CN107601581B - A kind of double pore dimension structure nano crystalline substance cobalt acetate powders and preparation method thereof - Google Patents
A kind of double pore dimension structure nano crystalline substance cobalt acetate powders and preparation method thereof Download PDFInfo
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Abstract
A kind of double pore dimension structure nano crystalline substance cobalt acetate powders and preparation method thereof, belong to field of material technology, the crystallite dimension of powder is 50~100nm, and crystal grain accumulation constitutes space structure, the meso-hole structure of macrovoid and 2~40nm with 150~500nm forms double pore dimension structures；The preparation method comprises the following steps: cobalt nitrate aqueous solution is made in cobalt nitrate and water by (1)；(2) dehydrated alcohol, butyl titanate and complexing agent are stirred evenly into mixing, solution A is made；(3) glacial acetic acid is added and B solution is made；(4) cobalt nitrate aqueous solution is instilled and forms cobalt titanate colloidal sol in B solution；(5) stirring in water bath is to obtaining gel；(6) it is roasted after drying at 550~750 DEG C.Product of the invention has many advantages, such as large specific surface area, and gas diffusion transports easy progress and specific surface area effective rate of utilization is high；Method is easy to operate, and synthesis temperature is low, without complex device, at low cost.
Description
Technical field
The invention belongs to porous material technical field, in particular to a kind of double pore dimension structure nano crystalline substance cobalt acetate powders
And preparation method thereof.
Background technique
The cobalt titanate of perovskite structure is a kind of novel inorganic functional material, in gas sensing, gasoline desulfurization catalyst, wet
Quick detection and photocatalytic degradation etc. suffer from very extensive application.Nanocrystalline barium titanate cobalt is because it is with biggish specific surface
Long-pending and skin effect, small-size effect and quantum size effect etc. have more excellent table than common cobalt titanate when application
It is existing.The method of preparation cobalt titanate nano material includes liquid phase method, vapor phase method and solid phase method, the cobalt titanate of these methods preparation at present
Nano material is light concentration gas poor sensitivity, low, the operating temperature model of selectivity using existing main problem in terms of air-sensitive
It is longer to enclose narrow and response recovery time.
Double scale pore structure nanocrystalline barium titanate cobalt powder bodies can both retain the high-specific surface area and active sites of original nano material
The advantages that point is more, while also there is the classification pore canal system being mutually communicated, provide more gas transport spaces and selectivity
Duct is adsorbed, its adsorbance to object gas can be effectively increased, so as to contract while improving its sensitivity and selectivity
The response of short corresponding gas sensor, recovery time；The preparation method about porous cobalt acetate powder material has template at present
With fused salt assisted self assembling method.Template configuration based on template, pore structure are single；Fused salt assisted self assembling method preparation process
Complexity, high production cost are unfavorable for industrialization.About double scale pore structure nanocrystalline barium titanate cobalt powder body materials and its preparation side
Method has not yet to see relevant report.
Summary of the invention
The purpose of the present invention is intended to provide a kind of double pore dimension structure nano crystalline substance cobalt acetate powders and preparation method thereof, leads to
Cross sol-gal process and be made double pore dimension structures, double pore dimension structures can dramatically increase material effective use area and
To the adsorbance of object gas, to improve corresponding gas sensing performance.
The crystallite dimension of double pore dimension structure nano crystalline substance cobalt acetate powders of the invention is 50~100nm, and crystal grain accumulates structure
At space structure, which has the macrovoid of 150~500nm, while macroporous hole wall is with the mesoporous of 2~40nm
Structure forms double pore dimension structures.
The specific surface area of above-mentioned double pore dimension structure nano crystalline substance cobalt acetate powders is 90.3~102.5m2/g。
Weight content >=98.1% of cobalt titanate in above-mentioned double pore dimension structure nano crystalline substance cobalt acetate powders.
The preparation method of double pore dimension structure nano crystalline substance cobalt acetate powders of the invention sequentially includes the following steps:
(1) by cobalt nitrate and water according to molar ratio 1:(12~50) ratio mixing, obtain cobalt nitrate aqueous solution；
(2) dehydrated alcohol, butyl titanate and complexing agent are stirred evenly into mixing, solution A is made, wherein butyl titanate
Molar ratio with complexing agent is 1:(0.7~3.5)；The mass ratio of dehydrated alcohol and butyl titanate is (9~21): 1；
(3) under agitation, glacial acetic acid is instilled in solution A, until B solution is made 2.5~6 in pH value；
(4) under agitation, cobalt nitrate aqueous solution is instilled in B solution, the additional amount of cobalt nitrate aqueous solution presses nitric acid
The molar ratio of cobalt and butyl titanate is 1:1, continues stirring until to form cobalt titanate colloidal sol after instillation；
(5) cobalt titanate colloidal sol is stirred continuously until under water bath condition and obtains cobalt titanate gel, bath temperature range 40
~70 DEG C；
(6) gained cobalt titanate gel is dried at least 2h under the conditions of 80~105 DEG C, then roasts 1 at 550~750 DEG C
~4h obtains double pore dimension structure nano crystalline substance cobalt acetate powders.
Above-mentioned complexing agent is diethanol amine or acetylacetone,2,4-pentanedione.
In above-mentioned step (4), the instillation speed of cobalt nitrate aqueous solution is 1~4mL/min.
In above-mentioned step (4), mixing speed is 500~1000rpm.
The invention has the following beneficial effects: (1) by sol-gal process be prepared have 2~40nm and 150~
The nanocrystalline barium titanate cobalt powder body material of the high gas sensitivity of two kinds of pore dimension structures of 500nm；(2) nanocrystalline barium titanate prepared
Cobalt powder body has three-D pore structure, and macroporous wall surface is accumulated by cobalt titanate nano-crystalline granule, particle packing fine pore
It is interlaced with macrovoid, there is large specific surface area, gas diffusion, which transports, is easy progress and specific surface area effective rate of utilization height etc.
Advantage；(3) when overcoming existing via sol-gel template method and preparing porous material, template synthesizes difficulty, complex process, cost
The disadvantages of being mutually communicated property between excessively high and duct is poor, and easy to operate, synthesis temperature is low, without complex device, at low cost.
Detailed description of the invention
Fig. 1 is the XRD diagram of double pore dimension structure nano crystalline substance cobalt acetate powders in embodiment 2；
Fig. 2 is the scanning electron microscope (SEM) photograph of double pore dimension structure nano crystalline substance cobalt acetate powders in embodiment 2；(a) is in figure
The pattern of big pore size distribution on 10000 × powder is (b) 60000 × lower nano-crystalline granule accumulation pattern mesoporous into small scale；
Fig. 3 be double pore dimension structure nano crystalline substance cobalt acetate powders in embodiment 2 BJH absorption pore size distribution curve and
Absorption/desorption isothermal curve figure.
Specific embodiment
Cobalt nitrate hexahydrate, dehydrated alcohol, butyl titanate, diethanol amine, the acetylacetone,2,4-pentanedione used in the embodiment of the present invention
It is market analytical pure reagents with glacial acetic acid.
The water used in the embodiment of the present invention is deionized water.
Material phase analysis test uses Shimadzu XRD-7000 type X-ray diffractometer in the embodiment of the present invention.
Microscopic appearance detection uses Hitachi SU8010 field emission scanning electron microscope in the embodiment of the present invention.
The equipment that the detection of central hole structure of the embodiment of the present invention uses is 4800 specific surface area of V-Sorb and Porosimetry.
Embodiment 1
Using 1.94g cobalt nitrate hexahydrate, cobalt nitrate and water are mixed according to the ratio of molar ratio 1:20, obtain cobalt nitrate water
Solution；
Dehydrated alcohol, butyl titanate and complexing agent diethanol amine are stirred evenly into mixing, solution A, four fourth of metatitanic acid is made
The molar ratio of ester and complexing agent is 1:0.7；The mass ratio of dehydrated alcohol and butyl titanate is 18:1；
Under agitation, glacial acetic acid is instilled in solution A, until pH value is 4.5, B solution is made；
Under the conditions of low whipping speed 500rpm, cobalt nitrate aqueous solution is instilled in B solution, instillation speed is 1mL/min, nitre
The additional amount of sour cobalt aqueous solution is 1:1 by the molar ratio of cobalt nitrate and butyl titanate, continues stirring until to be formed after instillation
Cobalt titanate colloidal sol (according to Tyndall phenomenon)；
Container equipped with cobalt titanate colloidal sol is placed in water-bath, is stirred continuously until and obtains cobalt titanate gel, bath temperature
40℃；
Gained cobalt titanate gel is put into baking oven, dry 3h under the conditions of 90 DEG C；It is then placed in Muffle furnace, at 550 DEG C
4h is roasted, double pore dimension structure nano crystalline substance cobalt acetate powders are obtained；
The crystallite dimension of double pore dimension structure nano crystalline substance cobalt acetate powders is 50~100nm, and crystal grain accumulation constitutes space
Structure, which has the macrovoid of 150~500nm, while macroporous hole wall has the meso-hole structure of 2~40nm,
Form double pore dimension structures, specific surface area 92.6m2/ g, cobalt titanate weight content 98.7%.
Embodiment 2
With embodiment 1, difference is method:
(1) the molar ratio 1:12 of cobalt nitrate and water；
(2) molar ratio of butyl titanate and complexing agent is 1:1.5 in solution A；The matter of dehydrated alcohol and butyl titanate
Measuring ratio is 21:1；
(3) it is 3.5 that glacial acetic acid, which instills solution A to pH value,；
(4) under the conditions of low whipping speed 600rpm, cobalt nitrate aqueous solution is instilled in B solution, instillation speed is 1.5mL/
min；
(5) 45 DEG C of bath temperature；
(6) 105 DEG C of drying temperature, time 2h；650 DEG C of maturing temperature, time 2h；
The specific surface area of double pore dimension structure nano crystalline substance cobalt acetate powders is 102.5m2/ g, cobalt titanate weight content
98.9%；
Object phase composition XRD analysis roasted as shown in Figure 1, as seen from the figure, at 650 DEG C cobalt titanate that 2h is obtained 23.9 °,
32.8 °, 35.39 °, 40.5 °, 49.0 °, 53.4 °, 56.8 °, 61.9 °, 63.8 ° and 71.3 ° have characteristic peak, respectively correspond metatitanic acid
(012) of cobalt, (104), (110) (113), (024), (116), (018), (214), (300) and (119) crystal face, with standard card
It is consistent in piece JCPDS:15-0866；
Electron-microscope scanning result is as shown in Fig. 2, as it can be seen that product has, there are two types of pore dimension structures from Fig. 2 (a) and (b), greatly
Pore diameter is evenly distributed on powder body material within the scope of 150~500nm；The large scale hole be using polymer phase with
Solvent split-phase and formed, " solvent phase " volatilizees in drying process, to form the more uniform large scale hole of distribution；It is another
Aspect, the hole wall after roasting around large scale hole are accumulated by nanocrystalline barium titanate cobalt crystal grain, 50~100nm of crystallite dimension,
Crystal grain accumulates the pore diameter to be formed between 2~40nm, forms the hole of second of scale；
BJH adsorbs pore size distribution curve and absorption/desorption isotherm as shown in figure 3, the specific surface area that BET is calculated is
102.5m2/g；As seen from the figure, in N2 adsorption test pore diameter range (2~150nm), containing the mesoporous of 2~40nm in product,
Most probable pore size is 2-10nm；Absorption/desorption isotherm hysteresis loop is from low pressure point P/P0=0.35 initially forms, and arrives P/P0=
Adsorbance is significantly raised at 0.95, shows nanocrystalline barium titanate cobalt powder body material prepared by the present invention in addition to mesoporous, also containing certain
The macropore of quantity.
Embodiment 3
With embodiment 1, difference is method:
(1) the molar ratio 1:50 of cobalt nitrate and water；
(2) molar ratio of butyl titanate and complexing agent is 1:2 in solution A；The quality of dehydrated alcohol and butyl titanate
Than being 15:1；
(3) it is 2.5 that glacial acetic acid, which instills solution A to pH value,；
(4) under the conditions of low whipping speed 700rpm, cobalt nitrate aqueous solution is instilled in B solution, instillation speed is 2mL/
min；
(5) 50 DEG C of bath temperature；
(6) 95 DEG C of drying temperature, time 4h；600 DEG C of maturing temperature, time 3.5h；
The specific surface area of double pore dimension structure nano crystalline substance cobalt acetate powders is 95.3m2/ g, cobalt titanate weight content
98.3%.
Embodiment 4
With embodiment 1, difference is method:
(1) the molar ratio 1:30 of cobalt nitrate and water；
(2) complexing agent is acetylacetone,2,4-pentanedione, and the molar ratio of butyl titanate and complexing agent is 1:2.5 in solution A；Dehydrated alcohol
Mass ratio with butyl titanate is 17:1；
(3) it is 5.5 that glacial acetic acid, which instills solution A to pH value,；
(4) under the conditions of low whipping speed 800rpm, cobalt nitrate aqueous solution is instilled in B solution, instillation speed is 2.5mL/
min；
(5) 55 DEG C of bath temperature；
(6) 85 DEG C of drying temperature, time 4.5h；700 DEG C of maturing temperature, time 2.5h；
The specific surface area of double pore dimension structure nano crystalline substance cobalt acetate powders is 90.3m2/ g, cobalt titanate weight content
98.5%.
Embodiment 5
With embodiment 1, difference is method:
(1) the molar ratio 1:40 of cobalt nitrate and water；
(2) complexing agent is acetylacetone,2,4-pentanedione, and the molar ratio of butyl titanate and complexing agent is 1:3 in solution A；Dehydrated alcohol with
The mass ratio of butyl titanate is 14:1；
(3) it is 6 that glacial acetic acid, which instills solution A to pH value,；
(4) under the conditions of low whipping speed 900rpm, cobalt nitrate aqueous solution is instilled in B solution, instillation speed is 3mL/
min；
(5) 60 DEG C of bath temperature；
(6) 80 DEG C of drying temperature, time 5h；730 DEG C of maturing temperature, time 2h；
The specific surface area of double pore dimension structure nano crystalline substance cobalt acetate powders is 97.4m2/ g, cobalt titanate weight content
98.2%.
Embodiment 6
With embodiment 1, difference is method:
(1) the molar ratio 1:35 of cobalt nitrate and water；
(2) complexing agent is acetylacetone,2,4-pentanedione, and the molar ratio of butyl titanate and complexing agent is 1:3.5 in solution A；Dehydrated alcohol
Mass ratio with butyl titanate is 9:1；
(3) it is 6 that glacial acetic acid, which instills solution A to pH value,；
(4) under the conditions of low whipping speed 1000rpm, cobalt nitrate aqueous solution is instilled in B solution, instillation speed is 4mL/
min；
(5) 70 DEG C of bath temperature；
(6) 100 DEG C of drying temperature, time 2h；750 DEG C of maturing temperature, time 1h；
The specific surface area of double pore dimension structure nano crystalline substance cobalt acetate powders is 91.5m2/ g, cobalt titanate weight content
98.1%.
Claims (4)
1. a kind of preparation method of double pore dimension structure nano crystalline substance cobalt acetate powders, it is characterised in that sequentially include the following steps:
(1) by cobalt nitrate and water according to molar ratio 1:(12 ~ 50) ratio mixing, obtain cobalt nitrate aqueous solution；
(2) dehydrated alcohol, butyl titanate and complexing agent are stirred evenly into mixing, solution A is made, wherein butyl titanate and network
The molar ratio of mixture is 1:(0.7 ~ 3.5)；The mass ratio of dehydrated alcohol and butyl titanate is (9 ~ 21): 1；
(3) under agitation, glacial acetic acid is instilled in solution A, until B solution is made 2.5 ~ 6 in pH value；
(4) under agitation, cobalt nitrate aqueous solution is instilled in B solution, the additional amount of cobalt nitrate aqueous solution by cobalt nitrate with
The molar ratio of butyl titanate is 1:1, continues stirring until to form cobalt titanate colloidal sol after instillation；
(5) cobalt titanate colloidal sol is stirred continuously until under water bath condition and obtains cobalt titanate gel, bath temperature range 40 ~ 70
℃；
(6) by gained cobalt titanate gel, dry at least 2h is obtained then in 550 ~ 750 DEG C of 1 ~ 4h of roasting under the conditions of 80 ~ 105 DEG C
Double pore dimension structure nano crystalline substance cobalt acetate powders are obtained, crystallite dimension is 50 ~ 100nm, and crystal grain accumulation constitutes space structure, is somebody's turn to do
Space structure has the macrovoid of 150 ~ 500 nm, while macroporous hole wall has the meso-hole structure of 2 ~ 40 nm, forms double rulers
Spend pore structure.
2. the preparation method of double pore dimension structure nano crystalline substance cobalt acetate powders according to claim 1, it is characterised in that
The complexing agent is diethanol amine or acetylacetone,2,4-pentanedione.
3. the preparation method of double pore dimension structure nano crystalline substance cobalt acetate powders according to claim 1, it is characterised in that
In step (4), the instillation speed of cobalt nitrate aqueous solution is 1 ~ 4mL/min.
4. the preparation method of double pore dimension structure nano crystalline substance cobalt acetate powders according to claim 1, it is characterised in that
In step (4), mixing speed is 500 ~ 1000rpm.
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| CN109607518A (en) * | 2018-12-10 | 2019-04-12 | 陕西科技大学 | A kind of preparation method of the highly selective sensitive thin film of pair of alcohol gas |
| CN110104678B (en) * | 2019-05-16 | 2021-10-08 | 沈阳工业大学 | Cobalt titanate gas-sensitive material with high sensitivity to low-concentration ethanol and preparation method thereof |
| CN115304986A (en) * | 2022-08-25 | 2022-11-08 | 安徽中科思沃生物科技有限公司 | Shell powder-based photocatalytic self-cleaning mildew-proof interior wall coating and preparation method thereof |
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| CN103730259A (en) * | 2013-12-27 | 2014-04-16 | 沈阳工业大学 | Nanocrystalline titanium dioxide film of two-specification pore structure and manufacturing method of nanocrystalline titanium dioxide film |
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| CN103730259A (en) * | 2013-12-27 | 2014-04-16 | 沈阳工业大学 | Nanocrystalline titanium dioxide film of two-specification pore structure and manufacturing method of nanocrystalline titanium dioxide film |
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| Low-temperature ultrasound synthesis of nanocrystals CoTiO3 without a calcination step: Effect of ultrasonic waves on formation of the crystal growth mechanism;Abdolmajid Moghtada等;《Advanced Powder Technology》;20161122;1109–1117页 |
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