CN103663559B - Dibismuth trimolybdenum dodecaoxide nanocrystalline as well as preparation method and application thereof - Google Patents
Dibismuth trimolybdenum dodecaoxide nanocrystalline as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to dibismuth trimolybdenum dodecaoxide nanocrystalline as well as a preparation method and application thereof. The dibismuth trimolybdenum dodecaoxide nanocrystalline is synthesized by virtue of the following three steps: 1) hydro-thermally synthesizing a monocrystal molybdenum oxide nanometer quadrate bar shaped material; 2) depositing Bi species on a crystal face at the outer surface {100} of the monocrystal molybdenum oxide nanometer quadrate bar shaped structure to form an 'embedded composite structure'; 3) performing solid-state chemical reaction under controlled nanoscale on the crystal face of the monocrystal molybdenum oxide {100} to form alpha-dibismuth trimolybdenum dodecaoxide nanocrystalline. The dibismuth trimolybdenum dodecaoxide nanocrystalline can be used for industrially producing acraldehyde by selective oxidizing of propylene.
Description
Technical field
The present invention relates to that a kind of bismuth molybdate is nanocrystalline, preparation method and application thereof.
Background technology
In field of catalytic chemistry, bismuth molybdate is the catalytic material important in petrochemical industry of a class.In selective oxidation reaction, the catalyst series of molybdenum bismuth system is one of most important Industrial Catalysis material.In the company's oxidation that first catalyst series of bismuth molybdate system is applied to propylene of USS oil and ammonia oxidation.Domestic, Shanghai Petroleum Chemical Engineering Institute of China Petrochemical Industry have developed a series of catalyst of ammoxidation for propylene in industrial production in the eighties in last century.Meanwhile, bismuth molybdate catalysts also may be used in the reactions such as Oxidative Dehydrogenation of Butene into Butadiene.Generally believe that in the molybdenum bismuth System Catalyst of multi-component metal oxide, active ingredient is bismuth molybdate.
It is large that nano structural material has specific surface area, interface atoms is many, and interface zone atomic diffusivity is high, and has preferentially high preferred orientation and very high chemically reactive, therefore, nano-particle catalyst has the attention of high activity and the excellent selectivity person that caused catalyst operation.Active ingredient in molybdenum bismuth System Catalyst is bismuth molybdate, and preparing the nanocrystalline innovation for molybdenum bismuth System Catalyst of bismuth molybdate provides new thinking.
Because molybdate has complicated crystalline structure, therefore, the relatively difficult synthesis of nanostructure molybdate material, particularly bismuth molybdate is nanocrystalline.
Summary of the invention
It is nanocrystalline that one of technical problem to be solved by this invention is to provide a kind of new bismuth molybdate.Two of technical problem to be solved by this invention is to provide the nanocrystalline preparation method of a kind of described bismuth molybdate.Three of technical problem to be solved by this invention is to provide the nanocrystalline purposes of a kind of described bismuth molybdate.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of bismuth molybdate is nanocrystalline, and its structure is monoclinic structure α-Bi
2mo
3o
12, size is 20 ~ 50 nanometers.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the preparation method that a kind of bismuth molybdate is nanocrystalline, comprises the following steps:
A) molybdenum source is dissolved in solvent I, forms mixture I; By mixture I under 150 ~ 200 DEG C of conditions, hydrothermal crystallizing 1 ~ 48 hour, obtains intermediate A; Wherein, described molybdenum source is selected from molybdenum oxide or Ammonium Heptamolybdate; Solvent I is selected from the hydrogen peroxide of 5 ~ 15 mol/L, hydrochloric acid, nitric acid or aqueous sulfuric acid; The weight ratio of molybdenum source and solvent I is 1/4 ~ 1/50;
B) intermediate A is added in solvent II, form mixture II; At room temperature joined in Bi source among mixture II, ageing 0.5 ~ 24 hour, obtains intermediate B after washing; Wherein, the weight ratio of intermediate A and solvent II is 1/10 ~ 1/50, and solvent II is the mixture of water and alcohol, and the weight ratio of water and alcohol is 1/1 ~ 25/1, and alcohol is selected from ethanol, propyl alcohol or propylene glycol; Mixture II is 1/5 ~ 1/40 with the weight ratio of inorganic salt;
C) intermediate B heats 1 ~ 48 hour under 350 ~ 450 DEG C of conditions, obtains described bismuth molybdate nanocrystalline.
In technique scheme, step a), hydrothermal crystallizing temperature preferable range is 155 ~ 190 DEG C, and hydrothermal crystallizing time preferable range is 10 ~ 30 hours; Molybdenum source preferred version is for being selected from molybdenum oxide, and solvent I preferred version is for being selected from hydrogen peroxide or hydrochloric acid soln.Step b), in solvent II, the weight ratio preferable range of water and alcohol is 10/1 ~ 20/1.Step c), temperature preferable range is 320 ~ 400 DEG C, and time preferable range is 5 ~ 20 hours.Bi source preferred version is for being selected from Bismuth trinitrate or bismuth chloride.
In technique scheme, described intermediate A is the α-MoO of nanometer monocrystalline four square rod
3, belong to rhombic system, outside surface is { the 100} crystal face of rhombic system.Described intermediate B structure is BiO
xload { " the preparation structure " of 100} crystal face bar-shaped in monocrystalline molybdenum oxide four directions.
The preparation method that bismuth molybdate of the present invention is nanocrystalline, first, by the method for hydrothermal recrystallization method, prepares monocrystalline molybdenum oxide nanometer four square rod; Then, by controlled hydrolysis sedimentation chemistry method, so that the outside surface of monocrystalline molybdenum oxide nanometer four directions club shaped structure to deposit Bi
3+species, { 100} crystal face supports " the preparation structure " of Bi species to form monocrystalline molybdenum oxide nanometer four square rod outside surface; Finally, by controlling at monocrystalline molybdenum oxide nanometer four square rod, { on 100} crystal face, solid state reaction occurs, and to the thermal treatment under still air of different composite structure, the α-bismuth molybdate finally preparing different size is nanocrystalline.Wherein, nano-crystalline granule is all less than 50nm.
In technique scheme, described monocrystalline molybdenum oxide precursor is homogeneous cubic club shaped structure, and single cubic club shaped structure length is 1 ~ 10 μm, and wide is 100 ~ 200nm, and height is 20 ~ 40nm; Described cubic club shaped structure is the growth of [001] direction, and outside surface is { the 100} crystal face of rhombic system.
The inventive method utilizes monocrystalline molybdenum oxide nano rod, the molybdenum oxide nanometer four directions club shaped structure of controlled hydrolysis formation of deposits Bi species load, then control at rhombic system molybdenum oxide { 100} outside surface generation solid state reaction, α-the bismuth molybdate preparing below 50nm is nanocrystalline, achieves good technical result.Research find, this α-bismuth molybdate nanocrystalline molybdenum oxide { 100} crystal face grows along oblique system [011] direction.
Bismuth molybdate has three kinds of crystal formations, is α-Bi respectively
2mo
3o
12, β-Bi
2mo
2o
9, γ-Bi
2moO
6.α-Bi
2mo
3o
12crystalline structure be similar to tetragonal spheroidal scheelite-type structure, there is no obvious laminate structure.Scheelite-type structure (AMO4) there is no obvious reactive behavior, and the defect scheelite-type structure containing positively charged ion hole has reactive behavior, changes this is because defect structure can cause in the anionic nature of oxygen.α-Bi
2mo
3o
12containing two MoO
4tetrahedron correspond to Bi
3+ion, another one MoO
4tetrahedron correspond to cationic room, and therefore the scheelite-type structure of this defect is conducive to lattice oxygen in the inner mutually flowing of catalyst body, in the selective oxidation reaction of low-carbon (LC) hydro carbons, have very high reactive behavior.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: described bismuth molybdate is nanocrystalline produces the catalyzer of propenal for Selective Oxidation of Propylene.Wherein with propylene and air for raw material, propylene and oxygen molar ratio are 1/5 ~ 1/10, and temperature of reaction is 300 ~ 400 DEG C, and reaction pressure is 0.8 ~ 2MPa, and air speed is 1000 ~ 5000 hours
-1.
Bismuth molybdate of the present invention is nanocrystalline can be used for the reaction that Selective Oxidation of Propylene generates propenal, and bismuth molybdate is nanocrystalline just propylene oxidation activity (573 K) at low temperatures, and common bismuth molybdate material until 623 K just respond activity.Under same reaction temperature, the nanocrystalline converting propylene number in unit surface of bismuth molybdate is higher than nearly 2 orders of magnitude of common bismuth molybdate material.In reaction kinetics research, the rate constant of the nanocrystalline catalyzing propone of bismuth molybdate is higher than 7 to 8 times of common bismuth molybdate material, therefore, in propylene oxidation performance, be better than common bismuth molybdate material so that the bismuth molybdate of [011] direction growth is nanocrystalline comprehensively, achieve good technique effect.
Accompanying drawing explanation
Fig. 1 is the X-ray powder diffraction of intermediate A, B and the finished product bismuth molybdate synthesized in the present invention's [embodiment 2].
Fig. 2 is the projection Electronic Speculum figure of the finished product bismuth molybdate of synthesis in the present invention's [embodiment 2].
Fig. 3 is the scanning electron microscope (SEM) photograph of the finished product bismuth molybdate of synthesis in the present invention's [embodiment 2].
In Fig. 1, a is monocrystalline molybdenum oxide nano rod, i.e. intermediate A.B is the molybdenum oxide nano rod of bismuth hydroxide parcel, i.e. intermediate B, and this illustrates that shell is amorphous.C is that the bismuth molybdate of the finished product 20 ~ 30nm of synthesis in [embodiment 2] is nanocrystalline, and display finally defines α-bismuth molybdate.
Fig. 2, in display [embodiment 2], the α-bismuth molybdate of synthesis is nanocrystalline, and size is 20 ~ 50nm, and nanocrystalline load is in molybdenum oxide nano rod.
Fig. 3, in display [embodiment 2], α-bismuth molybdate of synthesis is nanocrystalline, nanocrystallinely bar-shapedly { 100} crystal face to grow in monocrystalline molybdenum oxide four directions with [011] direction.
Below by embodiment, the present invention is further elaborated.
Embodiment
α-bismuth molybdate Syntheses the method for open below 50nm in the present invention, whole technique is divided into three parts: first, utilizes the chemical process of hydrothermal recrystallization method, prepares molybdenum oxide nanometer four directions club shaped structure; Secondly, use the chemical synthesis process of controlled hydrolysis deposition, load Bi species on the bar-shaped outside surface in molybdenum oxide nanometer four directions prepared by previous step, form the molybdenum oxide nanometer four directions club shaped structure of different amount Bi load; Finally, in still air atmosphere, the molybdenum oxide nanometer four directions club shaped structure of difference amount Bi load prepared by previous step is heat-treated, molybdenum oxide nanometer four directions club shaped structure { 100} crystal face controls solid state reaction, finally, the α-bismuth molybdate obtained based on below the 50nm of molybdenum oxide nanometer four directions club shaped structure load is nanocrystalline.
[embodiment 1]
Get 30% H that commodity molybdenum oxide powder 10mmol joins 70ml
2o
2in solution, stirring at room temperature 1 day, then transfers in hydrothermal reaction kettle, keeps 24 hours at 180 DEG C of baking ovens.Then take out, centrifugation, adopt deionized water wash three times, then washing with alcohol three times, oven drying at low temperature obtains white powder, is molybdenum oxide nanometer four directions club-shaped material.
Join in water and ethanol mixed system by the molybdenum oxide nanometer of above-mentioned preparation four directions club-shaped material, form mixture, wherein, the ratio of water and ethanol is 5/1.Then, 48.0g Bismuth trinitrate is dissolved in 100ml aqueous ethanolic solution, the mol ratio of water and ethanol is 1/10, join in mixture, ageing 5 ~ 10 hours, centrifugal, washing, dry, obtain " preparation structure " that monocrystalline molybdenum oxide nanometer four square rod outside surface supports Bi species.
" the preparation structure " of above-mentioned preparation is transferred to baking oven, and in static atmosphere of air, keep 10 hours with the temperature rise rate to 400 of 10K/min DEG C, naturally cooling, obtains the powder of grey; α-the bismuth molybdate being molybdenum oxide load is nanocrystalline, and nanocrystalline size is 40 ~ 50nm.
[embodiment 2]
Get 30% H that commodity molybdenum oxide powder 10mmol joins 70ml
2o
2in solution, stirring at room temperature 1 day, then transfers in hydrothermal reaction kettle, keeps 24 hours at 180 DEG C of baking ovens.Then take out, centrifugation, adopt deionized water wash three times, then washing with alcohol three times, oven drying at low temperature obtains white powder, is molybdenum oxide nanometer four directions club-shaped material.
Join in water and ethanol mixed system by the molybdenum oxide nanometer of above-mentioned preparation four directions club-shaped material, form mixture, wherein, the ratio of water and ethanol is 5/1.Then, 48.0g Bismuth trinitrate is dissolved in 100ml aqueous glycol solution, the mol ratio of water and ethylene glycol is 1/5, join in mixture, ageing 5 ~ 10 hours, centrifugal, washing, dry, obtain " preparation structure " that monocrystalline molybdenum oxide nanometer four square rod outside surface supports Bi species.
" the preparation structure " of above-mentioned preparation is transferred to baking oven, and in static atmosphere of air, keep 10 hours with the temperature rise rate to 400 of 10K/min DEG C, naturally cooling, obtains the powder of grey; α-the bismuth molybdate being molybdenum oxide load is nanocrystalline, and nanocrystalline size is 20 ~ 30nm.
[embodiment 3]
The hydrochloric acid of 2 M is dropwise joined in the Ammoniun Heptamolybdate Solution of 10mmol, stirring at room temperature 1 day, then get 70ml solution and transfer in hydrothermal reaction kettle, keep 24 hours at 180 DEG C of baking ovens.Then take out, centrifugation, adopt deionized water wash three times, then washing with alcohol three times, oven drying at low temperature obtains white powder, is molybdenum oxide nanometer four directions club-shaped material.
Join in water and ethanol mixed system by the molybdenum oxide nanometer of above-mentioned preparation four directions club-shaped material, form mixture, wherein, the ratio of water and ethanol is 5/1.Then, 48.0g Bismuth trinitrate is dissolved in 100ml aqueous propanol solution, the mol ratio of water and propyl alcohol is 1/5, join in mixture, ageing 5 ~ 10 hours, centrifugal, washing, dry, obtain " preparation structure " that monocrystalline molybdenum oxide nanometer four square rod outside surface supports Bi species.
" the preparation structure " of above-mentioned preparation is transferred to baking oven, and in static atmosphere of air, keep 10 hours with the temperature rise rate to 400 of 10K/min DEG C, naturally cooling, obtains the powder of grey; α-the bismuth molybdate being molybdenum oxide load is nanocrystalline, and nanocrystalline size is 20 ~ 30nm.
[embodiment 4]
The hydrochloric acid of 2 M is dropwise joined in the Ammoniun Heptamolybdate Solution of 10mmol, stirring at room temperature 1 day, then get 70ml solution and transfer in hydrothermal reaction kettle, keep 24 hours at 180 DEG C of baking ovens.Then take out, centrifugation, adopt deionized water wash three times, then washing with alcohol three times, oven drying at low temperature obtains white powder, is molybdenum oxide nanometer four directions club-shaped material.
Join in water and ethanol mixed system by the molybdenum oxide nanometer of above-mentioned preparation four directions club-shaped material, form mixture, wherein, the ratio of water and ethanol is 5/1.Then, 48.0g Bismuth trinitrate is dissolved in 100ml aqueous solution of propylene glycol, the mol ratio of water and propylene glycol is 1/8, join in mixture, ageing 5 ~ 10 hours, centrifugal, washing, dry, obtain " preparation structure " that monocrystalline molybdenum oxide nanometer four square rod outside surface supports Bi species.
" the preparation structure " of above-mentioned preparation is transferred to baking oven, and in static atmosphere of air, keep 10 hours with the temperature rise rate to 400 of 10K/min DEG C, naturally cooling, obtains the powder of grey; α-the bismuth molybdate being molybdenum oxide load is nanocrystalline, and nanocrystalline size is 30 ~ 40nm.
[embodiment 5]
Catalyzed reaction characterizes: get α-bismuth molybdate nanocrystalline catalyst that 0.2 gram above-mentioned [embodiment 2] synthesize and join in heterogeneous fixed bed micro-reaction device, by propylene and air, heat and react.Wherein, temperature of reaction is 350 DEG C, and reaction pressure is 1.2MPa, and the mol ratio of propylene and oxygen is 1/10, and air speed is 2200 h
-1.α-bismuth molybdate is nanocrystalline is designated as MoBi-n, and reaction result is in table 1.
[comparative example 1]
By 2mmol Bi (NO
3)
3with the aqueous solution of 3mmol Sodium orthomolybdate, coprecipitation method mixes, and ageing 1 ~ 10 hour is centrifugal, and for several times, 80 DEG C of dryings 10 hours, then, 500 DEG C of roastings 1 ~ 10 hour, form block α-bismuth molybdate material, be designated as MoBi-c, react with [embodiment 5] in washing.Reaction result is in table 1.
[comparative example 2]
The intermediate A molybdenum oxide nanometer four directions club-shaped material [embodiment 2] synthesized, reacts with [embodiment 5].Reaction result is in table 1.
Table 1
[a] specific activity: the propylene molecules number of catalytic conversion in unit time per surface area.
[b]
k: propylene oxidation reaction rate constant (mol min
-1pa
-0.6).
Claims (5)
1. the preparation method that bismuth molybdate is nanocrystalline, described bismuth molybdate nanocrystalline structure is monoclinic structure α-Bi
2mo
3o
12, grain size is 20 ~ 50 nanometers, comprises the following steps:
A) molybdenum source is dissolved in solvent I, forms mixture I; By mixture I under 150 ~ 200 DEG C of conditions, hydrothermal crystallizing 1 ~ 48 hour, obtains intermediate A; Wherein, described molybdenum source is selected from molybdenum oxide or Ammonium Heptamolybdate; Solvent I is selected from the hydrogen peroxide of 5 ~ 15 mol/L, hydrochloric acid, nitric acid or aqueous sulfuric acid; The weight ratio of molybdenum source and solvent I is 1/4 ~ 1/50;
B) intermediate A is added in solvent II, form mixture II; At room temperature joined in Bi source among mixture II, ageing 0.5 ~ 24 hour, obtains intermediate B after washing; Wherein, the weight ratio of intermediate A and solvent II is 1/10 ~ 1/50, and solvent II is the mixture of water and alcohol, and the weight ratio of water and alcohol is 1/1 ~ 25/1, and alcohol is selected from ethanol, propyl alcohol or propylene glycol; Mixture II is 1/5 ~ 1/40 with the weight ratio in described Bi source;
C) intermediate B heats 1 ~ 48 hour under 350 ~ 450 DEG C of conditions, obtains described bismuth molybdate nanocrystalline;
Described Bi source is selected from Bismuth trinitrate or bismuth chloride.
2. the preparation method that bismuth molybdate is nanocrystalline according to claim 1, is characterized in that step a), and hydrothermal crystallizing temperature is 155 ~ 190 DEG C, and the hydrothermal crystallizing time is 10 ~ 30 hours; Molybdenum source is selected from molybdenum oxide, and solvent I is selected from hydrogen peroxide or hydrochloric acid soln.
3. the preparation method that bismuth molybdate is nanocrystalline according to claim 1, is characterized in that step b), in solvent II, the weight ratio of water and alcohol is 10/1 ~ 20/1.
4. the preparation method that bismuth molybdate is nanocrystalline according to claim 1, is characterized in that described intermediate A is the α-MoO of nanometer monocrystalline four square rod
3, belong to rhombic system, outside surface is { the 100} crystal face of rhombic system.
5. the preparation method that bismuth molybdate is nanocrystalline according to claim 1, is characterized in that described intermediate B structure is BiO
xload { " the preparation structure " of 100} crystal face bar-shaped in monocrystalline molybdenum oxide four directions.
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| CN104190450B (en) * | 2014-09-03 | 2016-08-24 | 江南大学 | A kind of Basic bismuth iodide/bismuth molybdate composite photo-catalyst and preparation method thereof |
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| CN105540670A (en) * | 2016-02-02 | 2016-05-04 | 济南大学 | Preparation method of In2O3 nanoparticles/MoO3 nanorod composite materials |
| CN106799223A (en) * | 2016-12-29 | 2017-06-06 | 广州凯耀资产管理有限公司 | A kind of synthetic method of Bi systems compound semiconductor photocatalytic material |
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