CN103212708B - Hollow and echinoid nanometer material of copper oxide compounded with gold and preparing method thereof - Google Patents
Hollow and echinoid nanometer material of copper oxide compounded with gold and preparing method thereof Download PDFInfo
- Publication number
- CN103212708B CN103212708B CN201310141957.3A CN201310141957A CN103212708B CN 103212708 B CN103212708 B CN 103212708B CN 201310141957 A CN201310141957 A CN 201310141957A CN 103212708 B CN103212708 B CN 103212708B
- Authority
- CN
- China
- Prior art keywords
- oxide
- suspension
- nano material
- revs
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses a hollow and echinoid nanometer material of copper oxide compounded with gold and a preparing method of the nanometer material. In a preparation process, copper chloride, sodium hydroxide, ascorbic acid and chloroauric acid which are friendly in environment and can be obtained conveniently and easily are utilized to be raw materials, and an aqueous-phase synthesis preparing method of the nanometer material with a multilevel structure of copper oxide compounded with gold is provided, wherein the preparing method is simple to operate, high in productivity, low in cost, green and environment-friendly. An obtained material is the nanometer material with the multilevel structure of the copper oxide compounded with gold, appearance is hollow and echinoid, and the size is uniform. The material prepared through the preparing method is applied to a gas sensor.
Description
Technical field
The present invention relates to a kind of preparation method of the nano material as semiconductor gas sensor, more particularly, refer to a kind of Cu oxide and golden compound nano material and preparation method thereof of hollow sea urchin shape.
Background technology
Gas sensor is a kind of sensor that the gas componant detecting and concentration is converted to the signal of telecommunication.It mainly comprises semiconductor gas sensor, catalytic combustion type gas sensor and Electro-chemical Gas Sensor etc., and wherein the maximum of use are semiconductor gas sensors.Such sensor can effective monitoring quality of air environment, control the discharge of various toxic and imflammable gas.
It is " Metal Oxide Gas Sensors " literary composition that the 6th the 10th phase of volume of October in 2007 discloses exercise question at " Guangdong University journal " natural science edition.In literary composition, introduce and multiplely prepared metal oxide and partly lead the method for powder.
Desirable gas sensor should have following advantage in performance: highly sensitive, selectively good, low in energy consumption, long-term work situation stability inferior is good, cost is low etc.But actual gas sensor, due to the restriction of the various factors such as material, preparation technology, is not often well positioned to meet the demand of application.
Summary of the invention
The nano material that the Cu oxide that one of object of the present invention is to provide a kind of hollow sea urchin shape is compound with gold, this material is a kind ofly to have the multilevel hierarchy cupric oxide nano material compound with gold, and pattern is that hollow sea urchin shape, size homogeneous, specific area are high.
Two of object of the present invention is to propose a kind of Cu oxide of hollow sea urchin shape and method of golden compound nano material prepared, utilize in the methods of the invention environmental friendliness, the copper chloride, NaOH, ascorbic acid and the gold chloride that are conveniently easy to get are raw material, provide a kind of simple to operate, productive rate is high, cost is low, the multilevel hierarchy Cu oxide of environmental protection and the water synthesis preparation method of golden composite nano materials.
Prepare the Cu oxide of hollow sea urchin shape of the present invention and the method for golden compound nano material, include the following step:
First step: at 15 DEG C～25 DEG C temperature by Copper dichloride dihydrate (CuCl
22H
2o) after being dissolved in and mixing in deionized water, obtaining copper chloride mass percent concentration is the first solution of 1.5g/L～2.0g/L;
Second step: in 45 DEG C～60 DEG C bath temperatures, slowly drip NaOH (NaOH) aqueous solution in the first solution under stirring; After dripping sodium hydrate aqueous solution, continue to stir 10 minutes～30 minutes, obtain the second solution;
Rate of addition is 50 droplets/minute～80 droplets/minute;
Mixing speed is 200 revs/min～400 revs/min;
The mass percent concentration of sodium hydrate aqueous solution is 80g/L;
In the first solution of 1L, add the sodium hydrate aqueous solution of 0.088L～0.118L;
Third step: in 45 DEG C～60 DEG C bath temperatures, slowly drip ascorbic acid (C in the second solution under stirring
6h
8o
6) aqueous solution; After dripping aqueous ascorbic acid, continue to stir 150 minutes～200 minutes, obtain the first suspension;
Rate of addition is 10 droplets/minute～30 droplets/minute;
Mixing speed is 200 revs/min～400 revs/min;
The mass percent concentration of aqueous ascorbic acid is 105.7g/L;
In the first solution of 1L, add the aqueous ascorbic acid of 0.088L～0.118L;
The 4th step: the first suspension is carried out to centrifugation, obtain the first sediment;
The first sediment is first carried out to centrifuge washing 1～3 time by deionized water, carry out centrifuge washing 1～3 time with absolute ethyl alcohol subsequently, obtain the second sediment;
The second sediment, after baking temperature is to be dried 1 hour～6 hours under 40 DEG C～50 DEG C conditions, is obtained to the first pressed powder;
Centrifugation condition: 4000 revs/min～5000 revs/min, centrifugation time 3 minutes～10 minutes;
The 5th step: the first pressed powder is adopted to ultrasonic being scattered in ethanol water, obtain the second suspension;
The mass percent concentration of ethanol water is 10%;
Consumption: the first pressed powder of 1g is added in 0.8L～1.2L ethanol water;
The 6th step: at 15 DEG C～25 DEG C temperature, slowly drip gold chloride (HAuCl in the second suspension under stirring
4) aqueous solution; After dripping aqueous solution of chloraurate, continue to stir 10 minutes～30 minutes, obtain the 3rd suspension;
Rate of addition is 10 droplets/minute～30 droplets/minute;
Mixing speed is 200 revs/min～400 revs/min;
The mass percent concentration of aqueous solution of chloraurate is 0.17g/L;
In the second suspension of 0.1L, add the aqueous solution of chloraurate of 0.015L～0.025L;
The 7th step: the 3rd suspension is placed under the temperature conditions of 50 DEG C～70 DEG C, reacts after 2～4 hours and take out, be cooled to 15 DEG C～25 DEG C, obtain the 4th suspension;
The 8th step: the 4th suspension is carried out to centrifugation, obtain the 3rd sediment;
The 3rd sediment is first carried out to centrifuge washing 1～3 time by deionized water, carry out centrifuge washing 1～3 time with absolute ethyl alcohol subsequently, obtain the 4th sediment;
Centrifugation condition: 4000 revs/min～5000 revs/min, centrifugation time 3 minutes～10 minutes;
The 4th sediment, after baking temperature is to be dried 1 hour～6 hours under 40 DEG C～50 DEG C conditions, is obtained to the Cu oxide nano material compound with gold.
Preparation method's of the present invention advantage is:
1. the inventive method is utilized environmental friendliness, the copper chloride, NaOH, ascorbic acid and the gold chloride that are conveniently easy to get are raw material, provide a kind of simple to operate, productive rate is high, cost is low, the multilevel hierarchy Cu oxide of environmental protection and the water synthesis preparation method of golden composite nano materials.
2. in the time making the multilevel hierarchy Cu oxide of hollow composite construction of high-specific surface area without template, and the generation of noble metal (gold element) nano particle and a compound step complete, precious metal raw material consumption is few, utilization rate is high.Simplified synthesis step and cycle, waste material is few, is applicable to streamline batch production, and production cost is minimized, and has market using value.
3. the present invention is a kind of solution synthetic method of gentleness, and building-up process is simple to operation, and synthesis temperature is low, and required synthesis device is conveniently easy to get, the multilevel hierarchy cupric oxide obtaining and golden composite nano materials size and comparatively homogeneous of pattern.
4. to select the copper chloride cheap, environment is nontoxic, NaOH and ascorbic acid etc. be raw material in the present invention, and raw material availability is high, has advantages of environment protecting and power-saving.
Brief description of the drawings
Fig. 1 is the XRD diffraction pattern of the first pressed powder of preparing of the embodiment of the present invention 1.
Fig. 2 is the SEM figure of the first pressed powder of preparing of the embodiment of the present invention 1.
Fig. 3 A is the Cu oxide for preparing of the embodiment of the present invention 1 and the XRD diffraction pattern of the compound nano material of gold.
Fig. 3 B is the Cu oxide for preparing of the embodiment of the present invention 1 and the X ray energy spectrometer spectrum of the compound nano material of gold.
Fig. 4 is that the Cu oxide that the embodiment of the present invention 1 prepares is schemed with the SEM of golden compound nano material.
Fig. 5 A is that the Cu oxide that the embodiment of the present invention 1 prepares is schemed with the TEM of golden compound nano material.
Fig. 5 B is TEM figure and high-resolution transmission electron microscope (HRTEM) figure that in Fig. 5 A, part is amplified.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further detail.
The Cu oxide of preparing a kind of hollow sea urchin shape of the present invention includes the following step with golden compound nano material:
First step: at 15 DEG C～25 DEG C temperature by Copper dichloride dihydrate (CuCl
22H
2o) after being dissolved in and mixing in deionized water, obtaining copper chloride mass percent concentration is the first solution of 1.5g/L～2.0g/L;
Second step: in 45 DEG C～60 DEG C bath temperatures, slowly drip NaOH (NaOH) aqueous solution in the first solution under stirring; After dripping sodium hydrate aqueous solution, continue to stir 10 minutes～30 minutes, obtain the second solution;
Rate of addition is 50 droplets/minute～80 droplets/minute;
Mixing speed is 200 revs/min～400 revs/min;
The mass percent concentration of sodium hydrate aqueous solution is 80g/L;
In the first solution of 1L, add the sodium hydrate aqueous solution of 0.088L～0.118L;
Third step: in 45 DEG C～60 DEG C bath temperatures, slowly drip ascorbic acid (C in the second solution under stirring
6h
8o
6) aqueous solution; After dripping aqueous ascorbic acid, continue to stir 150 minutes～200 minutes, obtain the first suspension;
Rate of addition is 10 droplets/minute～30 droplets/minute;
Mixing speed is 200 revs/min～400 revs/min;
The mass percent concentration of aqueous ascorbic acid is 105.7g/L;
In the first solution of 1L, add the aqueous ascorbic acid of 0.088L～0.118L;
The 4th step: the first suspension is carried out to centrifugation, obtain the first sediment;
The first sediment is first carried out to centrifuge washing 1～3 time by deionized water, carry out centrifuge washing 1～3 time with absolute ethyl alcohol subsequently, obtain the second sediment;
The second sediment, after baking temperature is to be dried 1 hour～6 hours under 40 DEG C～50 DEG C conditions, is obtained to the first pressed powder;
Centrifugation condition: 4000 revs/min～5000 revs/min, centrifugation time 3 minutes～10 minutes;
The 5th step: the first pressed powder is adopted to ultrasonic being scattered in ethanol water, obtain the second suspension;
The mass percent concentration of ethanol water is 10%;
Consumption: the first pressed powder of 1g is added in 0.8L～1.2L ethanol water;
The 6th step: at 15 DEG C～25 DEG C temperature, slowly drip gold chloride (HAuCl in the second suspension under stirring
4) aqueous solution; After dripping aqueous solution of chloraurate, continue to stir 10 minutes～30 minutes, obtain the 3rd suspension;
Rate of addition is 10 droplets/minute～30 droplets/minute;
Mixing speed is 200 revs/min～400 revs/min;
The mass percent concentration of aqueous solution of chloraurate is 0.17g/L;
In the second suspension of 0.1L, add the aqueous solution of chloraurate of 0.015L～0.025L;
The 7th step: the 3rd suspension is placed under the temperature conditions of 50 DEG C～70 DEG C, reacts after 2～4 hours and take out, be cooled to 15 DEG C～25 DEG C, obtain the 4th suspension;
The 8th step: the 4th suspension is carried out to centrifugation, obtain the 3rd sediment;
The 3rd sediment is first carried out to centrifuge washing 1～3 time by deionized water, carry out centrifuge washing 1～3 time with absolute ethyl alcohol subsequently, obtain the 4th sediment;
Centrifugation condition: 4000 revs/min～5000 revs/min, centrifugation time 3 minutes～10 minutes;
The 4th sediment, after baking temperature is to be dried 1 hour～6 hours under 40 DEG C～50 DEG C conditions, is obtained to the Cu oxide nano material compound with gold.
embodiment 1
Preparation has the Cu of hollow sea urchin shape
2the step of O/Au/CuO composite nano materials has:
First step: at 22 DEG C of temperature by Copper dichloride dihydrate (CuCl
22H
2o) after being dissolved in and mixing in deionized water, obtaining copper chloride mass percent concentration is the first solution of 1.7g/L;
In the present invention, color and luster is with GSB05-1426-2001, and the contrast of GB colour atla-paint film color standard scale obtains.The color and luster of described the first solution is eggshell green (26G07).
Second step: in 55 DEG C of bath temperatures, slowly drip NaOH (NaOH) aqueous solution in the first solution under stirring; After dripping sodium hydrate aqueous solution, continue to stir 30 minutes, obtain the second solution;
Rate of addition is 50 droplets/minute;
Select the RET basic C IKA heating magnetic stirring apparatus that Hangzhou spectrometer Science and Technology Ltd. produces to process, mixing speed is 200 revs/min;
The mass percent concentration of sodium hydrate aqueous solution is 80g/L;
In the first solution of 1L, add the sodium hydrate aqueous solution of 0.100L;
In the present invention, the first solution is in dropping NaOH process, and color and luster becomes muddy scape blueness (20B14) by eggshell green, becomes subsequently brown (57YR05), therefore the color and luster of the second solution is brown.
Third step: in 55 DEG C of bath temperatures, slowly drip ascorbic acid (C in the second solution under stirring
6h
8o
6) aqueous solution; After dripping aqueous ascorbic acid, continue to stir 180 minutes, obtain the first suspension;
Rate of addition is 20 droplets/minute;
Mixing speed is 200 revs/min;
The mass percent concentration of aqueous ascorbic acid is 105.7g/L;
In the first solution of 1L, add the aqueous ascorbic acid of 0.100L;
In the present invention, the second solution is in dropping aqueous ascorbic acid process, and color and luster gradually becomes dark brown yellow (55YR07) by brown, therefore the color and luster of the first suspension is dark brown yellow.
The 4th step: the first suspension is carried out to centrifugation, obtain the first sediment;
The first sediment is first carried out to centrifuge washing 2 times by deionized water, carry out centrifuge washing 2 times with absolute ethyl alcohol subsequently, obtain the second sediment; Select Hunan instrument TG16-WS table model high speed centrifuge to carry out centrifugal treating, centrifugation condition is 5000 revs/min, centrifugation time 5 minutes;
The second sediment, after baking temperature is to be dried 2 hours under 40 DEG C of conditions, is obtained to the first pressed powder; The color and luster of the first pressed powder is rust (64R01).Select Medical Equipment Plant of Shanghai Boxun Industrial Co., Ltd., GZX-9140MBE digital display air dry oven.
Adopt X-ray diffraction to carry out constituent analysis to the first pressed powder, as shown in Figure 1, the diffract spectral line in figure and standard P DF card Cu
2the diffraction maximum of O (JCPDS No.77-0199) better meets.Diffraction maximum in figure is corresponding Cu respectively
2(1,1,1) of O, (2,0,0), the diffraction maximum of (2,2,0) and (3,1,1) face.Do not have other impurity peaks to occur, show that the purity of the first pressed powder is fine.
Adopt SEM to carry out morphology analysis to the first pressed powder, as shown in Figure 2, the overall pattern that has shown product in Fig. 2 is the cubic particle of the length of side at 400～600nm, smooth surface, and seamed edge and angle are clearly demarcated.
The 5th step: the first pressed powder is adopted to ultrasonic being scattered in ethanol water, obtain the second suspension;
The mass percent concentration of ethanol water is 10%;
Consumption: the first pressed powder of 0.1g is added in 0.1L ethanol water;
In the present invention, select Kunshan He Chuan ultrasonic instrument Co., Ltd, the ultrasonic cleaning machine that model is kh3200e, power 150W.
The 6th step: slowly drip gold chloride (HAuCl in the second suspension at 22 DEG C of temperature, under stirring
4) aqueous solution; After dripping aqueous solution of chloraurate, continue to stir 30 minutes, obtain the 3rd suspension;
Rate of addition is 20 droplets/minute;
Mixing speed is 300 revs/min;
The mass percent concentration of aqueous solution of chloraurate is 0.17g/L;
In the second suspension of 0.1L, add the aqueous solution of chloraurate of 0.02L;
The 7th step: the 3rd suspension is placed in the baking oven of 60 DEG C, reacts after 3 hours and take out, be cooled to 25 DEG C, obtain the 4th suspension;
The 8th step: the 4th suspension is carried out to centrifugation, obtain the 3rd sediment;
The 3rd sediment is first carried out to centrifuge washing 2 times by deionized water, carry out centrifuge washing 2 times with absolute ethyl alcohol subsequently, obtain the 4th sediment; Select Hunan instrument TG16-WS table model high speed centrifuge to carry out centrifugal treating, centrifugation condition is 5000 revs/min, centrifugation time 5 minutes;
The 4th sediment, after baking temperature is to be dried 3 hours under 50 DEG C of conditions, is obtained to the Cu oxide nano material compound with gold.
In the present invention, Cu oxide is purple brown (58YR03) with the color and luster of golden compound nano material.
Adopt X-ray diffraction to carry out constituent analysis to the compound nano material of Cu oxide and gold, as shown in Figure 3A, the diffract spectral line in figure and standard P DF card Cu
2the diffraction maximum of O (JCPDS No.77-0199) and CuO (JCPDS48-1548) better meets.Diffraction maximum in figure is corresponding Cu respectively
2(1,1,1) of O, (2,0,0), (2,2,0) and the diffraction maximum of (3,1,1) face and CuO (1,1,0), (0,0,2), (1,1,1), (2,0,2), (2,0,2), (1,1,3), (3,1,1), (1,1,3), (3,1,1), the diffraction maximum of (0,0,4) and (2,2,2) face.The content of gold in composite construction is less, can not in XRD diffraction spectrogram, embody, with X ray energy spectrometer spectral results as shown in Figure 3 B.In figure, the mass percentage content of gold (Au) in nano composite material is 3.7%.
Adopt SEM to carry out morphology analysis to the compound nano material of Cu oxide and gold, as shown in Figure 4, the overall pattern that shows the compound nano material of Cu oxide and gold in figure is the hollow sea urchin shape particle of the length of side at 450～700nm, this multilevel hierarchy rough surface, have many burr structure, thorn length is 60～150nm.
Adopt transmission electron microscope to carry out morphology analysis to the compound nano material of Cu oxide and gold, as shown in Fig. 5 A, Fig. 5 B.In Fig. 5 A, show that the compound multi-stage nano material of Cu oxide and gold has obvious hollow and burr structure.In Fig. 5 B, be the TEM figure that in Fig. 5 A, part is amplified, show the surperficial burr ordered arrangement of the compound multi-stage nano material of Cu oxide and gold, and there is polycrystalline feature.High-resolution transmission electron microscope (HRTEM) figure in the upper right corner is that amplify the part of burr structure, spacing of lattice is wherein 0.25nm, (0,0 of corresponding CuO crystal, 2) spacing of crystal face, illustrates that the burr structure of the compound multi-stage nano material of Cu oxide and gold is CuO composition.
embodiment 2
Preparation has the Cu of hollow sea urchin shape
2the step of O/Au/CuO composite nano materials has:
First step: at 15 DEG C of temperature by Copper dichloride dihydrate (CuCl
22H
2o) after being dissolved in and mixing in deionized water, obtaining copper chloride mass percent concentration is the first solution of 1.5g/L;
In the present invention, the color and luster of described the first solution is eggshell green.
Second step: in 60 DEG C of bath temperatures, slowly drip NaOH (NaOH) aqueous solution in the first solution under stirring; After dripping sodium hydrate aqueous solution, continue to stir 10 minutes, obtain the second solution;
Rate of addition is 60 droplets/minute;
Mixing speed is 300 revs/min;
The mass percent concentration of sodium hydrate aqueous solution is 80g/L;
In the first solution of 1L, add the sodium hydrate aqueous solution of 0.088L;
In the present invention, the first solution is dripping in NaOH process, and color and luster becomes muddy scape blueness by eggshell green, become subsequently brown, therefore the color and luster of the second solution is brown.
Third step: in 60 DEG C of bath temperatures, slowly drip ascorbic acid (C in the second solution under stirring
6h
8o
6) aqueous solution; After dripping aqueous ascorbic acid, continue to stir 150 minutes, obtain the first suspension;
Rate of addition is 30 droplets/minute;
Mixing speed is 300 revs/min;
The mass percent concentration of aqueous ascorbic acid is 105.7g/L;
In the first solution of 1L, add the aqueous ascorbic acid of 0.088L;
In the present invention, the second solution is in dropping aqueous ascorbic acid process, and color and luster gradually becomes dark brown yellow by brown, therefore the color and luster of the first suspension is dark brown yellow.
The 4th step: the first suspension is carried out to centrifugation, obtain the first sediment;
The first sediment is first carried out to centrifuge washing 1 time by deionized water, carry out centrifuge washing 1 time with absolute ethyl alcohol subsequently, obtain the second sediment; Centrifugation condition is 4000 revs/min, centrifugation time 10 minutes;
The second sediment, after baking temperature is to be dried 1 hour under 50 DEG C of conditions, is obtained to the first pressed powder;
The 5th step: the first pressed powder is adopted to ultrasonic being scattered in ethanol water, obtain the second suspension;
The mass percent concentration of ethanol water is 10%;
The first pressed powder of consumption: 0.1g needs 0.08L ethanol water;
The 6th step: slowly drip gold chloride (HAuCl in the second suspension at 15 DEG C of temperature, under stirring
4) aqueous solution; After dripping aqueous solution of chloraurate, continue to stir 10 minutes, obtain the 3rd suspension;
Mixing speed is 200 revs/min;
The mass percent concentration of aqueous solution of chloraurate is 0.17g/L;
In the second suspension of 0.1L, add the aqueous solution of chloraurate of 0.025L;
The 7th step: the 3rd suspension is placed under the temperature conditions of 70 DEG C, reacts after 2 hours and take out, be cooled to 20 DEG C, obtain the 4th suspension;
The 8th step: the 4th suspension is carried out to centrifugation, obtain the 3rd sediment;
The 3rd sediment is first carried out to centrifuge washing 3 times by deionized water, carry out centrifuge washing 3 times with absolute ethyl alcohol subsequently, obtain the 4th sediment; Centrifugation condition is 4000 revs/min, centrifugation time 10 minutes;
The 4th sediment, after baking temperature is to be dried 6 hours under 40 DEG C of conditions, is obtained to the Cu oxide nano material compound with gold.
In the present invention, Cu oxide is purple brown with the color and luster of golden compound nano material.
embodiment 3
Preparation has the Cu of hollow sea urchin shape
2the step of O/Au/CuO composite nano materials has:
First step: at 25 DEG C of temperature by Copper dichloride dihydrate (CuCl
22H
2o) after being dissolved in and mixing in deionized water, obtaining copper chloride mass percent concentration is the first solution of 2.0g/L;
In the present invention, the color and luster of described the first solution is eggshell green.
Second step: in 45 DEG C of bath temperatures, slowly drip NaOH (NaOH) aqueous solution in the first solution under stirring; After dripping sodium hydrate aqueous solution, continue to stir 25 minutes, obtain the second solution;
Rate of addition is 80 droplets/minute;
Mixing speed is 400 revs/min;
The mass percent concentration of sodium hydrate aqueous solution is 80g/L;
In the first solution of 1L, add the sodium hydrate aqueous solution of 0.118L;
In the present invention, the first solution is dripping in NaOH process, and color and luster becomes muddy scape blueness by eggshell green, become subsequently brown, therefore the color and luster of the second solution is brown.
Third step: in 60 DEG C of bath temperatures, slowly drip ascorbic acid (C in the second solution under stirring
6h
8o
6) aqueous solution; After dripping aqueous ascorbic acid, continue to stir 200 minutes, obtain the first suspension;
Rate of addition is 10 droplets/minute;
Mixing speed is 400 revs/min;
The mass percent concentration of aqueous ascorbic acid is 105.7g/L;
In the first solution of 1L, add the aqueous ascorbic acid of 0.118L;
In the present invention, the second solution is in dropping aqueous ascorbic acid process, and color and luster gradually becomes dark brown yellow by brown, therefore the color and luster of the first suspension is dark brown yellow.
The 4th step: the first suspension is carried out to centrifugation, obtain the first sediment;
The first sediment is first carried out to centrifuge washing 3 times by deionized water, carry out centrifuge washing 3 times with absolute ethyl alcohol subsequently, obtain the second sediment; Centrifugation condition is 4500 revs/min, centrifugation time 3 minutes;
The second sediment, after baking temperature is to be dried 6 hours under 45 DEG C of conditions, is obtained to the first pressed powder;
The 5th step: the first pressed powder is adopted to ultrasonic being scattered in ethanol water, obtain the second suspension;
The mass percent concentration of ethanol water is 10%;
The first pressed powder of consumption: 0.1g needs 0.12L ethanol water;
The 6th step: slowly drip gold chloride (HAuCl in the second suspension at 25 DEG C of temperature, under stirring
4) aqueous solution; After dripping aqueous solution of chloraurate, continue to stir 25 minutes, obtain the 3rd suspension;
Mixing speed is 400 revs/min;
The mass percent concentration of aqueous solution of chloraurate is 0.17g/L;
In the second suspension of 0.1L, add the aqueous solution of chloraurate of 0.015L;
The 7th step: the 3rd suspension is placed under the temperature conditions of 50 DEG C, reacts after 4 hours and take out, be cooled to 15 DEG C, obtain the 4th suspension;
The 8th step: the 4th suspension is carried out to centrifugation, obtain the 3rd sediment;
The 3rd sediment is first carried out to centrifuge washing 1 time by deionized water, carry out centrifuge washing 1 time with absolute ethyl alcohol subsequently, obtain the 4th sediment; Centrifugation condition is 4500 revs/min, centrifugation time 3 minutes;
The 4th sediment, after baking temperature is to be dried 6 hours under 40 DEG C of conditions, is obtained to the Cu oxide nano material compound with gold.
In the present invention, Cu oxide is purple brown with the color and luster of golden compound nano material.
In the present invention, if not explanation especially, the device adopting, instrument, equipment, material, technique, method, step, preparation condition etc. are all that the conventional technology that adopt or that those of ordinary skill in the art adopt according to this area routine in this area can easily obtain.
Claims (8)
1. the Cu oxide of a kind of hollow sea urchin shape of preparation and the method for golden compound nano material, is characterized in that including the following step:
First step: after mixing in Copper dichloride dihydrate being dissolved in to deionized water at 15 DEG C～25 DEG C temperature, obtaining copper chloride mass percent concentration is the first solution of 1.5g/L～2.0g/L;
Second step: in 45 DEG C～60 DEG C bath temperatures, slowly drip sodium hydrate aqueous solution in the first solution under stirring; After dripping sodium hydrate aqueous solution, continue to stir 10 minutes～30 minutes, obtain the second solution;
Rate of addition is 50 droplets/minute～80 droplets/minute;
Mixing speed is 200 revs/min～400 revs/min;
The mass percent concentration of sodium hydrate aqueous solution is 80g/L;
In the first solution of 1L, add the sodium hydrate aqueous solution of 0.088L～0.118L;
Third step: in 45 DEG C～60 DEG C bath temperatures, slowly drip aqueous ascorbic acid in the second solution under stirring; After dripping aqueous ascorbic acid, continue to stir 150 minutes～200 minutes, obtain the first suspension;
Rate of addition is 10 droplets/minute～30 droplets/minute;
Mixing speed is 200 revs/min～400 revs/min;
The mass percent concentration of aqueous ascorbic acid is 105.7g/L;
In the first solution of 1L, add the aqueous ascorbic acid of 0.088L～0.118L;
The 4th step: the first suspension is carried out to centrifugation, obtain the first sediment;
The first sediment is first carried out to centrifuge washing 1～3 time by deionized water, carry out centrifuge washing 1～3 time with absolute ethyl alcohol subsequently, obtain the second sediment;
The second sediment, after baking temperature is to be dried 1 hour～6 hours under 40 DEG C～50 DEG C conditions, is obtained to the first pressed powder;
Centrifugation condition: 4000 revs/min～5000 revs/min, centrifugation time 3 minutes～10 minutes;
The 5th step: the first pressed powder is adopted to ultrasonic being scattered in ethanol water, obtain the second suspension;
The mass percent concentration of ethanol water is 10%;
Consumption: the first pressed powder of 1g is added in 0.8L～1.2L ethanol water;
The 6th step: at 15 DEG C～25 DEG C temperature, slowly drip aqueous solution of chloraurate in the second suspension under stirring; After dripping aqueous solution of chloraurate, continue to stir 10 minutes～30 minutes, obtain the 3rd suspension;
Rate of addition is 10 droplets/minute～30 droplets/minute;
Mixing speed is 200 revs/min～400 revs/min;
The mass percent concentration of aqueous solution of chloraurate is 0.17g/L;
In the second suspension of 0.1L, add the aqueous solution of chloraurate of 0.015L～0.025L;
The 7th step: the 3rd suspension is placed under the temperature conditions of 50 DEG C～70 DEG C, reacts after 2～4 hours and take out, be cooled to 15 DEG C～25 DEG C, obtain the 4th suspension;
The 8th step: the 4th suspension is carried out to centrifugation, obtain the 3rd sediment;
The 3rd sediment is first carried out to centrifuge washing 1～3 time by deionized water, carry out centrifuge washing 1～3 time with absolute ethyl alcohol subsequently, obtain the 4th sediment;
Centrifugation condition: 4000 revs/min～5000 revs/min, centrifugation time 3 minutes～10 minutes;
The 4th sediment, after baking temperature is to be dried 1 hour～6 hours under 40 DEG C～50 DEG C conditions, is obtained to the Cu oxide nano material compound with gold;
The Cu oxide making is Cu with the composition of golden compound nano material
2o/Au/CuO composite nano materials.
2. the method for the Cu oxide of preparation hollow sea urchin shape according to claim 1 and golden compound nano material, it is characterized in that: the Cu oxide making is the hollow sea urchin shape particle of the length of side at 450～700nm with the overall pattern of golden compound nano material, and rough surface, the thorn length of burr is 60～150nm.
3. the method for the Cu oxide of preparation hollow sea urchin shape according to claim 1 and golden compound nano material, is characterized in that: the color and luster of described the first solution is eggshell green.
4. the method for the Cu oxide of preparation hollow sea urchin shape according to claim 1 and golden compound nano material, is characterized in that: the color and luster of the second solution is brown.
5. the method for the Cu oxide of preparation hollow sea urchin shape according to claim 1 and golden compound nano material, is characterized in that: the color and luster of the first suspension is dark brown yellow.
6. the method for the Cu oxide of preparation hollow sea urchin shape according to claim 1 and golden compound nano material, is characterized in that: the color and luster of the first pressed powder is rust.
7. the method for the Cu oxide of preparation hollow sea urchin shape according to claim 1 and golden compound nano material, is characterized in that: Cu oxide is purple brown with the color and luster of golden compound nano material.
8. the method for the Cu oxide of preparation hollow sea urchin shape according to claim 1 and golden compound nano material, is characterized in that: the Cu oxide making and golden compound nano material are for making gas sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310141957.3A CN103212708B (en) | 2013-04-13 | 2013-04-13 | Hollow and echinoid nanometer material of copper oxide compounded with gold and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310141957.3A CN103212708B (en) | 2013-04-13 | 2013-04-13 | Hollow and echinoid nanometer material of copper oxide compounded with gold and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103212708A CN103212708A (en) | 2013-07-24 |
| CN103212708B true CN103212708B (en) | 2014-12-10 |
Family
ID=48811045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310141957.3A Expired - Fee Related CN103212708B (en) | 2013-04-13 | 2013-04-13 | Hollow and echinoid nanometer material of copper oxide compounded with gold and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103212708B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105621473B (en) * | 2014-11-06 | 2017-11-14 | 中国科学院宁波材料技术与工程研究所 | The preparation method and pattern and size control method of nano cuprous oxide particle |
| CN107470649B (en) * | 2017-08-01 | 2019-09-10 | 江苏理工学院 | A kind of preparation method of tetrahedral CuCl/Pt alloy |
| CN109632894B (en) * | 2019-01-11 | 2021-05-14 | 东北大学 | Noble metal in-situ co-doped CuO-based NO2Preparation and application of gas-sensitive material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102357659A (en) * | 2011-07-27 | 2012-02-22 | 西安交通大学 | Preparation method of Cu-Cu2O heterogenous junction |
| CN102515243A (en) * | 2011-12-06 | 2012-06-27 | 青岛大学 | Method for preparation of Cu2O and Au/Cu2O core-shell heterostructure nano cube through thermal oxidation |
-
2013
- 2013-04-13 CN CN201310141957.3A patent/CN103212708B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102357659A (en) * | 2011-07-27 | 2012-02-22 | 西安交通大学 | Preparation method of Cu-Cu2O heterogenous junction |
| CN102515243A (en) * | 2011-12-06 | 2012-06-27 | 青岛大学 | Method for preparation of Cu2O and Au/Cu2O core-shell heterostructure nano cube through thermal oxidation |
Non-Patent Citations (8)
| Title |
|---|
| A new strategy for the surface-free-energy-distribution induced selective growth and controlled formation of Cu2O–Au hierarchical heterostructures with a series of morphological evolutions;Zhu, Han, et al.;《Journal of Materials Chemistry A》;20130131;第1卷(第3期);第919-929页 * |
| Cu2O-Au nanocomposites with novel structures and remarkable chemisorption capacity and photocatalytic activity;Hua, Qing, et al.;《Nano Research》;20111031;第4卷(第10期);第948-962页 * |
| Hua, Qing, et al..Cu2O-Au nanocomposites with novel structures and remarkable chemisorption capacity and photocatalytic activity.《Nano Research》.2011,第4卷(第10期), * |
| In situ growth of Au nanoparticles on the surfaces of Cu2O nanocubes for chemical sensors with enhanced performance;Liu,Xiao-Wang,et al.;《RSC Advances》;20121231;第2卷(第20期);第7647-7651页 * |
| Liu,Xiao-Wang,et al..In situ growth of Au nanoparticles on the surfaces of Cu2O nanocubes for chemical sensors with enhanced performance.《RSC Advances》.2012,第2卷(第20期),7647-7651. * |
| Zhu, Han, et al..A new strategy for the surface-free-energy-distribution induced selective growth and controlled formation of Cu2O–Au hierarchical heterostructures with a series of morphological evolutions.《Journal of Materials Chemistry A》.2013,第1卷(第3期), * |
| Zhu，Han et al..Selective growth of Au nanograins on specific positions (tips * |
| Zhu,Han,et al..Selective growth of Au nanograins on specific positions (tips, edges and facets) of Cu 2 O octahedrons to form Cu 2 O–Au hierarchical heterostructures.《Dalton Transactions》.2012,第41卷(第45期),13795-13799. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103212708A (en) | 2013-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103212708B (en) | Hollow and echinoid nanometer material of copper oxide compounded with gold and preparing method thereof | |
| Kolekar et al. | Synthesis by sol–gel method and characterization of ZnO nanoparticles | |
| CN101559973B (en) | Method for preparing nano zinc oxide and crystal whisker zinc oxide by using industrial zinc sulfate as raw material | |
| CN106365204B (en) | Preparation method for the tungstic acid sensitive material of ammonia gas sensor | |
| CN103641165A (en) | Method for preparing titanium dioxide nanotube by using natural mineral as formwork | |
| CN103787401B (en) | Cuprous oxide nanowire material and preparation method thereof | |
| CN103991896A (en) | Spherical zinc oxide nanometer material preparation method | |
| CN108046309B (en) | A kind of super-branched composite nanostructure of hydroxyl zinc fluoride and its synthetic method | |
| CN104591265A (en) | Method for preparing copper-zinc-tin-sulfur nano particles | |
| CN109319826A (en) | A kind of In with core-shell structure2O3The synthetic method of dodecahedron | |
| CN103896323B (en) | A kind of microemulsion prepares the method for nano zine oxide | |
| CN103922399A (en) | Preparation method of zirconium oxide nanospheres | |
| CN104192914A (en) | Preparation method of manganese tungsten single-crystalline nanowire | |
| CN102849786A (en) | Method for preparing cluster indium sulfide material | |
| CN105954325B (en) | A kind of preparation method of rodlike tungsten trioxide nano gas sensitive | |
| CN106938331A (en) | Mesoporous dusty materials of NiAl and preparation method thereof | |
| CN103641147A (en) | Preparation method for micron-order ellipsoidal cerium oxide | |
| CN103950981B (en) | A kind of preparation method of zinc molybdate micro mist | |
| CN105272183A (en) | Preparation method of leucite | |
| CN111099654A (en) | Nano ZnSnO3Preparation method of gas-sensitive material | |
| CN103787402B (en) | Method for preparing cuprous oxide nanowire material | |
| CN104057098A (en) | Preparation method for micro-nano-structure porous copper powder | |
| CN106077694B (en) | A kind of preparation method of spherical cobalt powder | |
| CN104495891A (en) | Preparation method of completely-dispersed aluminum oxide nanoparticles | |
| CN102765944B (en) | Method for preparing mullite powder from fly ash |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141210 Termination date: 20180413 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |