CN108160085A - A kind of preparation method of silicon-based nano selenium - Google Patents
A kind of preparation method of silicon-based nano selenium Download PDFInfo
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- CN108160085A CN108160085A CN201810038175.XA CN201810038175A CN108160085A CN 108160085 A CN108160085 A CN 108160085A CN 201810038175 A CN201810038175 A CN 201810038175A CN 108160085 A CN108160085 A CN 108160085A
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- sodium borohydride
- silicon
- selenium
- based nano
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/294—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with hydrogen peroxide
Abstract
A kind of preparation method of silicon-based nano selenium is related to chemosynthesis technical field, and for the present invention using sodium borohydride, selenium powder and silica as raw material, odium stearate and N, N ' diisobutyl thiocarbamide are auxiliary agent synthesis of silica-base nanometer selenium material.The method of the present invention is simple, and raw material is easy to get, and can be applied to catalyzing alcohols selective oxidation.
Description
Technical field
The present invention relates to the methods of chemosynthesis technical field, particularly synthesis of silica-base nanometer selenium material.
Background technology
Selenium element has unique chemistry and bioactivity.Recently, the catalytic activity of selenium element starts concerned.
Common selenium catalysis reaction, mainly uses Organic Selenium catalyst.These catalyst amounts are larger, lead to the catalyst conversion number of reaction
（TON）It is relatively low, and the more difficult recycling of catalyst, catalyst use efficiency are low.In addition, the Organic Selenium catalyst of synthesis substitution,
It needs, using raw material costly, therefore, to limit its prospects for commercial application.
Invention content
The object of the present invention is to provide a kind of high income, the preparation methods of silicon-based nano selenium at low cost.
The technical scheme is that：Under freezing point environment temperature by the ethanol solution of sodium borohydride, selenium powder, silica,
Odium stearate and N, N '-diisobutyl thiocarbamide mix, and are warming up to 20~50 DEG C and are stirred to react, and obtain precipitation, through filtering after 450
~550 DEG C of calcinings, obtain silicon-based nano selenium.
The present invention is using sodium borohydride, selenium powder and silica as raw material, odium stearate and N, N '-diisobutyl thiocarbamide is helps
Agent synthesis of silica-base nanometer selenium material.Method is simple, and raw material is easy to get, and can be applied to catalyzing alcohols selective oxidation.
Specific advantage is as follows：Reaction condition is mild, product is easily isolated, it is easily operated to react, has good safety；
Sodium hydrogen selenide that this method uses is easily prepared, dosage is few；Finally, this method participates in reaction using silica, raw material is easy to get,
Solid waste is few, corrosivity is low, it is environmentally protective, meet environmental-friendly principle, be suitable for industrial production.
The present invention develops a kind of using the silica being easy to get as carrier, to be loaded by alkaline corrosion method, prepares silicon
The method of base nanometer selenium.Nanometer selenium material prepared by this method, can be with catalytic alcohol selective oxidation, wherein for primary alconol, can
With selective oxidation to aldehyde, without generating carboxylic acid.Use of the invention is easy to get raw material, the synthesis application prospect of nanometer selenium material compared with
It is good.
Further, in the ethanol solution of sodium borohydride of the present invention sodium borohydride, selenium powder and silica mixing mole
Than being 100: 20~80: 1000~1200.Under this condition, it can improve the utilization rate of selenium with fully dispersed selenium element, reach
Best catalytic effect.It is experimentally verified that, the catalyst activity of silicon-based nano selenium synthesized on this condition is higher, and whole silicon substrate is received
Rice selenium yield is ideal.
It is furthermore preferred that in the ethanol solution of the sodium borohydride sodium borohydride, selenium powder and silica mixing molar ratio
It is 100: 60: 1100.The catalyst activity highest of silicon-based nano selenium on this condition, silicon-based nano selenium yield highest.
The mixing of sodium borohydride, odium stearate and N, N in the ethanol solution of the sodium borohydride '-diisobutyl thiocarbamide rubs
You are than being 100: 1.25~2.75: 0.1~0.6.Under this condition, it convenient for forming the larger material structure of specific surface area, reaches
To best catalytic effect.
As the reaction odium stearate of used additives and N, N '-diisobutyl thiocarbamide in this dosage condition, can also carry significantly
The catalyst activity of high silicon-based nano selenium.
Also, work as sodium borohydride in the ethanol solution of the sodium borohydride, odium stearate and N, N '-diisobutyl thiocarbamide
When mixing molar ratio is 100: 2: 0.4, the catalyst activity highest of synthesis of silica-base nanometer selenium, yield highest.
A concentration of 0.1~1.0 mol/L of sodium borohydride in the ethanol solution of the sodium borohydride.It is preferred a concentration of
0.7 mol/L.Under this condition, catalyst precarsor can be caused to be combined with appropriate speed, avoid making due to reunion is hardened
Decline into subsequent catalyst activity.
Silicon-based nano selenium catalyst activity highest under the conditions of this.
In addition, silica of the present invention is dried silica gel H or silica G.Dried silica gel is selected, can be kept away
Exempting from a small amount of moisture content causes silicic acid to generate, so as to influence catalyst preparation environment.
The reaction temperature is that condition is 40 DEG C.Under this condition, related raw material can be caused with appropriate speed phase
Contact, it is higher so as to form catalyst activity.
The calcination temperature is 500 DEG C.This temperature can fully decompose unwanted impurity, but can avoid temperature mistake
It is high and lose selenium element, so that catalyst activity highest.
Above each condition, is all the yield of synthesis of silica-base nanometer selenium and the further safeguard of catalyst activity.
Specific embodiment
The present invention is illustrated the following examples in more detail rather than limitation of the invention further.Implement
Example 1：
Under ice-water bath cooling, by 20 mL, the ethanol solution of sodium borohydride of 0.7 mol/L and selenium powder, silica gel H（Predrying, water
Part is no more than 1%, and mole dosage is 11 times of sodium borohydride）, odium stearate（Mole dosage is the 2% of sodium borohydride）With N, N '-
Diisobutyl thiocarbamide（Mole dosage is the 0.4% of sodium borohydride）Mixture is then heated at 40 DEG C and is stirred to react 24 hours.
The precipitation that should be generated is negated, by filtering off water phase, is subsequently placed at 500 DEG C and calcines 6 hours, obtain silicon-based nano selenium
Material.
Electronic Speculum shows that silica size under alkaline corrosion significantly reduces, about in 20~100 nanoscales.And selenium is first
Element is highly dispersed on silica（XRD tests do not observe the peak of crystallization selenium）, ICP show wherein Se content for 3.890 ×
10-3%。
Nanometer selenium applied to alcohol is aoxidized, examines its catalytic activity.
The specific steps are：1 mmol benzyl alcohols is taken to be dissolved in 1 mL acetonitriles, add in 20 mg nanometer selenium catalyst, add in 1
The aqueous hydrogen peroxide solution of mmol, 30% mass concentration, 50 DEG C are reacted 24 hours, obtain oxidation product benzaldehyde, and gas composes yield 92%,
Do not observe that benzoic acid generates.
Embodiment 2：Other conditions examine the reaction of various concentration sodium borohydride, experimental result is shown in Table 2 with embodiment 1.
The inspection of the different sodium borohydride concentration of table 2
From the above results, the preferred 0.7mol/L of reaction sodium borohydride concentration.
Embodiment 3：Other conditions examine the reaction of different selenium powder dosages, experimental result is as shown in table 3 with embodiment 1.
The inspection of the different selenium powder dosages of table 3
| Selenium powder mole/sodium borohydride mole | 20% | 40% | 60% | 80% | 100% |
| Catalytic activity（Oxidation reaction yield/%） | 63 | 78 | 92 | 88 | 79 |
From the above results, best results when selenium powder dosage is sodium borohydride mole 60%.
Embodiment 4：Other conditions examine the reaction of different silica, experimental result is as shown in table 4 with embodiment 1.
The inspection of the different silica of table 4
From the above results, using the silica gel H of predrying, best results.
Embodiment 5：Other conditions examine the reaction of different silica contents, experimental result such as 5 institute of table with embodiment 1
Show.
The inspection of 5 silica content of table
Reaction is best when sugared dosage is 11 times of sodium borohydride mole from the above results（Embodiment 1）.
Embodiment 6：Other conditions examine the reaction of different auxiliary agents and its dosage, experimental result such as 6 institute of table with embodiment 1
Show.
The inspection of 6 auxiliary dosage of table
From the above results, odium stearate（2.0%）, N, N '-diisobutyl thiocarbamide（0.4%）Adjuvant system best results.Change
Become adjuvant component dosage and change auxiliary agent type, catalyst activity can all decline.
Embodiment 7：Other conditions examine the reaction under different temperatures, experimental result is as shown in table 7 with embodiment 1.
The inspection of 7 differential responses temperature of table
From the above results, react best at 40 DEG C.
Embodiment 8：Other conditions examine the calcining under different temperatures, experimental result is as shown in table 8 with embodiment 1.
The inspection of the different calcination temperatures of table 8
From the above results, it is best when calcining for 500 DEG C.
Claims (10)
1. a kind of preparation method of silicon-based nano selenium, it is characterised in that：It is under freezing point environment temperature that the ethyl alcohol of sodium borohydride is molten
Liquid, selenium powder, silica, odium stearate and N, N '-diisobutyl thiocarbamide mix, and are warming up to 20~50 DEG C and are stirred to react, and obtain
Precipitation through filtering after 450~550 DEG C of calcinings, obtains silicon-based nano selenium.
2. the preparation method of silicon-based nano selenium according to claim 1, it is characterised in that：The ethanol solution of the sodium borohydride
The mixing molar ratio of middle sodium borohydride, selenium powder and silica is 100: 20~80: 1000~1200.
3. the preparation method of silicon-based nano selenium according to claim 2, it is characterised in that：The ethanol solution of the sodium borohydride
The mixing molar ratio of middle sodium borohydride, selenium powder and silica is 100: 60: 1100.
4. the preparation method of silicon-based nano selenium according to Claims 2 or 3, it is characterised in that：The ethyl alcohol of the sodium borohydride
The mixing molar ratio of sodium borohydride, odium stearate and N, N in solution '-diisobutyl thiocarbamide for 100: 1.25~2.75: 0.1~
0.6。
5. the preparation method of silicon-based nano selenium according to claim 4, it is characterised in that：The ethanol solution of the sodium borohydride
The mixing molar ratio of middle sodium borohydride, odium stearate and N, N '-diisobutyl thiocarbamide is 100: 2: 0.4.
6. according to claims 1 or 2 or the preparation method of the 3 silicon-based nano selenium, it is characterised in that：The second of the sodium borohydride
A concentration of 0.1~1.0 mol/L of sodium borohydride in alcoholic solution.
7. the preparation method of silicon-based nano selenium according to claim 6, it is characterised in that：The ethanol solution of the sodium borohydride
A concentration of 0.7 mol/L of middle sodium borohydride.
8. according to claims 1 or 2 or the preparation method of the 3 silicon-based nano selenium, it is characterised in that：The silica is silicon
Glue H or silica G.
9. according to claims 1 or 2 or the preparation method of the 3 silicon-based nano selenium, it is characterised in that：The reaction temperature of the reaction
It is 40 DEG C to spend for condition.
10. according to claims 1 or 2 or the preparation method of the 3 silicon-based nano selenium, it is characterised in that：The calcination temperature is
500℃。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109317168A (en) * | 2018-11-20 | 2019-02-12 | 扬州大学 | A kind of synthetic method of selenium doped zirconia catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686789A (en) * | 2005-04-19 | 2005-10-26 | 浙江大学 | Load type nano selenium and preparation method |
| CN106432739A (en) * | 2016-09-18 | 2017-02-22 | 扬州大学 | Method for synthesizing selenium-containing high polymer |
| CN106495105A (en) * | 2016-10-17 | 2017-03-15 | 扬州大学 | A kind of method of synthesis nanometer selenium material |
| CN106824249A (en) * | 2017-03-14 | 2017-06-13 | 扬州大学 | One species graphite-phase nitrogen carbide loads the preparation method of selenium catalysis material |
-
2018
- 2018-01-16 CN CN201810038175.XA patent/CN108160085B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686789A (en) * | 2005-04-19 | 2005-10-26 | 浙江大学 | Load type nano selenium and preparation method |
| CN106432739A (en) * | 2016-09-18 | 2017-02-22 | 扬州大学 | Method for synthesizing selenium-containing high polymer |
| CN106495105A (en) * | 2016-10-17 | 2017-03-15 | 扬州大学 | A kind of method of synthesis nanometer selenium material |
| CN106824249A (en) * | 2017-03-14 | 2017-06-13 | 扬州大学 | One species graphite-phase nitrogen carbide loads the preparation method of selenium catalysis material |
Non-Patent Citations (2)
| Title |
|---|
| YUFAN YANG ET AL.: ""Fabrication of Se/C using carbohydrates as biomass starting materials: an efficient catalyst for regiospecific epoxidation of β-ionone with ultrahigh turnover numbers"", 《CATALYSIS SCIENCE & TECHNOLOGY》 * |
| 王文兴: "《工业催化》", 31 December 1978, 化学工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109317168A (en) * | 2018-11-20 | 2019-02-12 | 扬州大学 | A kind of synthetic method of selenium doped zirconia catalyst |
| CN109317168B (en) * | 2018-11-20 | 2021-07-13 | 扬州大学 | Synthetic method of selenium-doped zirconia catalyst |
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