, with conventional water well known to those skilled in the art
The step of washing and parameter, those skilled in the art can according to practical condition, product requirement and quality requirement into
Row selection and adjustment, washing of the present invention preferably repeatedly washing.
Gel intermediate, water and the intercalator that the present invention then obtains above-mentioned steps carry out aging, using rear place
After reason and annealing, tungsten oxide nanometer material is obtained.
The selection of the intercalator (setting agent) is not particularly limited in the present invention, with use well known to those skilled in the art
In such material preparation common intercalator, those skilled in the art can according to practical condition, product requirement with
And quality requirement is selected and is adjusted, intercalator of the present invention is preferably organic acid, can specifically include oxalic acid, lemon
One of acid, acetic acid, salicylic acid and glutamic acid are a variety of, or be oxalic acid, citric acid, acetic acid, salicylic acid or glutamic acid, most
Preferably oxalic acid.
The additional proportion of the intercalator is not particularly limited in the present invention, is used for this with well known to those skilled in the art
The conventional ratio of class material preparation, those skilled in the art can be according to practical condition, product requirement and quality
It is required that being selected and being adjusted, the present invention is to improve the performance of final products, and the intercalator and the mass ratio in the tungsten source are excellent
It is selected as (0.1~1): 1, more preferably (0.3~0.8): 1, more preferably (0.5~0.7): 1.
The additional proportion of the water is not particularly limited in the present invention, is used for such material with well known to those skilled in the art
Expect the conventional ratio of preparation, those skilled in the art can be according to practical condition, product requirement and quality requirement
Selected and adjusted, the present invention is to improve the performance of final products, the mass ratio in the water and the tungsten source be preferably (5~
20): 1, more preferably (7~18): 1, more preferably (10~15): 1.
The present invention is to further increase the performance of final products, guarantees the form of final products, prepared by complete and optimization
Journey, the step B) it is specifically as follows:
B1 it after) being dispersed gel intermediate and water that above-mentioned steps obtain, adds intercalator and carries out aging, obtain
To suspension;
B2) suspension for obtaining above-mentioned steps obtains tungsten oxide nanometer material after post treatment and after annealing.
The parameter of the aging is not particularly limited in the present invention, with the normal of such reaction well known to those skilled in the art
The parameter of aging is advised, those skilled in the art can carry out according to practical condition, product requirement and quality requirement
Selection and adjustment, the present invention are to improve the performance of final products, and the temperature of the aging is preferably 25~80 DEG C, more preferably 35
~70 DEG C, more preferably 45~60 DEG C.The time of aging of the present invention is preferably 6~30h, more preferably 10~25h, more excellent
It is selected as 15~20h.
The step of present invention is to the post-processing and parameter are not particularly limited, with well known to those skilled in the art such
The step of conventional post-processing of reaction and parameter, those skilled in the art can be according to practical conditions, product requirement
And quality requirement is selected and is adjusted, it is of the present invention post-processing preferably include separation, washing and drying one of or
It is a variety of, more preferably separate, wash and drying in it is a variety of, most preferably successively separated, washed and baking step.This hair
The bright design parameter to the separation, washing and drying is not particularly limited, and those skilled in the art can be according to actual production
Situation, product requirement and quality requirement are selected and are adjusted.
The parameter of the annealing is not particularly limited in the present invention, with such reaction well known to those skilled in the art
Conventional annealing processing parameter, those skilled in the art can be according to practical condition, product requirement and quality
It is required that selected and adjusted, the present invention is to improve the performance of final products, the temperature of the annealing is preferably 200~
500 DEG C, more preferably 250~450 DEG C, more preferably 300~400 DEG C.The time of annealing of the present invention is preferably 3~
30h, more preferably 5~28h, more preferably 10~23h, more preferably 15~18h.
Setting agent is added using soluble tungstate salt as presoma in the present invention, manufactures ultra-thin rectangular wolframic acid piece, i.e. nanoscale
Two-dimentional wolframic acid thermally decomposes to yield ultra-thin tungstic oxide nano-sheets by high annealing.
The present invention under conditions of hydrogen or hydrogen mixed gas, carries out the tungsten oxide nanometer material that above-mentioned steps obtain again
Heat treatment, obtains the defective tungsten oxide nanometer material in surface.
The parameter of the hydrogen mixed gas is not particularly limited in the present invention, with well known to those skilled in the art such anti-
The parameter for the conventional hydrogen gaseous mixture answered, those skilled in the art can according to practical condition, product requirement and
Quality requirement is selected and is adjusted, and the present invention is to improve the safety of preparation process, it is preferred to use hydrogen mixed gas, more preferably
For hydrogen and the gaseous mixture of nitrogen or inert gas, more preferably hydrogen and inert gas, such as the gaseous mixture of argon gas.
The parameter of the heat treatment is not particularly limited in the present invention, with such reaction well known to those skilled in the art
The parameter of normative heat treatment, those skilled in the art can be according to practical condition, product requirement and quality requirements
It is selected and is adjusted, the present invention is to improve the performance of final products, and the temperature of the heat treatment is preferably 300~600 DEG C, more
Preferably 350~550 DEG C, more preferably 400~500 DEG C.The time of heat treatment of the present invention is preferably 10~100min, more
Preferably 30~80min, more preferably 50~70min.
The defective tungsten oxide nanometer material in the surface that the present invention finally obtains above-mentioned steps and monatomic source solution are again
Secondary mixing then under conditions of hydrogen or hydrogen mixed gas, after being restored, obtains being compounded with list by post-processing again
The composite material of atom.
The selection in the monatomic source is not particularly limited in the present invention, with well known to those skilled in the art for such
The monatomic source of material preparation, those skilled in the art can want according to practical condition, product requirement and quality
It asks and is selected and adjusted, monatomic source of the present invention is preferably the salt containing the atom, is particularly preferred as platinum salt, Ke Yiwei
Soluble platinum salt more specifically preferably includes one of potassium chloroplatinate, platinic sodium chloride, chloroplatinic acid and ammonium chloroplatinate or a variety of, more
Preferably potassium chloroplatinate, platinic sodium chloride, chloroplatinic acid or ammonium chloroplatinate, most preferably potassium chloroplatinate.The present invention is to described monatomic
The specific concentration of source solution is not particularly limited, those skilled in the art can according to practical condition, product requirement and
Quality requirement is selected and is adjusted.
The additional proportion in the monatomic source is not particularly limited in the present invention, is used for well known to those skilled in the art
The amount of being routinely added to of such material, those skilled in the art can be according to practical condition, product requirement and quality
It is required that being selected and being adjusted, the present invention is to improve the performance of final products, and the monatomic source and the surface are defective
The mass ratio of tungsten oxide nanometer material is preferably (0.01~0.15): 1, more preferably (0.03~0.13): 1, more preferably
(0.05~0.11): 1, more preferably (0.07~0.09): 1.
Described the step of post-processing again and parameter is not particularly limited in the present invention, with well known to those skilled in the art
The step of conventional post-processing of such reaction and parameter, those skilled in the art can be according to practical conditions, product
It is required that and quality requirement selected and adjusted, it is of the present invention again post-processing preferably include separation, washing and drying in
It is one or more, more preferably separate, wash and drying in it is a variety of, most preferably successively carry out separation and baking step.
The design parameter of the separation and drying is not particularly limited in the present invention, and those skilled in the art can be according to actual production feelings
Condition, product requirement and quality requirement are selected and are adjusted.
The parameter of the reduction is not particularly limited in the present invention, with the normal of such reaction well known to those skilled in the art
Advise thermal reduction parameter, those skilled in the art can according to practical condition, product requirement and quality requirement into
Row selection and adjustment, the present invention are to improve the performance of final products, and the mode of the reduction preferably heat-treats, the reduction
Temperature is preferably 100~400 DEG C, more preferably 150~350 DEG C, more preferably 200~300 DEG C.Reduction of the present invention when
Between preferably 10~100min, more preferably 30~80min, more preferably 50~70min.
Setting agent is added using soluble tungstate salt as presoma in the present invention, manufactures ultra-thin rectangular wolframic acid piece, i.e. nanoscale
Two-dimentional wolframic acid thermally decomposes to yield ultra-thin tungstic oxide nano-sheets by high annealing, then lacks nanometer sheet by hydrogen manufacture
It falls into, adsorbs platinum salt ion, reuse hydrogen reducing.This method can be used for manufacturing other monatomic.
The present invention is further to improve and optimize preparation process, guarantees the pattern and performance of final products, above-mentioned preparation step
Suddenly it is specifically as follows:
Step 1, hydrochloric acid is added to sodium tungstate solution, mixed solution is then stirred into a period of time again;
Step 2, mixed solution step 1 obtained obtains spawn, then use moisture with water centrifuge washing 3~5 times
After dissipating, oxalic acid is added and is put into baking oven, 60 DEG C of progress agings;
Step 3, suspension centrifuge washing step 2 obtained, drying, is put into tube furnace and is warming up to 200~500 DEG C;
Step 4, the dusty material that step 3 obtains is heat-treated using hydrogen, manufactures surface defect;
Step 5, platinum element is loaded on the material that step 4 obtains using potassium chloroplatinate solution using absorption method, then
With hydrogen reducing, the gas sensitive of required single atomic dispersion can be obtained.
The present invention also provides a kind of gas sensitive, including composite material described in above-mentioned technical proposal any one or on
State composite material prepared by preparation method described in technical solution any one.
The definition of the gas sensitive and purposes is not particularly limited in the present invention, with gas well known to those skilled in the art
The usual definition and purposes of quick material, those skilled in the art can be according to practical condition, product requirement and matter
Amount requires to be selected and adjusted, and gas sensitive of the present invention is preferably Semiconductor gas sensors material, more preferably highly sensitive
Semiconductor gas sensors material is particularly preferred as being directed to the highly sensitive Semiconductor gas sensors material of detection acetone.
Above-mentioned steps of the present invention, which provide a kind of Dispersion on surface, the monoatomic oxidation composite tungsten material of platinum and its preparation side
Method, gas sensitive.The present invention starts with from nano material doping vario-property direction, promotes the responsiveness of oxide, more using monatomic
The nano material technology of rank, by monatomic Mouding on base material, each atom all can serve as activated centre, thus
The composite material of manufacture has very strong activity.Meanwhile Mouding on base material it is monatomic can to partially reacting insensitive,
And it is very sensitive to certain reactions, and then bring highly selective.
The present invention by the monatomic Mouding of platinum on the tungsten oxide base material of manufacturing defect, bring excellent sensitivity and
Selectivity, can will test lower limit and reach ppb rank.And the platinum carrying capacity needed in synthesis is extremely low (thousand classifications), manufactures gas
Sample required for quick element is also considerably less (several milligrams), so can't substantially mention because of introducing expensive platinum
Rise cost.It is provided by the invention to be compounded with monoatomic composite material, gas sensitive obtained table in detecting to acetone gas
Reveal superior response performance and selectivity, and preparation method is simple, thermal stability is good, and yield is high, cheap.This hair
Monatomic material is used for gas sensitive detection by bright be put forward for the first time, and gas sensitive obtained shows excellent in detecting to acetone gas
Response performance and selectivity more, and preparation method is simple, thermal stability is good, and yield is high, and it is cheap, have good
Application potential.This synthetic method will provide a kind of new direction and strategy for chemical sensor.
The experimental results showed that the gas sensitive of platinum single atomic dispersion provided by the invention can be kept at 300~350 DEG C
Good stability and good response to acetone gas.Test has been loaded the monoatomic tungsten oxide of platinum than pure zirconia
Tungsten is well very much.At 350 DEG C, there is very high sensitivity to the acetone of 5ppm, the response time only needs 8 seconds.To 5ppm
Acetone carries out short time retest, and discovery reproducibility is good;Meanwhile under 0.1ppm acetone, it may have good response.Together
When acetone is had good selectivity, and cheap, stability is good, fast response time, high sensitivity, can promote list
The development in atom air-sensitive direction.
In order to further illustrate the present invention, one kind provided by the invention is compounded with reference to embodiments monoatomic multiple
Condensation material and preparation method thereof, gas sensitive are described in detail, but it is to be understood that these embodiments are with skill of the present invention
Implemented under premised on art scheme, the detailed implementation method and specific operation process are given, is only further explanation
The features and advantages of the present invention, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following
Embodiment.
Embodiment 1
The preparation of tungsten oxide ultrathin nanometer piece:
(1) suitable concentrated hydrochloric acid (37%) acidification is added, when stirring one section in the wolframic acid sodium water solution for configuring 0.2mol/L
Between, the wolframic acid colloidal sol of available yellow;Wherein, the molar ratio of sodium tungstate and acid is 1:10.
(2) wolframic acid colloidal sol water centrifuge washing 3~5 times will obtained, again plus water dispersion;Wherein, water and sodium tungstate
Mass ratio is 15:1.
(3) oxalic acid will be added in obtained wolframic acid colloidal sol, is put into 60 DEG C of baking oven, carry out aging 24 hours for being formed, so
Centrifuge washing 3~5 times afterwards are put into dehydration in vacuum oven 12 hours and obtain ultra-thin wolframic acid nanometer sheet;Wherein, oxalic acid and sodium tungstate
Mass ratio be 0.3:1.
(4) wolframic acid nanometer sheet is put into porcelain boat, 300 DEG C obtain ultra-thin tungstic oxide nano-sheets in high annealing 24 hours.It is thick
Degree is 20~30nm, and side length is 200~300nm.
The preparation of the tungsten oxide of the monatomic load of platinum:
(1) tungsten oxide uses hydrogen-argon-mixed (10%H2) be heat-treated, in its surface fabrication defects, tungsten oxide at this time
Navy blue can be changed into from yellow, surface can generate a large amount of defects;Wherein, the temperature of heat treatment is 500 DEG C;The time of heat treatment
For 60min.
(2) chloroplatinic acid radical ion platinum salt is adsorbed onto the surface of blue tungsten oxide using potassium chloroplatinate solution, then uses hydrogen
Platinum salt is restored, the defective oxidation composite tungsten material in surface of the monatomic load of platinum is obtained.Wherein, monatomic source and table
The mass ratio of the defective tungsten oxide nanometer material in face is 0.05:1.The temperature of reduction is 200 DEG C.The time of reduction is 30min.
The product of above-mentioned steps of the present invention preparation is characterized.
Referring to Fig. 1, Fig. 1 is the tungsten oxide of the preparation of the embodiment of the present invention 1, the defective tungsten oxide in surface and monatomic point of platinum
The sample photo of the defective tungsten oxide in scattered surface.
As shown in Figure 1, base material is yellow tungsten oxide, and material is blue tungsten oxide after continuing manufacturing defect.
Referring to fig. 2, Fig. 2 is the stereoscan photograph of tungsten oxide prepared by the embodiment of the present invention 1.
Referring to Fig. 3, Fig. 3 is the stereoscan photograph of the defective tungsten oxide in surface prepared by the embodiment of the present invention 1.
Referring to fig. 4, Fig. 4 is sweeping for the defective tungsten oxide in surface of platinum single atomic dispersion prepared by the embodiment of the present invention 1
Retouch electromicroscopic photograph.
Referring to Fig. 5, Fig. 5 is the ball of the defective tungsten oxide in surface of platinum single atomic dispersion prepared by the embodiment of the present invention 1
Poor electromicroscopic photograph.
By Fig. 2~5 it is found that the defective oxidation composite tungsten material in the surface of the monatomic load of platinum prepared by the present invention, platinum
It is monatomic to be evenly distributed on the base material of tungsten oxide.
The preparation of gas sensor:
The gas sensitive of platinum single atomic dispersion is appropriate, it is tuned into paste with ethyl alcohol, is coated in the pottery that there is gold electrode at both ends
On porcelain tube, drying.It is then welded on the collet of gas sensor, is placed on aging 5 days on agingtable, the stability of lift elements.
The gas sensor prepared to the embodiment of the present invention 1 detects.
Gas sensor is placed in test device HW-30A (HanweiElectronics Co., Ltd., PRChina),
Heating voltage 5V, test voltage 5V.A certain amount of acetone liquid is injected using micro syringe, is tested using Chinese prestige gas sensor
System software collecting signal.
It is that gas sensor prepared by the embodiment of the present invention 1 is bent to the reproducibility of 5ppm acetone gas sensitive signal referring to Fig. 6, Fig. 6
Line.
It will be appreciated from fig. 6 that the gas sensor has very strong responsiveness, sensitivity R to 5ppm acetonea/RgReach 48.11, rings
It is only 8 seconds between seasonable, recovery time is 24 seconds, and signal reproducibility is good.
Referring to the gas sensor that Fig. 7, Fig. 7 are the preparation of the embodiment of the present invention 1 to the detection curve of 0.1ppm acetone air-sensitive.
As shown in Figure 7, which also has good response, sensitivity R to the acetone of 0.1ppma/RgReach
4.54。
Tungsten oxide (yellow) prepared by the embodiment of the present invention 1, defect tungsten oxide (blue) are had with the monatomic load of platinum
The oxidation composite tungsten material of defect manufactures gas sensor respectively as gas sensitive according to the method described above, after aging, carries out identical
The test of parameter.
Referring to Fig. 8, Fig. 8 is the defective oxidation composite tungsten material of tungsten oxide, defect tungsten oxide and the monatomic load of platinum
To the air-sensitive response diagram of comparative sample under 5ppm acetone.
As seen from contrast in Figure 8, the two is far short of what is expected to the defect tungsten oxide of the response load more monatomic than platinum of acetone, this hair
The defect tungsten oxide of the monatomic load of the platinum of bright preparation has excellent responsiveness.
The gas sensor of the defect tungsten oxide of the monatomic load of platinum prepared using embodiment 1 is to some other common gas
Quick test gas is tested to be compared with acetone, and there are many bad response, shows that it has good selectivity acetone, and
Cheap, stability is good, fast response time, high sensitivity, can promote the development in monatomic air-sensitive direction.
Embodiment 2
The preparation of tungsten oxide ultrathin nanometer piece:
(1) suitable concentrated hydrochloric acid (37%) acidification is added, when stirring one section in the wolframic acid sodium water solution for configuring 0.2mol/L
Between, the wolframic acid colloidal sol of available yellow;Wherein, the molar ratio of sodium tungstate and acid is 1:8.
(2) wolframic acid colloidal sol water centrifuge washing 3~5 times will obtained, again plus water dispersion;Wherein, water and sodium tungstate
Mass ratio is 10:1.
(3) oxalic acid will be added in obtained wolframic acid colloidal sol, is put into 60 DEG C of baking oven, carry out aging 20 hours for being formed, so
Centrifuge washing 3~5 times afterwards are put into dehydration in vacuum oven 12 hours and obtain ultra-thin wolframic acid nanometer sheet;Wherein, oxalic acid and sodium tungstate
Mass ratio be 0.2:1.
(4) wolframic acid nanometer sheet is put into porcelain boat, 300 DEG C obtain ultra-thin tungstic oxide nano-sheets in high annealing 12 hours.It is thick
Degree is 20~30nm, and side length is 200~300nm.
The preparation of the tungsten oxide of the monatomic load of platinum:
(1) tungsten oxide uses hydrogen-argon-mixed (10%H2) be heat-treated, in its surface fabrication defects, tungsten oxide at this time
Navy blue can be changed into from yellow, surface can generate a large amount of defects;Wherein, the temperature of heat treatment is 450 DEG C;The time of heat treatment
For 90min.
(2) chloroplatinic acid radical ion platinum salt is adsorbed onto the surface of blue tungsten oxide using potassium chloroplatinate solution, then uses hydrogen
Platinum salt is restored, the defective oxidation composite tungsten material in surface of the monatomic load of platinum is obtained.Wherein, monatomic source and table
The mass ratio of the defective tungsten oxide nanometer material in face is 0.03: 1.The temperature of reduction is 250 DEG C.The time of reduction is 45min.
The preparation of gas sensor:
The gas sensitive of platinum single atomic dispersion is appropriate, it is tuned into paste with ethyl alcohol, is coated in the pottery that there is gold electrode at both ends
On porcelain tube, drying.It is then welded on the collet of gas sensor, is placed on aging 5 days on agingtable, the stability of lift elements.
The gas sensor prepared to the embodiment of the present invention 2 detects.
Gas sensor is placed in test device HW-30A (HanweiElectronics Co., Ltd., PRChina),
Heating voltage 5V, test voltage 5V.A certain amount of acetone liquid is injected using micro syringe, is tested using Chinese prestige gas sensor
System software collecting signal.
Test result shows that the gas sensor has very strong responsiveness, sensitivity R to 5ppm acetonea/RgReach
42.72, the response time is only 11 seconds, and recovery time is 28 seconds, and has good reproducibility;Also have to the acetone of 0.1ppm
There are good response, sensitivity Ra/RgReach 4.12.
The gas sensor of the defect tungsten oxide of the monatomic load of platinum prepared using embodiment 2 is to some other common gas
Quick test gas is tested to be compared with acetone, and there are many bad response, shows that it has good selectivity acetone, and
Cheap, stability is good, fast response time, high sensitivity, can promote the development in monatomic air-sensitive direction.
Embodiment 3
The preparation of tungsten oxide ultrathin nanometer piece:
(1) suitable concentrated hydrochloric acid (37%) acidification is added, when stirring one section in the wolframic acid sodium water solution for configuring 0.2mol/L
Between, the wolframic acid colloidal sol of available yellow;Wherein, the molar ratio of sodium tungstate and acid is 1:12.
(2) wolframic acid colloidal sol water centrifuge washing 3~5 times will obtained, again plus water dispersion;Wherein, water and sodium tungstate
Mass ratio is 20: 1.
(3) oxalic acid will be added in obtained wolframic acid colloidal sol, is put into 60 DEG C of baking oven, carry out aging 30 hours for being formed, so
Centrifuge washing 3~5 times afterwards are put into dehydration in vacuum oven 12 hours and obtain ultra-thin wolframic acid nanometer sheet;Wherein, oxalic acid and sodium tungstate
Mass ratio be 0.4:1.
(4) wolframic acid nanometer sheet is put into porcelain boat, 300 DEG C obtain ultra-thin tungstic oxide nano-sheets in high annealing 30 hours.It is thick
Degree is 20~30nm, and side length is 200~300nm.
The preparation of the tungsten oxide of the monatomic load of platinum:
(1) tungsten oxide uses hydrogen-argon-mixed (10%H2) be heat-treated, in its surface fabrication defects, tungsten oxide at this time
Navy blue can be changed into from yellow, surface can generate a large amount of defects;Wherein, the temperature of heat treatment is 550 DEG C;The time of heat treatment
For 75min.
(2) chloroplatinic acid radical ion platinum salt is adsorbed onto the surface of blue tungsten oxide using potassium chloroplatinate solution, then uses hydrogen
Platinum salt is restored, the defective oxidation composite tungsten material in surface of the monatomic load of platinum is obtained.Wherein, monatomic source and table
The mass ratio of the defective tungsten oxide nanometer material in face is 0.08:1.The temperature of reduction is 300 DEG C.The time of reduction is 60min.
The preparation of gas sensor:
The gas sensitive of platinum single atomic dispersion is appropriate, it is tuned into paste with ethyl alcohol, is coated in the pottery that there is gold electrode at both ends
On porcelain tube, drying.It is then welded on the collet of gas sensor, is placed on aging 5 days on agingtable, the stability of lift elements.
The gas sensor prepared to the embodiment of the present invention 3 detects.
Gas sensor is placed in test device HW-30A (HanweiElectronics Co., Ltd., PRChina),
Heating voltage 5V, test voltage 5V.A certain amount of acetone liquid is injected using micro syringe, is tested using Chinese prestige gas sensor
System software collecting signal.
Test result shows that the gas sensor has very strong responsiveness, sensitivity R to 5ppm acetonea/RgReach
44.32, the response time is only 9 seconds, and recovery time is 26 seconds, and has good reproducibility;Also have to the acetone of 0.1ppm
There are good response, sensitivity Ra/RgReach 4.19.
The gas sensor of the defect tungsten oxide of the monatomic load of platinum prepared with embodiment 3 is adopted to some other common gas
Quick test gas is tested to be compared with acetone, and there are many bad response, shows that it has good selectivity acetone, and
Cheap, stability is good, fast response time, high sensitivity, can promote the development in monatomic air-sensitive direction.
There are the monoatomic composite material and preparation method of platinum, air-sensitive material to a kind of Dispersion on surface provided by the invention above
Material is described in detail, and used herein a specific example illustrates the principle and implementation of the invention, with
The explanation of upper embodiment is merely used to help understand method and its core concept of the invention, including best mode, and also makes
The present invention, including any device or system of manufacture and use can be practiced by obtaining any person skilled in the art, and implement to appoint
The method what is combined.It should be pointed out that for those skilled in the art, before not departing from the principle of the invention
It puts, can be with several improvements and modifications are made to the present invention, these improvement and modification also fall into the guarantor of the claims in the present invention
It protects in range.The range of the invention patent protection is defined by the claims, and may include that those skilled in the art can think
The other embodiments arrived.If these other embodiments have the structural element for being not different from claim character express, or
If person they include equivalent structural elements with the character express of claim without essence difference, these other embodiments
It should also be included in the scope of the claims.
Claims (10)
1. one kind is compounded with monoatomic composite material, which is characterized in that including the defective tungsten oxide material in surface and again
It closes in the monatomic of the tungsten oxide material surface.
2. composite material according to claim 1, which is characterized in that it is described it is monatomic for platinum it is monatomic;
The monoatomic load capacity is 0.5~2.5 ‰.
3. composite material according to claim 2, which is characterized in that the platinum is monatomic in the form of monodispersed, load
On the tungsten oxide material surface;
The platinum it is monatomic it is monatomic with platinum between metallic bond interconnected is not present.
4. composite material according to claim 1, which is characterized in that the tungsten oxide material is sheet tungsten oxide material;
The tungsten oxide material with a thickness of 10~60nm;
The piece diameter of the tungsten oxide material is 100~300nm;
The color of the composite material is blue.
5. a kind of preparation method for being compounded with monoatomic composite material, which comprises the following steps:
A after) closing tungsten source solution and acid-mixed, using washing, gel intermediate is obtained;
B gel intermediate, water and the intercalator for) obtaining above-mentioned steps carry out aging, using post-processing and annealing
Afterwards, tungsten oxide nanometer material is obtained;
C) under conditions of hydrogen or hydrogen mixed gas, the tungsten oxide nanometer material that above-mentioned steps obtain is heat-treated, is obtained
To the defective tungsten oxide nanometer material in surface;
D) the defective tungsten oxide nanometer material in surface that above-mentioned steps obtain and monatomic source solution are mixed again, by again
Secondary post-processing after being restored, obtains being compounded with monoatomic composite wood then under conditions of hydrogen or hydrogen mixed gas
Material.
6. preparation method according to claim 5, which is characterized in that tungsten source solution includes sodium tungstate solution, wolframic acid
One of potassium solution, ammonium tungstate solution, tungstate lithium solution and secondary tungsten acid ammonium solution are a variety of;
The acid includes one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and hydrobromic acid or a variety of;
The molar ratio of the tungsten source and the acid is 1:(5~20);
The washing is repeatedly washing.
7. preparation method according to claim 5, which is characterized in that the step B) specifically:
B1 it after) being dispersed gel intermediate and water that above-mentioned steps obtain, adds intercalator and carries out aging, hanged
Turbid;
B2) suspension for obtaining above-mentioned steps obtains tungsten oxide nanometer material after post treatment and after annealing;
The intercalator includes one of oxalic acid, citric acid, acetic acid, salicylic acid and glutamic acid or a variety of;
The water and the mass ratio in the tungsten source are (5~20): 1;
The intercalator and the mass ratio in the tungsten source are (0.1~1): 1.
8. preparation method according to claim 5, which is characterized in that the temperature of the aging is 25~80 DEG C;
The time of the aging is 6~30h;
The post-processing includes one of separation, washing and drying or a variety of;
The temperature of the annealing is 200~500 DEG C;
The time of the annealing is 3~30h.
9. preparation method according to claim 5, which is characterized in that the temperature of the heat treatment is 300~600 DEG C;
The time of the heat treatment is 10~100min;
The monatomic source includes platinum salt;
The platinum salt includes one of potassium chloroplatinate, platinic sodium chloride, chloroplatinic acid and ammonium chloroplatinate or a variety of;
The mass ratio of the monatomic source and the defective tungsten oxide nanometer material in the surface is (0.01~0.15): 1;
The temperature of the reduction is 100~400 DEG C;
The time of the reduction is 10~100min.
10. a kind of gas sensitive, which is characterized in that wanted including composite material described in Claims 1 to 4 any one or right
Seek composite material prepared by preparation method described in 5~9 any one.
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