CN104828780A - Colorful environmentally friendly pearl powder bismuth oxychloride preparation method - Google Patents
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Abstract
The present invention belongs to the solar energy light catalyst preparation technical field, particularly relates to a colorful environmentally friendly pearl powder bismuth oxychloride preparation method, and mainly solves the technical problems of complex preparation technology and high cost of bismuth oxychloride in the prior art. The technical scheme is white, off-white, black, green and orange bismuth oxychloride (BiOCl) pearl powder preparation method, bismuth source and chlorine source solutions are evenly mixed, the mixture is heated until the solution is completely evaporated, and cooled to room temperature; deionized water is added, the mixture is stirred well, an upper white suspension is filtered, washed and dried to obtain white bismuth oxychloride (BiOCl) pearl powder; the rest part, after the upper white suspension is poured, is filtered, washed and dried to obtain off-white white bismuth oxychloride (BiOCl) pearl powder; and other color pearl powder is obtained by xe-lamp irradiation and heating and other operation on the white bismuth oxychloride (BiOCl) pearl powder. The preparation method is simple in process, convenient in operation and high in repeatability, and the obtained BiOCl pearl powder is obvious in pearl effect and high in purity.
Description
Technical field
The invention belongs to the preparing technical field of solar energy photocatalytic agent, be specifically related to the preparation method of color environmental protection pearlescence pearl white.
Background technology
In recent years, semiconductor light-catalyst is that the organic pollutant of degrading in environment provides a kind of green, free of contamination new way.Photocatalyst for degrading organism has the advantages such as nontoxic, efficient, cheap, causes the extensive concern of domestic and international scientist.BiOCl is as a kind of emerging photocatalyst, and the laminate structure of its uniqueness promotes the separation that photo-generate electron-hole is right and stable existence, makes it have good photocatalytic activity and stability, becomes the study hotspot of photocatalysis field.
In practice, BiOCl is a kind of novel high-grade environmental protection pearlescent material, nontoxicity, and Low grease absorbs, the strong and pearl effect of skin adhesion, and BiOCl itself has the function absorbing UV-light, makes it in makeup, become important interpolation raw material.Same, BiOCl is also widely used in the middle of pearly pigment, compare with mica titanium nacreous material, BiOCl pearly pigment is except having the pearliness of gazing at, also there is the very trickle sheen effect not available for mica titanium nacreous material, add its nontoxicity, become the green pearlescent pigment of a new generation.BiOCl, as photocatalyst, has the ability of photocatalysis degradation organic contaminant, and therefore it is not only green, pollution-free, more can play the effect of environmental purification, in the industries such as coating, plastics, makeup, leather, printing, pottery, show huge potentiality.But the color of current BiOCl pearlescence, effect show under the help by other additive, and complex manufacturing technology, cost are high, and add the feature of environmental protection and the environmental purification function that other material too much also can reduce BiOCl.
Summary of the invention
The technical problem to be solved in the present invention is existing pearl white complicated process of preparation, and cost is high.
Technical scheme of the present invention is the preparation method of white, beige, black, green and orange BiOCl pearlescence.
The invention provides the preparation method of white BiOCl pearlescence, comprise the steps:
1) bismuth source is mixed with chlorine source solution, be heated to liquid and evaporate completely, be cooled to room temperature;
2) add deionized water, stir, filtered by upper strata white suspension liquid, deionized water wash is to pH 6 ~ 7, and finally at 80 DEG C ~ 100 DEG C, drying obtains white BiOCl pearlescence for 2 ~ 4 hours.
Concrete, step 1) in bismuth source be analytical pure AR grade bismuth oxide.
Concrete, step 1) in chlorine source be the concentrated hydrochloric acid of massfraction 36% ~ 38%.
Concrete, step 1) in the mol ratio in bismuth source and chlorine source be 1 ︰ 12 ~ 1 ︰ 15.
Preferably, step 1) in the mol ratio in bismuth source and chlorine source be 1 ︰ 12.
Concrete, step 1) in Heating temperature be 600 DEG C ~ 800 DEG C.
Concrete, step 2) in deionized water wash to pH 7.
Concrete, step 2) in drying temperature be 80 DEG C, time of drying is 2 hours.
Present invention also offers the preparation method of beige BiOCl pearlescence, comprise the steps:
1) bismuth source is mixed with chlorine source solution, be heated to liquid and evaporate completely, be cooled to room temperature;
2) add deionized water, stir, filtered by upper strata white suspension liquid, deionized water wash reaches 6 ~ 7 to pH value, and finally at 80 DEG C ~ 100 DEG C, drying obtains white BiOCl pearlescence for 2 ~ 4 hours;
3) by step 1) in outwell the remaining Partial filtration of upper suspension, and reach 6 ~ 7 with deionized water wash to pH value, finally dryly at 80 DEG C ~ 100 DEG C within 2 ~ 4 hours, obtain beige BiOCl pearlescence.
Concrete, step 1) in bismuth source be analytical pure AR grade bismuth oxide.
Concrete, step 1) in chlorine source be the concentrated hydrochloric acid of massfraction 36% ~ 38%.
Concrete, step 1) in the mol ratio in bismuth source and chlorine source be 1 ︰ 12 ~ 1 ︰ 15.
Preferably, step 1) in the mol ratio in bismuth source and chlorine source be 1 ︰ 12.
Concrete, step 1) in Heating temperature be 600 DEG C ~ 800 DEG C.
Concrete, step 2) and 3) middle deionized water wash is to pH 7.
Concrete, step 2) and 3) middle drying temperature is 80 DEG C, time of drying is 2 hours.
Present invention also offers the preparation method of black BiOCl pearlescence, comprise the steps:
1) bismuth source is mixed with chlorine source solution, be heated to liquid and evaporate completely, be cooled to room temperature;
2) add deionized water, stir, filtered by upper strata white suspension liquid, deionized water wash reaches 6 ~ 7 to pH value, and finally at 80 DEG C ~ 100 DEG C, drying obtains white BiOCl pearlescence for 2 ~ 4 hours;
3) by step 2) obtained white pearlescent powder adds ethylene glycol solution, boils, until color blackening, process rear filtration and with deionized water wash 3 ~ 5 times, finally drying arrives black pearlescence in 2 ~ 4 hours at 80 DEG C ~ 100 DEG C.
Concrete, step 1) in bismuth source be analytical pure AR grade bismuth oxide.
Concrete, step 1) in chlorine source be the concentrated hydrochloric acid of massfraction 36% ~ 38%.
Concrete, step 1) in the mol ratio in bismuth source and chlorine source be 1 ︰ 12 ~ 1 ︰ 15.
Preferably, step 1) in the mol ratio in bismuth source and chlorine source be 1 ︰ 12.
Concrete, step 1) in Heating temperature be 600 DEG C ~ 800 DEG C.
Concrete, step 2) in deionized water wash to pH 7.
Concrete, step 2) and 3) middle drying temperature is 80 DEG C, time of drying is 2 hours.
Concrete, step 3) in Heating temperature be 300 DEG C ~ 400 DEG C.
Present invention also offers the preparation method of green BiOCl pearlescence, comprise the steps:
1) bismuth source is mixed with chlorine source solution, be heated to liquid and evaporate completely, be cooled to room temperature;
2) add deionized water, stir, filtered by upper strata white suspension liquid, deionized water wash reaches 6 ~ 7 to pH value, and finally at 80 DEG C ~ 100 DEG C, drying obtains white BiOCl pearlescence for 2 ~ 4 hours;
3) obtained white pearlescent powder is joined in copper-bath, stir under being placed on 500W xenon source and irradiate, and constantly stir with magnetic stirring apparatus, time is 15 ~ 25 minutes, then filter and use deionized water wash 3 ~ 5 times, finally at 70 DEG C ~ 90 DEG C, drying obtains green pearlescence in 2 ~ 4 hours.
Concrete, step 1) in bismuth source be analytical pure AR grade bismuth oxide.
Concrete, step 1) in chlorine source be the concentrated hydrochloric acid of massfraction 36% ~ 38%.
Concrete, step 1) in the mol ratio in bismuth source and chlorine source be 1 ︰ 12 ~ 1 ︰ 15.
Preferably, step 1) in the mol ratio in bismuth source and chlorine source be 1 ︰ 12.
Concrete, step 1) in Heating temperature be 600 DEG C ~ 800 DEG C.
Concrete, step 2) and 3) middle drying temperature is 80 DEG C, time of drying is 2 hours.
Concrete, step 2) in deionized water wash to pH 7.
Concrete, step 3) in copper-bath concentration be 1mol/L ~ 2mol/L.
Preferably, copper-bath concentration is 1mol/L.
Concrete, step 3) in magnetic stirring apparatus rotating speed used be 1400r/min ~ 1500r/min, xenon source irradiation time is 20 minutes.
Present invention also offers the preparation method of orange BiOCl pearlescence, comprise the steps:
1) bismuth source is mixed with chlorine source solution, be heated to liquid and evaporate completely, be cooled to room temperature;
2) add deionized water, stir, filtered by upper strata white suspension liquid, deionized water wash reaches 6 ~ 7 to pH value, and finally at 80 DEG C ~ 100 DEG C, drying obtains white BiOCl pearlescence for 2 ~ 4 hours;
3) obtained white pearlescent powder to be added in ferric chloride Solution and to stir with glass stick, mix to be placed on and to irradiate under 500W xenon source and constantly to stir with magnetic stirring apparatus, time is 20 ~ 30 minutes, then filter and use deionized water wash 3 ~ 5 times, finally at 70 DEG C ~ 90 DEG C, drying obtains green pearlescence in 2 ~ 4 hours.
Concrete, step 1) in bismuth source be analytical pure AR grade bismuth oxide.
Concrete, step 1) in chlorine source be the concentrated hydrochloric acid of massfraction 36% ~ 38%.
Concrete, step 1) in the mol ratio in bismuth source and chlorine source be 1 ︰ 12 ~ 1 ︰ 15.
Preferably, step 1) in the mol ratio in bismuth source and chlorine source be 1 ︰ 12.
Concrete, step 1) in Heating temperature be 600 DEG C ~ 800 DEG C.
Concrete, step 2) in deionized water wash to pH 7.
Concrete, step 3) in ferric chloride Solution concentration be 1mol/L ~ 2mol/L.
Preferably, ferric chloride Solution concentration is 1mol/L.
Concrete, step 2) and 3) in dry drying temperature be 80 DEG C, time of drying is 2 hours.
Concrete, step 3) in magnetic stirring apparatus rotating speed used be 1400r/min ~ 1500r/min, xenon source irradiation time is 20 minutes.
Beneficial effect of the present invention: this preparation method's technique is simple, easy to operate, repeatable high, white, beige BiOCl pearlescence can be obtained simultaneously, green, black and orange BiOCl pearlescence just can be obtained through simple process, pearl effect is obvious, and without other additive too much, the BiOCl pearlescence high purity obtained, has the function of organic pollutant in degraded environment.
Accompanying drawing explanation
The white BiOCl pearlescence that Fig. 1 the inventive method prepares.
The beige BiOCl pearlescence that Fig. 2 the inventive method prepares.
The black BiOCl pearlescence that Fig. 3 the inventive method prepares.
The green BiOCl pearlescence that Fig. 4 the inventive method prepares.
The orange BiOCl pearlescence that Fig. 5 the inventive method prepares.
Fig. 6 is the XRD figure spectrum of white, beige, black, green and orange BiOCl pearlescence, and X-coordinate is 2theta (2 θ), and unit is degree (degree).
Fig. 7 be 100mg white BiOCl pearlescence under 500W xenon lamp, 200mL concentration of degrading in 60 minutes is 4 × 10
-5the photocatalytic degradation curve of the rhodamine B solution of mol/L.
Fig. 8 be 100mg beige BiOCl pearlescence under 500W xenon lamp, 200mL concentration of degrading in 60 minutes is 4 × 10
-5the photocatalytic degradation curve of the rhodamine B solution of mol/L.
Fig. 9 be 100mg black BiOCl pearlescence under 500W xenon lamp, 200mL concentration of degrading in 60 minutes is 4 × 10
-5the photocatalytic degradation curve of the rhodamine B solution of mol/L.
Figure 10 be the green BiOCl pearlescence of 100mg under 500W xenon lamp, 200mL concentration of degrading in 60 minutes is 4 × 10
-5the photocatalytic degradation curve of the rhodamine B solution of mol/L.
Figure 11 be the orange BiOCl pearlescence of 100mg under 500W xenon lamp, 200mL concentration of degrading in 60 minutes is 4 × 10
-5the photocatalytic degradation curve of the rhodamine B solution of mol/L.
In Fig. 7 ~ 11, the upper right corner is respectively the speed of the BiOCl rhodamine B degradation solution being calculated often kind of color by K value method.
Embodiment
The preparation of embodiment color environmental protection pearlescence pearl white
Comprise white, beige, black, green and orange BiOCl pearlescence, its step is as follows:
(1) 20g bismuth oxide (analytical pure AR) and 100mL concentrated hydrochloric acid (36% ~ 38%) are added in 500mL beaker, constantly stirring with glass stick makes powder dissolve completely, after dissolving, beaker is placed in the upper heating evaporation of universal electric furnace (2000W), hydrochloric acid is evaporated completely, naturally cooling subsequently, to be cooledly to room temperature, in beaker, add 400mL deionized water and stir with glass stick, after stirring, upper strata white suspension liquid is poured in filtration unit and filter and use deionized water repetitive scrubbing, until pH value is close with 7, finally in vacuum drying oven, within 2 hours, obtain white BiOCl pearlescence with 80 DEG C of dryings.
(2) pour in filtration unit filter outwelling the remaining part of upper suspension in above-mentioned steps, then use deionized water repetitive scrubbing, direct pH value, close to 7, obtains beige BiOCl pearlescence in 2 hours with 80 DEG C of dryings in last vacuum drying oven.
(3) 100mL ethylene glycol solution is got in 500mL beaker, the white pearlescent powder that step (1) is obtained is got 500mg to add in solution, boil, until after color blackening, the powder being deposited in beaker bottom is filtered in filtration unit, then use deionized water wash 3 ~ 5 times, in last vacuum drying oven, within 2 hours, obtain black pearlescence with 80 DEG C of dryings.
(4) 100mL copper-bath is got in 500mL beaker, then white pearlescent powder obtained for step (1) is got 500mg to add in solution and constantly to stir with glass stick, mix to be placed on and to irradiate under 500W xenon source and constantly to stir (rotating speed is 1400r/min) with magnetic stirring apparatus, time is 20 minutes, then filter in filtration unit and use deionized water wash 3 ~ 5 times, in last vacuum drying oven, within 2 hours, obtaining green pearlescence with 80 DEG C of dryings.
(5) 100mL ferric chloride Solution is got in 500mL beaker, then white pearlescent powder obtained for step (1) is got 500mg to add in solution and constantly to stir with glass stick, mix to be placed on and to irradiate under 500W xenon source and constantly to stir (rotating speed is 1400r/min) with magnetic stirring apparatus, time is 20 minutes, then filter in filtration unit and use deionized water wash 3 ~ 5 times, in last vacuum drying oven, within 2 hours, obtaining green pearlescence with 80 DEG C of dryings.
The BiOCl pearlescence of preparation-obtained five kinds of colors is shown in Fig. 1 ~ 5.
Fig. 6 is shown in by XRD (X-ray diffraction) collection of illustrative plates of the BiOCl pearlescence of the five kinds of colors prepared.As can be seen from Figure 6, all there is not the characteristic diffraction peak except BiOCl in the XRD figure spectrum of the BiOCl pearlescence of shades of colour, shows that the BiOCl pearlescence of the shades of colour prepared is all pure BiOCl.
(concentration is 4 × 10 to get 200mL rhodamine B solution
-5mol/L) in 250mL beaker, white BiOCl pearlescence obtained for step (1) is got 100mg and adds in beaker, after mixing in dark by magnetic stirrer 4 hours (rotating speed is 1300r/min).Then take off standing 5 minutes, get 5mL rhodamine B solution, measure its point of luminosity with ultraviolet-visible spectrophotometer.Irradiate under remaining solution being placed in 500W xenon source and constantly stir (rotating speed is 1600r/min) with magnetic stirring apparatus, taking off beaker every 15 minutes, leaving standstill and get a 5ml solution measurement point luminosity after 5 minutes, until light application time reaches 60 minutes.Fig. 6 is white pearlescent powder degradation curve to rhodamine B solution in 60 minutes.The BiOCl pearlescence testing method of other colors is identical, Fig. 7 is beige pearlescence degradation curve to rhodamine B solution in 60 minutes, Fig. 8 is black pearlescence degradation curve to rhodamine B solution in 60 minutes, Fig. 9 is green pearlescence degradation curve to rhodamine B solution in 60 minutes, and Figure 10 is orange pearl powder degradation curve to rhodamine B solution in 60 minutes.Pass through degradation curve, can see within the time of experiment (60 minutes), the concentration of rhodamine B solution constantly reduces, the speed (upper right corner) of often kind of BiOCl rhodamine B degradation solution is calculated by K value method, its degradation rate convergence fixed value can be found, obviously do not decay, show that the shades of colour BiOCl sample prepared all shows the sustaining degradation ability to rhodamine B.
Claims (10)
1. the preparation method of white BiOCl pearlescence, is characterized in that: comprise the steps:
1) bismuth source is mixed with chlorine source solution, be heated to liquid and evaporate completely, be cooled to room temperature;
2) add deionized water, stir, filtered by upper strata white suspension liquid, deionized water wash is to pH 6 ~ 7, and finally at 80 DEG C ~ 100 DEG C, drying obtains white BiOCl pearlescence for 2 ~ 4 hours.
2. the preparation method of beige BiOCl pearlescence, is characterized in that: comprise the steps:
1) bismuth source is mixed with chlorine source solution, be heated to liquid and evaporate completely, be cooled to room temperature;
2) add deionized water, stir, filtered by upper strata white suspension liquid, deionized water wash reaches 6 ~ 7 to pH value, and finally at 80 DEG C ~ 100 DEG C, drying obtains white BiOCl pearlescence for 2 ~ 4 hours;
3) by step 1) in outwell the remaining Partial filtration of upper suspension, and reach 6 ~ 7 with deionized water wash to pH value, finally dryly at 80 DEG C ~ 100 DEG C within 2 ~ 4 hours, obtain beige BiOCl pearlescence.
3. the preparation method of black BiOCl pearlescence, is characterized in that: comprise the steps:
1) bismuth source is mixed with chlorine source solution, be heated to liquid and evaporate completely, be cooled to room temperature;
2) add deionized water, stir, filtered by upper strata white suspension liquid, deionized water wash reaches 6 ~ 7 to pH value, and finally at 80 DEG C ~ 100 DEG C, drying obtains white BiOCl pearlescence for 2 ~ 4 hours;
3) by step 2) obtained white pearlescent powder joins in ethylene glycol solution, boils, until color blackening, process rear filtration and with deionized water wash 3 ~ 5 times, finally drying arrives black pearlescence in 2 ~ 4 hours at 80 DEG C ~ 100 DEG C.
4. method as claimed in claim 3, is characterized in that: step 3) in Heating temperature be 300 DEG C ~ 400 DEG C.
5. the preparation method of green BiOCl pearlescence, is characterized in that: comprise the steps:
1) bismuth source is mixed with chlorine source solution, be heated to liquid and evaporate completely, be cooled to room temperature;
2) add deionized water, stir, filtered by upper strata white suspension liquid, deionized water wash reaches 6 ~ 7 to pH value, and finally at 80 DEG C ~ 100 DEG C, drying obtains white BiOCl pearlescence for 2 ~ 4 hours;
3) obtained white pearlescent powder is joined in copper-bath, stir under being placed on 500W xenon source and irradiate, and constantly stir with magnetic stirring apparatus, time is 15 ~ 25 minutes, then filter and use deionized water wash 3 ~ 5 times, finally at 70 DEG C ~ 90 DEG C, drying obtains green pearlescence in 2 ~ 4 hours.
6. method as claimed in claim 5, is characterized in that: step 3) in copper-bath concentration be 1mol/L ~ 2mol/L.
Preferably, copper-bath concentration is 1mol/L.
7. the preparation method of orange BiOCl pearlescence, is characterized in that: comprise the steps:
1) bismuth source is mixed with chlorine source solution, be heated to liquid and evaporate completely, be cooled to room temperature;
2) add deionized water, stir, filtered by upper strata white suspension liquid, deionized water wash reaches 6 ~ 7 to pH value, and finally at 80 DEG C ~ 100 DEG C, drying obtains white BiOCl pearlescence for 2 ~ 4 hours;
3) obtained white pearlescent powder to be added in ferric chloride Solution and to stir with glass stick, mix to be placed on and to irradiate under 500W xenon source and constantly to stir with magnetic stirring apparatus, time is 20 ~ 30 minutes, then filter and use deionized water wash 3 ~ 5 times, finally at 70 ~ 90 DEG C, drying obtains orange pearl powder in 2 ~ 4 hours.
8. method as claimed in claim 7, is characterized in that: step 3) in ferric chloride Solution concentration be 1mol/L ~ 2mol/L.
Preferably, ferric chloride Solution concentration is 1mol/L.
9. the method as described in any one of claim 1 ~ 8, is characterized in that: step 1) in bismuth source be analytical pure AR grade bismuth oxide, chlorine source is the concentrated hydrochloric acid of massfraction 36% ~ 38%, and the mol ratio in bismuth source and chlorine source is 1 ︰ 12 ~ 1 ︰ 15.
Preferably, the mol ratio in bismuth source and chlorine source is 1 ︰ 12.
10. the method as described in any one of claim 1 ~ 9, is characterized in that: step 1) in Heating temperature be 600 DEG C ~ 800 DEG C.
Preferably, in described method, deionized water wash is to pH 7.
Preferably, in described method, drying temperature is 80 DEG C, and time of drying is 2 hours.
Preferably, step 3) in magnetic stirring apparatus rotating speed used be 1400r/min ~ 1500r/min, xenon source irradiation time is 20 minutes.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106193952A (en) * | 2016-08-31 | 2016-12-07 | 南通苏通人防防护设备有限公司 | A kind of closed guard gate |
| CN106320920A (en) * | 2016-08-31 | 2017-01-11 | 南通苏通人防防护设备有限公司 | High strength civil air-defense door |
| CN106319384A (en) * | 2016-08-31 | 2017-01-11 | 南通苏通人防防护设备有限公司 | Disguised door used in cooperation with civil air defense door |
| CN106320901A (en) * | 2016-08-31 | 2017-01-11 | 南通苏通人防防护设备有限公司 | Method for manufacturing steel disguising door and steel plate used for human preventing door |
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| CN1730568A (en) * | 2005-08-26 | 2006-02-08 | 清华大学 | Method of synthesizing perite nanometer pearlescent pigment |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106193952A (en) * | 2016-08-31 | 2016-12-07 | 南通苏通人防防护设备有限公司 | A kind of closed guard gate |
| CN106320920A (en) * | 2016-08-31 | 2017-01-11 | 南通苏通人防防护设备有限公司 | High strength civil air-defense door |
| CN106319384A (en) * | 2016-08-31 | 2017-01-11 | 南通苏通人防防护设备有限公司 | Disguised door used in cooperation with civil air defense door |
| CN106320901A (en) * | 2016-08-31 | 2017-01-11 | 南通苏通人防防护设备有限公司 | Method for manufacturing steel disguising door and steel plate used for human preventing door |
| CN106368580A (en) * | 2016-08-31 | 2017-02-01 | 南通苏通人防防护设备有限公司 | Steel civil defense door and manufacturing method of steel plate |
| CN106401407A (en) * | 2016-08-31 | 2017-02-15 | 南通苏通人防防护设备有限公司 | Civil air defense door and manufacturing method of steel plate for manufacturing civil air defense door |
| CN106401409A (en) * | 2016-08-31 | 2017-02-15 | 南通苏通人防防护设备有限公司 | Steel civil air defense door |
| CN108514885A (en) * | 2018-02-11 | 2018-09-11 | 吉林大学 | A kind of Cu（Ⅱ）The preparation method and applications of the BiOCl of modification |
| CN108514885B (en) * | 2018-02-11 | 2020-12-29 | 吉林大学 | Preparation method and application of Cu (II) -modified BiOCl |
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