CN103274452A

CN103274452A - Method for preparing petal-like nickel-oxide-doped stannic oxide

Info

Publication number: CN103274452A
Application number: CN2013102184503A
Authority: CN
Inventors: 李冬梅; 詹爽; 梁圣法; 陈鑫; 谢常青; 刘明
Original assignee: Institute of Microelectronics of CAS
Current assignee: Institute of Microelectronics of CAS
Priority date: 2013-06-04
Filing date: 2013-06-04
Publication date: 2013-09-04
Anticipated expiration: 2033-06-04
Also published as: CN103274452B

Abstract

The invention discloses a method for preparing petal-like nickel-oxide-doped stannic oxide. The method comprises the following steps of: mixing, namely, dissolving dihydrate stannic oxide, nickel acetate and oxalic acid in water, adding hydrazine hydrate with the mass fraction of 80% and 3-4 drops of HCl, and stirring the solution for 3-4 hours under the magnetic stirring at the rotating speed of 10 turns/minute to 180 turns/minute to obtain muddy solution; reacting, namely, carrying out thermal reaction on the obtained muddy solution at 0-180 DEG C for 0.5-36 hours, and filtering, washing and drying the precipitates to obtain a precursor of the petal-like nickel-oxide-doped stannic oxide; and calcining, including calcining the obtained precursor of the petal-like nickel-oxide-doped stannic oxide at 300-1000 DEG C for 0.5-4 hours and carrying out natural cooling to be a room temperature. By using the method for doping in materials, materials can be easily obtained, the operation is simple; and the prepared product is petal-like without other shapes, and the specific surface area is large.

Description

A kind of method for preparing the tindioxide of petal doping nickel oxide

Technical field

The present invention relates to tinbase compound technical field, be specifically related to a kind of tindioxide (SnO for preparing petal doping nickel oxide ₂/ NiO) method.

Background technology

The application of gas sensor is various, and because semiconductor gas sensor has higher sensitivity, and therefore fast, long service life of time of response and low cost and other advantages are widely used.Tindioxide (SnO ₂) be typical n N-type semiconductorN, be the preferred material of gas sensor, be mainly used in the detection to inflammable gass such as ethanol, hydrogen and hydrogen sulfide, obtained using widely in the gas sensor production at present.

About the detection mechanism of tindioxide to gas, be commonly considered as surface adsorption control type mechanism, namely in the air of dried and clean, when sensitive membrane is heated to certain temperature, film surface adsorption gas to be measured forms potential barrier, this barrier energy fixed electron drift motion under electric field action at the crystal boundary of material place, make it to be difficult for passing potential barrier, thereby cause that conductivity of material reduces.

And in reducing gas such as NiO, sensitive membrane is adsorbed gas to be measured and with the adsorb oxygen switch or react, is made the adsorb oxygen desorption at crystal boundary place, causes surface potential barrier to reduce, thereby cause the increase of conductivity of material, come detected gas by the variation of measuring conductivity of material.

The preparation method of reducing gas air-sensitive detection sensitivity and tindioxide sensitive material and the microstructure of material are closely related, in order to improve the sensitivity of this class sensor, generally be to set about from the following aspects: 1, make material granule tiny as far as possible, increase the unit specific surface area, improve the sensitivity of sensor; 2, doped precious metal or oxide compound further improve sensitivity and the selectivity of sensor.3, gas sensitive is made film, so as the contact area of increase and gas, the sensitivity that improves sensor.But these methods are complex process simultaneously, and microstructure is wayward, cost is than problems such as height.Experimental implementation process of the present invention is fairly simple, low for equipment requirements, and expense is cheap.

NiO is a kind of typical reducing gas, and simultaneously, NiO is the p-type semi-conductor, SnO ₂Be the n N-type semiconductorN, the contact between them constitutes a p-n junction.Therefore, the SnO of NiO ₂The influence of air-sensitive character except the katalysis of NiO, it and SnO ₂The p-n junction that forms has played important effect.

Summary of the invention

(1) technical problem that will solve

In view of this, it is simple that main purpose of the present invention provides a kind of technology, the petal SnO of the preparation that cost is low ₂The method of/NiO is to prepare the SnO of petal Ni doped O ₂Powder.

(2) technical scheme

For achieving the above object, the invention provides a kind of method for preparing the tindioxide of petal doping nickel oxide, comprising:

Mixed processes: two hydration tindichloride, nickel acetate, oxalic acid are water-soluble, the adding mass percent is hydrazine hydrate and 3 to 4 HCl of 80%, be under 10 rev/mins to 180 rev/mins the magnetic agitation, above-mentioned solution stirring 3 to 4 hours, to be obtained turbid solution at rotating speed;

Reaction process: the turbid solution that obtains 0 ℃ to 180 ℃ following hydro-thermal reaction 0.5 hour to 36 hours, is filtered throw out, washing and dry then, obtain the presoma of the tindioxide of petal doping nickel oxide; And

Calcination process: the presoma of the tindioxide of the petal doping nickel oxide that will obtain naturally cools to room temperature then 300 ℃ to 1000 ℃ calcinings 0.5 hour to 4 hours.

In the such scheme, in the described mixed processes, be that 1.0153g two hydration tindichloride, 0.1244g nickel acetate and 2g oxalic acid are dissolved in the 100ml water, add 3 to 4 massfractions again and be 35% concentrated hydrochloric acid and the hydrazine hydrate of 2.16g80%, be under 50 rev/mins the magnetic agitation at rotating speed, stirred 3 hours, and obtained mixed solution.

In the such scheme, in the described reaction process, be the turbid solution that to obtain 180 ℃ of following hydro-thermal reactions 15 hours, obtain faint yellow precipitation.

In the such scheme, in the described calcination process, be the presoma of tindioxide of the petal doping nickel oxide that will obtain 800 ℃ of calcinings 4 hours, obtain the tin dioxide powder of petal doping nickel oxide.

(3) beneficial effect

The petal SnO of preparation provided by the invention ₂The method of/NiO at first uses two hydrated stannous chlorides, nickelous acetate, oxalic acid, hydrazine and water as raw material, and through stirring, hydro-thermal reaction, centrifugal, washing and drying and other steps obtain petal SnO ₂The presoma of/NiO; Pass through high-temperature calcination then, after the cooling, can obtain petal SnO ₂The powder of Ni doped O.The method of mixing is adopted in doping among the present invention in raw material, raw material is easy to get, and is simple to operate, and the product of preparation is petal, and does not contain other pattern, and specific surface area is big.

Description of drawings

Fig. 1 is according to the petal SnO of the preparation of the embodiment of the invention ₂The method flow diagram of/NiO;

Fig. 2 is the petal SnO according to embodiment of the invention preparation ₂The low power SEM figure of/NiO;

Fig. 3 is the petal SnO according to embodiment of the invention preparation ₂The high power SEM figure of/NiO;

Fig. 4 is the SnO according to embodiment of the invention preparation ₂The XRD characterization result of/NiO.

Embodiment

For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.

The petal SnO of preparation provided by the invention ₂The method of/NiO at first uses two hydrated stannous chlorides, nickelous acetate, oxalic acid, hydrazine and water as raw material, and through stirring, hydro-thermal reaction, centrifugal, washing and drying and other steps obtain petal SnO ₂The presoma of/NiO; Pass through high-temperature calcination then, after the cooling, can obtain petal SnO ₂The powder of Ni doped O.

As shown in Figure 1, Fig. 1 is according to the petal SnO of the preparation of the embodiment of the invention ₂The method flow diagram of/NiO, this method may further comprise the steps:

Step 1: mixed processes: two hydration tindichloride, nickel acetate, oxalic acid are water-soluble, the adding mass percent is hydrazine hydrate and 3 to 4 HCl of 80%, be under 10 rev/mins to 180 rev/mins the magnetic agitation, above-mentioned solution stirring 3 to 4 hours, to be obtained turbid solution at rotating speed;

Step 2: reaction process: the turbid solution that obtains 0 ℃ to 180 ℃ following hydro-thermal reaction 0.5 hour to 36 hours, is filtered throw out, washing and dry then, obtain petal SnO ₂The presoma of/NiO; And

Step 3: calcination process: the petal SnO that will obtain ₂The presoma of/NiO naturally cools to room temperature then and gets final product 300 ℃ to 1000 ℃ calcinings 0.5 hour to 4 hours.

In one embodiment of the invention, be that 1.0153g two hydration tindichloride, 0.1244g nickel acetate and 2g oxalic acid are dissolved in the 100ml water in the mixed processes, add 3 to 4 massfractions again and be 35% concentrated hydrochloric acid and the hydrazine hydrate of 2.16g80%, be under 50 rev/mins the magnetic agitation at rotating speed, stirred 3 hours, and obtained mixed solution.

In one embodiment of the invention, be the turbid solution that will obtain in the reaction process 180 ℃ of following hydro-thermal reactions 15 hours, obtain faint yellow precipitation.

In one embodiment of the invention, in the calcination process be the presoma of tindioxide of the petal doping nickel oxide that will obtain 800 ℃ of calcinings 4 hours, obtain the tin dioxide powder of petal doping nickel oxide.Fig. 2 shows the petal SnO according to embodiment of the invention preparation ₂The low power SEM figure of/NiO, Fig. 3 shows the petal SnO according to embodiment of the invention preparation ₂The high power SEM figure of/NiO, Fig. 4 is the SnO according to embodiment of the invention preparation ₂The XRD characterization result of/NiO.

The method of mixing is adopted in doping among the present invention in raw material, raw material is easy to get, and is simple to operate, and the product of preparation is petal, and does not contain other pattern, and specific surface area is big.

Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims

1. a method for preparing the tindioxide of petal doping nickel oxide is characterized in that, comprising:

2. the method for the tindioxide of the petal doping nickel oxide of preparation according to claim 1, it is characterized in that, in the described mixed processes, be that 1.0153g two hydration tindichloride, 0.1244g nickel acetate and 2g oxalic acid are dissolved in the 100ml water, add 3 to 4 massfractions again and be 35% concentrated hydrochloric acid and the hydrazine hydrate of 2.16g80%, be under 50 rev/mins the magnetic agitation, to stir 3 hours at rotating speed, obtain mixed solution.

3. the method for the tindioxide of the petal doping nickel oxide of preparation according to claim 1 is characterized in that, in the described reaction process, is the turbid solution that will obtain 180 ℃ of following hydro-thermal reactions 15 hours, obtains faint yellow precipitation.

4. the method for the tindioxide of the petal doping nickel oxide of preparation according to claim 1, it is characterized in that, in the described calcination process, be the presoma of tindioxide of the petal doping nickel oxide that will obtain 800 ℃ of calcinings 4 hours, obtain the tin dioxide powder of petal doping nickel oxide.