CN102649590B - Method for preparing mesoporous material NiAl2O4 without specific surface active agent - Google Patents

Method for preparing mesoporous material NiAl2O4 without specific surface active agent Download PDF

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CN102649590B
CN102649590B CN201210135017.9A CN201210135017A CN102649590B CN 102649590 B CN102649590 B CN 102649590B CN 201210135017 A CN201210135017 A CN 201210135017A CN 102649590 B CN102649590 B CN 102649590B
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salt
preparation
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nickel
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CN102649590A (en
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汪学广
尚兴付
丁伟中
陆东亮
黄震
鲁雄刚
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Abstract

The invention relates to a preparation method for a worm-like mesoporous material NiAl2O4 and belongs to the technical field of inorganic nano materials. The preparation method comprises the following steps: dissolving nickel salt and aluminum salt into a certain amount of deionized water to prepare stock solution; adding ammonium carbonate solution at the concentration of 1 mol/L into the stock solution dropwise by controlling the quantity of the ammonium carbonate, which is 1.5 times of the sum of the aluminum ions and the nickel ions; transferring colloid formed after titration into a drying oven and drying at the temperature of 110 DEG C for 12 hours; roasting at a temperature ranging from 500 and 800 DEG C for 20 hours at the heating speed of 10 DEG C per minute; and grinding to obtain the worm-like mesoporous material NiAl2O4 with the surface area of 80 to 250 m<2>/g and pore diameter distribution of 4 to 15 nm. The preparation method is simple in process, low in cost, high in purity, high in specific surface area, easy to control and easy to industrialize. The product can be applied in the fields of high-performance composite materials such as catalytic materials, adsorption materials, luminescent materials, magnetic materials, separating materials, high-temperature-resistant materials and the like.

Description

Incomparable tensio-active agent is prepared mesoporous NiAl 2o 4the method of material
Technical field
The present invention relates to the worm meso-porous NiAl of a kind of regular pore size distribution 2o 4the preparation method of material, belongs to technical field of inorganic nanometer material.
Background technology
The definition of pure according to the world in applied chemistry association (IUPAC), porous material can be divided three classes according to the size of their bore dias: the material that aperture is less than 2 nm is poromerics (microporousmaterials); Aperture is mesoporous material (mesoporous materials) at the material of 2-50 nm; The material that aperture is greater than 50 nm is large pore material (macroporous materials).Because mesoporous material has larger internal surface and the hole that allows molecule to enter, thus larger molecule or group can be processed, so the use of such material has been opened up new world for the catalytic cracking of heavy oil, residual oil.Due to the impact of quantum size effect and interface coupling effect, the order mesoporous heterogeneous material compound of acquisition, will have unusual physics, chemical property.In larger mesopore molecular sieve duct, carry out bioorganic chemistry simulation and also become possibility; In addition, at selective oxidation, perfect combustion, NO xthe fields such as degraded, hydrodesulfurization process, photocatalysis to degrade organic matter and solid acid catalysis, fractionation by adsorption have also caused people's extensive concern.Such material will have huge potential application foreground at numerous areas such as chemistry, photoelectronics, electromagnetism, materialogy, environmentalisms.
About NiAl 2o 4report is also few, Journal of Inorganic Materials 8(4), in 1993 499-502 by the Al that is 1:1 1350 ℃ of roasting mol ratios 2o 3obtain NiAl with NiO compounding substances 2o 4, and the NiAl that utilized XRD and XPS analysis 2o 4microtexture.In int ernational journal of hydrogen energy 35 (2010) 11725-11732, with urea combustion, synthesize specific surface and be less than 10 m 2the NiAl of/g 2o 4and studied the catalytic performance of methane reforming hydrogen manufacturing.At present about mesoporous NiAl 2o 4the report of material is also few, chem. Mater. 2000, 12,in 331-335, reported and used NH 4oH is as precipitation agent, 500-700 ℃ of roasting, prepares specific surface up to 177 m 2the mesoporous NiAl of/g 2o 4, but pore size distribution is very wide, very irregular, and the application of material is had to very large restriction.Mesoporous material synthetic generally will be used organism and be done template, and operational condition is generally harsher.Thereby develop a kind of raw material and be easy to get, with low cost, simple to operate, it is convenient to process, and reaction conditions is gentle, is easy to industrialized mesoporous NiAl 2o 4material synthesis method is significant.
Summary of the invention
The object of this invention is to provide a kind of vermiform mesoporous NiAl that has narrow pore size distribution 2o 4the preparation method of material.
A kind of mesoporous NiAl that has narrow pore size distribution of the present invention 2o 4the preparation method of material, is characterized in that having following preparation process and step:
A. a certain amount of aluminium salt and nickel salt are dissolved in deionized water to the preparation aluminum ion solution of 1～4 mol/L and the nickel ion solution of 0.5～2 mol/L; Aluminum ions concentration is 2 times of nickel ion concentration;
B. at 30～90 ℃, dropwise splash into while stirring the sal volatile that concentration is 1～4 mol/L, control the volume of volatile salt, making volatile salt amount of substance is 1.5 times of nickel aluminum ion amount sum; Through reaction, obtain gel;
C. by the gel forming after titration constant temperature ageing 24 hours under temperature of reaction, proceed to subsequently baking oven, at 110 ℃ dry 12 hours;
D. the temperature rise rate with 10 ℃/min by above-mentioned dried gel, 500～800 ℃ of calcinings 20 hours, finally makes mesoporous NiAl 2o 4material.
Described aluminium salt is any in aluminum nitrate, aluminum chloride, Tai-Ace S 150; Take aluminum nitrate as preferential; Described nickel salt is any in nickelous nitrate, nickelous chloride, single nickel salt, take nickelous nitrate as preferential.
Present method, by the method for aluminum soluble salt and nickel salt hydrolysis, is prepared aluminium hydroxide and nickel hydroxide colloidal sol.After dry, deviate from free water, form aluminium hydroxide and nickel hydroxide xerogel.Calcining and decomposing ammonium nitrate and losing in molecule after water, has formed mesoporous NiAl 2o 4material.Reaction equation is as follows:
2Al(NO 3) 3+3(NH 4) 2CO 3 + 3H 2O=2Al(OH) 3 +6NH 4NO 3 + 3CO 2↑
Ni(NO 3) 2+ (NH 4) 2CO 3 + H 2O=Ni(OH) 2+2NH 4NO 3+CO 2 ↑
NH 4nO 3=HNO 3+ NH 3↑ or NH 4nO 3=N 2o ↑+2H 2o
Ni(OH) 2 +2Al(OH) 3 NiAl 2O 4 + 4H 2O
The features and advantages of the invention are as described below:
(1) the present invention adopts saline hydrolysis sol-gel method, and product has a kind of worm meso-porous NiAl with narrow pore size distribution of favorable reproducibility 2o 4, for good basis has been established in the research and development of functional materials.
(2) to take the industrial volatile salt being easy to get be raw material to the selected system of the inventive method, synthesizes a kind of worm meso-porous NiAl 2o 4thereby, greatly reduce production cost, improved the production efficiency of nano material.
(3) the inventive method only needs two kinds of reactive material, by easy reaction, can synthesize the worm meso-porous NiAl of narrow pore size distribution 2o 4, and in reaction, solvent used is water, can recycling, therefore have easy and simple to handle, processing unit is simple, free of contamination advantage, is beneficial to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the structure iron that the product X ray powder diffraction (XRD) of the embodiment of the present invention one obtains.
Fig. 2 is product high power transmission electron microscope (TEM) photo of the embodiment of the present invention one.
Fig. 3 is Nitrogen in Products aspiration desorption and the graph of pore diameter distribution of the embodiment of the present invention one.
Fig. 4 is Nitrogen in Products aspiration desorption and the graph of pore diameter distribution of the embodiment of the present invention two.
Fig. 5 is Nitrogen in Products aspiration desorption and the graph of pore diameter distribution of the embodiment of the present invention three.
Fig. 6 is Nitrogen in Products aspiration desorption and the graph of pore diameter distribution of the embodiment of the present invention four.
Fig. 7 is Nitrogen in Products aspiration desorption and the graph of pore diameter distribution of the embodiment of the present invention five.
Embodiment
After now specific embodiments of the invention being described in.
embodiment 1
Preparation process in the present embodiment is as follows:
(a), under stirring, by 0.1mol aluminum nitrate 0.05mol nickelous nitrate be dissolved in 50 mL deionized waters, form the solution mixing;
(b) under 70 ℃ of constant temperature stir, by 225mL, the sal volatile of 1 mol/L dropwise splashes in above-mentioned solution, forms colloidal sol;
(c), by the ageing 24 hours under 70 ℃ of constant temperature of above-mentioned uniform colloidal sol, transfer in baking oven 110 ℃ and dry 12 hours;
(d) by the sample of step c gained with the temperature rise rate of 10 ℃/min 800 ℃ of roastings 20 hours, grind and obtain mesoporous NiAl 2o 4material.
By this example products therefrom, carry out XRD figure spectrum and measure, and N 2adsorption/desorption is measured BET specific surface area and the pore size distribution of material and is measured.As seen from Figure 1, XRD result shows that product is NiAl 2o 4(consistent with 10-0339 JCPDS card).Fig. 2 is high power transmission electron microscope (TEM) figure of sample.By figure, can clearly find out vermiform pore passage structure.Fig. 3 is example 1 sample N 2suction-desorption isothermal curve and pore size distribution curve (built-in figure).Pore distribution curve is with pore volume, aperture one subdifferential to be mapped, and ordinate zou should be dV/dr, the cm of unit -3.g -1.nm -1, representing that pore volume is with the velocity of variation in aperture, X-coordinate is aperture, unit is nm.Adsorption isotherm line chart, X-coordinate P/P0 represents relative pressure, is zero dimension numerical value, and P is the pounds per square inch absolute (psia) of test point nitrogen, and Po is the saturation vapour pressure of nitrogen under probe temperature, and the adsorption equilibrium pressure that relative pressure is nitrogen is with respect to its saturation vapour pressure size; Ordinate zou is adsorptive capacity, and being has dimension numerical value, the amount of the adsorbate that while referring to balance, unit vol sorbent material adsorbs under equilibrium temperature and pressure.(amount of sorbent material is measured in mass, and the amount of adsorbate is with volume, quality or amount of substance metering, but greatly mainly with adsorbate gas volume metering under the normal conditions (STP), therefore common unit dimension is cm 3/ g or mL/g, be with thereafter STP to be indicated as being the normal conditions.) products therefrom specific surface is 105.27 m 2/ g, mean pore size is 7.23 nm, pore volume is 0.19cm 3/ g, the narrow rule of pore size distribution.
embodiment 2
Concrete steps are as follows:
(a) under stirring, 0.1mol aluminum nitrate 0.05mol nickelous nitrate is dissolved in 20 mL deionized waters, forms the solution mixing;
(b) under 50 ℃ of constant temperature stir, by 225mL, the sal volatile of 1mol/L dropwise splashes in above-mentioned solution, forms colloidal sol;
(c) above-mentioned uniform colloidal sol is turned under 50 ℃ of constant temperature to ageing 24 hours, move on in baking oven 110 ℃ and dry 12 hours;
(d) by the sample of step c gained with the temperature rise rate of 10 ℃/min 500 ℃ of roastings 20 hours, grind and obtain mesoporous NiAl 2o 4material.
The pore size distribution curve of the present embodiment products therefrom and N 2suction-desorption isothermal curve as shown in Figure 4.Products therefrom specific surface is 234.01 m 2/ g, mean pore size is 4.6 nm, pore volume 0.27 cm 3/ g, the narrow rule of pore size distribution.
embodiment 3
Concrete steps are as follows:
(a), under stirring, by 0.1mol aluminum nitrate 0.05mol nickelous nitrate be dissolved in 50 mL deionized waters, form the solution mixing;
(b) under 30 ℃ of constant temperature stir, by 112.5mL, the sal volatile of 2 mol/L dropwise splashes in above-mentioned solution, forms colloidal sol;
(c), by the ageing 24 hours under 30 ℃ of constant temperature of above-mentioned uniform colloidal sol, transfer in baking oven 110 ℃ and dry 12 hours;
(d) by the sample of step c gained with the temperature rise rate of 10 ℃/min 800 ℃ of roastings 20 hours, obtain mesoporous NiAl 2o 4material.
Fig. 5 is the present embodiment gained sample pore size distribution curve and N 2suction-desorption isothermal curve.Products therefrom specific surface is 87.15m 2/ g, mean pore size is 13.5 nm, pore volume is 0.30 cm 3/ g, the narrow rule of pore size distribution.
embodiment 4
Concrete steps are as follows:
(a), under stirring, by 0.1mol aluminum nitrate 0.05mol nickelous nitrate be dissolved in 100 mL deionized waters, form the solution mixing;
(b) under 50 ℃ of constant temperature stir, by 225 mL, the sal volatile of 1mol/L dropwise splashes in above-mentioned solution, forms colloidal sol;
(c), by the ageing 24 hours under 50 ℃ of constant temperature of above-mentioned uniform colloidal sol, transfer in baking oven 110 ℃ and dry 12 hours;
(d) by the sample of step c gained with the temperature rise rate of 10 ℃/min 500 ℃ of roastings 20 hours, obtain mesoporous NiAl 2o 4material.
Fig. 6 is the present embodiment products therefrom pore size distribution curve and N 2suction-desorption isothermal curve.Products therefrom specific surface is 234.92 m 2/ g, mean pore size is 4.70 nm, pore volume is 0.28cm 3/ g, the narrow rule of pore size distribution.
embodiment 5
Concrete steps are as follows:
(a), under stirring, by 0.1mol aluminum nitrate 0.05mol nickelous nitrate be dissolved in 100 mL deionized waters, form the solution mixing;
(b) under 70 ℃ of constant temperature stir, by 56.25 mL, the sal volatile of 4mol/L dropwise splashes in above-mentioned solution, forms colloidal sol;
(c), by the ageing 24 hours under 70 ℃ of constant temperature of above-mentioned uniform colloidal sol, transfer in baking oven 110 ℃ and dry 12 hours;
(d) by the sample of step c gained with the temperature rise rate of 10 ℃/min 600 ℃ of roastings 20 hours, obtain mesoporous NiAl 2o 4material.
Fig. 7 is the present embodiment products therefrom N 2suction-desorption isothermal curve and pore size distribution curve.Products therefrom specific surface is 219.46 m 2/ g, mean pore size is 4.7 nm, pore volume is 0.26 cm 3/ g, the narrow rule of pore size distribution.
the project detecting and the instrument of use thereof
Gained sample is carried out to N 2adsorption/desorption is measured, and BET specific surface area and the pore size distribution of measuring material; Instrument is full-automatic specific surface area and pore size distribution determining instrument fast of the ASAP2020 of U.S. Micromeritics company.Sample need, at 250 ℃ of degassed 5h, be sloughed other material of moisture and physical adsorption.Sample carries out XRD figure spectrum at Rigaku D/max-2550 X-ray diffractometer to be measured, to determine the prepared target product of experiment and purity.Condition determination is CuK α (λ=1.5406), 40KV, 100mA, Scan speed:0.02 ゜/s.Transmission electron microscope photo instrument is JEM-2010F microscope acceleration voltage 200 kV.

Claims (2)

1. the worm meso-porous NiAl of narrow pore size distribution 2o 4the preparation method of material, is characterized in that having following preparation process and step:
A. a certain amount of aluminium salt and nickel salt are dissolved in deionized water to the preparation aluminum ion solution of 1～4 mol/L and the nickel ion solution of 0.5～2.0mol/L; Aluminum ions concentration is 2 times of nickel ion concentration;
B. at 30～70 ℃, dropwise splash into while stirring the sal volatile that concentration is 1～4 mol/L, control the volume of volatile salt, making volatile salt amount of substance is 1.5 times of nickel aluminum ion amount sum; Through reaction, obtain gel;
C. by the gel forming after titration constant temperature ageing 24 hours under temperature of reaction, proceed to subsequently baking oven, at 100-110 ℃ dry 12 hours;
D. the temperature rise rate with 10 ℃/min by above-mentioned dried gel, burns 20 hours 500～800 ℃ of roastings, finally makes mesoporous NiAl 2o 4material.
2. the worm meso-porous NiAl of a kind of narrow pore size distribution as claimed in claim 1 2o 4the preparation method of material, is characterized in that described aluminium salt is any in aluminum nitrate, aluminum chloride, Tai-Ace S 150; Described nickel salt is any in nickelous nitrate, nickelous chloride, single nickel salt.
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CN104028271A (en) * 2014-01-02 2014-09-10 上海大学 Preparation method of mesoporous nickel-magnesium-aluminum oxide with high specific surface area
CN104128187A (en) * 2014-07-02 2014-11-05 上海大学 Ni/La2O3 catalyst used for reforming LPG low water carbon ratio water vapor and preparation method thereof
CN104549289A (en) * 2014-11-26 2015-04-29 上海大学 Mesoporous alumina nickel-based catalyst with high activity and high stability for CO2 reforming CH4 reaction and preparation method of mesoporous alumina nickel-based catalyst
CN105771994A (en) * 2016-03-26 2016-07-20 上海大学 Nano-mesoporous alumina-loaded nickel aluminate catalyst for reforming CH4 by CO2 and preparation method of nano-mesoporous alumina-loaded nickel aluminate catalyst
CN107460019B (en) * 2017-07-14 2019-06-28 华南农业大学 A kind of preparation method of nano-nickel oxide/nickel aluminate carrier of oxygen
CN111180199B (en) * 2019-12-27 2021-09-10 东佳电子（郴州）有限公司 Capacitor with cooling and heat dissipation functions
CN112844296B (en) * 2021-01-14 2024-03-22 辽宁大学 Preparation method of amino modified aluminate adsorption material and application of amino modified aluminate adsorption material in removal of various pollutants

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