CN109833866A - A kind of nuclear shell structure nano catalyst and its application - Google Patents
A kind of nuclear shell structure nano catalyst and its application Download PDFInfo
- Publication number
- CN109833866A CN109833866A CN201910219055.4A CN201910219055A CN109833866A CN 109833866 A CN109833866 A CN 109833866A CN 201910219055 A CN201910219055 A CN 201910219055A CN 109833866 A CN109833866 A CN 109833866A
- Authority
- CN
- China
- Prior art keywords
- shell structure
- structure nano
- nuclear shell
- nano catalyst
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a kind of nuclear shell structure nano catalyst, preparation method: 10.0g lignin is added in the sodium hydroxide solution of 15mL 5wt%, it is stirred and heated to 35-45 DEG C, the formalin solution of 10mL 37wt% is added dropwise, after 75-85 DEG C of reaction 40-80min, it is cooled to room temperature, obtains lignin oligomer precursor；The CeCl of 20mL 7.5wt% is added dropwise while stirring2·7H2O aqueous solution after stirring and evenly mixing, is warming up to 70-90 DEG C and is reacted, and the obtained reaction product of reaction is dried, be then carbonized at pure Ar to get.The catalyst to prepare raw material sources abundant, and have the functional groups such as hydroxyl abundant, ehter bond, be bonded with rare earth, and prepare simple, can be applied to catalyze and synthesize benzimidazoles compound, high catalytic efficiency, preparation cost is low, and by-product is few, and separation is simple.
Description
Technical field
The present invention relates to a kind of nuclear shell structure nano catalyst and its applications, belong to chemosynthesis technical field.
Background technique
Benzimidazoles compound is a kind of Benzoheterocyclic compounds containing 2 nitrogen-atoms, in organic intermediate, green wood
The numerous areas such as material, pesticide have universal application, and nitrogen-containing heterocycle compound all has bioactivity, benzimidazole due to most
Class and its derivative especially anticancer, antibacterial, anti parasitic, it is antiviral, in terms of have broad prospect of application, benzimidazole
The synthesis and application of class compound are increasingly by the concern of chemist, currently, the glyoxaline compound sterilization of commercialization
Agent is applied extensively.
The conventional method of synthesizing benzimidazole class is that the progress high temperature dehydration such as o-phenylenediamine and carboxylic acid, acyl chlorides is made, the method
Higher reaction temperature or longer reaction time are usually required, and yield is undesirable, the high requirements on the equipment.Novel synthesis benzo
After carrying out catalysis oxidation with o-phenylenediamine and aldehyde, ketone etc. condensation reaction occurs for imidazoles, normal-temperature reaction and avoids using dehydrating agent,
The reaction process is easier but the more separation of by-product is difficult.In recent years, occur in succession it is a series of with lewis acid and
Transition metal complex etc. is the new synthesis route of the benzimidazoles compound of catalyst, but that there are waste acid quantities is big, and equipment is rotten
Erosion is serious or nanocatalyst preparation cost is high, reuses difficult.
Summary of the invention
Present invention aims to solve the deficiencies of the prior art, and provides a kind of a kind of nuclear shell structure nano catalyst, are applied
In catalyzing and synthesizing for benzimidazoles compound, the catalyst to prepare raw material sources abundant, and have hydroxyl (- OH) abundant,
The functional groups such as ehter bond (- O-), are bonded with rare earth, and preparing for catalyst is simple, topple over object catalysis effect to a variety of benzimidazoles
Rate is high.
Concrete scheme is as follows:
A kind of nuclear shell structure nano catalyst, the preparation method is as follows:
(1) 10.0g lignin is added in the sodium hydroxide solution of 15mL 5wt%, is stirred and heated to 35-45 DEG C,
The formalin solution of 10mL 37wt% is added dropwise, after 75-85 DEG C of reaction 40-80min, is cooled to room temperature, it is oligomeric to obtain lignin
Object precursor；
(2) CeCl of 20mL 7.5wt% is added dropwise when stirring lignin oligomer precursor2·7H2O aqueous solution, stirring are mixed
It after even, be warming up to 70-90 DEG C and reacted, the reaction product that reaction obtains is dried, is then carbonized at pure Ar,
Up to CeO2/ C nuclear shell structure nano catalyst.
In step (2), reaction temperature is 80 DEG C, reaction time 10-15h.
In step (2), the drying temperature is 105 DEG C, time 10-15h.
In step (2), the carburizing temperature is 550-700 DEG C, time 2-5h.
Above-mentioned nuclear shell structure nano catalyst is applied to catalyze and synthesize benzimidazoles compound.
Application method are as follows:
Using fragrant formaldehyde and o-phenylenediamine as raw material, above-mentioned nuclear shell structure nano catalyst is as catalyst, with pure O2
For carried out in a solvent under conditions of oxidant condensation reaction to get；The solvent be selected from dimethyl carbonate, ethyl alcohol, sulfolane,
Any one in tetrahydrofuran or 1,4- dioxane.
Further, the fragrant formaldehyde is selected from benzaldehyde, 4- nitrobenzaldehyde, 4- chlorobenzaldehyde, 4- bromobenzaldehyde, 4- first
Any one in oxygroup benzaldehyde, 2 furan carboxyaldehyde or 2 thiophene carboxaldehyde.
Further, in the above method, the molar ratio of fragrant formaldehyde and o-phenylenediamine is (1.1~1.5): 1.0.
Further, in the above method, the dosage of nuclear shell structure nano catalyst accounts for fragrant formaldehyde and o-phenylenediamine total weight
10%.
Further, the solvent is preferably dimethyl carbonate, and yield is higher.
Shown in synthetic route is specific as follows:
Ar=-C6H5,-C6H4NO2,-C6H4Cl,-C6H4Br,-C6H4OCH3,
Beneficial effects of the present invention: the present invention provides a kind of nuclear shell structure nano catalyst, the preparation of the catalyst is former
Expect abundance, and there are the functional groups such as hydroxyl abundant, ehter bond, be bonded with rare earth, and prepare simple, can be applied to urge
It is combined to benzimidazoles compound, high catalytic efficiency, preparation cost is low, and by-product is few, and separation is simple.
Detailed description of the invention
Fig. 1 is the XRD spectrum of nuclear shell structure nano catalyst made from embodiment 1；
Fig. 2 is the Raman spectrum of nuclear shell structure nano catalyst made from embodiment 1；
Fig. 3 is the transmission electron microscope picture of nuclear shell structure nano catalyst made from embodiment 1.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings and specific examples.
Embodiment 1
Prepare nuclear shell structure nano catalyst:
(1) 10.0g lignin is added in 15mL5% sodium hydroxide solution, is stirred and heated to 40 DEG C, 10mL is added dropwise
37wt% formalin solution after 80 DEG C of reaction 60min, is cooled to room temperature, obtains lignin oligomer precursor；
(2) 20mL 7.5%CeCl is added dropwise when stirring lignin oligomer precursor2·7H2O aqueous solution, after stirring and evenly mixing,
It is warming up to 80 DEG C and carries out reaction 12h, the reaction product that reaction is obtained is 12 hours dry at 105 DEG C, then 600 at pure Ar
3 hours are carbonized at DEG C to get CeO2/ C nuclear shell structure nano catalyst.
The XRD spectrum of the nuclear shell structure nano catalyst is shown in that Fig. 1, Raman spectrum are shown in Fig. 2.CeO as shown in Figure 12/ C-material
Characteristic peak appear in 2 θ values be 28.5 °, 33.0 °, 47.4 °, 56.3 °, 59.0 °, 69.4 °, 76.7 °, 79.0 °, 88.4 ° of position
It sets, corresponds respectively to (111), (200), (220), (311), (222), (400), (331), (420) and (422) nine features dissipate
Peak is penetrated, CeO is belonged to2(JCPDS 43-1002).In addition it is observed that having an apparent diffraction maximum in 2 θ=26.4 °, return
Belong to graphitized carbon (JCPDS No.41-1487).Figure it is seen that there are two the scattering strength peak peaks D on Raman map
(1368cm-1) and the peak G (1604cm-1), the former corresponds to raman bands, the referred to as peak D caused by single crystal graphite defect, after
Person corresponds to carbon atom sp2Stretching vibration in the face of hydridization, the referred to as peak G.The ratio at the usual peak D and the peak G is characterization material
One important parameter of degree of graphitization, ID/IGRatio is smaller, indicates that the degree of graphitization of carbon material is higher.As can be seen from Figure 2,
CeO2The I of/C-materialD/IGIt is 0.91, illustrates CeO2Carbon in/C-material has higher degree of graphitization, this data and XRD analysis
As a result consistent.
Fig. 3 is the transmission electron microscope picture of nuclear shell structure nano catalyst, and Cong Tuzhong is it will be clear that CeO2/ C-material has
Complete core-shell structure, orderly graphitized carbon being coated on around the stannic oxide particle of black tightly in layer, thus
Illustrate CeO2/ C-material has core-shell structure, figure (a) and CeO in (b)2@C particle in a highly dispersed state, without agglomeration,
Particle size concentrates between 8-10nm, schemes the lattice fringe that graphite is clearly seen that in (c) and (d), and every CeO2Particle
Surface all coats 4-8 layers of graphitized carbon, this is consistent with XRD and Raman analysis result.
It can be found that (1) higher degree of graphitization can promote electronics transfer from Fig. 1-3 catalyst characterization result, improves
Catalytic activity；(2) the confinement effect of core-shell structure, can effectively prevent CeO2It grows up, reunite during the reaction, be beneficial to mention
The stability of height catalysis.
Embodiment 2
O-phenylenediamine (2mmol), benzaldehyde (3mmol), core made from embodiment 1 are added into dry Schlenk pipe
Shell structural nano catalyst (dosage account for benzaldehyde and o-phenylenediamine total weight 10%) and solvent dimethyl carbonate
Reaction tube is placed in magnetic agitation under 85 DEG C of oil baths after sealing and reacts 10h by (5.0mL), the external oxygen ball of reaction tube, until
Raw material disappears (TLC tracking and monitoring), and ((5mL × 3) ethyl acetate wash-off mixed liquor, organic phase merging, vacuum rotary steam removing is added
Solvent dimethyl carbonate, with 300 mesh silicagel columns [solvent is V (petroleum ether): V (ethyl acetate)=6: 1] isolated target
Product 2-Phenylbenzimidazole, yield 91%.
2 product 2-Phenylbenzimidazole of embodiment: 289~291 DEG C of fusing point；1HNMR (500MHz, DMSO-d6): (s,
1H), 8.18 (d, J=8.5Hz, 2H), 7.50-7.57 (m, 5H), 7.21-7.22 (m, 2H).
Embodiment 3
Benzaldehyde is changed to 4- nitrobenzaldehyde, reaction time 11h, solvent is ethyl alcohol, remaining is same as Example 2,
2- (4- nitrobenzophenone) benzimidazole yield is 76%.
Embodiment 3 product 2- (4- nitrobenzophenone)-benzimidazole: 315~317 DEG C of fusing point；1HNMR (500MHz, DMSO-
D6): (d, J=9.0Hz, 2H), 8.26 (s, 1H), 7.00-7.03 (m, 1H), 6.74-6.76 (m, 1H), 6.55-6.59 (m,
1H)。
Embodiment 4
Benzaldehyde is changed to 4- chlorobenzaldehyde, reaction time 11h, solvent is sulfolane, remaining is same as Example 2,
2- (4- chlorphenyl) benzimidazole yield is 83%.
Embodiment 4 product 2- (4- chlorphenyl)-benzimidazole: 292~294 DEG C of fusing point；1HNMR (500MHz, DMSO-
D6): δ=12.99 (s, 1H), 8.19 (m, 2H), 7.54-7.65 (m, 4H), 7.22 (s, 2H).
Embodiment 5
Benzaldehyde is changed to 4- bromobenzaldehyde, reaction time 11h, solvent is tetrahydrofuran, remaining and 2 phase of embodiment
Together, 2- (4- bromophenyl) benzimidazole yield is 83%.
Embodiment 5 product 2- (4- bromophenyl)-benzimidazole: 298~299 DEG C of fusing point；1HNMR (500MHz, DMSO-
D6): δ (d, J=8.5Hz, 2H), 7.77 (d, J=9.0Hz, 2H), 7.67 (d, J=6.5Hz, 1H) d, J=7.5Hz, 1H),
7.22 (s, 2H).
Embodiment 6
Benzaldehyde is changed to 4-methoxybenzaldehyde, reaction time 10h, solvent is dimethyl carbonate, remaining and implementation
Example 2 is identical, and 2- (4- methoxyphenyl) benzimidazole yield is 85%.
Embodiment 6 product 2- (4- methoxyphenyl)-benzimidazole: 1HNMR (500MHz, DMSO-d6): (s, 1H),
8.12 (d, J=9.0Hz, 2H), 7.55 (s, 1H), 7.11-7.18 (m, 4H), 3.84 (s, 3H).
Embodiment 7
Benzaldehyde is changed to 2 furan carboxyaldehyde, reaction time 12h, solvent is dimethyl carbonate, remaining and 2 phase of embodiment
Together, 2- (2- furyl) benzimidazole yield is 88%.
Embodiment 7 product 2- (2- furyl) -1H- benzimidazole: 287~288 DEG C of fusing point；1HNMR (500MHz, DMSO-
D6): (s, 1H), 7.50-7.62 (m, 2H), 7.19-7.20 (m, 3H), 6.73-6.74 (m, 1H).
Embodiment 8
Benzaldehyde is changed to 2 thiophene carboxaldehyde, reaction time 12h, solvent is dimethyl carbonate, remaining and 2 phase of embodiment
Together, 2- (2- thienyl) benzimidazole yield is 82%.
Embodiment 8 product 2- (2- thienyl)-benzimidazole: 329~331 DEG C of fusing point；1HNMR (500MHz, DMSO-
D6): δ=12.93 (s, 1H), 7.83 (d, J=3.0Hz, 1H), 7.73 (d, J=5.0Hz, 1H) (d, J=8.0Hz, 1H),
7.50 (d, J=7.5Hz, 1H), 7.16-7.24 (m, 3H).
Embodiment 9
Solvent is ethyl alcohol, remaining is same as Example 2, and 2-Phenylbenzimidazole yield is 82%.
Embodiment 10
Solvent is sulfolane, remaining is same as Example 2, and 2-Phenylbenzimidazole yield is 78%.
Embodiment 11
Solvent is tetrahydrofuran, remaining is same as Example 2, and 2-Phenylbenzimidazole yield is 60%.
Embodiment 12
Oil bath temperature is 90 DEG C, remaining is same as Example 2, and 2-Phenylbenzimidazole yield is 80%.
Embodiment 13
Oil bath temperature is 80 DEG C, remaining is same as Example 2, and 2-Phenylbenzimidazole yield is 72%.
Claims (10)
1. a kind of nuclear shell structure nano catalyst, which is characterized in that preparation method is as follows:
(1) 10.0g lignin is added in the sodium hydroxide solution of 15mL 5wt%, is stirred and heated to 35-45 DEG C, be added dropwise
The formalin solution of 10mL 37wt% after 75-85 DEG C of reaction 40-80min, is cooled to room temperature, before obtaining lignin oligomer
Body；
(2) CeCl of 20mL 7.5wt% is added dropwise when stirring lignin oligomer precursor2·7H2O aqueous solution, after stirring and evenly mixing,
Be warming up to 70-90 DEG C to be reacted, the obtained reaction product of reaction be dried, be then carbonized at pure Ar to get.
2. nuclear shell structure nano catalyst as described in claim 1, which is characterized in that in step (2), reaction temperature is 80 DEG C,
Reaction time is 10-15h.
3. nuclear shell structure nano catalyst as described in claim 1, which is characterized in that in step (2), the drying temperature is
105 DEG C, time 10-15h.
4. the nuclear shell structure nano catalyst as described in claims 1 or 2 or 3, which is characterized in that in step (2), the carbonization temperature
Degree is 550-700 DEG C, time 2-5h.
5. the application of claims 1 or 2 or the 3 or 4 nuclear shell structure nano catalyst synthesizing benzimidazole class compounds,
It is characterized in that, application method are as follows: using fragrant formaldehyde and o-phenylenediamine as raw material, nuclear shell structure nano catalyst is as catalysis
Agent, with pure O2For carried out in a solvent under conditions of oxidant condensation reaction to get.
6. application as claimed in claim 5, which is characterized in that the molar ratio of fragrant formaldehyde and o-phenylenediamine be (1.1~
1.5): 1.0.
7. application as claimed in claim 5, which is characterized in that the solvent is selected from dimethyl carbonate, ethyl alcohol, sulfolane, four
Any one in hydrogen furans or 1,4- dioxane.
8. the use as claimed in claim 7, which is characterized in that the solvent is dimethyl carbonate
9. application as claimed in claim 5, which is characterized in that the fragrance formaldehyde is selected from benzaldehyde, 4- nitrobenzaldehyde, 4-
Any one in chlorobenzaldehyde, 4- bromobenzaldehyde, 4-methoxybenzaldehyde, 2 furan carboxyaldehyde or 2 thiophene carboxaldehyde.
10. such as the described in any item applications of claim 5 to 9, which is characterized in that the dosage of the nuclear shell structure nano catalyst
Account for the 10% of fragrant formaldehyde and o-phenylenediamine total weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910219055.4A CN109833866A (en) | 2019-03-21 | 2019-03-21 | A kind of nuclear shell structure nano catalyst and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910219055.4A CN109833866A (en) | 2019-03-21 | 2019-03-21 | A kind of nuclear shell structure nano catalyst and its application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109833866A true CN109833866A (en) | 2019-06-04 |
Family
ID=66886019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910219055.4A Pending CN109833866A (en) | 2019-03-21 | 2019-03-21 | A kind of nuclear shell structure nano catalyst and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109833866A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1053252B (en) * | 1963-05-23 | 1981-08-31 | Merck & Co Inc | FUNGICIDAL PREPARATIONS AND RELATED METHOD OF USE |
| CN102875752A (en) * | 2011-12-05 | 2013-01-16 | 山东圣泉化工股份有限公司 | Lignin modified thermoplastic phenolic resin and preparation method thereof |
| CN103301868A (en) * | 2013-07-10 | 2013-09-18 | 河北大学 | Core-shell structural nano catalyst as well as preparation method and application thereof |
| CN106824162A (en) * | 2017-01-19 | 2017-06-13 | 盐城工业职业技术学院 | A kind of graphene-supported cerium catalyst and preparation method thereof |
| CN108722414A (en) * | 2018-05-15 | 2018-11-02 | 江苏理工学院 | A kind of preparation method of Thinwall Graphite carbon coated metal Core-shell structure material |
-
2019
- 2019-03-21 CN CN201910219055.4A patent/CN109833866A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1053252B (en) * | 1963-05-23 | 1981-08-31 | Merck & Co Inc | FUNGICIDAL PREPARATIONS AND RELATED METHOD OF USE |
| CN102875752A (en) * | 2011-12-05 | 2013-01-16 | 山东圣泉化工股份有限公司 | Lignin modified thermoplastic phenolic resin and preparation method thereof |
| CN103301868A (en) * | 2013-07-10 | 2013-09-18 | 河北大学 | Core-shell structural nano catalyst as well as preparation method and application thereof |
| CN106824162A (en) * | 2017-01-19 | 2017-06-13 | 盐城工业职业技术学院 | A kind of graphene-supported cerium catalyst and preparation method thereof |
| CN108722414A (en) * | 2018-05-15 | 2018-11-02 | 江苏理工学院 | A kind of preparation method of Thinwall Graphite carbon coated metal Core-shell structure material |
Non-Patent Citations (4)
| Title |
|---|
| 刘耀华: "《有机化学中的选择性氧化作用》", 30 June 2008, 中国科学技术出版社, pages: 123 * |
| 周春隆: "《精细化工实验法》", 31 December 1998, 中国石化出版社, pages: 117 * |
| 罗宁: "《爆轰法制备核壳结构碳包覆金属纳米材料》", 31 July 2016, 中国矿业大学出版社, pages: 2 - 3 * |
| 郑春满等: "《高等合成化学-方法与实践》", 30 September 2018, 国防工业出版社, pages: 55 - 58 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Efficient Tandem Synthesis of Methyl Esters and Imines by Using Versatile Hydrotalcite‐Supported Gold Nanoparticles | |
| JP3763077B2 (en) | Porous material and method for producing the same | |
| CN102208658B (en) | Method for preparing nanometer Ti4O7 particles | |
| CN108855095B (en) | Methane reforming multi-core-shell hollow catalyst nickel-nickel silicate-SiO2Preparation method of (1) | |
| CN107597097B (en) | Preparation method and application of supported molybdenum oxide catalyst | |
| CN111068682A (en) | Biomass-based carbon material loaded monoatomic copper catalyst and preparation method and application thereof | |
| Ravi et al. | Sustainable route for the synthesis of flower-like Ni@ N-doped carbon nanosheets from bagasse and its catalytic activity towards reductive amination of nitroarenes with bio-derived aldehydes | |
| Lu et al. | Palladium Nanoparticles Supported on Titanate Nanobelts for Solvent‐Free Aerobic Oxidation of Alcohols | |
| CN108636412B (en) | Preparation method of multi-core-shell hollow catalyst nickel-nickel silicate for methane and carbon dioxide reforming | |
| CN106423144B (en) | A kind of carbon fiber@tungsten oxide nanoparticles core-shell structure and preparation method thereof | |
| CN103570070A (en) | Preparation method of self-assembly W18049 nanostructure | |
| CN109833866A (en) | A kind of nuclear shell structure nano catalyst and its application | |
| JP2005298324A (en) | Porous body and its production method | |
| JP2005298324A5 (en) | ||
| CN103007928B (en) | Preparation method and application of palladium nanoparticle catalyst | |
| CN110862364B (en) | Process for preparing furanylaldehydes | |
| Fareghi-Alamdari et al. | Solvent-free synthesis of trisphenols as starting precursors for the synthesis of calix [4] arenes using sulfonated multi-walled carbon nanotubes | |
| Song et al. | Recent advance in selective hydrogenation reaction catalyzed by biomass-derived non-noble metal nanocomposites | |
| CN105597757B (en) | Magnetic oxygenated graphen catalyst and preparation method thereof and its application | |
| CN101798109A (en) | Preparation method of tin oxide nanotubes | |
| CN113651313B (en) | Hollow submicron nitrogen-doped carbon tube and preparation method thereof | |
| CN116037954A (en) | Gold iridium core-shell nanowire and preparation method thereof | |
| JP6495065B2 (en) | Method for producing flaky carbon | |
| CN112452324B (en) | Silver-ruthenium bimetallic doped graphene catalyst and preparation method and application thereof | |
| CN110420663B (en) | Composite catalyst for producing small molecular acid by efficiently catalyzing and degrading straw and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190604 |
|
| RJ01 | Rejection of invention patent application after publication |