CN105329870B - A kind of magic square shape sillenite Bismugel (Biothrax). raw powder's production technology - Google Patents
A kind of magic square shape sillenite Bismugel (Biothrax). raw powder's production technology Download PDFInfo
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- CN105329870B CN105329870B CN201510926779.4A CN201510926779A CN105329870B CN 105329870 B CN105329870 B CN 105329870B CN 201510926779 A CN201510926779 A CN 201510926779A CN 105329870 B CN105329870 B CN 105329870B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/38—Particle morphology extending in three dimensions cube-like
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Abstract
The invention provides a kind of magic square shape sillenite Bismugel (Biothrax). raw powder's production technology, the method is by the NaH of certain mol proportion2PO4Solution is added to Bi (NO3)3Salpeter solution in, obtain white suspension.A certain amount of alkali hydroxide soln is added to above-mentioned white suspension, then carries out magnetic agitation up to suspension its colour changed into yellow.Gained yellow suspension is proceeded in hydrothermal reaction kettle and is reacted, after the completion of question response, cooling, take out the yellow mercury oxide in reactor, wash, be dried, that is, obtain magic square shape sillenite Bismugel (Biothrax). Bi12P0.86O20.14Powder body.The method has that device is simple, low temperature (120 140 DEG C), environmental protection (synthetic reaction is carried out in enclosed system) the features such as, hydro-thermal single sintering powder body, without high-temperature calcination, and the powder purity that synthesizes is high, degree of crystallinity is high, pattern rule, it is a kind of process is simple, efficiency high, energy consumption preparation method low, with low cost.
Description
Technical field
The invention belongs to field of functional materials is and in particular to a kind of magic square shape Bi12P0.86O20.14Raw powder's production technology.
Background technology
Carry out sewage disposal using photocatalysis technology, can effective degradation of organic substances, reducing heavy metal ion.And this technology institute
Need that energy consumption is low, easy and simple to handle, reaction condition gentle, do not have secondary pollution.Therefore, photocatalysis are that the very promising environment of one kind is controlled
Reason technology.
The research of bismuth phosphate photocatalyst concentrates on monoclinic phase Bismugel (Biothrax). (chemical formula BiPO4), its preparation method has high temperature
Solid phase method, hydro-thermal method, solvent-thermal method, microwave-hydrothermal method and microemulsion method, liquid-phase precipitation method, sol-gel method, ultrasonic synthesis
Method etc..However, due to wider energy gap (3.85eV), leading to BiPO4Only there is photocatalytic activity in ultra-violet (UV) band, i.e. BiPO4Right
The utilization rate of sunlight is relatively low, actually used is restricted.
The object of study of the present invention is sillenite Bismugel (Biothrax)., and the chemical formula of described sillenite Bismugel (Biothrax). is Bi12P0.86O20.14,
It belongs to body-centred cubic I23 space group.The population structure of sillenite Bismugel (Biothrax). is 7 oxygen atoms and Bi atomic arrangement composition
Polyhedral structure, it and other Bi-O polyhedrons and PO4Tetrahedron corner-sharing.Due to its special Bi, P, O stoichiometric proportion,
Therefore replicate and transplanting monoclinic phase BiPO4Preparation method be difficult to synthesize Bi12P0.86O20.14.Bi at present12P0.86O20.14Conjunction
One-tenth method uses high temperature solid-state method, after raw material is stoichiometrically prepared, realizes synthesis by pyroreaction, using water
Full-boiled process synthesis has the Bi of regular magic square shape pattern12P0.86O20.14There is not been reported for powder body.
Content of the invention
It is an object of the invention to provide a kind of magic square shape sillenite Bismugel (Biothrax). (Bi12P0.86O20.14) preparation method, should
Method pass through hydro-thermal reaction single sintering magic square shape sillenite Bismugel (Biothrax)., without high-temperature calcination, have process is simple, efficiency high,
Energy consumption is low, with low cost, eco-friendly feature, and the powder purity of synthesis is high, degree of crystallinity is high, pattern rule.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that：
A kind of magic square shape sillenite Bismugel (Biothrax). raw powder's production technology, comprises the following steps：
1) by Bi (NO3)3·5H2O is added in the salpeter solution of 2-3mol/L, obtains Bi (NO3)3Salpeter solution；Will
NaH2PO4·2H2O is added in distilled water, obtains NaH2PO4Aqueous solution；Again by NaH2PO4Aqueous solution is according to volume ratio 1:
(0.8-1.2) ratio is added to Bi (NO3)3In salpeter solution, bismuth ion is controlled to be 1 with the mol ratio of dihydrogen phosphate ions:
1-5:1, magnetic agitation, obtain white suspension；Bi (NO in described white suspension3)3Concentration be 0.15-0.48mol/
L, NaH2PO4Concentration be 0.03-0.48mol/L；
2) by concentration, the alkali hydroxide soln for 6-8mol/L is added to described white suspension, described alkali metal
The volume ratio of hydroxide solution and white suspension is：(20-30):(50-60)；Again magnetic agitation is carried out to it, until outstanding
Turbid liquid its colour changed into yellow, obtains hydro-thermal reaction precursor liquid；
3) described hydro-thermal reaction precursor liquid is proceeded in hydrothermal reaction kettle, after insulation 8-10 hour at 120 DEG C -140 DEG C
Stopped reaction, obtains yellow mercury oxide；
4) after question response temperature is down to room temperature, hydrothermal reaction kettle is taken out, centrifugation goes out the yellow mercury oxide that reaction obtains
Thing, carries out to yellow mercury oxide washing, is dried, that is, obtain magic square shape sillenite Bismugel (Biothrax). powder body.
Preferred version, step 1) according to volume ratio 1:1 by NaH2PO4Aqueous solution is added to Bi (NO3)3In salpeter solution.
Preferred version, step 1) in control bismuth ion to be 1 with the mol ratio of dihydrogen phosphate ions:1-2:1.
Preferred version, step 2) described in alkali metal hydroxide be NaOH or KOH.
Preferred version, step 1) and 2) in the magnetic agitation time be 30-50min.
Preferred version, step 3) in hydrothermal reaction kettle liner be politef material, hydrothermal reaction kettle packing ratio is
70%-80%.
Preferred version, step 4) in washing with distilled water and dehydrated alcohol, yellow mercury oxide is washed to neutrality, described
Drying be 10-20h to be dried at 70-80 DEG C.
Step 4) crystal formation of magic square shape sillenite Bismugel (Biothrax). powder body that is obtained is consistent with card JCPDS No.44-0199, magic
The particle diameter of square shape is 5-8 μm.
Below the present invention is further explained and illustrates：
Described magic square shape refers to the shape similar to magic square (a kind of general toy) for the form, is combined by multiple little square bodies
Consist of a big square body shape together.
By the method for the present invention, inventor's first passage hydro-thermal method has prepared magic square shape sillenite Bismugel (Biothrax).
Bi12P0.86O20.14Powder body, and find Bi first12P0.86O20.14There is good visible light catalysis activity.The reaction bar of the present invention
Part is most important.Alkali hydroxide soln concentration has a major impact to the thing phase of product.Control alkali metal hydrogen in the present invention
The volume ratio of oxide solution and white suspension is (20-30):(50-60) when, if alkali hydroxide soln concentration
CAlkaliLess than 6mol/L or more than 8mol/L, part Bi all can occur in product2O3, thing is mutually impure；Only work as 6mol/L<CAlkali<
8mol/L, products obtained therefrom thing phase is pure sillenite Bismugel (Biothrax). Bi12P0.86O20.14.Hydrothermal temperature is for Bi12P0.86O20.14
Degree of crystallinity have very important impact.Reaction temperature T<120 DEG C, products obtained therefrom has the non-crystalline product of a small amount of white gum；Instead
Answer 120 DEG C of temperature<T<140 DEG C, product crystallization is complete；Reaction temperature>140 DEG C, product grains size is substantially grown up.From energy-conservation
Angle is seen, reaction temperature preferably controls at 120 DEG C<T<140 DEG C of intervals.The hydro-thermal reaction time is for Bi12P0.86O20.14Pattern have
Very important impact, the Morphology of sample is a progressive process.Response time t<8h, products obtained therefrom has part not advise
Then pattern Bi12P0.86O20.14；Response time 8h<t<10h, product pattern develops into regular magic square shape pattern completely；Response time>
10h, pattern is still magic square shape, but particle diameter has and substantially grows up.From the point of view of energy-conservation, the response time preferably controls in 8h<t<10h area
Between.
Compared with prior art, the present invention has following beneficial outcomes：
1st, the magic square shape Bi that the present invention provides12P0.86O20.14Raw powder's production technology, with Bi (NO3)3·5H2O、
NaH2PO4·2H2O is raw material, first the two is configured to homogeneous solution respectively, is re-introduced into high concentration alkali metal hydroxide after mixing
Thing solution, forms strong basicity reaction medium, and the parameter such as controlling reaction temperature and response time, obtain a kind of degree of crystallinity high,
The novel magic square shape Bi of crystal morphology12P0.86O20.14Powder body.
2nd, the method have that device is simple, low temperature (120-140 DEG C), environmental protection (synthetic reaction is carried out in enclosed system) etc.
Feature, hydro-thermal single sintering powder body, without high-temperature calcination, and the powder purity synthesizing is high, degree of crystallinity is high, pattern rule, is one
Kind process is simple, efficiency high, energy consumption environmentally friendly preparation method low, with low cost.
Brief description
Fig. 1 is the magic square shape Bi of the embodiment of the present invention 1 preparation12P0.86O20.14The XRD figure of powder body；
Fig. 2 is the magic square shape Bi of the embodiment of the present invention 1 preparation12P0.86O20.14The SEM figure of powder body；
Fig. 3 is the magic square shape Bi of the embodiment of the present invention 1 preparation12P0.86O20.14The UV-vis of powder body diffuses spectrogram；
Fig. 4 is the magic square shape Bi of the embodiment of the present invention 1 preparation12P0.86O20.14Powder body is bent to the visible light photocatalysis of methyl orange
Line chart.
Specific embodiment
By specific embodiment, the method for the present invention is illustrated below in conjunction with the accompanying drawings, but the invention is not limited in
This, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., should be included in the present invention
Protection domain within.
Experimental technique described in following embodiments, if no special instructions, is conventional method；Described reagent and material, such as
No specified otherwise, all commercially obtains.
Reactant B i (NO used in the present invention3)3·5H2O、NaH2PO4·2H2O, NaOH, nitric acid etc. are commercially available point
Analysis is pure.
Embodiment 1
Step 1：Mol ratio is 1:1 Bi (NO3)3·5H2O and NaH2PO4·2H2It is 1 that O is added separately to volume ratio:1
2mol/L HNO3In solution and distilled water, magnetic agitation 50min, respectively obtain Bi (NO3)3Salpeter solution and NaH2PO4
Aqueous solution；By described NaH2PO4Aqueous solution is added to described Bi (NO3)3In salpeter solution, and magnetic force is carried out to mixed solution stir
Mix 50min, obtain white suspension；Bi (NO in white suspension3)3And NaH2PO4Concentration be 0.16mol/L；
Step 2：By 6mol/L NaOH solution be added to above-mentioned white suspension after magnetic agitation 50min, NaOH solution and
The volume ratio 30 of white suspension:50, obtain hydro-thermal reaction precursor liquid.
Step 3：Precursor liquid is proceeded in hydrothermal reaction kettle, the filling rate of hydrothermal reaction kettle is 80%, puts into constant temperature air blast
Drying baker, stopped reaction after being incubated 10 hours at 130 DEG C；
Step 4：After question response temperature is down to room temperature, hydrothermal reaction kettle is taken out, centrifugation goes out the yellow that reaction obtains
Precipitate, using distilled water and absolute ethanol washing precipitate to neutrality, is dried 10h, that is, obtains magic square shape at 80 DEG C
Bi12P0.86O20.14Powder body.Its XRD figure is as shown in Figure 1 it is seen that the Bi of synthesis12P0.86O20.14Powder purity is high, almost free from admixture
Peak detects.Its SEM figure is as shown in Figure 2 it is seen that Bi12P0.86O20.14The form of powder body is magic square shape, form rule.Its light absorbs is bent
Line is as shown in Figure 3 it is seen that it has preferable absorbability, optical absorption edge about 570nm to visible ray.Its visible ray to methyl orange
Photocatalysis curve chart is as shown in Figure 4 it is seen that it has preferable visible light catalytic performance.
Embodiment 2
Step 1：Mol ratio is 2:1 Bi (NO3)3·5H2O and NaH2PO4·2H2It is 1 that O is added separately to volume ratio:1
2.2mol/L HNO3In solution and distilled water, magnetic agitation 45min, respectively obtain Bi (NO3)3Salpeter solution and
NaH2PO4Aqueous solution；By NaH2PO4Aqueous solution is added to Bi (NO3)3In salpeter solution, and magnetic agitation is carried out to mixed solution
45min, obtains white suspension；Bi (NO in white suspension3)3And NaH2PO4Concentration be respectively 0.16mol/L and
0.08mol/L；
Step 2：6.5mol/L NaOH solution is added to magnetic agitation 45min after above-mentioned white suspension, NaOH solution
Volume ratio 28 with white suspension:52, obtain hydro-thermal reaction precursor liquid.
Step 3：Precursor liquid is proceeded in hydrothermal reaction kettle, the filling rate of hydrothermal reaction kettle is 78%, puts into constant temperature air blast
Drying baker, stopped reaction after being incubated 10 hours at 125 DEG C；
Step 4：After question response temperature is down to room temperature, hydrothermal reaction kettle is taken out, centrifugation goes out the yellow that reaction obtains
Precipitate, using distilled water and absolute ethanol washing precipitate to neutrality, is dried 12h, that is, obtains magic square shape at 78 DEG C
Bi12P0.86O20.14Powder body, testing result is similar to Example 1.
Embodiment 3
Step 1：Mol ratio is 3:1 Bi (NO3)3·5H2O and NaH2PO4·2H2It is 1 that O is added separately to volume ratio:1
2.4mol/L HNO3In solution and distilled water, magnetic agitation 40min, respectively obtain Bi (NO3)3Salpeter solution and
NaH2PO4Aqueous solution；By NaH2PO4Aqueous solution is added to Bi (NO3)3In salpeter solution, and magnetic agitation is carried out to mixed solution
40min, obtains white suspension；Bi (NO in white suspension3)3And NaH2PO4Concentration be respectively 0.24mol/L and
0.08mol/L；
Step 2：By 7mol/L NaOH solution be added to above-mentioned white suspension after magnetic agitation 40min, NaOH solution and
The volume ratio 26 of white suspension:54, obtain hydro-thermal reaction precursor liquid.
Step 3：Precursor liquid is proceeded in hydrothermal reaction kettle, the filling rate of hydrothermal reaction kettle is 76%, puts into constant temperature air blast
Drying baker, stopped reaction after being incubated 9 hours at 135 DEG C；
Step 4：After question response temperature is down to room temperature, hydrothermal reaction kettle is taken out, centrifugation goes out the yellow that reaction obtains
Precipitate, using distilled water and absolute ethanol washing precipitate to neutrality, is dried 14h, that is, obtains magic square shape at 76 DEG C
Bi12P0.86O20.14Powder body, testing result is similar to Example 1.
Embodiment 4
Step 1：Mol ratio is 4:1 Bi (NO3)3·5H2O and NaH2PO4·2H2It is 1 that O is added separately to volume ratio:1
2.6mol/L HNO3In solution and distilled water, magnetic agitation 35min, respectively obtain Bi (NO3)3Salpeter solution and
NaH2PO4Aqueous solution；By NaH2PO4Aqueous solution is added to Bi (NO3)3In salpeter solution, and magnetic agitation is carried out to mixed solution
35min, obtains white suspension；Bi (NO in white suspension3)3And NaH2PO4Concentration be respectively 0.4mol/L and
0.1mol/L；
Step 2：7.5mol/L NaOH solution is added to magnetic agitation 35min after above-mentioned white suspension, NaOH solution
Volume ratio 24 with white suspension:56, obtain hydro-thermal reaction precursor liquid.
Step 3：Precursor liquid is proceeded in hydrothermal reaction kettle, the filling rate of hydrothermal reaction kettle is 74%, puts into constant temperature air blast
Drying baker, stopped reaction after being incubated 8.5 hours at 138 DEG C；
Step 4：After question response temperature is down to room temperature, hydrothermal reaction kettle is taken out, centrifugation goes out the yellow that reaction obtains
Precipitate, using distilled water and absolute ethanol washing precipitate to neutrality, at 74 DEG C, hour is dried 16h, that is, obtain magic square shape
Bi12P0.86O20.14Powder body, testing result is similar to Example 1.
Embodiment 5
Using case study on implementation 1,2,3,4 gained magic square shape Bi12P0.86O20.14Catalyst 1,2,3 and 4 catalytic degradation methyl orange.
Experimentation：(enter from 350W and with optical filter>Xenon lamp 420nm) is as light source.Preparing 100mL concentration is
10-5The methyl orange solution of mol/L, adds 0.1g magic square shape Bi12P0.86O20.14Catalyst, is placed on magnetic agitation in camera bellows
30min, makes system reach absorption-desorption balance；After turning on light, take a sample every special time (15min), every sub-sampling 5mL,
721 visible spectrophotometers are adopted to detect the absorbance of the supernatant after centrifugation.
Claims (8)
1. a kind of magic square shape sillenite Bismugel (Biothrax). raw powder's production technology is it is characterised in that comprise the following steps：
1) by Bi (NO3)3·5H2O is added in the salpeter solution of 2-3mol/L, obtains Bi (NO3)3Salpeter solution；Will
NaH2PO4·2H2O is added in distilled water, obtains NaH2PO4Aqueous solution；Again by NaH2PO4Aqueous solution is according to volume ratio 1:
(0.8-1.2) ratio is added to Bi (NO3)3In salpeter solution, bismuth ion is controlled to be 1 with the mol ratio of dihydrogen phosphate ions:
1-5:1, magnetic agitation, obtain white suspension；Bi (NO in described white suspension3)3Concentration be 0.15-0.48mol/
L, NaH2PO4Concentration be 0.03-0.48mol/L；
2) by concentration, the alkali hydroxide soln for 6-8mol/L is added to described white suspension, described alkali metal hydrogen-oxygen
The volume ratio of compound solution and white suspension is：(20-30):(50-60)；Again magnetic agitation is carried out to it, until suspension
Its colour changed into yellow, obtains hydro-thermal reaction precursor liquid；
3) described hydro-thermal reaction precursor liquid is proceeded in hydrothermal reaction kettle, stop after insulation 8-10 hour at 120 DEG C -140 DEG C
Reaction, obtains yellow mercury oxide；
4) after question response temperature is down to room temperature, hydrothermal reaction kettle is taken out, centrifugation goes out the yellow mercury oxide that reaction obtains, right
Yellow mercury oxide carries out washing, is dried, that is, obtain magic square shape sillenite Bismugel (Biothrax). powder body.
2. according to claim 1 magic square shape sillenite Bismugel (Biothrax). raw powder's production technology it is characterised in that step 1) in press
According to volume ratio 1:1 by NaH2PO4Aqueous solution is added to Bi (NO3)3In salpeter solution.
3. according to claim 1 magic square shape sillenite Bismugel (Biothrax). raw powder's production technology it is characterised in that step 1) in control
Bismuth ion processed is 1 with the mol ratio of dihydrogen phosphate ions:1-2:1.
4. according to claim 1 magic square shape sillenite Bismugel (Biothrax). raw powder's production technology it is characterised in that step 2) in institute
Stating alkali metal hydroxide is NaOH or KOH.
5. according to claim 1 magic square shape sillenite Bismugel (Biothrax). raw powder's production technology it is characterised in that step 1) and 2)
The middle magnetic agitation time is 30-50min.
6. according to claim 1 magic square shape sillenite Bismugel (Biothrax). raw powder's production technology it is characterised in that step 3) in water
Thermal response kettle liner is politef material, and hydrothermal reaction kettle packing ratio is 70%-80%.
7. according to claim 1 magic square shape sillenite Bismugel (Biothrax). raw powder's production technology it is characterised in that step 4) in
Washing is washed yellow mercury oxide to neutrality with distilled water and dehydrated alcohol, and described drying is 10- to be dried at 70-80 DEG C
20h.
8. according to one of claim 1-7 described magic square shape sillenite Bismugel (Biothrax). raw powder's production technology it is characterised in that step
4) crystal formation of the magic square shape sillenite Bismugel (Biothrax). powder body being obtained is consistent with card JCPDS No.44-0199, and the particle diameter of magic square shape is
5-8μm.
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