阅读说明：本技术 无金属无孔催化剂材料的制备方法及应用 (preparation method and application of metal-free non-porous catalyst material ) 是由 吴孔林 黄飞 李君� 吴涛 柳守杰 陈郑 毛俊杰 魏先文 于 2019-08-23 设计创作，主要内容包括：本发明属于催化剂材料制备技术领域,具体涉及一种无金属无孔催化剂材料的制备方法,还涉及上述材料的应用。本发明的制备方法,包括以下的步骤：制备前驱体A：将淀粉、含硼化合物、氰胺类物质加入到水中,搅拌下干燥,即得到前驱体A；将前驱体A放入带盖的瓷舟中并置于管式炉内,在惰性气体氛围下,升温煅烧,保持,然后冷却至室温,得到无金属无孔催化剂材料。本发明的有益效果在于：采用淀粉作为碳源,廉价易得,绿色环保,可大规模生产,催化剂易分离,易于工业化；所得催化剂为无金属催化剂,合成方法简单；表现出较高催化活性和高选择性；具有广泛的催化底物适用性。(The invention belongs to the technical field of catalyst material preparation, and particularly relates to a preparation method of a metal-free non-porous catalyst material, and further relates to an application of the material. The preparation method comprises the following steps: preparing a precursor A: adding starch, a boron-containing compound and cyanamide substances into water, and drying under stirring to obtain a precursor A; and putting the precursor A into a porcelain boat with a cover, placing the porcelain boat in a tubular furnace, heating and calcining the porcelain boat under the atmosphere of inert gas, keeping the porcelain boat, and cooling the porcelain boat to room temperature to obtain the metal-free and non-porous catalyst material. The invention has the beneficial effects that: starch is used as a carbon source, so that the method is cheap and easy to obtain, green and environment-friendly, can be used for large-scale production, and is easy for catalyst separation and industrialization; the obtained catalyst is a metal-free catalyst, and the synthesis method is simple; the catalyst shows higher catalytic activity and high selectivity; has wide catalytic substrate applicability.)

1. The preparation method of the metal-free catalyst material is characterized in that the metal-free catalyst material is a metal-free non-porous catalyst material or a metal-free porous catalyst material;

The preparation method of the metal-free non-porous catalyst material comprises the following steps:

(1) Preparing a precursor A:

Adding 15-25 parts of starch, 1-4 parts of boron-containing compound and 15-25 parts of cyanamide substance into 450-550 parts of water, and drying under stirring to obtain a precursor A; the above parts are parts by weight;

(2) putting the precursor A into a porcelain boat with a cover, placing the porcelain boat in a tubular furnace, heating, keeping and cooling the porcelain boat under the atmosphere of inert gas to obtain a metal-free and non-porous catalyst material;

The preparation method of the metal-free porous catalyst material comprises the following steps:

(1) Adding 15-25 parts of silicon dioxide, 15-25 parts of starch, 1-4 parts of boron-containing compound and 15-25 parts of cyanamide substance into 450-550 parts of water, and drying under stirring to obtain a precursor A;

(2) And putting the precursor A into a porcelain boat with a cover, placing the porcelain boat into a tube furnace, and heating, keeping and cooling the porcelain boat under the inert gas atmosphere to obtain the metal-free porous catalyst material.

2. The method of preparing a metal-free, non-porous catalyst material of claim 1, wherein (1) the starch is soluble starch; preferably, (1) the boron-containing compound is boric acid;

preferably, in the step (1), the cyanamide-based substance is any one of cyanamide, dicyandiamide, melamine and urea; preferably, (1) the drying is freeze-drying or evaporation-drying.

3. The method for preparing a metal-free, non-porous catalyst material according to claim 1, wherein in (2), the temperature raising temperature: heating at 600-1200 ℃, and keeping for 1-6 h; preferably, the temperature rise temperature: heating at 900 deg.C, and maintaining for 3 hr; preferably, the temperature rise rate in the step (2) is 1-10 ℃/min;

preferably, (2) putting the precursor A into a porcelain boat with a cover, placing the porcelain boat in a tube furnace, adding a pore-forming agent in the inert gas atmosphere, heating, calcining, keeping, and cooling to room temperature to obtain a metal-free and non-porous catalyst material; preferably, the pore-forming agent is any one of silica or polystyrene spheres.

4. A method of preparing a metal-free, non-porous catalyst material as in claim 1, wherein the metal-free, non-porous catalyst material is prepared by:

(1) Preparing a precursor A:

Adding 15-25 parts of starch, 1-4 parts of boric acid, 15-25 parts of cyanamide, dicyandiamide, melamine or urea into 450-550 parts of water, and performing freeze drying or evaporation drying under stirring to obtain a precursor A; the above parts are parts by weight;

(2) putting the precursor A into a porcelain boat with a cover, placing the porcelain boat in a tubular furnace, heating, keeping and cooling the porcelain boat under the atmosphere of inert gas to obtain a metal-free and non-porous catalyst material;

the preparation method of the metal-free porous catalyst material comprises the following steps:

(1) adding 15-25 parts of silicon dioxide, 15-25 parts of starch, 1-4 parts of boric acid, 15-25 parts of one of cyanamide, dicyandiamide, melamine or urea into 450-550 parts of water, and heating and evaporating to dryness under stirring to obtain a precursor A;

(2) and putting the precursor A into a porcelain boat with a cover, placing the porcelain boat into a tube furnace, and heating, keeping and cooling the porcelain boat under the inert gas atmosphere to obtain the metal-free porous catalyst material.

5. use of a metal-free non-porous catalyst material and/or a metal-free porous catalyst material prepared by the process of claim 1 in the oxidative dehydrogenation of benzyl alcohol and its derivatives; and the use of a metal-free non-porous catalyst material and/or a metal-free porous catalyst material for the oxidative dehydrogenation of an azacyclic compound;

alternatively, the use of a metal-free non-porous catalyst material and/or a metal-free porous catalyst material prepared by the process of claim 1 in the oxidative dehydrogenation of 1,2,3, 4-tetrahydroquinoline.

6. The use of claim 5, wherein the method comprises: adding a metal-free non-porous catalyst material or a metal-free porous catalyst material into a reaction tube with a condensing device, adding deionized water as a solvent, performing ultrasonic dispersion in an ultrasonic instrument, adding benzyl alcohol, placing an oxygen ball filled with oxygen above the reaction tube, continuously ventilating to exhaust the air in the reaction tube, keeping the reaction tube filled with oxygen, then placing the reaction tube in an oil bath for heating, magnetically stirring, reacting at constant temperature, and cooling to room temperature after the reaction is finished;

preferably, a metal-free non-porous catalyst material or a metal-free porous catalyst material is added into a reaction tube with a condensing device, deionized water is added as a solvent, and the mass volume ratio of the metal-free non-porous catalyst material to the deionized water is 20-30: 1 mg/mL; dispersing in an ultrasonic instrument for 6-15 min by ultrasonic treatment, and adding benzyl alcohol, wherein the molar and mass ratio of the added amount of the benzyl alcohol to the metal-free non-porous catalyst material is 0.6-0.9: 20-30 mmol/mg; placing an oxygen ball filled with oxygen above the reaction tube, continuously ventilating to exhaust air in the reaction tube, keeping the reaction tube full of oxygen, then placing the reaction tube in an oil bath at 100-120 ℃ for heating, magnetically stirring, reacting at constant temperature for 15-20 h, cooling to room temperature after the reaction is finished, and extracting with ethyl acetate as an extracting agent to obtain a product.

7. The use of claim 6, wherein the selectivity of the metal-free non-porous catalyst material or the metal-free porous catalyst material is 100% after 10 cycles of the oxidative dehydrogenation of benzyl alcohol to benzaldehyde; and the yields of the metal-free nonporous catalyst material and the metal-free porous catalyst material in the oxidative dehydrogenation of the benzyl alcohol to benzaldehyde are respectively 87% and 100%, and the selectivities are both 100%.

8. The use of claim 4, wherein the method comprises: adding a metal-free non-porous catalyst material or a metal-free porous catalyst material into a reaction tube with a condensing device, adding deionized water as a solvent, performing ultrasonic dispersion in an ultrasonic instrument, adding 1,2,3, 4-tetrahydroquinoline, placing an oxygen ball filled with oxygen above the reaction tube, continuously ventilating to exhaust the air in the reaction tube, keeping the reaction tube filled with oxygen, then placing the reaction tube in an oil bath for heating, magnetically stirring, performing constant-temperature reaction, and cooling to room temperature after the reaction is finished;

Preferably, a metal-free non-porous catalyst material is added into a reaction tube with a condensing device, deionized water is added as a solvent, and the mass volume ratio of the metal-free non-porous catalyst material or the metal-free porous catalyst material to the deionized water is as follows: 20-30: 1 mg/mL; dispersing in an ultrasonic instrument by ultrasonic for 8-15 min, and then adding 1,2,3, 4-tetrahydroquinoline, wherein the molar and mass ratio of the 1,2,3, 4-tetrahydroquinoline to the metal-free non-porous catalyst material is 0.6-0.9: 20-30 mmol/mg; placing an oxygen ball filled with oxygen above the reaction tube, continuously ventilating to exhaust air in the reaction tube, keeping the reaction tube full of oxygen, then placing the reaction tube in an oil bath at 130 ℃ for heating, magnetically stirring, reacting at constant temperature for 15-20 h, cooling to room temperature after the reaction is finished, and extracting a product by using ethyl acetate as an extracting agent.

9. The use of claim 8, wherein the selectivity of the metal-free porous catalyst or metal-free porous catalyst material is 100% after 10 cycles of dehydrooxidation of 1,2,3, 4-tetrahydroquinoline to quinoline;

the yields of the metal-free non-porous catalyst material and the metal-free porous catalyst material in the dehydrooxidation of 1,2,3, 4-tetrahydroquinoline to quinoline were 89% and 100%, respectively.

Technical Field

The invention belongs to the technical field of catalyst material preparation, and particularly relates to a preparation method of a metal-free non-porous catalyst material, and further relates to an application of the material.

Background

shuicheng Chen et al published 2018 "design Boron Nitride Islands in Carbon Materials for efficient electronic Synthesis of HydrogenPeroxide"; the article discloses a boron and nitrogen co-doped carbon material, in the method, expensive aniline and aminophenylboronic acid are adopted as structural units, ammonium peroxydisulfate is used as an initiator, phytic acid is used as a cross-linking agent, the synthetic process is complex, the operation is complex, the cost is high, the application is only used for preparing hydrogen peroxide through electrochemical oxygen reduction, and organic catalysis research is not involved. In addition, based on the use of freeze drying and ammonium peroxodisulfate and phytic acid in the article, sulfur and phosphorus elements are necessarily introduced, namely the synthesized material is boron, nitrogen, phosphorus and sulfur quaternary co-doped carbon instead of boron and nitrogen co-doped carbon material, and the defect problem is not pointed out in the article.

furthermore, Sensen Shang et al published in 2018 "Metal-Free Nitrogen-and Boron-coded Mesoporous carbonates for Primary Amides Synthesis from Primary alcohol direct oxidative Dehydrogenation"; this article also reports a boron and nitrogen co-doped carbon material, but it is synthesized by a multi-step method, firstly synthesizing DAA ligand, then mixing DAA and boric acid together, putting them into N, N-dimethylformamide to react, and finally calcining to obtain the catalyst. Obviously, the synthesis process is extremely complex and tedious, and mass production is not easy; the organic solvent is used for a plurality of times in the synthetic process, the synthetic process is not green enough, the yield of the catalyst is low, and the production cost is high.

In the field of fine chemical catalysis, the method has important economic significance for obtaining the catalyst with high catalytic activity and selectivity and low price. For example, benzaldehyde is an important chemical raw material and is often obtained by oxidizing toluene, but the process involves excessive oxidation to benzoic acid and has poor selectivity. Jianshu Chen et al reported 2014 that a catalyst comprising gold nanoparticles of noble metals (acidic Study of Size Effects in the Au-catalytic oxidation and Non-Oxidative Dehydrogenation of Benzyl Alcohol, Chemistry-Asian Journal,2014,9,2187-2196) was used in the oxidation catalysis of Benzyl Alcohol, which employs p-xylene as a solvent, and the conversion rate at 120 ℃ was 72%, and was selected to be 99%. Yu-Zhen Chen et al reported in 2017 a platinum-porphyrin polymer-metal organic framework material (Singlet Oxygen-Engaged selected Photo-oxidation of Pt Nanocrystals/porous MOF: The circles of Phototermal Effect and electronic State, Journal of The American Chemical Society,2017,139,2035-2044) for The Selective oxidation of benzyl alcohol under The illumination condition, although The conversion and selectivity are good, it has The disadvantages of using noble metals, high cost, difficult mass production of catalyst, and some other difficulties in application of photocatalysis.

Pingyu Xin et al reported in 2018 a monoatomic palladium-ceria catalyst (reforming the active Catalysts for aqueous Alcohol Oxidation by Using a unidform supported palladium Catalysts, Angew. chem. int. Ed.,2018,57,4642-4646) with a reaction conversion of 26.6% in the presence of potassium carbonate at 100 ℃. Silver et al reported in 2014 a gold-palladium catalyst (Volcano-like Behavior of Au-Pd Core-shell nanoparticles in the selective oxidation of Alcohols, Scientific Reports,2014,4,5766) with a conversion of 65.1% at 100 ℃ under 6bar oxygen.

from the development of the above benzyl alcohol oxidation catalyst, the mainstream catalyst is also a noble metal catalyst, which obviously has a series of problems of high price, complex catalyst preparation method, difficult industrialization, low catalytic activity and the like.

Therefore, there is a need to improve the above prior art schemes, and invent a method for preparing a metal-free non-porous catalyst material with relatively simple process steps, easy mass production, high catalyst yield, environmental protection, and low production cost.

Disclosure of Invention

in order to solve the technical problems, the invention provides a preparation method of a metal-free non-porous catalyst material;

meanwhile, the invention also provides the application of the metal-free non-porous catalyst material prepared by the method.

in the preparation method of the metal-free catalyst material, the related metal-free catalyst material is a metal-free non-porous catalyst material or a metal-free porous catalyst material;

The preparation method of the metal-free non-porous catalyst material comprises the following steps:

(1) Preparing a precursor A:

Adding 15-25 parts of starch, 1-4 parts of boron-containing compound and 15-25 parts of cyanamide substance into 450-550 parts of water, and drying under stirring to obtain a precursor A; the above parts are parts by weight;

(2) Putting the precursor A into a porcelain boat with a cover, placing the porcelain boat in a tubular furnace, heating, keeping and cooling the porcelain boat under the atmosphere of inert gas to obtain a metal-free and non-porous catalyst material;

The preparation method of the metal-free porous catalyst material comprises the following steps:

(1) Adding 15-25 parts of silicon dioxide, 15-25 parts of starch, 1-4 parts of boron-containing compound and 15-25 parts of cyanamide substance into 450-550 parts of water, and drying under stirring to obtain a precursor A;

(2) And putting the precursor A into a porcelain boat with a cover, placing the porcelain boat into a tube furnace, and heating, keeping and cooling the porcelain boat under the inert gas atmosphere to obtain the metal-free porous catalyst material.

(1) the medium starch is soluble starch; preferably, (1) the boron-containing compound is boric acid;

preferably, in the step (1), the cyanamide-based substance is any one of cyanamide, dicyandiamide, melamine and urea; preferably, (1) the drying is freeze-drying or evaporation-drying.

(2) medium, temperature rise: heating at 600-1200 ℃, and keeping for 1-6 h; preferably, the temperature rise temperature: heating at 900 deg.C, and maintaining for 3 hr; preferably, the temperature rise rate in the step (2) is 1-10 ℃/min;

Preferably, (2) putting the precursor A into a porcelain boat with a cover, placing the porcelain boat in a tube furnace, adding a pore-forming agent in the inert gas atmosphere, heating, calcining, keeping, and cooling to room temperature to obtain a metal-free and non-porous catalyst material; preferably, the pore-forming agent is any one of silica or polystyrene spheres.

the preparation method of the metal-free non-porous catalyst material comprises the following steps:

(1) Preparing a precursor A:

adding 15-25 parts of starch, 1-4 parts of boric acid, 15-25 parts of cyanamide, dicyandiamide, melamine or urea into 450-550 parts of water, and performing freeze drying or evaporation drying under stirring to obtain a precursor A; the above parts are parts by weight;

(2) putting the precursor A into a porcelain boat with a cover, placing the porcelain boat in a tubular furnace, heating, keeping and cooling the porcelain boat under the atmosphere of inert gas to obtain a metal-free and non-porous catalyst material;

the preparation method of the metal-free porous catalyst material comprises the following steps:

(1) adding 15-25 parts of silicon dioxide, 15-25 parts of starch, 1-4 parts of boric acid, 15-25 parts of one of cyanamide, dicyandiamide, melamine or urea into 450-550 parts of water, and heating and evaporating to dryness under stirring to obtain a precursor A;

(2) And putting the precursor A into a porcelain boat with a cover, placing the porcelain boat into a tube furnace, and heating, keeping and cooling the porcelain boat under the inert gas atmosphere to obtain the metal-free porous catalyst material.

the application of the metal-free non-porous catalyst material and/or the metal-free porous catalyst material prepared by the method in the oxidative dehydrogenation of benzyl alcohol and derivatives thereof; and the use of a metal-free non-porous catalyst material and/or a metal-free porous catalyst material for the oxidative dehydrogenation of an azacyclic compound;

or, the use of the metal-free non-porous catalyst material and/or the metal-free porous catalyst material prepared by the method of claim 1 in oxidative dehydrogenation of 1,2,3, 4-tetrahydroquinoline; are all within the scope of the invention

the specific application method of the metal-free nonporous catalyst material and/or the metal-free porous catalyst material in the oxidative dehydrogenation of the benzyl alcohol and the derivatives thereof comprises the following steps: adding a metal-free non-porous catalyst material or a metal-free porous catalyst material into a reaction tube with a condensing device, adding deionized water as a solvent, performing ultrasonic dispersion in an ultrasonic instrument, adding benzyl alcohol, placing an oxygen ball filled with oxygen above the reaction tube, continuously ventilating to exhaust the air in the reaction tube, keeping the reaction tube filled with oxygen, then placing the reaction tube in an oil bath for heating, magnetically stirring, reacting at constant temperature, and cooling to room temperature after the reaction is finished;

Preferably, a metal-free non-porous catalyst material or a metal-free porous catalyst material is added into a reaction tube with a condensing device, deionized water is added as a solvent, and the mass volume ratio of the metal-free non-porous catalyst material to the deionized water is 20-30: 1 mg/mL; dispersing in an ultrasonic instrument for 6-15 min by ultrasonic treatment, and adding benzyl alcohol, wherein the molar and mass ratio of the added amount of the benzyl alcohol to the metal-free non-porous catalyst material is 0.6-0.9: 20-30 mmol/mg; placing an oxygen ball filled with oxygen above the reaction tube, continuously ventilating to exhaust air in the reaction tube, keeping the reaction tube full of oxygen, then placing the reaction tube in an oil bath at 100-120 ℃ for heating, magnetically stirring, reacting at constant temperature for 15-20 h, cooling to room temperature after the reaction is finished, and extracting with ethyl acetate as an extracting agent to obtain a product.

In the application, the selectivity of the metal-free non-porous catalyst material or the metal-free porous catalyst material is 100% after 10 times of cyclic use in the cycle from the oxidative dehydrogenation of the benzyl alcohol to the benzaldehyde; and the yields of the metal-free nonporous catalyst material and the metal-free porous catalyst material in the oxidative dehydrogenation of the benzyl alcohol to benzaldehyde are respectively 87% and 100%, and the selectivities are both 100%.

The application of the metal-free nonporous catalyst material and/or the metal-free porous catalyst material nitrogen heterocyclic compound oxidative dehydrogenation is taken as an example of the application of the metal-free nonporous catalyst material and/or the metal-free porous catalyst material nitrogen heterocyclic compound oxidative dehydrogenation, and specifically comprises the following steps: adding a metal-free non-porous catalyst material or a metal-free porous catalyst material into a reaction tube with a condensing device, adding deionized water as a solvent, performing ultrasonic dispersion in an ultrasonic instrument, adding 1,2,3, 4-tetrahydroquinoline, placing an oxygen ball filled with oxygen above the reaction tube, continuously ventilating to exhaust the air in the reaction tube, keeping the reaction tube filled with oxygen, then placing the reaction tube in an oil bath for heating, magnetically stirring, performing constant-temperature reaction, and cooling to room temperature after the reaction is finished;

preferably, a metal-free non-porous catalyst material is added into a reaction tube with a condensing device, deionized water is added as a solvent, and the mass volume ratio of the metal-free non-porous catalyst material or the metal-free porous catalyst material to the deionized water is as follows: 20-30: 1 mg/mL; dispersing in an ultrasonic instrument by ultrasonic for 8-15 min, and then adding 1,2,3, 4-tetrahydroquinoline, wherein the molar and mass ratio of the 1,2,3, 4-tetrahydroquinoline to the metal-free non-porous catalyst material is 0.6-0.9: 20-30 mmol/mg; placing an oxygen ball filled with oxygen above the reaction tube, continuously ventilating to exhaust air in the reaction tube, keeping the reaction tube full of oxygen, then placing the reaction tube in an oil bath at 130 ℃ for heating, magnetically stirring, reacting at constant temperature for 15-20 h, cooling to room temperature after the reaction is finished, and extracting a product by using ethyl acetate as an extracting agent.

In the application, the selectivity of the metal-free porous catalyst or the metal-free porous catalyst material is 100% after 10 cycles of the cycle from dehydrogenation and oxidation of 1,2,3, 4-tetrahydroquinoline to quinoline;

the yields of the metal-free non-porous catalyst material and the metal-free porous catalyst material in the dehydrooxidation of 1,2,3, 4-tetrahydroquinoline to quinoline were 89% and 100%, respectively.

The invention has the beneficial effects that:

(1) the method adopts starch as a carbon source, is cheap and easy to obtain, is green and environment-friendly, can realize large-scale production, has easy separation of the catalyst, and is easy for industrialization;

(2) The catalyst has the greatest advantages of no metal catalyst and simple synthesis method;

(3) the catalyst shows higher catalytic activity and high selectivity when deionized water is used as a solvent;

(4) The catalyst exhibits broad catalytic substrate applicability.

Drawings

FIG. 1 is an XRD spectrum of a metal free non-porous catalyst and a metal free porous catalyst material;

FIG. 2 is a Raman spectrum of a metal-free non-porous catalyst and a metal-free porous catalyst material;

FIG. 3 is a Transmission Electron Microscope (TEM) photograph of a metal-free, non-porous catalyst material;

FIG. 4 is a Transmission Electron Microscope (TEM) photograph of a metal-free porous catalyst material;

fig. 5 is a plot of elemental area distribution for a metal-free, non-porous catalyst material: (a) a high angle annular dark field image, (b) nitrogen, (c) boron, and (d) carbon;

FIG. 6 is a plot of the elemental area distribution of a metal-free porous catalyst material: (a) a high angle annular dark field image, (b) nitrogen, (c) boron, and (d) carbon;

FIG. 7 is a graph of the kinetics of oxidative dehydrogenation of benzyl alcohol to benzaldehyde using a metal-free porous catalyst material;

FIG. 8 is a bar graph of conversion and selectivity of a metal-free porous catalyst material over 10 cycles of oxidative dehydrogenation of benzyl alcohol to benzaldehyde;

FIG. 9 is a graph of the kinetics of the dehydrogenation oxidation of tetrahydroquinoline to quinoline of a metal-free porous catalyst material;

FIG. 10 is a bar graph of conversion and selectivity of a metal-free porous catalyst material over 10 cycles of dehydrooxidation of tetrahydroquinoline to quinoline.

Detailed Description