CN107199030A - A kind of preparation method of cellular porous bismuth oxide - Google Patents
A kind of preparation method of cellular porous bismuth oxide Download PDFInfo
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- CN107199030A CN107199030A CN201710519991.8A CN201710519991A CN107199030A CN 107199030 A CN107199030 A CN 107199030A CN 201710519991 A CN201710519991 A CN 201710519991A CN 107199030 A CN107199030 A CN 107199030A
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- bismuth oxide
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- 229910000416 bismuth oxide Inorganic materials 0.000 title claims abstract description 32
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 230000001413 cellular effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004202 carbamide Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000000855 fermentation Methods 0.000 claims abstract description 22
- 230000004151 fermentation Effects 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 238000007667 floating Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229920002472 Starch Polymers 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000008107 starch Substances 0.000 claims abstract description 7
- 235000019698 starch Nutrition 0.000 claims abstract description 7
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 5
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 abstract description 11
- 229940049676 bismuth hydroxide Drugs 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 5
- 239000005457 ice water Substances 0.000 abstract description 5
- 244000005700 microbiome Species 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 229910052797 bismuth Inorganic materials 0.000 abstract description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 230000005059 dormancy Effects 0.000 abstract description 2
- 239000000428 dust Substances 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000010564 aerobic fermentation Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000011521 glass Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 241000264877 Hippospongia communis Species 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 1
- 230000004103 aerobic respiration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000027272 reproductive process Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a kind of preparation method of cellular porous bismuth oxide, belong to semiconductor functional material preparing technical field.The present invention is first using dust technology as solvent, five nitric hydrate bismuths are bismuth source, urea liquid is precipitating reagent, the stirring reaction under ice-water bath cryogenic conditions, again through filtering, washing and vacuum freeze drying, the presoma material containing porous bismuth hydroxide is made, after the stirring of the organic matters such as presoma material and starch is mixed again, stood in greenhouse mouldy, must be gone mouldy slurry, and gained goes mouldy after slurry and ethanol solution etc. mix, aerobic fermentation, ozone is passed through into system again, make after microorganism dormancy, collect fermentation tank top layer floating object, after scrubbed drying, calcination processing, produce cellular porous bismuth oxide.Gained porous bismuth oxide of the invention is in honeycomb microstructure, and porosity is high, and specific surface area is big, with excellent photocatalysis performance and repeat performance.
Description
Technical field
The invention discloses a kind of preparation method of cellular porous bismuth oxide, belong to semiconductor functional material technology of preparing
Field.
Background technology
Metal oxide such as titanium oxide, zinc oxide, cupric oxide, iron oxide and bismuth oxide etc. are the important semiconductor materials of a class
Material, their extensive applications in the fields such as magnetic storage medium, solar energy conversion, electronic device and catalysis.Ding Peng, Zhang
Deng research show that bismuth oxide can use all kinds of environmental contaminants of photocatalyst catalytic degradation.But the bismuth oxide in suspension system
Photochemical catalyst is difficult to sedimentation separation, causes cost recovery to increase, and although the immobilization technology then developed solves catalyst point
The problem of from reclaiming, but be supported on supported catalyst and easily cause inactivation during long-term use, be on the one hand because of
Catalyst is combined loosely with carrier, and catalyst can depart from carrier surface unavoidably during use, reduces light-catalyzed reaction activity
The quantity of position；On the other hand, catalyst surface can be contaminated thing blocking, hinder expansion of the species to reaction active site that be degraded
Dissipate, thus cause catalytic efficiency to reduce.
There are some researches show the pattern of photochemical catalyst, size the photocatalysis effect that can directly influence catalyst different with structure
Rate.Therefore, it is attempted to prepare the bismuth oxide of various special appearances in recent years using a variety of methods, to obtain higher ratio
Surface area, constructs more carrier catalysis centers, so as to improve catalytic performance.Such as Muruganandham uses hydro-thermal reaction
Method successfully synthesizes honey comb like comb shape and worm shape bismuth oxide photocatalyst, and uses it for acid orange（AO7）The drop of dyestuff
Solution.
The bismuth oxide material of honeycomb has big, high and easy recovery of porosity of photocatalytic activity height, specific surface area etc.
Advantage, makes it be received much concern in catalytic field.Wherein, the porous network of honeycomb advantageously forms very big diffusion admittance,
Blocking of the thing to duct that be degraded can be suppressed in use, it is to avoid the inactivation of catalyst, therefore, even if continuously being followed
Ring is used, and can still keep higher photocatalytic activity, therefore, prepares a kind of bismuth oxide photocatalyst of honeycomb, has
Hope and provide brand-new thinking to solve the bottleneck problem in photocatalysis technology evolution.
The content of the invention
The present invention solves the technical problem of：For conventional method prepare bismuth oxide porosity is low, specific surface area
It is not high, in use, duct is easily blocked by reactant, so that cause the reduction of bismuth oxide catalytic activity, or even failure
There is provided a kind of preparation method of cellular porous bismuth oxide for problem.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
（1）It is 1 in mass ratio：8~1：10 mix five nitric hydrate bismuths with dilute nitric acid solution, obtain bismuth nitrate solution；
（2）It is 2 by volume：1~5：1 measures step（1）Gained bismuth nitrate solution and urea liquid, bismuth nitrate solution is poured into
Reactor, under low temperature stirring, urea liquid is added dropwise into reactor, treats completion of dropwise addition, continues low temperature stirring reaction 45
~60min, then through vacuum freeze drying, obtain presoma material；
（3）Count by weight, 60~80 parts of presoma materials, 10~15 parts of starch, 8~10 portions of sucrose, 20~40 are taken successively
Part water, after being uniformly mixed, stands mouldy, must go mouldy slurry in greenhouse；
（4）The slurry that will go mouldy is 1 in mass ratio with ethanol solution：80~1：100 add fermentation tank, then with 40~80mL/min speed
Rate is passed through air to fermenter base, is continually fed into after 4~6h, is left to ferment 2~4h, then with 10~30mL/min speed to hair
Ozone is passed through in fermentation tank, is continually fed into after 20~30min, 10~20min is stood, fermentation tank top layer floating object is collected, then through washing
Wash, drying and calcination, produce cellular porous bismuth oxide.
Step（1）The dilute nitric acid solution mass fraction is 4~6%.
Step（2）The urea solution mass fraction is 8~15%.
Step（2）The low temperature stirring is：Temperature is 0 DEG C, and speed of agitator is 200~400r/min.
Step（2）The drop rate that urea liquid is added dropwise into reactor is 3~8mL/min.
Step（4）The ethanol solution mass fraction is 8~10%.
Step（4）In the fermentation tank, the emulsifier op-10 for the stock quality 6~8% that goes mouldy can also be added.
Step（4）The calcination condition is：In Muffle furnace, 300~400 are warming up to 6~8 DEG C/min rate programs
DEG C, after 2~4h of insulation calcining, cool to room temperature with the furnace.
The beneficial effects of the invention are as follows：
（1）Technical solution of the present invention is first using five nitric hydrate bismuths as bismuth source, using dust technology as solvent, it is to avoid bismuth nitrate is in dissolving
During excessively hydrolysis and influence product pattern, then coordinate urea liquid be precipitating reagent, by the way that the process of urea is being slowly added dropwise
In, low temperature stirring reaction, the bismuth hydroxide nucleus of generation can as water freezing in system the nuclei of condensation, promote system in low temperature bar
Mixture of ice and water is formed under part, the bismuth hydroxide crystal of generation can be fixed in ice crystal, during vacuum freeze drying, ice
Crystalline substance distillation, leaves a large amount of pore structures after distillation, generate the bismuth hydroxide crystal of loose structure, and in this, as presoma thing
Material, is conducive to the raising of product porosity in end processing sequences；
（2）Technical solution of the present invention is to make the bismuth hydroxide crystal of loose structure by oneself as presoma material, with the organic matter such as starch
After mixing, standing is gone mouldy, and microorganism is grown in presoma surface of material and pore structure, micro- in subsequent fermentations
Biology is in the case where being passed through air conditionses, and the organic matter such as ethanol is nutriment using in system, amount reproduction, and is grown on bismuth hydroxide
Inside loose structure, corrosion forms cellular pore structure, in addition, in reproductive process, aerobic respiration produces carbon dioxide,
The carbon dioxide of generation makes the bismuth hydroxide in system float up to fermentation tank top layer, is then handled with ozone, makes microorganism
Dormancy, in calcination process, the microorganism in bismuth hydroxide pore structure is removed, and it is cellular porous that bismuth hydroxide decomposes generation
Bismuth oxide；
（3）In technical solution of the present invention, the addition of emulsifier op-10 is conducive to bismuth hydroxide crystal emulsion in system to disperse, together
When air is present in tiny bubble form in system, the content of dissolved oxygen in raising system, further improve microorganism life
Long speed, is conducive in fermentation process that bismuth hydroxide crystal floating upward quickly is to fermentation tank top layer, while facilitating collection of products, makes
Product porosity further increases, and specific surface area is further improved, and emulsifier op-10 can effectively be gone in later stage calcination process
Remove, product purity will not be impacted.
Embodiment
It is 1 in mass ratio：8~1：Five nitric hydrate bismuths and mass fraction are that 4~6% dilute nitric acid solutions pour into beaker by 10
In, stirred and mixed with glass bar, until five nitric hydrate bismuths are completely dissolved, obtain bismuth nitrate solution；It is then 2 by volume：1~
5：1 measures gained bismuth nitrate solution and mass fraction for 8~15% urea liquids, and bismuth nitrate solution first is poured into three-necked flask, and
Three-necked flask is moved into the ice-water bath that temperature is 0 DEG C, and stirred with magnetic stirring apparatus with 200~400r/min rotating speeds, in low
Under warm stirring, urea liquid is added dropwise into three-necked flask by dropping funel, regulation urea liquid drop rate is 3~
8mL/min, treats urea liquid completion of dropping, continues low temperature 45~60min of stirring reaction, and filtering obtains filter residue, and use deionized water
Wash filter residue 3~5 times, then the filter residue after washing is transferred to vacuum freezing drying oven, under the conditions of temperature is -55~-50 DEG C, very
6~8h of vacuum freecing-dry, obtains dry filter residue, as presoma material；Count by weight, 60~80 parts of presoma things are taken successively
Material, 10~15 parts of starch, 8~10 portions of sucrose, 20~40 parts of water are poured into beaker, with 10~20min of glass bar stirring mixing
Afterwards, by beaker move into temperature be 28~35 DEG C, humidity for 60~70% greenhouse in, stand mouldy 20~30 days, must go mouldy slurry
Material；It is then 1 in mass ratio：80~1：100 will go mouldy slurry and mass fractions are that 8~10% ethanol solutions are added in fermentation tank,
And addition is gone mouldy the emulsifier op-10 of stock quality 6~8% into fermentation tank, then with 40~80mL/min speed to fermentation tank bottom
Portion is passed through air, is continually fed into after 4~6h, is left to ferment 2~4h, then be passed through into fermentation tank with 10~30mL/min speed smelly
Oxygen, is continually fed into after 20~30min, stands 10~20min, collects fermentation tank top layer floating object, and institute is washed with deionized
Obtain top layer floating object 3~5 times, then the top layer floating object after washing is moved into baking oven, under the conditions of temperature is 105~110 DEG C
Dry to constant weight, obtain dry surface layer floating object, dry surface layer floating object is then moved into Muffle furnace, with 6~8 DEG C/min speed journeys
Sequence is warming up to after 300~400 DEG C, 2~4h of insulation calcining, is cooled to room temperature with the furnace, is discharged, produce cellular porous bismuth oxide.
Example 1
It is 1 in mass ratio：Five nitric hydrate bismuths and mass fraction are that 6% dilute nitric acid solution is poured into beaker by 10, are stirred with glass bar
Mixing is mixed, until five nitric hydrate bismuths are completely dissolved, bismuth nitrate solution is obtained；It is then 5 by volume：1 measures gained bismuth nitrate
Solution and mass fraction are 15% urea liquid, bismuth nitrate solution first are poured into three-necked flask, and be by three-necked flask immigration temperature
In 0 DEG C of ice-water bath, and stirred with magnetic stirring apparatus with 400r/min rotating speeds, under low temperature stirring, pass through dropping funel
Urea liquid is added dropwise into three-necked flask, regulation urea liquid drop rate is 8mL/min, treats urea liquid completion of dropping, after
Continuous low temperature stirring reaction 60min, filtering obtains filter residue, and filter residue is washed with deionized 5 times, then the filter residue after washing is transferred to
Vacuum freezing drying oven, under the conditions of temperature is -50 DEG C, vacuum freeze drying 8h obtains dry filter residue, as presoma material；
Count by weight, 80 parts of presoma materials are taken successively, 15 parts of starch, 10 portions of sucrose, 40 parts of water pour into beaker, use glass
Rod is stirred after mixing 20min, and it is 35 DEG C that beaker is moved into temperature, and humidity is in 70% greenhouse, mouldy 30 days of standing must go mouldy
Slurry；It is then 1 in mass ratio：100 will go mouldy slurry and mass fractions are that 10% ethanol solution is added in fermentation tank, and to hair
The emulsifier op-10 for the stock quality 8% that goes mouldy is added in fermentation tank, then air is passed through to fermenter base with 80mL/min speed, is held
It is continuous to be passed through after 6h, 4h is left to ferment, then ozone is passed through into fermentation tank with 30mL/min speed, it is continually fed into after 30min, stands
20min, collects fermentation tank top layer floating object, and gained top layer floating object is washed with deionized 5 times, then by the top layer after washing
Floating object is moved into baking oven, is dried under the conditions of temperature is 110 DEG C to constant weight, is obtained dry surface layer floating object, will then dry table
Layer floating object moves into Muffle furnace, is warming up to 8 DEG C/min rate programs after 400 DEG C, insulation calcining 4h, cools to room temperature with the furnace,
Discharging, produces cellular porous bismuth oxide.
Example 2
It is 1 in mass ratio：Five nitric hydrate bismuths and mass fraction are that 6% dilute nitric acid solution is poured into beaker by 10, are stirred with glass bar
Mixing is mixed, until five nitric hydrate bismuths are completely dissolved, bismuth nitrate solution is obtained；It is then 5 by volume：1 measures gained bismuth nitrate
Solution and mass fraction are 15% urea liquid, bismuth nitrate solution first are poured into three-necked flask, and be by three-necked flask immigration temperature
In 0 DEG C of ice-water bath, and stirred with magnetic stirring apparatus with 400r/min rotating speeds, under low temperature stirring, pass through dropping funel
Urea liquid is added dropwise into three-necked flask, regulation urea liquid drop rate is 8mL/min, treats urea liquid completion of dropping, after
Continuous low temperature stirring reaction 60min, filtering obtains filter residue, and filter residue is washed with deionized 5 times, then the filter residue after washing is transferred to
Vacuum freezing drying oven, under the conditions of temperature is -50 DEG C, vacuum freeze drying 8h obtains dry filter residue, as presoma material；
Presoma material is then moved into Muffle furnace, is warming up to 8 DEG C/min rate programs after 400 DEG C, insulation calcining 4h, furnace cooling
To room temperature, discharging produces porous bismuth oxide.
Example 3
It is 1 in mass ratio：Five nitric hydrate bismuths and mass fraction are that 6% dilute nitric acid solution is poured into beaker by 10, are stirred with glass bar
Mixing is mixed, until five nitric hydrate bismuths are completely dissolved, bismuth nitrate solution is obtained；It is then 5 by volume：1 measures gained bismuth nitrate
Solution and mass fraction are 15% urea liquid, bismuth nitrate solution first are poured into three-necked flask, and be by three-necked flask immigration temperature
In 0 DEG C of ice-water bath, and stirred with magnetic stirring apparatus with 400r/min rotating speeds, under low temperature stirring, pass through dropping funel
Urea liquid is added dropwise into three-necked flask, regulation urea liquid drop rate is 8mL/min, treats urea liquid completion of dropping, after
Continuous low temperature stirring reaction 60min, filtering obtains filter residue, and filter residue is washed with deionized 5 times, then the filter residue after washing is transferred to
Vacuum freezing drying oven, under the conditions of temperature is -50 DEG C, vacuum freeze drying 8h obtains dry filter residue, as presoma material；
Count by weight, 80 parts of presoma materials are taken successively, 15 parts of starch, 10 portions of sucrose, 40 parts of water pour into beaker, use glass
Rod is stirred after mixing 20min, and it is 35 DEG C that beaker is moved into temperature, and humidity is in 70% greenhouse, mouldy 30 days of standing must go mouldy
Slurry；Gained is washed with deionized again to go mouldy slurry 5 times, then the slurry that goes mouldy after washing is moved into baking oven, is in temperature
Dried under the conditions of 110 DEG C to constant weight, the slurry that goes mouldy must be dried, will then dried the slurry that goes mouldy and move into Muffle furnace, with 8 DEG C/min speed
Rate temperature programming after insulation calcining 4h, cools to room temperature with the furnace, discharges, produce porous bismuth oxide to 400 DEG C.
The products obtained therefrom of example 1 to 3 is subjected to performance detection respectively, specific detection method is as follows：
1. catalytic activity：Pipette 100mL concentration be 10mg/L methylene blue dye solution in test tube, add 100mg oxidation
Bismuth, first lucifuge adsorb 30min, are then turned on xenon lamp, and logical cooling water makes temperature of reaction system control at 25 DEG C or so, every
30min is sampled, and catalyst is removed with disposable membrane filtration, and the absorbance of destainer is surveyed on ultraviolet-visible spectrophotometer
Value, the catalytic activity of the catalyst is characterized with the percent of decolourization D% of dye solution；
Percent of decolourization D=（A0—At）/A0×100%
Wherein A0The absorbance for being dye solution before reflection, AtThe absorbance of dye solution when for the reaction time being t；
2. repeat performance：Using above-mentioned catalytic activity method of testing, it is carried out continuously after 4 times, dye solution is detected again
Percent of decolourization D% characterizes the repeat performance of the catalyst；
3. specific surface area is measured using JW-BK122F than surface and Porosimetry；
4. morphology analysis：Test analysis is carried out using Japanese JSE-6700F field emission scanning electron microscopes.
Specific testing result is as shown in table 1：
Table 1
From the testing result of table 1, bismuth oxide obtained by technical solution of the present invention is cellular structures, product specific surface area
Greatly, there is excellent catalytic degradation performance and repeat performance to organic dyestuff.
Claims (8)
1. a kind of preparation method of cellular porous bismuth oxide, it is characterised in that specifically preparation process is：
（1）It is 1 in mass ratio：8~1：10 mix five nitric hydrate bismuths with dilute nitric acid solution, obtain bismuth nitrate solution；
（2）It is 2 by volume：1~5：1 measures step（1）Gained bismuth nitrate solution and urea liquid, bismuth nitrate solution is poured into
Reactor, under low temperature stirring, urea liquid is added dropwise into reactor, treats completion of dropwise addition, continues low temperature stirring reaction 45
~60min, then through vacuum freeze drying, obtain presoma material；
（3）Count by weight, 60~80 parts of presoma materials, 10~15 parts of starch, 8~10 portions of sucrose, 20~40 are taken successively
Part water, after being uniformly mixed, stands mouldy, must go mouldy slurry in greenhouse；
（4）The slurry that will go mouldy is 1 in mass ratio with ethanol solution：80~1：100 add fermentation tank, then with 40~80mL/min speed
Rate is passed through air to fermenter base, is continually fed into after 4~6h, is left to ferment 2~4h, then with 10~30mL/min speed to hair
Ozone is passed through in fermentation tank, is continually fed into after 20~30min, 10~20min is stood, fermentation tank top layer floating object is collected, then through washing
Wash, drying and calcination, produce cellular porous bismuth oxide.
2. a kind of preparation method of cellular porous bismuth oxide according to claim 1, it is characterised in that：Step（1）Institute
It is 4~6% to state dilute nitric acid solution mass fraction.
3. a kind of preparation method of cellular porous bismuth oxide according to claim 1, it is characterised in that：Step（2）Institute
It is 8~15% to state urea solution mass fraction.
4. a kind of preparation method of cellular porous bismuth oxide according to claim 1, it is characterised in that：Step（2）Institute
Stating low temperature stirring is：Temperature is 0 DEG C, and speed of agitator is 200~400r/min.
5. a kind of preparation method of cellular porous bismuth oxide according to claim 1, it is characterised in that：Step（2）Institute
State and the drop rate of urea liquid is added dropwise into reactor for 3~8mL/min.
6. a kind of preparation method of cellular porous bismuth oxide according to claim 1, it is characterised in that：Step（4）Institute
It is 8~10% to state ethanol solution mass fraction.
7. a kind of preparation method of cellular porous bismuth oxide according to claim 1, it is characterised in that：Step（4）Institute
State in fermentation tank, the emulsifier op-10 for the stock quality 6~8% that goes mouldy can also be added.
8. a kind of preparation method of cellular porous bismuth oxide according to claim 1, it is characterised in that：Step（4）Institute
Stating calcination condition is：In Muffle furnace, it is warming up to 6~8 DEG C/min rate programs after 300~400 DEG C, 2~4h of insulation calcining,
Cool to room temperature with the furnace.
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| CN113333012B (en) * | 2021-06-02 | 2022-08-19 | 成都理工大学 | Bi-doped porous carbon nitrogen compound and preparation method thereof |
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