CN113680379B - Preparation method and application of microporous material loaded copper catalyst - Google Patents
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Abstract
The invention relates to a preparation method and application of a microporous material loaded copper catalyst, which comprises the steps of firstly, uniformly mixing DY-32 zeolite, sodium hydroxide, a template agent, water and seed crystals in an agate mortar, carrying out crystal transformation in an oven, washing and calcining a product to obtain Na-type SSZ-39 zeolite, and carrying out ion exchange to obtain H-type SSZ-39 zeolite; and carrying out incipient wetness impregnation on the H-SSZ-39 zeolite by using a copper salt solution, naturally drying in the shade, then drying in vacuum, and then roasting to obtain the microporous material loaded copper catalyst Cu/H-SSZ-39, wherein the microporous material loaded copper catalyst can be applied to catalytic decarboxylation coupling reaction. The catalyst has the advantages of high activity, easy separation, good stability, high activity, long service life, less metal residue, simple operation and simple equipment requirement; the catalyst has high activity after being recycled for many times, and has the advantages of economy, high efficiency, environmental protection and the like.
Description
Technical Field
The invention belongs to the technical field of metal organic catalysis, and particularly relates to a preparation method of a microporous material loaded copper catalyst and application of the microporous material loaded copper catalyst in catalytic decarboxylation coupling reaction.
Background
Decarboxylation cross-coupling is a very important method for flexibly constructing C-C bond compounds in modern organic chemical synthesis. Alpha-acylated ethers are important molecular fragments that can be used to prepare a variety of biologically active products and pharmaceutical intermediates. The synthesis method reported in the prior literature mainly takes homogeneous precious metal as a catalyst, and the industrial application is limited by the expensive price and the difficult recycling of toxic ligand, so that the heterogeneous transition metal supported catalyst is in the spotlight.
In recent years, the development of transition metal catalytic organic synthesis just meets the demand of the current generation, and the preparation of cheap, efficient and nontoxic supported metal catalysts is a key point and a difficulty for promoting the development of the field. The zeolite compound is an ideal raw material for synthesizing the metal organic catalyst carrier as a porous material which is cheap, easy to obtain and nontoxic. Heterogeneous reactions have many advantages over homogeneous reactions. For example, after the reaction is completed, the catalyst and the product are simple to separate, and can be recycled, so that the cost is greatly reduced, and the reaction stereoselectivity can be better controlled in the reaction. After seeing these great advantages, researchers have focused on the design and synthesis of various catalyst supports and the loading of homogeneous catalysts on various supports. Common carriers include silicon dioxide, biomass, magnetic materials, high molecular polymers and the like, and zeolite is a green and environment-friendly porous material, so that the zeolite meets the green and environment-friendly requirements and plays an important role in the catalytic reaction of transition metals, thereby receiving attention of people.
Disclosure of Invention
The invention aims to provide a preparation method of a microporous material supported copper catalyst and application of the microporous material supported copper catalyst in catalytic decarboxylation coupling reaction 2 -Csp 3 A coupling compound.
A preparation method of a microporous material loaded copper catalyst comprises the following steps:
(1) Uniformly mixing DY-32 zeolite, sodium hydroxide, a template agent, water and seed crystals in an agate mortar, carrying out crystal transformation (crystallization) in an oven, washing and calcining a product to obtain Na-type SSZ-39 zeolite, and carrying out ion exchange to obtain H-type SSZ-39 zeolite;
(2) Carrying out incipient wetness impregnation on H-SSZ-39 zeolite by using a copper salt solution, naturally drying in the shade, then drying in vacuum, and then roasting to obtain the microporous material loaded copper catalyst Cu/H-SSZ-39.
Preferably, the template agent is N, N-dimethyl-3,5-dimethyl piperidine hydroxide solution, and the seed crystal is H-SSZ-39 seed crystal.
Preferably, the mass ratio of the DY-32 zeolite to the sodium hydroxide to the template is 1: 0.115-0.135: 0.85 to 1.05. More preferably, the mass ratio of the DY-32 zeolite to the sodium hydroxide to the template is 1:0.125:0.95.
preferably, the crystal transformation temperature in the step (1) is 120-160 ℃, and the crystal transformation time is 2-4 days; in the step (2), the vacuum drying temperature is 60-120 ℃, the drying time is 8-16 hours, and the roasting temperature is 300-600 ℃. More preferably, the temperature of the vacuum drying is 100 ℃, the drying time is 12 hours, and the baking temperature is 450 ℃.
Preferably, the copper salt is one of copper acetate, copper sulfate, copper nitrate and copper chloride; more preferably, the copper salt is copper nitrate; the copper salt solution is a copper salt aqueous solution, a copper salt ethanol solution or a copper salt methanol solution.
Preferably, the preparation method of the microporous material supported copper catalyst comprises the following steps:
(1) 1g of DY-32 zeolite is added into an agate mortar, 0.95g of N, N-dimethyl-3,5-dimethylpiperidine hydroxide solution is added, and the mixture is uniformly ground; adding 0.05g of deionized water into the mixture, and uniformly grinding; adding 0.125g of granular sodium hydroxide into the mixture, and uniformly grinding; adding 0.02g H-SSZ-39 zeolite seed crystal into the mixture, and uniformly grinding; transferring the mixture to a hydrothermal kettle, and crystallizing for 3 days at 150 ℃; the product was calcined at 550 ℃ for 4 hours; the obtained product is subjected to ion exchange at 80 ℃ twice in 1M ammonium nitrate solution to obtain H-type product H-SSZ-39-0.95 zeolite;
(2) Adding H-SSZ-39-0.95 zeolite into a beaker, slowly dropwise adding a copper nitrate solution until the zeolite is completely wet, and naturally drying in the shade; transferring to a vacuum oven for drying for 12 hours at 100 ℃; the catalyst solid was crushed and placed in a porcelain boat, heated at 5 ℃ per minute, and calcined at 450 ℃ for 3 hours to give Cu/H-SSZ-39.
The preparation scheme of the microporous material supported copper catalyst (Cu/H-SSZ-39) is shown in figure 1.
The invention also provides application of the microporous material loaded copper catalyst in catalysis of decarboxylation coupling reaction.
Preferably, the microporous material supported copper catalyst is applied to the catalytic decarboxylation coupling reaction by adopting the following method: adding benzoylformic acid, a microporous material loaded copper catalyst, an ether compound and tert-butyl hydroperoxide into a reactor, vacuumizing, introducing nitrogen, and performing decarboxylation coupling reaction for 1.5-3 hours under a heating condition; after the reaction is finished, cooling the reaction liquid to room temperature, filtering, and evaporating the solvent to obtain a decarboxylation coupling product.
The invention takes benzoylformic acid as raw material, a microporous material loaded copper catalyst and a liquid ether compound as solvent, and the raw material is treated by Csp at reflux temperature 2 -Csp 3 Decarboxylation coupling to synthesize the benzoyl methine ether compound.
Preferably, the amount ratio of the benzoylformic acid to the copper catalyst-supported substance of the microporous material is 100:5 to 25. More preferably, the amount ratio of the benzoyl formic acid to the substance of the microporous material loading the copper catalyst is 100:10.
preferably, the mass/solution volume ratio of the benzoylformic acid to the ether compound is 1: 1-4; more preferably 1:3, e.g. 1mmol:3mL.
Preferably, the decarboxylation coupling reaction temperature is 80 to 170 ℃. More preferably, the reaction temperature is 120 ℃.
The route for synthesizing the benzoyl methine ether compound by the catalytic decarboxylation coupling of Cu/H-SSZ-39 is as follows:
compared with the prior art, the invention has the beneficial effects that:
the catalyst has the advantages of high activity, easy separation, good stability, high activity, long service life, less metal residue, simple operation and simple equipment requirement; the catalyst has high activity after being recycled for many times, and has the advantages of economy, high efficiency, environmental protection and the like.
Drawings
FIG. 1 is a schematic preparation scheme of a zeolite-supported copper catalyst (Cu/H-SSZ-39) according to the present invention;
FIG. 2 shows the preparation of 2- (1,4-dioxane) benzophenone which is the product of the present invention 1 H NMR spectrum;
FIG. 3 shows the preparation of 2- (1,4-dioxane) benzophenone which is the product of the present invention 13 C NMR spectrogram;
FIG. 4 shows the preparation of 2,3-dimethoxyphenylacetone 1 H NMR spectrum;
FIG. 5 is a graph showing the catalytic effect of the catalyst of the present invention after 5 cycles of use.
Detailed Description
The invention is further illustrated with reference to specific examples, without however being limited thereto. It will be appreciated by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Example 1
Synthesis of H-SSZ-39
1g of DY-32, 0.95g of DMDMPOH, 0.05g of deionized water, 0.125g of granular sodium hydroxide and 0.02g H-SSZ-39 seed crystals are added and ground into an agate mortar in sequence. And (3) placing the mixture in a hydrothermal kettle, crystallizing for 3 days at 140 ℃, washing and drying the product, calcining for 4 at 550 ℃ to obtain Na-SSZ-39, and performing ion exchange on the obtained product twice in 1M ammonium nitrate solution at 80 ℃ to obtain a hydrogen-type product H-SSZ-39.
Preparation of Cu/H-SSZ-39-300 (400, 450, 500) -A
Adding H-SSZ-39 zeolite into a beaker, slowly dropwise adding a copper nitrate aqueous solution until the zeolite is completely wet, naturally drying in the shade, and transferring to a vacuum oven for drying at 100 ℃ for 12 hours. The catalyst solid is crushed and put into a porcelain boat, the temperature is raised by 5 ℃ per minute, and the catalyst Cu/H-SSZ-39-300-A, cu/H-SSZ-39-400-A, cu/H-SSZ-39-450-A, cu/H-SSZ-39-500-A is obtained by roasting at 300 ℃, 400 ℃, 450 ℃ and 500 ℃ for 3 hours.
Example 2
Preparation of Cu/H-SSZ-39-400-E
Adding H-SSZ-39 zeolite into a beaker, slowly dropwise adding a cupric nitrate ethanol solution until the zeolite is completely wet, naturally drying in the shade, and transferring to a vacuum oven for drying at 100 ℃ for 12 hours. And (3) crushing the catalyst solid, putting the crushed catalyst solid into a porcelain boat, heating the porcelain boat at the temperature of 5 ℃ per minute, and roasting the porcelain boat for 3 hours at the temperature of 400 ℃ to obtain the catalyst Cu/H-SSZ-39-400-E.
Example 3
A150 mL round bottom flask was charged with benzoylformic acid (25mmol, 3.753g), cu/H-SSZ-39-450-A (10 mol%,0.3 g), and 1,4-dioxane (75 mL), and after uniform mixing with sonication, tert-butyl hydroperoxide (37.5 mmol, 3.380g) was added. Installing a thorn-shaped fractionating column and a three-way pipe, and heating and refluxing for 3 hours at 120 ℃ under the protection of nitrogen. After the reaction is finished, cooling the reaction liquid to room temperature, filtering the catalyst, adding excessive alkali liquor into the filtrate to neutralize the benzoylformic acid, extracting the mixed liquid with ethyl acetate, taking the organic phase, and performing rotary evaporationRemoving the organic solvent by an instrument to obtain the product 2- (1,4-dioxane) benzophenone with the yield of 98 percent and the product 2- (1,4-dioxane) benzophenone 1 The H NMR spectrum is shown in figure 2, 13 the C NMR spectrum is shown in FIG. 3.
1 H NMR(400MHz,DMSO-d 6 )δ8.05–8.01(m,2H),7.72–7.67(m,1H),7.56(t,J＝7.7Hz,2H),6.03(s,1H),4.05(ddd,J＝3.2,10.3,11.6Hz,1H),3.78(dt,J＝2.3,19.0Hz,3H),3.74–3.68(m,1H),3.63(dt,J＝2.4,11.7Hz,1H)。
13 C NMR(101MHz,DMSO-d 6 )δ164.44,133.69,129.44,129.34,128.85,89.59,67.06,65.37。
Example 4
A150 mL round bottom flask was charged with benzoylformic acid (25mmol, 3.753g), cu/H-SSZ-39-400-A (10 mol%,0.3 g), and 1,4-dioxane (75 mL), and after uniform mixing with sonication, tert-butyl hydroperoxide (37.5mmol, 3.380g) was added. Installing a thorn-shaped fractionating column and a three-way pipe, and heating and refluxing for 3 hours at 120 ℃ under the protection of nitrogen. After the reaction is finished, cooling the reaction liquid to room temperature, filtering the catalyst, adding excessive alkali liquor into the filtrate to neutralize the benzoylformic acid, extracting the mixed liquid by using ethyl acetate, taking an organic phase, and removing the organic solvent by using a rotary evaporator to obtain the product 2- (1,4-dioxane) benzophenone with the yield of 95%.
Example 5
In a 150mL round bottom flask, benzoylformic acid (25mmol, 3.753g), cu/H-SSZ-39-500-A (10 mol%,0.3 g), 1,4-dioxane (75 mL) were charged, and after uniform mixing by sonication, t-butyl hydroperoxide (37.5 mmol, 3.380g) was added. Installing a thorn-shaped fractionating column and a three-way pipe, and heating and refluxing for 3 hours at 120 ℃ under the protection of nitrogen. After the reaction is finished, cooling the reaction liquid to room temperature, filtering the catalyst, adding excessive alkali liquor into the filtrate to neutralize the benzoylformic acid, extracting the mixed liquid by using ethyl acetate, taking an organic phase, and removing the organic solvent by using a rotary evaporator to obtain the product 2- (1,4-dioxane) benzophenone with the yield of 92%.
Example 6
A150 mL round bottom flask was charged with benzoylformic acid (25mmol, 3.753g), cu/H-SSZ-39-400-E (10 mol%,0.3 g), and 1,4-dioxane (75 mL), and after uniform mixing with sonication, tert-butyl hydroperoxide (37.5 mmol, 3.380g) was added. Installing a thorn-shaped fractionating column and a three-way pipe, and heating and refluxing for 3 hours under the protection of nitrogen. After the reaction is finished, cooling the reaction liquid to room temperature, filtering the catalyst, adding excessive alkali liquor into the filtrate to neutralize the benzoylformic acid, extracting the mixed liquid by using ethyl acetate, taking an organic phase, and removing the organic solvent by using a rotary evaporator to obtain the product 2- (1,4-dioxane) benzophenone with the yield of 90%.
Example 7
A150 mL round-bottomed flask was charged with benzoylformic acid (25mmol, 3.753g), cu/H-SSZ-39-450-A (10 mol%,0.3 g), and ethylene glycol dimethyl ether (75 mL), and the mixture was uniformly mixed by sonication, followed by addition of tert-butyl hydroperoxide (37.5mmol, 3.380g). Installing a thorn-shaped fractionating column and a three-way pipe, and heating and refluxing for 3 hours at 100 ℃ under the protection of nitrogen. After the reaction is finished, cooling the reaction liquid to room temperature, filtering the catalyst, adding excessive alkali liquor into the filtrate to neutralize the benzoylformic acid, extracting the mixed liquid with ethyl acetate, taking the organic phase, removing the organic solvent with a rotary evaporator to obtain the product 2,3-dimethoxyphenylacetone with the yield of 90 percent and the product 2,3-dimethoxyphenylacetone 1 The H NMR spectrum is shown in FIG. 4.
1 H NMR(400MHz,CDCl 3 )δ8.10(t,J＝8.0Hz,2H),7.59(t,J＝7.8Hz,1H),7.47(q,J＝7.3,7.7Hz,2H),6.14(t,J＝4.9Hz,1H),3.64(t,J＝4.5Hz,2H),3.55(s,3H),3.44(s,3H)。
Example 8
Recycle of Cu/H-SSZ-39-450-A
A150 mL round bottom flask was charged with benzoylformic acid (25mmol, 3.753g), cu/H-SSZ-39-450-A (10 mol%,0.3 g), and 1,4-dioxane (75 mL), and after uniform mixing with sonication, tert-butyl hydroperoxide (37.5 mmol, 3.380g) was added. Installing a thorn-shaped fractionating column and a three-way pipe, and heating and refluxing for 3 hours at 120 ℃ under the protection of nitrogen. After the reaction is finished, cooling the reaction liquid to room temperature, centrifugally recovering the catalyst, adding excessive alkali liquor into the filtrate to neutralize the benzoylformic acid, extracting the mixed liquid by using ethyl acetate, taking an organic phase, removing the organic solvent by using a rotary evaporator to obtain a product 2- (1,4-dioxane) benzophenone, using the dried catalyst under the same catalytic condition, wherein the catalytic effect is shown in figure 5 after 5 times of recycling, and the result shows that the catalytic effect of the catalyst is not obviously reduced after 5 times of recycling.
The present invention is described in detail with reference to the examples, but the description is only a specific embodiment of the present invention, and the present invention is not to be construed as being limited to the claims. It should be noted that, for those skilled in the art, variations and modifications made within the scope of the present invention shall fall within the scope of the claims of the present invention without departing from the spirit of the present invention.
Claims (8)
1. The application of the microporous material supported copper catalyst is characterized in that the microporous material supported copper catalyst comprises the following steps:
(1) Uniformly mixing DY-32 zeolite, sodium hydroxide, a template agent, water and seed crystals in an agate mortar, carrying out crystal transfer in an oven, washing and calcining a product to obtain Na-type SSZ-39 zeolite, and carrying out ion exchange to obtain H-type SSZ-39 zeolite;
(2) Carrying out primary wet impregnation on H-SSZ-39 zeolite by using a copper salt solution, naturally drying in the shade, then drying in vacuum, and then roasting to obtain a microporous material loaded copper catalyst Cu/H-SSZ-39;
the microporous material loaded copper catalyst is applied to catalytic decarboxylation coupling reaction: adding benzoylformic acid, a microporous material loaded copper catalyst, an ether compound and tert-butyl hydroperoxide into a reactor, vacuumizing, introducing nitrogen, and performing decarboxylation coupling reaction for 1.5-3 hours under a heating condition; after the reaction is finished, cooling the reaction liquid to room temperature, filtering, and evaporating the solvent to obtain a decarboxylation coupling product.
2. The use of the microporous material supported copper catalyst of claim 1, wherein: the template agent is N, N-dimethyl-3,5-dimethyl piperidine hydroxide solution, and the seed crystal is H-SSZ-39 seed crystal.
3. The use of the microporous material supported copper catalyst of claim 1, wherein: the mass ratio of the DY-32 zeolite to the sodium hydroxide to the template agent is 1: 0.115-0.135: 0.85 to 1.05.
4. The use of the microporous material supported copper catalyst of claim 1, wherein: the crystal transformation temperature in the step (1) is 120-160 ℃, and the crystal transformation time is 2-4 days; in the step (2), the vacuum drying temperature is 60-120 ℃, the drying time is 8-16 hours, and the roasting temperature is 300-600 ℃.
5. The use of the microporous material supported copper catalyst of claim 1, wherein: the copper salt is one of copper acetate, copper sulfate, copper nitrate and copper chloride; the copper salt solution is a copper salt aqueous solution, a copper salt ethanol solution or a copper salt methanol solution.
6. The use of the microporous material supported copper catalyst as claimed in claim 1, comprising the steps of:
(1) Adding 1g of DY-32 zeolite into an agate mortar, adding 0.95g N, N-dimethyl-3, 5-dimethylpiperidine hydroxide solution, and uniformly grinding; adding 0.05g of deionized water into the mixture, and uniformly grinding; adding 0.125g of granular sodium hydroxide into the mixture, and uniformly grinding; adding 0.02g H-SSZ-39 zeolite seed crystal into the mixture, and uniformly grinding; transferring the mixture to a hydrothermal kettle, and crystallizing for 3 days at 150 ℃; the product was calcined at 550 ℃ for 4 hours; the obtained product is subjected to ion exchange at 80 ℃ twice in 1M ammonium nitrate solution to obtain H-type product H-SSZ-39-0.95 zeolite;
(2) Adding H-SSZ-39-0.95 zeolite into a beaker, slowly dropwise adding a copper nitrate solution until the zeolite is completely wet, and naturally drying in the shade; transferring to a vacuum oven for drying for 12 hours at 100 ℃; and (3) crushing the catalyst solid, putting the crushed catalyst solid into a porcelain boat, raising the temperature at 5 ℃ per minute, and roasting the catalyst solid for 3 hours at 450 ℃ to obtain Cu/H-SSZ-39.
7. The use of the microporous material supported copper catalyst of claim 1, wherein: the mass ratio of the benzoylformic acid to the substance of the microporous material loaded with the copper catalyst is 100:5 to 25.
8. The use of the microporous material supported copper catalyst of claim 1, wherein: the temperature of the decarboxylation coupling reaction is 80-170 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614927A (en) * | 2012-03-15 | 2012-08-01 | 苏州大学 | Copper catalyst system for decarboxylation coupling reaction |
| ES2586770A1 (en) * | 2015-04-16 | 2016-10-18 | Consejo Superior De Investigaciones Científicas (Csic) | Method of direct synthesis of the cu-silicoaluminato material with the aei zeolithic structure, and its catalytic applications (Machine-translation by Google Translate, not legally binding) |
| CN109796426A (en) * | 2019-03-05 | 2019-05-24 | 常州大学 | A method of utilizing basic zeolite molecular sieve catalytic cortex cinnamomi acid decarboxylation coupling reaction |
| CN110980761A (en) * | 2019-11-22 | 2020-04-10 | 中触媒新材料股份有限公司 | Method for preparing SSZ-39 molecular sieve by taking sulfur modified Y-type molecular sieve as raw material |
| CN112958148A (en) * | 2021-02-05 | 2021-06-15 | 中化学科学技术研究有限公司 | Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with core-shell structure and synthesis method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101186311B (en) * | 2007-11-22 | 2012-02-22 | 复旦大学 | Y/MCM-48 composite molecular screen and preparation method thereof |
| CN105985248B (en) * | 2015-02-15 | 2018-10-26 | 上海泰禾国际贸易有限公司 | A kind of method of synthesizing amino Diaromatic compound |
| US20190218181A1 (en) * | 2016-05-10 | 2019-07-18 | Basf Se | Process for the manufacture of hydroxy-substituted aromatic compounds |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614927A (en) * | 2012-03-15 | 2012-08-01 | 苏州大学 | Copper catalyst system for decarboxylation coupling reaction |
| ES2586770A1 (en) * | 2015-04-16 | 2016-10-18 | Consejo Superior De Investigaciones Científicas (Csic) | Method of direct synthesis of the cu-silicoaluminato material with the aei zeolithic structure, and its catalytic applications (Machine-translation by Google Translate, not legally binding) |
| CN109796426A (en) * | 2019-03-05 | 2019-05-24 | 常州大学 | A method of utilizing basic zeolite molecular sieve catalytic cortex cinnamomi acid decarboxylation coupling reaction |
| CN110980761A (en) * | 2019-11-22 | 2020-04-10 | 中触媒新材料股份有限公司 | Method for preparing SSZ-39 molecular sieve by taking sulfur modified Y-type molecular sieve as raw material |
| CN112958148A (en) * | 2021-02-05 | 2021-06-15 | 中化学科学技术研究有限公司 | Cu-SSZ-39@ Cu-SSZ-13 composite molecular sieve with core-shell structure and synthesis method thereof |
Non-Patent Citations (5)
| Title |
|---|
| "Design and synthesis of the basic Cu-doped zeolite X catalyst with high activity in oxidative coupling reactions";Shengchun Chen et al.;《Journal of Catalysis》;20160307;第338卷;38-46页 * |
| "Solvent-free synthesis of aluminosilicate SSZ-39 zeolite";Hao Xu et al.;《Microporous and Mesoporous Materials》;20201030;第312卷;第2页第2.2节，第2.4节，第3节 * |
| "Transition-Metal-Free Formal Decarboxylative Coupling of α-Oxocarboxylates with α-Bromoketones under Neutral Conditions: A Simple Access to 1,3-Diketones";Zhen He et al.;《Angewandte Chemie International Edition》;20141120;第54卷(第3期);855-859页 * |
| "酸性Cu/ZSM-5-NA催化剂提高肉桂酸脱羧偶联反应活性";傅雯倩 等;《常州大学学报(自然科学版)》;20200928;第32卷(第5期);第41页第1段 * |
| Hao Xu et al.."Solvent-free synthesis of aluminosilicate SSZ-39 zeolite".《Microporous and Mesoporous Materials》.2020,第312卷110736:1-6页. * |
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