CN104003454A - Porous cobalt oxide nanowire, and preparation method and application thereof - Google Patents
Porous cobalt oxide nanowire, and preparation method and application thereof Download PDFInfo
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- CN104003454A CN104003454A CN201410218728.1A CN201410218728A CN104003454A CN 104003454 A CN104003454 A CN 104003454A CN 201410218728 A CN201410218728 A CN 201410218728A CN 104003454 A CN104003454 A CN 104003454A
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Abstract
The invention discloses a porous cobalt oxide nanowire, and a preparation method and application thereof. The tricobalt tetraoxide nanowire preparation method provided by the invention comprises the following steps: evenly mixing soluble inorganic cobalt salt, inorganic villiaumite, an alkali source and water, then performing hydrothermal reaction, collecting flocculent precipitate after the reaction is finished, and calcining to obtain the tricobalt tetraoxide nanowire. The surface fluorine-doped one-dimensional porous cobalt oxide nanowire provided by the invention has the advantages of novel and unique structure, wide raw material applicability, low cost and the like; and the method is simple, safe and easy to realize industrial production. The porous cobalt oxide nanowire can be widely used in gas-sensitive monitoring (inspection) of combustible, explosive and toxic carbon monoxide gas in the environment, and has wide application space.
Description
Technical field
The invention belongs to field of nanometer material technology, relate to a kind of porous oxidation cobalt nanowire and preparation method thereof and application.
Background technology
One-dimensional nano structure material, because it has higher table body ratio, more exposes avtive spot and excellent physics characteristic, has broad application prospects in the field such as the energy, environment.The fluorine-ion-doped cobaltosic oxide nano line of one dimension porous surface that the present invention relates to has had both physics advantage that one-dimensional material is good and porous material specific surface area is large, expose the chemical advantage that avtive spot is many.This one dimension vesicular structure, is very beneficial for gas molecule and spreads at material surface, promotes surface reaction to carry out; Simultaneously, by introducing fluorine-ion-doped at material surface, can improve the electron transport ability of material, promote chemical signal to electrical signal transmission, the realization of above 2 plays a key effect to the low temperature air-sensitive performance that improves MOS type gas sensitive.This is because gas sensing complicated mechanism, influence factor are more, in the time carrying out design of material, should fully take into account, good gas sensitive not only will have the good chemical property such as surface catalysis, surface reaction, also should have the suitable physics characteristic such as semiconductor energy level structure and electroconductibility simultaneously.In document, there is not yet at present the structure report of this kind of fluorine-ion-doped porous cobaltosic oxide nano line.
Physicochemical property are stable, preparation cost is low owing to having for MOS type gas sensor, applied range, be easy to the plurality of advantages such as integrated, first since successful commercial applications, be one of the study hotspot in gas sensitive research and development field from it always.Cobaltosic oxide nano material is the p-type semi-conductor transition metal oxide material (E of a quasi-representative
g≈ 1.48eV～2.19eV), because thering is good catalytic performance and good electric property, more and more come into one's own in gas sensing field.。But, at present, tricobalt tetroxide also exist during as gas sensitive and other MOS type gas sensitive similarly not enough, for example response sensitivity is low, poor selectivity, working temperature are more high.This is because metal-oxide semiconductor (MOS) resistivity under room temperature or nearly room temperature condition (is often greater than 10 very greatly mostly on the one hand
8Ω cm), relatively little resistance change is difficult for detecting; On the other hand, a lot of sensitive materials only could produce abundant, effective active specy at higher temperature lower surface, cause that surface conductivity changes.But, higher working temperature has required additional heating system to maintain its best working order in actual applications, this not only can increase energy consumption and use cost, simultaneously, when as the source of the gas monitoring element such as inflammable, explosive, the gas sensor of high heat itself can become potential initiating source, and use have low working temperature even the gas sensor of working and room temperature not only can effectively reduce or avoid the impact of above-mentioned unfavorable factor, and lower working temperature is highly beneficial to improving the selectivity of gas sensitive.Therefore the high-performance gas sensitive that, developing low-cost preparation has a low working temperature has great practical significance.
Summary of the invention
The object of this invention is to provide a kind of porous oxidation cobalt nanowire and preparation method thereof and application.
The method of preparing cobaltosic oxide nano line provided by the invention, comprises the steps:
After inorganic solubility cobalt salt, inorganic fluoride salt, alkali source and water are mixed, carry out hydro-thermal reaction, collect after completion of the reaction flocks and calcine, obtain described cobaltosic oxide nano line.
In aforesaid method, the inorganic cobalt salt of described solubility is selected from least one in cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and rose vitriol;
Described inorganic fluoride salt is Sodium Fluoride, Neutral ammonium fluoride or Potassium monofluoride;
Described alkali source is urea, sodium carbonate or sodium bicarbonate.
The mol ratio of described solubility cobalt salt, inorganic fluoride salt, alkali source is 1:1:1, and the mol ratio of described solubility cobalt salt and water is 1:3000～4000, is specially 1:3556;
In described hydro-thermal reaction step, temperature is 120-160 DEG C, is specially 120 DEG C, 140 DEG C, 150 DEG C or 160 DEG C, and the reaction times is 2-12 hour, is specially 2 hours, 4 hours, 8 hours or 12 hours.
In described calcining step, calcining temperature is 300-500 DEG C, be specially 300 DEG C, 350 DEG C, 400 DEG C or 450 DEG C, the temperature rise rate that is risen to calcining temperature used by room temperature is 1-5 DEG C/min, be specially 1 DEG C/min, 2 DEG C/min or 4 DEG C/min, time is 1-3 hour, is specially 1 hour, 2 hours or 3 hours.
In addition, the cobaltosic oxide nano line preparing according to the method described above, also belongs to protection scope of the present invention.Wherein, described nano wire is one dimension vesicular structure; The specific surface area of described nano wire is 60-20m
2/ g, is specially 45m
2/ g; The diameter of described nano wire is 50-150nm, is specially 100nm; The aperture of described nano wire mesopore is 2-50nm, is specially 3-30nm.
In addition, the cobaltosic oxide nano line that the invention described above provides, at the gas sensor of preparing the application in gas sensor and containing this cobaltosic oxide nano line, also belongs to protection scope of the present invention.Wherein, described gas sensor is the gas sensor to carbon monoxide sensitivity; The working temperature of described gas sensor is not more than 100 DEG C, is nearly room temperature (T
op≤ 100 DEG C).
It is main raw material that the present invention utilizes cheap cobalt salt, fluorinated inorganic salt and the organic or inorganic alkali (salt) of solubility, processes integrated process made a kind of nano-cobaltic-cobaltous oxide material with one dimension vesicular structure by hydro-thermal-solid-phase thermal.
The method has the following advantages: the one, and raw material cheapness, under relatively simple gentle experiment condition, can realize the preparation of porous oxidation cobalt nanowire gas sensitive, this makes the choice of raw material very large, and actually operating is flexible and changeable, and method is simple, safety, cost are low, is easy to suitability for industrialized production; The 2nd, the porous oxidation cobalt nanowire of preparation has larger specific surface area and specific one dimension vesicular structure, be very beneficial for the carrying out of detected gas molecular diffusion and surface reaction, be very beneficial for transporting of surface charge simultaneously, its nearly room temperature air-sensitive response performance is far superior to commercial oxidation cobalt, and the air-sensitive response selectivity with height, is particularly useful for carbon monoxide gas sensor.
Brief description of the drawings
Fig. 1 is the obtained porous oxidation cobalt nanowire of embodiment 1 XRD figure spectrum.
Fig. 2 is the obtained porous oxidation cobalt nanowire of embodiment 1 SEM detection figure.
Fig. 3 is the obtained porous oxidation cobalt nanowire of embodiment 1 TEM detection figure.
Fig. 4 is the obtained porous oxidation cobalt nanowire of embodiment 1 HRTEM detection figure.
Fig. 5 is the obtained porous oxidation cobalt nanowire of embodiment 1 XPS spectrum figure
Fig. 6 is the obtained porous oxidation cobalt nanowire of embodiment 1 nitrogen Adsorption and desorption isotherms.
Fig. 7 is the obtained porous oxidation cobalt nanowire of embodiment 1 pore size distribution curve.
Fig. 8 is the obtained porous oxidation cobalt nanowire of embodiment 1 response-working temperature curve.
Fig. 9 is the obtained porous oxidation cobalt nanowire of embodiment 1 CO gas concentration response dynamics scope curve.
Figure 10 is the obtained porous oxidation cobalt nanowire of embodiment 1 H
2gas concentration response dynamics scope curve.
Figure 11 is the obtained porous oxidation cobalt nanowire of embodiment 2 XRD figure spectrum.
Figure 12 is the obtained porous oxidation cobalt nanowire of embodiment 2 SEM detection figure.
Figure 13 is the obtained porous oxidation cobalt nanowire of embodiment 2 TEM detection figure.
Figure 14 is the obtained porous oxidation cobalt nanowire of embodiment 2 nitrogen Adsorption and desorption isotherms.
Figure 15 is the obtained porous oxidation cobalt nanowire of embodiment 2 pore size distribution curve.
Figure 16 is the obtained porous oxidation cobalt nanowire of embodiment 3 XRD figure spectrum.
Figure 17 is the obtained porous oxidation cobalt nanowire of embodiment 3 SEM detection figure.
Figure 18 is the obtained porous oxidation cobalt nanowire of embodiment 3 TEM detection figure.
Figure 19 is the obtained porous oxidation cobalt nanowire of embodiment 3 nitrogen Adsorption and desorption isotherms.
Figure 20 is the obtained porous oxidation cobalt nanowire of embodiment 3 pore size distribution curve.
Figure 21 is the obtained porous oxidation cobalt nanowire of embodiment 4 XRD figure spectrum.
Figure 22 is the obtained porous oxidation cobalt nanowire of embodiment 4 SEM detection figure.
Figure 23 is the obtained porous oxidation cobalt nanowire of embodiment 4 TEM detection figure.
Figure 24 is the obtained porous oxidation cobalt nanowire of embodiment 4 nitrogen Adsorption and desorption isotherms.
Figure 25 is the obtained porous oxidation cobalt nanowire of embodiment 4 pore size distribution curve.
Embodiment
The experimental technique using in following embodiment if no special instructions, is ordinary method.
Material, reagent etc. used in following embodiment, if no special instructions, all can obtain from commercial channels.
In following embodiment, adopt JEOL6701F type scanning electronic microscope (SEM) and JEOL JEM2100 type high resolution transmission electron microscope (HRTEM) to observe material sign pattern and microtexture;
Rigaku D/max-2500 type x-ray powder diffraction instrument characterizes its crystalline structure;
Adopt XPS test material surface-element composition;
Adopt Quantachrome Autosorb-1 type specific surface area and pore distribution analyser to characterize its pore structure.
The air-sensitive performance that adopts drop-coating assess sample, concrete grammar is as follows:
Measure the aqueous dispersion 10 μ L of the 40mg/mL embodiment gained cobaltosic oxide nano line after ultrasonic being uniformly dispersed with pipettor, evenly drip in sensing sample table, after volatilization is done naturally, in air at room temperature more than static 12h, after complete drying, above-mentioned sample table is moved in gas sensing system and prepares to test, and working temperature is by the online control of heating resistor, and CO gas concentration is by the online automatic control of mass type digital flowmeter.
Embodiment 1: taking cobalt chloride as cobalt source
1.25mmol cobalt chloride, 1.25mmol urea are dissolved and is scattered in 40ml deionized water, as solution A;
1.25mmol Sodium Fluoride is dissolved and is scattered in 40ml deionized water, as solution B.
After solution A and solution B are mixed, be transferred in 100ml water heating kettle, leave standstill 12 hours in 120 DEG C.
After naturally cooling, pale pink flocks product after the reaction of centrifugation gained, after washing with water several times, in 100 DEG C of baking ovens, dry, gained dried powder temperature rise rate with 1 DEG C/min in retort furnace is slowly warming up to 300 DEG C, and calcining at constant temperature 3 hours, obtains product after naturally cooling.
Product is accredited as Emission in Cubic tricobalt tetroxide (as shown in Figure 1) through x-ray powder diffraction instrument;
To its morphology characterization, can find out that products therefrom is one dimension vesicular structure with SEM (as shown in Figure 2) and TEM (as shown in Figure 3), the diameter of nano wire is about 100nm.
Further HRTEM characterizes (as shown in Figure 4), can clearly be seen that, a large amount of defects, step, hole etc. are contained in one dimension porous nano line surface.
XPS characterization result shows to have obvious fluorine element characteristic peak (as shown in Figure 5).
Utilize nitrogen adsorption method to carry out pore texture sign (as shown in Figure 6) to it, record its BET method specific surface area and reach 56m
2/ g, utilizes BJH method to carry out characterizing (as shown in Figure 7) to its pore size distribution, and result shows that aperture mainly concentrates between 3～30nm.
Adopt a coating method that this sample is made to gas sensitive device, CO gas has been carried out to gas sensing performance test, result shows that resulting materials can show best air-sensitive performance under near the working temperature 100 DEG C.(as shown in Figure 8), from its gas concentration responding range curve (as shown in Figure 9), in 10ppm～200ppm concentration range, CO (carbon monoxide converter) gas is shown to higher response sensitivity, and under same condition, hydrogen is carried out to air-sensitive test (as shown in figure 10), show very weak air-sensitive performance, show that this method gained gas sensitive has better air-sensitive response selectivity to CO.
Embodiment 2: taking Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES as cobalt source
1.25mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and the dissolving of 1.25mmol urea are scattered in 40ml deionized water, as solution A;
1.25mmol Sodium Fluoride dissolves and is scattered in 40ml deionized water, as solution B.
After solution A and solution B are mixed, be transferred in 100ml water heating kettle, in 150 DEG C of Water Under thermal responses 2 hours.After naturally cooling, pale pink flocks product after the reaction of centrifugation gained, after washing with water several times, in 100 DEG C of baking ovens, dry, gained dried powder is slowly warming up to 350 DEG C with the temperature rise rate of 2 DEG C/min in retort furnace, and calcining at constant temperature is after 2 hours, naturally cooling obtains products therefrom.
X-ray powder diffraction spectrogram identical with embodiment 1 (as shown in figure 11);
To its morphology characterization, can find out that it is also the one dimension porous nano line structure that diameter is about 100nm with SEM and TEM (respectively as shown in Figure 12 and Figure 13).
Utilize nitrogen adsorption method to carry out pore texture sign (Figure 14) to it, recording its BET method specific surface area is 45m
2/ g, utilizes BJH method to carry out characterizing (Figure 15) to its pore size distribution, and result shows that aperture mainly concentrates between 8～30nm.
The gas sensing performance test results of CO gas and embodiment 1, without substantive difference, repeat no more herein.
Embodiment 3: inorganic carbonate sodium is made alkali source
1.25mmol cobalt chloride, 1.25mmol anhydrous sodium carbonate are dissolved and be scattered in 40ml deionized water, as solution A;
1.25mmol Sodium Fluoride dissolves and is scattered in 40ml deionized water, as solution B.
After solution A and solution B are mixed, be transferred in 100ml water heating kettle, leave standstill 4 hours in 140 DEG C.After naturally cooling, pale pink flocks product after the reaction of centrifugation gained, after washing with water several times, in 100 DEG C of baking ovens, dry, gained dried powder temperature rise rate with 4 DEG C/min in retort furnace is slowly warming up to 400 DEG C, and calcining at constant temperature is after 1 hour, and naturally cooling obtains product.
X-ray powder diffraction spectrogram identical with embodiment 1 (as shown in figure 16);
To its morphology characterization, can find out that its products therefrom is also that diameter is the one dimension porous nano line structure of 100nm with SEM and TEM (respectively as shown in Figure 17 and Figure 18).
Utilize nitrogen adsorption method to carry out pore texture sign (as Figure 19) to it, recording its BET method specific surface area is 32m
2/ g, utilizes BJH method to carry out characterizing (as Figure 20) to its pore size distribution, and result shows that aperture mainly concentrates between 10～45nm.
The gas sensing performance test results of CO gas and embodiment 1, without substantive difference, repeat no more herein.
Embodiment 4: using Neutral ammonium fluoride as fluorine source
1.25mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, 1.25mmol urea are dissolved and is scattered in 40ml deionized water, as solution A;
1.25mmol Neutral ammonium fluoride dissolves and is scattered in 40ml deionized water, as solution B.
After solution A and solution B are mixed, be transferred in 100ml water heating kettle, leave standstill 2 hours in 160 DEG C.After naturally cooling, pale pink flocks product after the reaction of centrifugation gained, after washing with water several times, in 100 DEG C of baking ovens, dry, gained dried powder temperature rise rate with 4 DEG C/min in retort furnace is slowly warming up to 450 DEG C, and calcining at constant temperature is after 1 hour, and naturally cooling obtains product.
Products therefrom is carried out to pattern and structural characterization (respectively as shown in Figure 21, Figure 22 and Figure 23), and result shows that products therefrom is substantially the same manner as Example 2.
Utilize nitrogen adsorption method to carry out pore texture sign (as Figure 24) to it, record its BET method specific surface area and reach 21m
2/ g, utilizes BJH method to carry out characterizing (as Figure 25) to its pore size distribution, and result shows that aperture mainly concentrates between 3～40nm.
The gas sensing performance test results of CO gas and embodiment 1, without substantive difference, repeat no more herein.
Claims (10)
1. a method of preparing cobaltosic oxide nano line, comprises the steps:
After inorganic solubility cobalt salt, inorganic fluoride salt, alkali source and water are mixed, carry out hydro-thermal reaction, collect after completion of the reaction the dry rear calcining of flocks, obtain described cobaltosic oxide nano line.
2. method according to claim 1, is characterized in that: the inorganic cobalt salt of described solubility is selected from least one in cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and rose vitriol;
Described inorganic fluoride salt is Sodium Fluoride, Neutral ammonium fluoride or Potassium monofluoride;
Described alkali source is urea, sodium carbonate or sodium bicarbonate.
3. method according to claim 1 and 2, is characterized in that: the mol ratio of described solubility cobalt salt, inorganic fluoride salt, alkali source is 1:1:1, and the mol ratio of described solubility cobalt salt and water is 1:3000～4000.
4. according to the arbitrary described method of claim 1-3, it is characterized in that: in described hydro-thermal reaction step, temperature is 120-160 DEG C, and the time is 2-12 hour.
5. according to the arbitrary described method of claim 1-4, it is characterized in that: in described calcining step, temperature is 300-500 DEG C, the temperature rise rate that is risen to calcining temperature used by room temperature is 1-5 DEG C/min, is specially 4 DEG C/min, and the time is 1-3 hour.
6. the cobaltosic oxide nano line that the arbitrary described method of claim 1-5 prepares.
7. nano wire according to claim 6, is characterized in that: described nano wire is one dimension vesicular structure;
The specific surface area of described nano wire is 60-20m
2/ g, is specially 45m
2/ g;
The diameter of described nano wire is 50-150nm, is specially 100nm;
The aperture of described nano wire mesopore is 2-50nm, is specially 3-30nm.
Described in claim 6 or 7 cobaltosic oxide nano line in the application of preparing in gas sensor.
9. contain the gas sensor of cobaltosic oxide nano line described in claim 6 or 7.
10. application according to claim 8 or gas sensor claimed in claim 9, is characterized in that: described gas sensor is the gas sensor to carbon monoxide sensitivity;
The working temperature of described gas sensor is not more than 100 DEG C.
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