CN112439439A - Application of catalyst with metal particles deposited in carbon nano tube in reaction of synthesizing cinnamyl alcohol through selective catalytic hydrogenation of cinnamyl aldehyde - Google Patents
Application of catalyst with metal particles deposited in carbon nano tube in reaction of synthesizing cinnamyl alcohol through selective catalytic hydrogenation of cinnamyl aldehyde Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 92
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 87
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 87
- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 title claims abstract description 54
- 239000002923 metal particle Substances 0.000 title claims abstract description 31
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 title claims abstract description 20
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
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- 238000011049 filling Methods 0.000 claims description 15
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- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 8
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- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
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- 150000001450 anions Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
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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
- B01J27/24—Nitrogen compounds
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
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- B01J35/40—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
Abstract
The invention discloses an application of a catalyst for depositing metal particles in a carbon nano tube in the reaction of synthesizing cinnamyl alcohol by selective catalytic hydrogenation of cinnamyl aldehyde, wherein the catalyst consists of a carbon nano tube, sulfur and nitrogen co-doped carbon quantum dots and metal nano particles, the carbon nano tube is a single-wall or multi-wall carbon tube with an opening, the carbon quantum dots are loaded on the outer wall of the carbon nano tube, and the metal nano particles are embedded in the inner wall of the carbon nano tube; the metal is one of palladium, platinum, gold, ruthenium, iridium, nickel and cobalt; the size of the sulfur and nitrogen co-doped carbon quantum dot is not more than 10nm, the nitrogen content is 0.1-10.0 wt%, and the sulfur content is 0.1-3.0 wt%. When the catalyst is used for synthesizing cinnamyl alcohol by selective catalytic hydrogenation of cinnamyl aldehyde, high conversion rate, high selectivity and high stability are realized under the synergistic effect of the carbon quantum dots, the internally deposited metal particles and the confinement effect of the carbon nano tubes, the catalytic efficiency is high, and the service life of the catalyst is long.
Description
(I) technical field
The invention relates to application of a catalyst for depositing metal particles in a carbon nano tube in the reaction of synthesizing cinnamyl alcohol by selective catalytic hydrogenation of cinnamyl aldehyde.
(II) technical background
Carbon nanotubes have structural defects, curved surfaces, unique lumen structures, and electrical conductivity properties, and are excellent catalytic materials. Based on the collision theory of chemical reaction, the reaction space in the tube is obviously reduced, and the unique interaction of reactants and products with the inner wall of the carbon nano tube can influence the progress of the chemical reaction. Santis et al have learned through theoretical calculations that when the chemical reaction is confined to a small pore size, the reaction kinetics change significantly and the reaction rate can jump by orders of magnitude. Lu et al calculated the mechanism of the limited-domain reaction in carbon nanotubes using DFT theory, found that after the reaction limited-domain was inside the carbon nanotubes, the barrier affecting the reaction progress was significantly reduced, and the reactivity of the reactants in the tubes was enhanced with the reduction of the tube diameter of the carbon nanotubes. Thus, the deposition of metal particle catalysts in carbon nanotubes for the conversion of syngas to ethanol, Fischer-Tropsch reactions, benzene hydrogenation reactions, and NH3The catalyst shows excellent catalytic performance in the decomposition reaction.
The preparation method of the prior metal catalyst loaded in the tube mainly comprises the following steps: in-situ filling methods, gas phase filling methods, and liquid phase filling methods. The in-situ filling method adopts the means of an electric arc method, a microwave method and the like to generate metal or compound in situ in the cavity channel and the shell layer of the carbon nano tube in the process of preparing the carbon nano tube. Generally, the in-situ filling method can fill a plurality of metals with higher melting points and higher surface tension, but the in-situ filling method has lower filling yield, and some metal carbides or metal particles are assembled into the carbon nanotube shell during the filling process. The gas phase filling method is a method of performing a high-temperature reaction in a gas phase. That is, the carbon nanotubes are mixed with the filler under a certain pressure and temperature, and the filler is vaporized by heating and introduced into the carbon nanotubes. The gas phase method has the advantages that only gas capable of reacting with the carbon nano tube is needed in the reaction, more reagents are not needed, the environment is not polluted, and other substances are not introduced into the system; the method has the disadvantages that the carbon nano tube has low opening rate, needs high temperature of 500-1000 ℃, is difficult to control proper reaction time and temperature, and is not easy to fill because amorphous carbon is accumulated in a tube cavity. The liquid phase filling method mixes and grinds the filler and the carbon nano tube to ensure that the filler and the carbon nano tube are fully contacted, then the temperature is raised to be higher than the melting point of the filler, and the melted filler enters the interior of the carbon nano tube under the capillary action. The filling of salts such as metal halides and oxides is usually carried out by melting the filling.
It can be seen that the existing preparation method for depositing metal particles in the carbon nano tube has the problems of complex process, difficult regulation and control of the deposition process in the metal particles, low proportion of the metal particles in the tube, low metal utilization rate and the like. The catalytic performance in the reaction process of synthesizing cinnamyl alcohol by catalyzing hydrogenation of cinnamyl aldehyde also shows the phenomena of slow reaction rate, low selectivity and excessive hydrogenation [ Applied Catalysis A: general 288(2005)203-210 ].
Disclosure of the invention
The invention aims to provide application of a catalyst for depositing metal particles in a carbon nano tube with an outer tube loaded with sulfur and nitrogen co-doped carbon quantum dot in the reaction of synthesizing cinnamyl alcohol by selective catalytic hydrogenation of cinnamyl aldehyde, and the catalyst realizes high conversion rate, high selectivity and high stability, high catalytic efficiency and long service life of the catalyst under the synergistic effect of the carbon quantum dot, the inner deposited metal particles and the confinement effect of the carbon nano tube.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an application of a catalyst for depositing metal particles in a carbon nano tube in the reaction of synthesizing cinnamyl alcohol by selective catalytic hydrogenation of cinnamyl aldehyde, wherein the catalyst consists of a carbon nano tube, sulfur and nitrogen co-doped carbon quantum dots and metal nano particles, the carbon nano tube is a single-wall or multi-wall carbon tube with an opening, the carbon quantum dots are loaded on the outer wall of the carbon nano tube, and the metal nano particles are embedded in the inner wall of the carbon nano tube; the metal is one of palladium, platinum, gold, ruthenium, iridium, nickel and cobalt; the size of the sulfur and nitrogen co-doped carbon quantum dot is not more than 10nm, the nitrogen content is 0.1-10.0 wt%, and the sulfur content is 0.1-3.0 wt%; in the catalyst for depositing metal particles in the carbon nano tube, the loading capacity (mass ratio of the carbon quantum dot to the carbon nano tube) of the sulfur-nitrogen co-doped carbon quantum dot is 0.5-8.0 wt%, and the loading capacity of the metal is 0.1-10.0 wt%.
Preferably, in the catalyst for depositing metal particles in the carbon nanotube, the loading amount of the sulfur-nitrogen co-doped carbon quantum dots is 0.5-5.0 wt%. Preferably, the loading of metal in the catalyst is 0.5 to 5.0 wt%.
Preferably, the size of the sulfur and nitrogen co-doped carbon quantum dots is 1.5-3.5 nm.
Preferably, the catalyst for depositing metal particles in the carbon nano tube can be prepared by the following method:
1) placing the carbon nano tube in concentrated nitric acid (65-68 wt%) for heating reflux treatment, cooling to room temperature after the reflux treatment is finished, washing with water until the filtrate is neutral, and drying to obtain the carbon nano tube subjected to acid treatment; because the freshly prepared carbon nano tube is a tube which grows out on metal particles and is usually closed, in order to utilize the space in the tube and remove the metal particles of the long carbon tube, concentrated nitric acid is adopted for pretreatment;
2) preparing a sulfur and nitrogen co-doped carbon quantum dot solution and the carbon nano tube subjected to acid treatment obtained in the step 1) into a dispersion liquid, fully stirring to enable the carbon quantum dots to be loaded on the outer wall of the carbon nano tube, and performing suction filtration and drying to obtain the carbon nano tube loaded with the carbon dots;
3) preparing the carbon nano tube loaded with the carbon dots obtained in the step 2) and deionized water into slurry, adding aqueous solution containing metal ions under the stirring state, forming complex anions by the metal ions and chloride ions in the aqueous solution, fully stirring, performing suction filtration, washing until the pH value of filtrate is neutral, and drying to obtain the catalyst of metal particles deposited in the carbon nano tube.
According to the preparation method, the sulfur-nitrogen co-doped carbon quantum dots and the carbon nano tubes are adsorbed on the outer walls of the carbon nano tubes through pi-pi conjugation so as to be converted into excellent electron-donating centers, and then metal complex ions with negative charges are induced to spontaneously enter the tubes and deposit on the inner walls by utilizing the electron-donating characteristics of the sulfur-nitrogen co-doped carbon quantum dots, wherein the electrical enrichment property of heteroatoms is favorable for the metal ions to enter the tubes and be loaded on the inner walls of the tubes, so that the small-particle-size and uniform distribution of metal active components in the carbon nano tubes is realized.
In the step 1), the nitric acid treatment is a conventional treatment method for opening the carbon tube and removing residual metal. Preferably, in the acid treatment process of the carbon nano tube in the step 1), the ratio of the carbon nano tube to the nitric acid is 1-10 g: 20-100ml, the treatment temperature is 45-95 ℃, and the condensation reflux is carried out for 2-15 h. Preferably, the drying conditions are: drying at 30-80 deg.C for 1-10 hr. Preferably, the diameter distribution of the carbon nanotubes is 20-40nm, and the specific surface area is more than 150m2/g。
In the invention, the sulfur and nitrogen co-doped carbon quantum dots can be prepared by referring to the prior art. Preferably, the sulfur-nitrogen co-doped carbon quantum dot is formed by using citric acid and L-cysteine as raw materials and using esterification reaction or amidation reaction of carboxyl and amino to generate the nitrogen-sulfur co-doped carbon dot under the assistance of microwaves. The microwave method is simple to operate, and the doping content of sulfur and nitrogen is high. The specific process is as follows: adding deionized water, citric acid and L-cysteine in a ratio of 1-15mL to 0.5-5.0g to 0.01-1.0mL into a crucible, and mechanically stirring until the mixture is uniformly mixed; then placing the solution in a microwave oven with the power of 300-1500W and the heating time of 0.5-10min to obtain a light yellow carbon quantum dot solution; then, centrifugal treatment is carried out (organic matter particles which are not completely carbonized are removed) under the condition that the rotating speed is 20000r/min, supernatant is transferred into a two-layer dialysis bag with the molecular weight cutoff of 100-10000 Dalton for dialysis treatment, the carbon dot solution in the middle of the two layers can be the carbon dot solution, and finally, the solution is concentrated to the concentration of 0.5-25.0mg/L under the condition of shading low temperature. Preferably, the cut-off of the dialysis bag is 1500-.
Step 2) of the present invention is preferably carried out as follows: and feeding the sulfur and nitrogen co-doped carbon quantum dot solution and the carbon nano tube subjected to acid treatment according to the loading capacity of the sulfur and nitrogen co-doped carbon quantum dots, stirring for 10-60min, and drying the filtered solid particles in a vacuum oven at the temperature of 50-100 ℃ for 2-15h to obtain the carbon nano tube loaded with the carbon dots.
Step 3) of the present invention is preferably carried out as follows: preparing the carbon nano tube loaded with the carbon dots obtained in the step 2) into slurry according to the charging ratio of the carbon nano tube loaded with the carbon dots to water of 1 g: 5-35ml, adding the corresponding aqueous solution containing the metal ions according to the metal loading capacity at the temperature of 5-40 ℃ under the stirring state, wherein the dropping speed of the aqueous solution containing the metal ions is 1d/1-10s, continuously stirring for 2-6h after dropping, performing suction filtration, washing until the pH value is neutral, and drying for 3-15h at the temperature of 50-100 ℃ to obtain the catalyst.
Preferably, the application method comprises the following steps: placing a catalyst of metal particles deposited in a carbon nano tube into an autoclave, and then sequentially adding cinnamaldehyde and distilled water, wherein the ratio of the catalyst of metal particles deposited in the carbon nano tube to the cinnamaldehyde to the distilled water is 1-5 mg: 4-10 mmol: 5-10ml, and filling H into the closed high-pressure kettle2To remove the air completely, and finally filling 1-3MPa of H2And (3) keeping the pressure constant, placing the high-pressure kettle in an oil bath kettle at the temperature of between 50 and 80 ℃, adjusting the rotating speed to be 1000-2000r/min for reaction, and stopping the reaction when the pressure in the kettle is not reduced. The hydrogenation product was analyzed by Agilent 7890A gas chromatography.
Compared with the prior art, the invention has the beneficial effects that:
1) in the process of depositing metal particle catalyst in carbon nanotube, the present invention designs the catalyst structure into carbon quantum dot supported outside the tube, and the carbon quantum dot embedded inside the tube has specific catalytic characteristic caused by the electron donating characteristic of the carbon quantum dot, the carbon tube to the metal particle and the carbon tube to the limiting effect of reactant molecule. When the catalyst is used for synthesizing cinnamyl alcohol by selective catalytic hydrogenation of cinnamyl aldehyde, high conversion rate, high selectivity and high stability are realized under the synergistic effect of the carbon quantum dots, the inner deposited metal particles and the confinement effect of the carbon nano tubes, the catalytic efficiency is high, and the service life of the catalyst is long.
2) In the preparation method of the catalyst, metal ions of anions are driven to the inner wall of the carbon tube through electrostatic action by virtue of the electron-rich characteristic of the carbon quantum dots loaded on the outer wall of the carbon tube, so that the metal utilization rate is remarkably improved. The method is simple, convenient and easy to control, and has low cost.
(IV) description of the drawings
A and b in fig. 1 are electron micrographs of the catalysts prepared in comparative example 1 and example 1, respectively.
Fig. 2 is a graph showing the percentage of metal particles in carbon nanotubes in the catalysts prepared in example 1, comparative example 1, and comparative example 3, where 1 is comparative example 1; 2 is comparative example 3; example 3 data from randomly selected 500 particles (TEM characterization) are obtained for example 1.
(V) detailed description of the preferred embodiments
The technical solution of the present invention is specifically described below with specific examples, but the scope of the present invention is not limited thereto:
in the examples, the activated carbon used was Norit 800, the carbon tubes were obtained from Nanjing Xiancheng nanomaterial science and technology Co., Ltd, and the graphene was obtained from Chengdu organic chemistry Co., Ltd, academy of sciences of China.
Example 1
1) Deionized water, citric acid and L-cysteine are added into a crucible, the dosage is respectively 10 mL: 2.5 g: 0.5mL, and the materials are mechanically stirred until the materials are uniformly mixed. Then placing the mixture in a microwave oven with the power of 1000W and the heating time of 2min to obtain a light yellow carbon quantum dot solution. Then carrying out centrifugal treatment (removing organic particles which are not completely carbonized) at the rotation speed of 20000r/min, transferring the supernatant into a two-layer dialysis bag with the molecular weight of 2000-3500 Dalton for dialysis treatment, wherein the carbon dots in the middle of the two layers are the required carbon dot solution, and finally concentrating under shading low temperature to the concentration of 5.0 mg/L. Through detection, the content of nitrogen in the carbon dots is 5%, and the content of sulfur in the carbon dots is 2.0%.
2) Weighing 10g of carbon nano-tube (diameter distribution is 20-40nm, specific surface area is more than 150 m)2Putting the carbon nanotubes into a round-bottom flask, then measuring concentrated nitric acid (65-68 wt%) into the round-bottom flask, wherein the ratio of the carbon nanotubes to the nitric acid is 5 g: 50ml, and then putting the round-bottom flask into a hydrothermal pot to heat the round-bottom flask back to 90 DEG CStream 5 h. And after the reflux is finished, taking out the flask, cooling to a room temperature state, transferring to a funnel, adding deionized water, continuously washing, performing suction filtration until the filtrate is neutral, and then putting the filter cake into an oven to dry for 10 hours at the temperature of 80 ℃. Obtaining the carbon nano tube treated by acid for standby.
3) Preparing a mixed solution of the carbon quantum dot solution prepared in the step 1) and the carbon nano tube treated by acid, wherein the mass ratio of the carbon dots to the carbon nano tube is 5.0 wt%, then placing the solution on a magnetic stirrer for stirring, carrying out suction filtration after 30min, and then placing the obtained solid particles into a vacuum oven for drying for 5h at 100 ℃ to obtain the carbon nano tube loaded with the carbon dots.
4) Preparing the solid obtained in the step 3) and deionized water into slurry, wherein the solid: the ratio of water is 1g to 5ml, and palladium ions [ PdCl ] with the corresponding load of 5.0 wt% are added under the condition of stirring at the temperature of 40 DEG C4]2-The dropping rate of the aqueous solution of (4) was 1 d/5S. Stirring for 6 hours, carrying out suction filtration, washing until the pH value is neutral, and drying for 15 hours at 100 ℃ to obtain the catalyst.
Examples 2 to 15
The catalyst was prepared according to example 1, with specific parameters as shown in Table 1.
TABLE 1
Note: metal ion form in the impregnation: [ PdCl4]2-，[PtCl4]2-，[IrCl4]2-，[AuCl4]2-，[NiCl4]2-，[CoCl4]2-，[RuCl4]2-。
Comparative example 1
The preparation method is the same as that of example 1 except that carbon quantum dots are not added.
Comparative example 2
Graphene was used instead of carbon nanotubes, and the other preparation methods were the same as in example 1. Graphene is a polymer made of carbon atoms in sp2The hybrid orbit forms a hexagonal honeycomb lattice two-dimensional carbon nano material without a tubular structure。
Comparative example 3
1) Citric acid and ethanol are taken in a beaker, the proportion is 0.5 g: 15mL, and the mixture is mechanically stirred until the mixture is uniformly mixed. Then transferred to a hydrothermal kettle, hydrothermal for 15 hours at 160 ℃, and then naturally cooled. Then, centrifugal treatment is carried out (organic matter particles which are not completely carbonized are removed) under the condition that the rotating speed is 20000r/min, supernatant is transferred into a two-layer dialysis bag with the molecular weight of 2000-3500 Dalton for dialysis treatment, the carbon dot solution in the middle of the two layers is the required carbon dot solution (the carbon dot does not contain heteroatoms), and finally, concentration is carried out at low temperature under shading until the concentration is 5.0 mg/L.
Steps 2) to 4) the catalyst was obtained in the same manner as in example 1.
Comparative example 4
The literature Applied Catalysis A was used: general, 2005, 288: 203-210, and 5 wt% of Pd/MWNT catalyst prepared by the preparation method.
Comparative example 5
The dialysis was performed using a dialysis membrane having a molecular weight of 1000-.
Example 16
The catalyst of example 1 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 3 mg: 8 mmol: 5 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 1.5MPa of H2And (5) placing the autoclave in a 50 ℃ oil bath kettle at constant pressure, and adjusting the rotating speed to 1500r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed with an Agilent 7890A gas chromatography enhancement. The reaction time was 120 minutes, the conversion was 100%, and the selectivity of hydrogenation of C ═ C double bonds was 98.5%.
Example 17
The catalyst of example 2 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 1 mg: 4 mmol: 10 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging for 5 times to removeAir, and finally filling 2.5MPa of H2And (5) placing the autoclave in a 50 ℃ oil bath kettle at constant pressure, and adjusting the rotating speed to 2000r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed with an Agilent 7890A gas chromatography enhancement. The reaction time was 125 minutes, the conversion was 100%, and the selectivity of the C ═ C double bond hydrogenation was 99.5%.
Example 18
The catalyst of example 3 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 5 mg: 5 mmol: 10 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 3MPa of H2And (5) placing the autoclave in an oil bath kettle at 80 ℃ under constant pressure, and adjusting the rotating speed to 1500r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed with an Agilent 7890A gas chromatography enhancement. The reaction time was 115 minutes, the conversion was 100%, and the selectivity for the hydrogenation of C ═ C double bonds was 98.8%.
Example 19
The catalyst of example 4 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 1 mg: 4 mmol: 10 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 1.5MPa of H2And (5) placing the autoclave in a 50 ℃ oil bath kettle at constant pressure, and adjusting the rotating speed to 1500r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed with an Agilent 7890A gas chromatography enhancement. The reaction time was 119 minutes, the conversion was 100%, and the selectivity for the hydrogenation of C ═ C double bonds was 99.5%.
Example 20
The catalyst of example 5 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of the catalyst, cinnamaldehyde and water was 2 mg: 10 mmol: 5 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 2MPa of H2And (5) placing the autoclave in an oil bath kettle at 60 ℃ under constant pressure, and adjusting the rotating speed to 1400r/min for reaction. Until the pressure in the kettle is notThe reaction was stopped after the drop. The hydrogenation product was analyzed with an Agilent 7890A gas chromatography enhancement. The reaction time was 125 minutes, the conversion was 100%, and the selectivity of the C ═ C double bond hydrogenation was 99.9%.
Example 21
The catalyst of example 6 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 1 mg: 10 mmol: 5 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 1.5MPa of H2And (5) placing the autoclave in a 50 ℃ oil bath kettle at constant pressure, and adjusting the rotating speed to 1000r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed with an Agilent 7890A gas chromatography enhancement. The reaction time was 130 minutes, the conversion was 100%, and the selectivity of the C ═ C double bond hydrogenation was 100%.
Example 22
The catalyst of example 7 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 5 mg: 4 mmol: 8 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 1.5MPa of H2And (3) placing the autoclave in a 50 ℃ oil bath kettle at constant pressure, and adjusting the rotating speed to 1800r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed with an Agilent 7890A gas chromatography enhancement. The reaction time was 120 minutes, the conversion was 100%, and the selectivity of C ═ C double bond hydrogenation was 99.9%.
Example 23
The catalyst of example 8 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 2 mg: 8 mmol: 8 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 1.5MPa of H2And (5) placing the autoclave in an oil bath pan with the temperature of 70 ℃ under constant pressure, and adjusting the rotating speed to 1400r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed with an Agilent 7890A gas chromatography enhancement. Reaction time 126 min, conversion 100%, hydrogenation of C ═ C double bondsThe selectivity was 99.5%.
Example 24
The catalyst of example 9 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 1 mg: 4 mmol: 10 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 2.5MPa of H2And (5) placing the autoclave in an oil bath kettle at 60 ℃ under constant pressure, and adjusting the rotating speed to 1000r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed by Agilent 7890A gas chromatography. The reaction time was 119 minutes, the conversion was 100%, and the selectivity for the hydrogenation of C ═ C double bonds was 99.8%.
Example 25
The catalyst of example 10 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 2 mg: 5 mmol: 6 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 1.5MPa of H2And (5) placing the autoclave in an oil bath kettle at 70 ℃ under constant pressure, and adjusting the rotating speed to 1000r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed by Agilent 7890A gas chromatography. The reaction time was 121 minutes, the conversion was 100%, and the selectivity of the C ═ C double bond hydrogenation was 100%.
Example 26
The catalyst of example 11 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 3 mg: 9 mmol: 6 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 2MPa of H2And (3) placing the autoclave in a 50 ℃ oil bath kettle at constant pressure, and adjusting the rotating speed to 1600r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed with an Agilent 7890A gas chromatography enhancement. The reaction time was 130 minutes, the conversion was 100%, and the selectivity of the C ═ C double bond hydrogenation was 100%.
Example 27
The catalyst of example 12 was placed in 50mlIn the autoclave, cinnamaldehyde and distilled water were then added in this order. The ratio of catalyst, cinnamaldehyde and water was 4 mg: 10 mmol: 5 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 1.5MPa of H2And (5) placing the autoclave in an oil bath kettle at 60 ℃ under constant pressure, and adjusting the rotating speed to 1500r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed with an Agilent 7890A gas chromatography enhancement. The reaction time was 125 minutes, the conversion was 100%, and the selectivity of the C ═ C double bond hydrogenation was 99.5%.
Example 28
The catalyst of example 13 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 2 mg: 9 mmol: 7 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 2.5MPa of H2And (5) placing the autoclave in a 65 ℃ oil bath kettle at constant pressure, and adjusting the rotating speed to 1500r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed with an Agilent 7890A gas chromatography enhancement. The reaction time was 128 minutes, the conversion was 100%, and the selectivity of C ═ C double bond hydrogenation was 99.8%.
Example 29
The catalyst of example 14 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 1 mg: 4 mmol: 8 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 1.5MPa of H2And (5) placing the autoclave in a 50 ℃ oil bath kettle at constant pressure, and adjusting the rotating speed to 1000r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed with an Agilent 7890A gas chromatography enhancement. The reaction time was 118 minutes, the conversion was 100%, and the selectivity of C ═ C double bond hydrogenation was 99.7%.
Example 30
The catalyst of example 15 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 3 mg: 10 mmol: 6 ml. Closed autoclave towardsFilled with H of about 0.5MPa2Then charging and discharging 5 times to remove air therein, and finally charging 1.5MPa of H2And (3) placing the autoclave in an oil bath pan with the temperature of 70 ℃ at constant pressure, and adjusting the rotating speed to 1800r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed by Agilent 7890A gas chromatography. The reaction time was 105 minutes, the conversion was 100%, and the selectivity of the C ═ C double bond hydrogenation was 99.9%.
Example 31
The catalyst of comparative example 1 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 3 mg: 8 mmol: 5 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 1.5MPa of H2And (5) placing the autoclave in a 50 ℃ oil bath kettle at constant pressure, and adjusting the rotating speed to 1500r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed with an Agilent 7890A gas chromatography enhancement. The reaction time was 110 minutes, the conversion was 95.5%, and the selectivity of C ═ C double bond hydrogenation was 67.5%.
Example 32
The catalyst of comparative example 2 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 3 mg: 8 mmol: 5 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 1.5MPa of H2And (5) placing the autoclave in a 50 ℃ oil bath kettle at constant pressure, and adjusting the rotating speed to 1500r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed with an Agilent 7890A gas chromatography enhancement. The reaction time was 110 minutes, the conversion was 92.5%, and the selectivity of C ═ C double bond hydrogenation was 70.5%.
Example 33
The catalyst of comparative example 3 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 3 mg: 8 mmol: 5 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 1.5MPa of H2Constant pressure, will be highThe autoclave is placed in an oil bath pan with the temperature of 50 ℃ and the rotating speed is adjusted to 1500r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed by Agilent 7890A gas chromatography. The reaction time was 110 minutes, the conversion was 99.5%, and the selectivity of C ═ C double bond hydrogenation was 90.5%.
Example 34
The catalyst of comparative example 4 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 3 mg: 8 mmol: 5 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 1.5MPa of H2And (5) placing the autoclave in a 50 ℃ oil bath kettle at constant pressure, and adjusting the rotating speed to 1500r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed by Agilent 7890A gas chromatography. The reaction time was 110 minutes, the conversion was 96.5%, and the selectivity of C ═ C double bond hydrogenation was 75.5%.
Example 35
The catalyst of comparative example 5 was placed in a 50ml autoclave, and then cinnamaldehyde and distilled water were added in this order. The ratio of catalyst, cinnamaldehyde and water was 3 mg: 8 mmol: 5 ml. The closed autoclave was charged with about 0.5MPa of H2Then charging and discharging 5 times to remove air therein, and finally charging 1.5MPa of H2And (5) placing the autoclave in a 50 ℃ oil bath kettle at constant pressure, and adjusting the rotating speed to 1500r/min for reaction. And stopping the reaction after the pressure in the kettle does not decrease. The hydrogenation product was analyzed by Agilent 7890A gas chromatography. The reaction time was 115 minutes, the conversion was 98.9%, and the selectivity of C ═ C double bond hydrogenation was 96.8%.
Example 36
Example 20 a catalyst stability application test was performed, in which the catalyst was taken out for the next catalytic reaction after the end of the reaction, and fresh catalyst in an amount of 5% by mass of the initial catalyst was added after every five reactions. The results show that the average conversion is 100% when used 20 times, and the selectivity evaluated for C ═ C double bond hydrogenation is 99.9%.
Claims (8)
1. The application of the catalyst for depositing metal particles in the carbon nano tube in the reaction of synthesizing cinnamyl alcohol by selective catalytic hydrogenation of cinnamyl aldehyde is characterized in that: the catalyst consists of a carbon nano tube, sulfur and nitrogen co-doped carbon quantum dots and metal nano particles, wherein the carbon nano tube is a single-walled or multi-walled carbon tube with an opening, the carbon quantum dots are loaded on the outer wall of the carbon nano tube, and the metal nano particles are embedded in the inner wall of the carbon nano tube; the metal is one of palladium, platinum, gold, ruthenium, iridium, nickel and cobalt; the size of the sulfur and nitrogen co-doped carbon quantum dot is not more than 10nm, the nitrogen content is 0.1-10.0 wt%, and the sulfur content is 0.1-3.0 wt%; in the catalyst for depositing metal particles in the carbon nano tube, the loading capacity of the sulfur-nitrogen co-doped carbon quantum dots is 0.5-8.0 wt%, and the loading capacity of the metal is 0.1-10.0 wt%.
2. The use of claim 1, wherein: the size of the sulfur and nitrogen co-doped carbon quantum dot is 1.5-3.5 nm.
3. The use of claim 1, wherein: the catalyst for depositing metal particles in the carbon nano tube is prepared by the following method:
1) placing the carbon nano tube in concentrated nitric acid, heating and refluxing, cooling to room temperature after the heating and refluxing treatment, washing with water until filtrate is neutral, and drying to obtain the carbon nano tube subjected to acid treatment;
2) preparing a sulfur and nitrogen co-doped carbon quantum dot solution and the carbon nano tube subjected to acid treatment obtained in the step 1) into a dispersion liquid, fully stirring to enable the carbon quantum dots to be loaded on the outer wall of the carbon nano tube, and performing suction filtration and drying to obtain the carbon nano tube loaded with the carbon dots;
3) preparing the carbon nano tube loaded with the carbon dots obtained in the step 2) and deionized water into slurry, adding aqueous solution containing metal ions under the stirring state, forming complex anions by the metal ions and chloride ions in the aqueous solution, fully stirring, performing suction filtration, washing until the pH value of filtrate is neutral, and drying to obtain the catalyst of metal particles deposited in the carbon nano tube.
4. Use according to claim 3, characterized in that: the sulfur and nitrogen co-doped carbon quantum dot is prepared by the following method: adding deionized water, citric acid and L-cysteine into a crucible at a ratio of 1-15 mL: 0.5-5.0 g: 0.01-1.0mL, mechanically stirring until the mixture is uniformly mixed; then placing the solution in a microwave oven with the power of 300-1500W and the heating time of 0.5-10min to obtain a light yellow carbon quantum dot solution; then, the centrifugation treatment is carried out under the condition that the rotating speed is 20000r/min, the supernatant is transferred into a two-layer dialysis bag with the molecular weight cutoff of 100-10000 Dalton for dialysis treatment, and the carbon point solution between the two layers is the carbon point solution with the concentration of 0.5-25.0 mg/L.
5. The use of claim 4, wherein: the cut-off of the dialysis bag was 1500-.
6. Use according to one of claims 3 to 5, characterized in that: step 2) is carried out as follows: and feeding the sulfur and nitrogen co-doped carbon quantum dot solution and the carbon nano tube subjected to acid treatment according to the loading capacity of the sulfur and nitrogen co-doped carbon quantum dots, stirring for 10-60min, and drying the filtered solid particles in a vacuum oven at the temperature of 50-100 ℃ for 2-15h to obtain the carbon nano tube loaded with the carbon dots.
7. Use according to claim 3, characterized in that: step 3) is carried out as follows: the carbon nano tube loaded with the carbon dots obtained in the step 2) is mixed with water according to the feeding ratio of the carbon nano tube loaded with the carbon dots to the water of 1 g: preparing 5-35ml of prepared slurry, adding corresponding aqueous solution containing metal ions according to the metal loading capacity at the temperature of 5-40 ℃ under the stirring state, wherein the dropping speed of the aqueous solution containing the metal ions is 1d/1-10s, continuing stirring for 2-6h after the dropping is finished, performing suction filtration, washing until the pH value is neutral, and drying for 3-15h at the temperature of 50-100 ℃ to obtain the catalyst.
8. Use according to claim 1 or 2, characterized in that: the application method comprises the following steps: putting the catalyst of depositing metal particles in the carbon nano tube into a high-pressure autoclave, and then sequentially adding cinnamyl aldehyde, distilled water and carbon nanoThe proportion of the metal particle catalyst deposited in the rice tube, the cinnamaldehyde and the water is 1-5 mg: 4-10 mmol: 5-10ml, and the closed high-pressure kettle is filled with H2To remove the air completely, and finally filling 1-3MPa of H2And (3) keeping the pressure constant, placing the high-pressure kettle in an oil bath kettle at the temperature of between 50 and 80 ℃, adjusting the rotating speed to be 1000-2000r/min for reaction, and stopping the reaction when the pressure in the kettle is not reduced.
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| Title |
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| HONGFEI MA ET AL: "Confinement effect of carbon nanotubes on the product distribution of selective hydrogenation of cinnamaldehyde", 《CHINESE JOURNAL OF CATALYSIS》 * |
| 化学工业出版社《化工百科全书》编辑部: "《化工百科全书 第17卷》", 30 April 1998, 化学工业出版社 * |
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