CN105268462A - Preparation method of nitrogen doped bismuth-containing oxides at low temperature - Google Patents
Preparation method of nitrogen doped bismuth-containing oxides at low temperature Download PDFInfo
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- CN105268462A CN105268462A CN201510391165.0A CN201510391165A CN105268462A CN 105268462 A CN105268462 A CN 105268462A CN 201510391165 A CN201510391165 A CN 201510391165A CN 105268462 A CN105268462 A CN 105268462A
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Abstract
The invention relates to a preparation method of nitrogen doped bismuth-containing oxides at a room temperature. The method is characterized in that the synthesis is performed at a temperature of 15-40 DEG C and under a normal pressure; bismuth-containing inorganic salt is used as a bismuth source, a nitrogen-containing surfactant is used as a nitrogen source, and material of the bismuth source and the nitrogen source can be replaced; a chemical coprecipitation method is adopted and a solution is mixed to prepare nitrogen doped bismuth-containing oxides. The preparation method of the invention needs a simple preparation device; the operation is convenient and can be produced in large scale; the prepared nitrogen doped bismuth-containing oxide material has good photocatalysis performance.
Description
Technical field
Patent of the present invention is the preparation method of N doping bismuth system oxide.Adopt chemical coprecipitation to prepare the method for N doping bismuth system oxide under relating to a kind of room temperature, belong to photochemical catalyst preparations and applicatio field.
Background technology
Bismuth system oxide has become the research focus of photocatalysis field in recent years.With traditional TiO
2catalysis material is compared, and bismuth system oxide is due to [Bi ubiquitous in structure
2o
2]
2-layer and other sheath easily form built in field, thus can be separated light induced electron and hole fast, produce high efficiency photocatalysis activity.But, be similar to TiO
2, bismuth system oxide, as Bi
2o
2cO
3, BiOCl, BiWO
6excessive Deng also there is energy gap, the shortcoming of visible light-responded difference.N doping increases broad stopband catalysis material visible absorption performance, promotes the effective ways of material solar energy utilization ratio.Hydro-thermal method is conventional bismuth system oxide N doping method (FanDong, YanjuanSun, MinFu, Wing-KeiHo, ShunChengLee, ZhongbiaoWu.Langmuir2012,28,766 – 773; QiuyanLi, HaitaoLiu, FanDong, MinFu.JournalofColloidandInterfaceScience.2013,408,33 – 42; FanDong, TingXiong, RuiWang, YanjuanSun, YankeJiang.DaltonTransactions, 2014,43,6631-6642.), this method needs to form special sealed pressure resistant reaction environment with stainless steel sleeve and polytetrafluoroethylplastic plastic usually, reaction temperature generally needs for a long time reaction more than 180 degree, and thus this type of nitrogen-doping method energy consumption is higher, equipment pouring is high, production efficiency is low, is unsuitable for large-scale industrial production.In addition, other semiconductor nitrogen-doping method such as high-temperature calcination, vapour deposition, wet chemistry method etc. are not also expected because of the deficiency in energy consumption, environmental protection etc.Therefore, searching environmental protection, the bismuth system oxide N doping method that energy consumption is low, preparation condition is gentle are the study hotspots of current photocatalysis field, and this is to promoting that the extensive Synthesis and applications of visible-light response type bismuth system oxide catalysis material means a great.This patent provides a kind of easy room temperature co-precipitation bismuth system oxide N doping preparation method being nitrogenous source with nitrogen-containing surfactants and be bismuth source with common bismuth salt.With method ratio in the past, N doping method energy consumption involved in the present invention is low, environmental friendliness, equipment simple, is suitable for large-scale industrial production.
Summary of the invention
For the shortcoming that current bismuth system oxide N doping method exists, object of the present invention aims to provide a kind of preparation method of N doping bismuth system oxide photochemical catalyst.
Content of the present invention is: the preparation method of N doping bismuth system oxide under a kind of room temperature, it is characterized in that the configuration comprising the following steps: a) reaction liquid: under room temperature, by the bismuth salt of 0.005 ~ 2mol, as bismuth nitrate (Bi (NO
3)
3) be dissolved in the 1mol/L dust technology (HNO of 0.005 ~ 2L
3) stir to clarify in solution, form solution A.By 0.1 ~ 120g nitrogen-containing surfactants, as softex kw (CTAB) and 0.05 ~ 10mol carbonate, or and 0.05 ~ 10mol halide, or and 4 ~ 10mol phosphate, or and 0.05 ~ 10mol tungstates, as sodium carbonate (Na
2cO
3), or sodium chloride (NaCl), or sodium hydrogen phosphate (Na
2hPO
4), or sodium tungstate (Na
2wO
4) dissolve in 0.02 ~ 12L deionized water, and stir to clarify, form solution B.B) precipitation method synthesis: at 15 ~ 40 DEG C, B solution be dropwise added dropwise in solution A, in whole instillation process, solution A is in stirring always.Stir after 10 ~ 60 minutes, suction filtration is carried out to reactant liquor, and respectively clean three times by small molecular alcohol and deionized water, under being finally placed in 40-80 DEG C of condition, carry out drying, 6 ~ 20 hours drying times, N doping bismuth system oxide can be obtained.
In content of the present invention: described bismuth salt, except bismuth nitrate, also replaceable one-tenth bismuth trichloride (BiCl
3) or bismuth sulfate (Bi
2sO
4) etc. bismuth-containing inorganic salts.
In content of the present invention: the surfactant of described Nitrogen element, except softex kw (CTAB), also alternative one-tenth dodecyl dimethyl ammonium chloride, and nitrogen-containing surfactants and the derivative thereof such as amine salt type, quaternary, primary amine type, secondary amine type and tertiary amine-type.
In content of the present invention: described carbonate also comprises sodium acid carbonate (NaHCO
3), potash (K
2cO
3), saleratus (KHCO
3)
In content of the present invention: described halide also comprises potassium chloride (KCl), calcium chloride (CaCl
2), ammonium chloride (NH
4cl) magnesium chloride (MgCl
2), iron chloride (FeCl
3), frerrous chloride (FeCl
2), butter of tin (SnCl
4), stannous chloride (SnCl
2), KI (KI), sodium iodide (NaI), hydroiodic acid (HI), KBr (KBr), ammonium bromide (NH
4br), sodium bromide (NaBr), hydrobromic acid (HBr)
In content of the present invention: described phosphate also comprises sodium phosphate (Na
3pO
4), sodium dihydrogen phosphate (NaH
2pO
4), potassium phosphate (K
3pO
4), dipotassium hydrogen phosphate (K
2hPO
4), potassium dihydrogen phosphate (KH
2pO
4), diammonium hydrogen phosphate ((NH
4)
2hPO
4), ammonium dihydrogen phosphate (ADP) (NH
4h
2pO
4), ammonium phosphate ((NH
4)
3pO
4)
In content of the present invention: described tungstates also comprises potassium tungstate (Na
2wO
4), ammonium tungstate (K
2wO
4)
In content of the present invention: the preparation process in the described precipitation method, B solution being instilled solution A, also can be changed into and solution A is instilled B solution.
In content of the present invention: the dry run of described sample is carried out in atmosphere, also can at N
2dry in the inert atmospheres such as gas or Ar gas.
In content of the present invention: the synthesis temperature of described sample is the room temperature condition of 15 ~ 40 DEG C.
Relative to existing N-doping technology, the feature that patent of the present invention relates to N doping bismuth system oxide preparation method is: reaction condition gentleness is low for equipment requirements, easy and simple to handle, energy consumption is little, reaction speed is fast.
Accompanying drawing explanation
Bi before Fig. 1 CTAB adds
2o
2cO
3scanning electron microscope (SEM) photograph.
Bi after Fig. 2 CTAB adds
2o
2cO
3scanning electron microscope (SEM) photograph.
Fig. 3 specific area figure.
Fig. 4 specific area figure
Bi under Fig. 5 visible ray
2o
2cO
3photocatalysis performance resolution chart.
The photocatalysis performance resolution chart of BiOCl under Fig. 6 visible ray.
Detailed description of the invention
Following specific embodiment is only three kinds of embodiments of the present invention, but the present invention is confined to following examples incessantly.
Embodiment 1:4.85gBi (NO
3)
35H
2o is dissolved into 10mLof1mol/LHNO
3middle as solution A.8.45gNa
2cO
3be dissolved in 90mL deionized water with 1gCTAB and form solution B. then solution B is dropwise added drop-wise in solution A, 30 DEG C are kept in course of reaction, Keep agitation 30 minutes, then carries out suction filtration by white suspension, and cleans by isopropyl alcohol and deionized water successively.Finally white powder is placed in the baking oven inner drying 12 hours of 60 DEG C, obtains N-Bi
2o
2cO
3.
Embodiment 2:A solution: 2.425gBi (NO
3)
35H
2o is dissolved in the HNO of 5ml1mol/L
3solution A is obtained in solution.0.5gCTAB and 2.98gKCl is dissolved in 45mlUP water and obtains solution B.Then B solution stirs clarification at 30 DEG C, after solution A stirs clarification, solution A is added drop-wise to B solution and stirs 30min, use isopropyl alcohol and UP water and alcohol flushing suction filtration afterwards, and drying obtains N-BiOCl at 60 DEG C.
Below in conjunction with accompanying drawing, patent of the present invention is described further.
As depicted in figs. 1 and 2, the sample before and after being added by contrast CTAB, finds Bi
2o
2cO
3still become 7-16nm (Fig. 2) for layer structure thickness from 34nm (Fig. 1).
As shown in Figure 3 and Figure 4, find in specific area test result, add the Bi of CTAB synthesis
2o
2cO
3specific area is by 7.911m
2/ g increases to 17.119m
2/ g.
As shown in Figure 5, found by catalytic performance test, add CTAB Bi later
2o
2cO
3catalytic performance is significantly improved under visible light.
As shown in Figure 6, the BiOCl catalytic performance under visible light adopting same procedure to prepare obtains remarkable lifting equally.
Claims (12)
1. the preparation method of N doping bismuth system oxide under room temperature, is characterized in that the configuration comprising the following steps: a) reaction liquid: under room temperature, by the bismuth salt of 0.005 ~ 2mol, as bismuth nitrate (Bi (NO
3)
3) be dissolved in the 1mol/L dust technology (HNO of 0.005 ~ 2L
3) stir to clarify in solution, form solution A.By 0.1 ~ 120g nitrogen-containing surfactants, as softex kw (CTAB) and 0.05 ~ 10mol carbonate, or and 0.05 ~ 10mol halide, or and 4 ~ 10mol phosphate, or and 0.05 ~ 10mol tungstates, as sodium carbonate (Na
2cO
3), or sodium chloride (NaCl), or sodium hydrogen phosphate (Na
2hPO
4), or sodium tungstate (Na
2wO
4) dissolve in 0.02 ~ 12L deionized water, and stir to clarify, form solution B.B) precipitation method synthesis: at 15 ~ 40 DEG C, B solution be dropwise added dropwise in solution A, in whole instillation process, solution A is in stirring always.Stir after 10 ~ 60 minutes, suction filtration is carried out to reactant liquor, and respectively clean three times by small molecular alcohol and deionized water, under being finally placed in 40-80 DEG C of condition, carry out drying, 6 ~ 20 hours drying times, N doping bismuth system oxide can be obtained.
2., according to the preparation method of N doping bismuth system oxide described in claim 1, it is characterized in that: this N doping adopts coprecipitation synthesis.
3., according to claim 1, described in 2, the preparation method of N doping bismuth system oxide, is characterized in that: this preparation method's reaction temperature is room temperature, temperature range 15-40 DEG C.
4. according to claim 1,2, the preparation method of N doping bismuth system oxide described in 3, is characterized in that: this preparation method is for opening wide system.
5. according to claim 1,2,3, described in 4, the preparation method of N doping bismuth system oxide, is characterized in that: the dry run of described sample is carried out in atmosphere, also can at N
2dry in the inert atmospheres such as gas or Ar gas.
6. according to claim 1,2,3,4, described in 5, the preparation method of N doping bismuth system oxide, is characterized in that: the preparation process in the described precipitation method, B solution being instilled solution A, also can be changed into and solution A is instilled B solution.
7. according to claim 1,2,3,4,5, the preparation method of N doping bismuth system oxide described in 6, it is characterized in that: the surfactant of described Nitrogen element, except softex kw (CTAB), also alternative one-tenth dodecyl dimethyl ammonium chloride, and nitrogen-containing surfactants and the derivative thereof such as amine salt type, quaternary, primary amine type, secondary amine type and tertiary amine-type.
8. according to claim 1,2,3,4,5,6, described in 7, the preparation method of N doping bismuth system oxide, is characterized in that: described bismuth salt, except bismuth nitrate, also replaceable one-tenth bismuth trichloride (BiCl
3) or bismuth sulfate (Bi
2sO
4) etc. bismuth-containing inorganic salts.
9. according to claim 1,2,3,4,5,6,7, described in 8, the preparation method of N doping bismuth system oxide, is characterized in that: in content of the present invention: described carbonate also comprises sodium acid carbonate (NaHCO
3), potash (K
2cO
3), saleratus (KHCO
3).
10. according to claim 1,2,3,4,5,6,7,8, described in 9, the preparation method of N doping bismuth system oxide, is characterized in that: described halide also comprises potassium chloride (KCl), calcium chloride (CaCl
2), ammonium chloride (NH
4cl) magnesium chloride (MgCl
2), iron chloride (FeCl
3), frerrous chloride (FeCl
2), butter of tin (SnCl
4), stannous chloride (SnCl
2), KI (KI), sodium iodide (NaI), hydroiodic acid (HI), KBr (KBr), ammonium bromide (NH
4br), sodium bromide (NaBr), hydrobromic acid (HBr).
11. according to claim 1, and 2,3,4,5,6,7,8,9, described in 10, the preparation method of N doping bismuth system oxide, is characterized in that: described phosphate also comprises sodium phosphate (Na
3pO
4), sodium dihydrogen phosphate (NaH
2pO
4), potassium phosphate (K
3pO
4), dipotassium hydrogen phosphate (K
2hPO
4), potassium dihydrogen phosphate (KH
2pO
4), diammonium hydrogen phosphate ((NH
4)
2hPO
4), ammonium dihydrogen phosphate (ADP) (NH
4h
2pO
4), ammonium phosphate ((NH
4)
3pO
4).
12. according to claim 1, and 2,3,4,5,6,7,8,9,10, described in 11, the preparation method of N doping bismuth system oxide, is characterized in that: described tungstates also comprises potassium tungstate (Na
2wO
4), ammonium tungstate (K
2wO
4).
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108821339A (en) * | 2018-07-12 | 2018-11-16 | 盐城工学院 | A kind of bismuthyl carbonate nanometer plate and preparation method thereof with photocatalysis performance |
| CN108927137A (en) * | 2018-07-20 | 2018-12-04 | 河南师范大学 | A kind of preparation method of carbon doping bismuth oxide catalysis material |
| CN109395761A (en) * | 2018-11-22 | 2019-03-01 | 江苏大学 | A kind of N doping BiOIO3The preparation method and applications of photochemical catalyst |
| CN111790419A (en) * | 2020-08-10 | 2020-10-20 | 牡丹江师范学院 | Silver phosphate-bismuth oxycarbonate photocatalyst with sunlight catalytic activity and preparation method thereof |
| CN115093683A (en) * | 2022-06-08 | 2022-09-23 | 青岛普诺恩生物科技有限公司 | Modified degradable material with controllable degradation rate and preparation method thereof |
| CN117380245A (en) * | 2023-10-25 | 2024-01-12 | 海南师范大学 | N-bismuth subcarbonate composite graphite-phase carbon nitride material and preparation method and application thereof |
| CN117643891A (en) * | 2024-01-30 | 2024-03-05 | 西南石油大学 | Boron doped metal oxide/hydroxide oxygen evolution catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070238608A1 (en) * | 2003-03-24 | 2007-10-11 | Saudi Basic Industries Corporation | Catalyst compostion for the selective conversion of alkanes to unsaturated carboxylic acids, method of making and method of using thereof |
| CN103359789A (en) * | 2013-07-26 | 2013-10-23 | 台山市新宁制药有限公司 | Preparation method of bismuth subcarbonate |
| CN103586062A (en) * | 2013-11-28 | 2014-02-19 | 阜阳师范学院 | Preparation method of bismuthyl carbonate catalyst for pollution treatment |
| CN103774217A (en) * | 2012-10-26 | 2014-05-07 | 北京师范大学 | Preparation method for micron-sized bismuth monocrystal flower |
-
2015
- 2015-07-03 CN CN201510391165.0A patent/CN105268462A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070238608A1 (en) * | 2003-03-24 | 2007-10-11 | Saudi Basic Industries Corporation | Catalyst compostion for the selective conversion of alkanes to unsaturated carboxylic acids, method of making and method of using thereof |
| CN103774217A (en) * | 2012-10-26 | 2014-05-07 | 北京师范大学 | Preparation method for micron-sized bismuth monocrystal flower |
| CN103359789A (en) * | 2013-07-26 | 2013-10-23 | 台山市新宁制药有限公司 | Preparation method of bismuth subcarbonate |
| CN103586062A (en) * | 2013-11-28 | 2014-02-19 | 阜阳师范学院 | Preparation method of bismuthyl carbonate catalyst for pollution treatment |
Non-Patent Citations (6)
| Title |
|---|
| FAN DONG ET AL.: "Novel in situ N-doped (BiO)2CO3 hierarchical microspheres self-assembly by nanosheets as efficient and durable visible light driven photocatalyst", 《LANGMUIR》 * |
| LANG CHEN ET AL.: "Flower-like Bi2O2CO3：facile synthesis and their photocatalytic application in treatment of dye-containing wastewater", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 崔玉民等: "(BiO)2CO3光催化剂的制备及性能", 《稀有金属》 * |
| 张金龙等: "《光催化》", 31 August 2012, 华东理工大学出版社 * |
| 王伟华等: "含铋光催化材料的研究进展", 《化工进展》 * |
| 田禾等: "《应用化学与技术》", 31 July 2007, 科学出版社 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108821339A (en) * | 2018-07-12 | 2018-11-16 | 盐城工学院 | A kind of bismuthyl carbonate nanometer plate and preparation method thereof with photocatalysis performance |
| CN108927137A (en) * | 2018-07-20 | 2018-12-04 | 河南师范大学 | A kind of preparation method of carbon doping bismuth oxide catalysis material |
| CN108927137B (en) * | 2018-07-20 | 2021-08-13 | 河南师范大学 | Preparation method of carbon-doped bismuth oxide photocatalytic material |
| CN109395761A (en) * | 2018-11-22 | 2019-03-01 | 江苏大学 | A kind of N doping BiOIO3The preparation method and applications of photochemical catalyst |
| CN109395761B (en) * | 2018-11-22 | 2021-05-25 | 江苏大学 | Nitrogen-doped BiOIO3Preparation method and application of photocatalyst |
| CN111790419A (en) * | 2020-08-10 | 2020-10-20 | 牡丹江师范学院 | Silver phosphate-bismuth oxycarbonate photocatalyst with sunlight catalytic activity and preparation method thereof |
| CN115093683A (en) * | 2022-06-08 | 2022-09-23 | 青岛普诺恩生物科技有限公司 | Modified degradable material with controllable degradation rate and preparation method thereof |
| CN117380245A (en) * | 2023-10-25 | 2024-01-12 | 海南师范大学 | N-bismuth subcarbonate composite graphite-phase carbon nitride material and preparation method and application thereof |
| CN117643891A (en) * | 2024-01-30 | 2024-03-05 | 西南石油大学 | Boron doped metal oxide/hydroxide oxygen evolution catalyst and preparation method thereof |
| CN117643891B (en) * | 2024-01-30 | 2024-04-09 | 西南石油大学 | Boron doped metal oxide/hydroxide oxygen evolution catalyst and preparation method thereof |
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