A preparation method of polyacrylonitrile carbon flower particle loaded ruthenium catalyst and application thereof in catalytic glucose deuteration

Abstract

The application discloses a preparation method of polyacrylonitrile carbon flower particle loaded ruthenium catalyst and application of the catalyst in catalyzing glucose deuteration, and the preparation method of the catalyst is as follows: acrylonitrile and N, N-bisazoisobutyronitrile are added into acetone, polyacrylonitrile (PACN) particles are synthesized through a simple one-step free radical polymerization process to obtain a first precursor; the first precursor is vacuum dried and milled, and then is placed in air to be subjected to stabilization treatment to obtain a second precursor; the second precursor is pyrolyzed at high temperature under inert gas condition to finally synthesize polyacrylonitrile carbon flower particles in petal shape, then the polyacrylonitrile carbon flower particles are obtained through a wet impregnation method to obtain the polyacrylonitrile carbon flower particle loaded ruthenium catalyst, and finally, the catalyst is reduced through hydrogen calcination. The polyacrylonitrile carbon flower particle loaded ruthenium catalyst synthesized by the application has the advantages of mild reaction condition, easy recovery, green environmental protection, good catalyst stability, and the ability of efficiently catalyzing anhydrous glucose to prepare anhydrous deuterated glucose.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of preparation of heterogeneous catalysts, in particular to a preparation method of polyacrylonitrile carbon flower particle supported ruthenium catalyst and its application in catalyzing deuterium glucose. BACKGROUND

[0002] Positron Emission Computed Tomography (PET) is a relatively advanced clinical examination imaging technology in the field of nuclear medicine. PET is particularly suitable for early diagnosis of diseases, detection of subclinical lesions and evaluation of treatment effects before morphological changes. PET shows important value in the diagnosis and treatment of three major diseases: tumors, coronary heart disease and brain diseases. Before scanning, people use a radioisotope tracer with a short half-life (or called imaging agent, such as fluorinated deoxyglucose, whose radioisotope is fluorine-18, commonly used for tumor imaging) whose decay process emits positrons. The positrons are replaced into molecules that are easily metabolized by the body through chemical reactions, and then injected into the body (usually into the blood circulation).

[0003] PET can be used for oncology diagnosis. Before such examination, the subject will be injected with the imaging agent fluorinated deoxyglucose (18F-FDG). Fluorinated deoxyglucose is a glucose analogue. Compared with ordinary glucose molecules, one hydroxyl group of fluorinated deoxyglucose is replaced by the radioisotope 18F, so it is radioactive and continuously emits positrons. Because the hydroxyl group at the two-carbon position is replaced by a fluorine atom, fluorinated deoxyglucose cannot be further metabolized after being phosphorylated; also, it cannot be transported out of the cell through channel proteins on the cell membrane. Therefore, once fluorinated deoxyglucose enters the cell, it will remain in the cell in the form of phosphorylation for a long time before 18F decays. Cancer cells consume more glucose, so if there are cancer cells in the subject's body, after injecting fluorinated deoxyglucose, cancer cells will take in relatively more fluorinated deoxyglucose. Thus, using PET to detect the location with strong signal (radioactivity) may indicate the presence of cancer cells. Based on the detection results obtained, the diagnosis of malignant tumors can be made.

[0004] 18F-FDG, as a tumor metabolism drug, plays an important role in the diagnosis and differential diagnosis of malignant tumors. However, the fluorine in 18F-FDG is 18F, which is a positron-emitting radioisotope. Multiple detections on patients can cause secondary harm, and compared with other imaging markers such as 150, 13N, and 11C, its half-life has been significantly improved, but it still cannot be used to track the entire metabolic process. Therefore, the existing technology still needs to be improved and developed.

[0005] Since the 1960s, various synthetic methods for synthesizing deuterated compounds have been proposed. The hydrogen isotope exchange (HIE) process, also known as the hydrogen-deuterium exchange process, represents a reaction in which hydrogen atoms in a molecule are replaced by deuterium atoms. Under appropriate conditions, the HIE reaction can control the selectivity of the deuterium substitution site. However, for more challenging substrates, increased temperature and pressure are required to facilitate the exchange. Since the HIE reaction can directly label target molecules with D2O or D2, avoiding additional synthetic steps, the HIE reaction method is a relatively effective and simple method for preparing deuterium-labeled compounds, considering factors such as reaction selectivity, economy, etc. The use of strong acid catalysis for HIE reaction is one of the oldest methods for preparing deuterated compounds. This method is mainly used for the preparation of corresponding deuterated compounds of aromatic compounds and olefin compounds. However, there are obvious limitations in the preparation of most of the above compounds. In particular, high temperature and stoichiometrically concentrated strong acid result in the inability to preserve some functional groups during the catalytic reaction. The range of substrates suitable for base catalysts is very limited, and the range is smaller than that of acid catalysts.

[0006] In heterogeneous catalysis, the catalyst is usually solid, and the reagent and solvent belong to different phases. Therefore, the technical advantage of heterogeneous catalysis is that the catalyst can be removed by simple filtration when the reaction is complete, thereby improving the recovery rate of the catalyst and the purity of the product, improving the post-reaction processing capability, reducing the loss of the product in the complex separation process, and achieving higher economic benefits, which is more suitable for large-scale preparation of organic matter. SUMMARY

[0007] In view of the above technical problems existing in the prior art, the purpose of the present application is to provide a preparation method of polyacrylonitrile carbon flower particle loaded ruthenium catalyst and its application in catalyzing deuterium substitution of glucose.

[0008] The technical scheme adopted by the present application is:

[0009] A preparation method of polyacrylonitrile carbon flower particle loaded ruthenium catalyst, comprising the following steps:

[0010] Step one: mixing acrylonitrile monomer, initiator N,N-methylenebisacrylamide and organic solvent, refluxing under inert gas protection condition, and synthesizing polyacrylonitrile carbon flower particles through one-step free radical polymerization process;

[0011] Step two: vacuum drying and grinding the polyacrylonitrile carbon flower particles, and calcining under the condition of air inlet to obtain stabilized polyacrylonitrile carbon flower particles;

[0012] Step three: the stabilized polyacrylonitrile carbon flower particles are calcined and pyrolyzed in an inert gas to obtain high-temperature pyrolyzed polyacrylonitrile carbon flower particles;

[0013] Step four: the high-temperature pyrolyzed polyacrylonitrile carbon flower particles are immersed in a ruthenium salt solution by a wet immersion method, dried, and finally calcined and reduced under hydrogen to obtain polyacrylonitrile carbon flower particle supported ruthenium catalyst.

[0014] Further, in step one, the feeding ratio of acrylonitrile monomer, initiator N, N-azoisobutyronitrile and organic solvent is 15-45 mL: 10-30 mg: 15-45 mL, the inert gas is nitrogen or argon, and the organic solvent is acetone.

[0015] Further, in step one, the reflux temperature is 85-95℃, preferably 90℃, and the reflux time is 2-4h.

[0016] Further, in step two, the temperature program for calcination under the condition of air flow is: from room temperature to 220-240℃, preferably 230℃, at a heating rate of 2-10℃ / min, then keep constant temperature for 1-3h, preferably 2h, and then cool to room temperature; the heating rate is preferably 4-5℃ / min.

[0017] Further, in step three, the inert gas is nitrogen, and the temperature program for calcination and pyrolysis in the inert gas is: from room temperature to 600-1000℃ at a heating rate of 5-15℃ / min, then keep constant temperature for pyrolysis for 2-4h, and finally cool to room temperature. The calcination and pyrolysis temperature is preferably 750-800℃.

[0018] Further, in step four, the mass ratio of Ru element in the ruthenium salt to the polyacrylonitrile carbon flower particles is 1:15-25, preferably 1:20-22, and the process of immersion treatment and drying is: mixing the high-temperature pyrolyzed polyacrylonitrile carbon flower particles, ruthenium salt and aqueous solvent in a container, and stirring at 80-95℃ with the container open until the water is completely evaporated.

[0019] Further, in step four, the process of calcination and reduction under hydrogen is: in a hydrogen-nitrogen mixed gas stream with a hydrogen volume fraction of 15-25%, from room temperature to 300-600℃ at a heating rate of 5-15℃ / min, then keep constant temperature for calcination for 4-8h, and finally cool to room temperature.

[0020] The application provides application of polyacrylonitrile carbon flower particle loaded ruthenium catalyst in catalyzing glucose deuterium substitution, and the application method is as follows: polyacrylonitrile carbon flower particle loaded ruthenium catalyst, anhydrous glucose and heavy water are sequentially added into a high-pressure reaction kettle at room temperature, air in the kettle is discharged, hydrogen is filled, stirring and heating are carried out to heat to a reaction temperature, and after reaction at the temperature until completion, the reaction kettle is statically placed and hydrogen is discharged, the reaction liquid is collected and filtered, and vacuum distillation is carried out to obtain a solid product.

[0021] Further, the feeding ratio of the polyacrylonitrile carbon flower particle loaded ruthenium catalyst, the anhydrous glucose and the heavy water is 5-30 mg: 30-60 mg: 0.5-4 mL, the hydrogen pressure is 0.5-3 MPa, preferably 1 MPa, the reaction temperature is 65-125 DEG C, preferably 85-90 DEG C, and the reaction time is 4-16 h, preferably 10-12 h.

[0022] Compared with the prior art, the application has the beneficial effects that:

[0023] (1) The application provides a Ru-based catalyst preparation method and its application in glucose deuterium substitution, and the purpose is to provide a method for preparing deuterium glucose with easy separation and recovery of the catalyst, mild reaction conditions, simple operation and high yield, to enhance the drug metabolic stability in the human body through the stability of C-D bond, so as to reduce the drug dosage, and the deuterium compound is also used to clarify the metabolic mechanism of most molecular drugs due to its unique isotope tracing technology, and is expected to replace fluorinated deoxyglucose (18F-FDG) as a developing agent.

[0024] (2) The preparation method of the polyacrylonitrile carbon flower particle loaded ruthenium catalyst is simple, and the catalyst has excellent catalytic efficiency in the reaction of catalyzing glucose deuterium substitution. DETAILED DESCRIPTION

[0025] The application will be further described below in combination with specific embodiments, but the protection scope of the application is not limited thereto.

[0026] In the embodiment of the application, the deuterium substitution rate calculation formula is as follows: deuterium substitution rate = 1- (mole amount of dimethyl sulfoxide * number of deuterium atoms of dimethyl sulfoxide * area of deuterium atoms of glucose in nuclear magnetic resonance) / (mole amount of glucose * number of deuterium atoms of glucose * area of deuterium atoms of dimethyl sulfoxide in nuclear magnetic resonance).

[0027] Example 1

[0028] A mixture of 20 mL of acrylonitrile (monomer), 20 mg of N,N-methylenebisacetoamide (initiator) and 20 mL of acetone (solvent) was refluxed under nitrogen at 90 °C for 2 h to obtain polyacrylonitrile carbon flower particles; the polyacrylonitrile carbon flower particles were first vacuum dried at 75 °C for 12 h, then ground and calcined in a stable air flow at a flow rate of 60 mL / min at a temperature rising rate of 7 °C / min to 230 °C for 2 h to obtain stabilized polyacrylonitrile carbon flower particles; the stabilized polyacrylonitrile carbon flower particles were calcined in a stable nitrogen flow at a flow rate of 60 mL / min at a temperature rising rate of 10 °C / min to 800 °C for 3 h to obtain high-temperature pyrolyzed polyacrylonitrile carbon flower particles; a mixture of 600 mg of the high-temperature pyrolyzed polyacrylonitrile carbon flower particles, 12 mL of a 5 mg / mL ruthenium chloride solution and 40 mL of deionized water was stirred at 90 °C until the water was completely evaporated, then calcined in a mixed gas stream of hydrogen at a flow rate of 20 mL / min and nitrogen at a flow rate of 80 mL / min at a temperature rising rate of 10 °C / min to 450 °C for 5 h to obtain a 10% Ru / PACN-3-H2 catalyst.

[0029] A mixture of 20 mL of acrylonitrile (monomer), 20 mg of N,N-methylenebisacetoamide (initiator) and 20 mL of acetone (solvent) was refluxed under nitrogen at 90 °C for 2 h to obtain polyacrylonitrile carbon flower particles; the polyacrylonitrile carbon flower particles were first vacuum dried at 75 °C for 12 h, then ground and calcined in a stable air flow at a flow rate of 60 mL / min at a temperature rising rate of 7 °C / min to 230 °C for 2 h to obtain stabilized polyacrylonitrile carbon flower particles; the stabilized polyacrylonitrile carbon flower particles were calcined in a stable nitrogen flow at a flow rate of 60 mL / min at a temperature rising rate of 10 °C / min to 800 °C for 3 h to obtain high-temperature pyrolyzed polyacrylonitrile carbon flower particles; a mixture of 600 mg of the high-temperature pyrolyzed polyacrylonitrile carbon flower particles, 12 mL of a 5 mg / mL ruthenium chloride solution and 40 mL of deionized water was stirred at 90 °C until the water was completely evaporated, then calcined in a mixed gas stream of hydrogen at a flow rate of 20 mL / min and nitrogen at a flow rate of 80 mL / min at a temperature rising rate of 10 °C / min to 450 °C for 5 h to obtain a 10% Ru / PACN-3-H2 catalyst.

[0030] Example 2

[0031] The preparation steps of the catalyst in Example 2 were repeated, except that the "amount of raw materials mixed was 40 mL of acrylonitrile (monomer), 30 mg of N,N-methylenebisacetoamide (initiator) and 40 mL of acetone", and the other conditions were the same as in Example 1.

[0032] The catalyst in Example 2 was applied to the reaction of catalytic deuteration of glucose, and the operating conditions were as described in Example 1. The final experimental result was that the deuteration rate of glucose was 90%.

[0033] Example 3

[0034] The preparation steps of the catalyst in Example 3 were repeated, except that the "stabilized polyacrylonitrile carbon flower particles were calcined in a stable nitrogen flow at a flow rate of 60 mL / min at a temperature rising rate of 10 °C / min to 600 °C for 3 h", and the other conditions were the same as in Example 1.

[0035] The catalyst of Example 3 was applied to the reaction of catalyzing the deuteration of glucose, and the operating conditions were as described in Example 1. The final experimental result was that the deuteration rate of glucose was 70.6%.

[0036] Example 4

[0037] The preparation steps of the catalyst of Example 4 were repeated as in Example 1, except that "the stabilized polyacrylonitrile carbon flower particles were calcined at a temperature increasing rate of 10 ℃ / min to 1000 ℃ for 3 h in a stable nitrogen flow with a flow rate of 60 mL / min" and the rest of the conditions were the same as in Example 1.

[0038] The catalyst of Example 4 was applied to the reaction of catalyzing the deuteration of glucose, and the operating conditions were as described in Example 1. The final experimental result was that the deuteration rate of glucose was 43%.

[0039] Example 5

[0040] The preparation steps of the catalyst of Example 5 were repeated as in Example 1, except that "the polyacrylonitrile carbon flower particles were first vacuum dried at 75 ℃ for 12 h, and then were calcined at a temperature increasing rate of 10 ℃ / min to 230 ℃ for 2 h in a stable air flow with a flow rate of 60 mL / min" and the rest of the conditions were the same as in Example 1.

[0041] The catalyst of Example 5 was applied to the reaction of catalyzing the deuteration of glucose, and the operating conditions were as described in Example 1. The final experimental result was that the deuteration rate of glucose was 81%.

[0042] Example 6

[0043] The preparation steps of the catalyst of Example 6 were repeated as in Example 1, except that "the amount of 5 mg / mL ruthenium chloride solution was replaced by 10 mL" and the rest of the conditions were the same as in Example 1.

[0044] The catalyst of Example 6 was applied to the reaction of catalyzing the deuteration of glucose, and the operating conditions were as described in Example 1. The final experimental result was that the deuteration rate of glucose was 73.3%.

[0045] Example 7

[0046] The preparation steps of the catalyst of Example 7 were repeated as in Example 1, except that "the amount of 5 mg / mL ruthenium chloride solution was replaced by 15 mL" and the rest of the conditions were the same as in Example 1.

[0047] The catalyst of Example 7 was applied to the reaction of catalyzing the deuteration of glucose, and the operating conditions were as described in Example 1. The final experimental result was that the deuteration rate of glucose was 78.6%.

[0048] Example 8

[0049] The preparation procedure of the catalyst in Example 8 was repeated as in Example 1, except that "calcination was carried out for 8 h in a mixed gas stream of hydrogen at a flow rate of 20 mL / min and nitrogen at a flow rate of 80 mL / min at a temperature- increasing rate of 10 °C / min up to 450 °C" and the rest of the conditions were the same as in Example 1.

[0050] The catalyst in Example 8 was used in the reaction of catalyzing the deuteration of glucose, and the operating conditions were as described in Example 1. The final experimental result was that the deuteration rate of glucose was 69%.

[0051] Example 9

[0052] The preparation procedure of the catalyst in Example 9 was repeated as in Example 1, except that "calcination was carried out for 7 h in a mixed gas stream of hydrogen at a flow rate of 20 mL / min and nitrogen at a flow rate of 80 mL / min at a temperature- increasing rate of 10 °C / min up to 450 °C" and the rest of the conditions were the same as in Example 1.

[0053] The catalyst in Example 9 was used in the reaction of catalyzing the deuteration of glucose, and the operating conditions were as described in Example 1. The final experimental result was that the deuteration rate of glucose was 85%.

[0054] Example 10

[0055] The preparation procedure of the catalyst in Example 10 was repeated as in Example 1;

[0056] The catalyst in Example 10 was used in the reaction of catalyzing the deuteration of glucose, except that "the hydrogen pressure was replaced by 0.5 MPa" and the rest of the conditions were the same as in Example 1. The final experimental result was that the deuteration rate of glucose was 83%.

[0057] Example 11

[0058] The preparation procedure of the catalyst in Example 11 was repeated as in Example 1;

[0059] The catalyst in Example 11 was used in the reaction of catalyzing the deuteration of glucose, except that "the amount of heavy water used in the reaction was replaced by 0.5 mL" and the rest of the conditions were the same as in Example 1. The final experimental result was that the deuteration rate of glucose was 75%.

[0060] Example 12

[0061] The preparation procedure of the catalyst in Example 12 was repeated as in Example 1;

[0062] The catalyst in Example 12 was used in the reaction of catalyzing the deuteration of glucose, except that "2 MPa of hydrogen was filled" and the rest of the conditions were the same as in Example 1. The final experimental result was that the deuteration rate of glucose was 87.3%.

[0063] Example 13

[0064] The preparation procedure of the catalyst of Example 13 was repeated to Example 1;

[0065] The catalyst of Example 13 was applied to the reaction of catalyzing the deuteration of glucose, with the exception of "the reaction temperature was 65°C", and the rest of the conditions were the same as Example 1. The final experimental result was that the deuteration rate of glucose was 72.4%.

[0066] Example 14

[0067] The preparation procedure of the catalyst of Example 14 was repeated to Example 1;

[0068] The catalyst of Example 14 was applied to the reaction of catalyzing the deuteration of glucose, with the exception of "the reaction temperature was 105°C", and the rest of the conditions were the same as Example 1. The final experimental result was that the deuteration rate of glucose was 82.8%.

[0069] Example 15

[0070] The preparation procedure of the catalyst of Example 15 was repeated to Example 1;

[0071] The catalyst of Example 15 was applied to the reaction of catalyzing the deuteration of glucose, with the exception of "the reaction time was 6h", and the rest of the conditions were the same as Example 1. The final experimental result was that the deuteration rate of glucose was 80.6%.

[0072] Example 16

[0073] The preparation procedure of the catalyst of Example 16 was repeated to Example 1;

[0074] The catalyst of Example 16 was applied to the reaction of catalyzing the deuteration of glucose, with the exception of "the reaction time was 16h", and the rest of the conditions were the same as Example 1. The final experimental result was that the deuteration rate of glucose was 88%.

[0075] Comparative Example 1

[0076] 20 mL of acrylonitrile (monomer), 20 mg of N,N-methylenebisacrylamide (initiator), and 20 mL of acetone (solvent) were mixed and refluxed under nitrogen at 90°C for 2h to obtain polyacrylonitrile carbon flower particles; the polyacrylonitrile carbon flower particles were first vacuum dried at 75°C for 12h, then 600 mg of the milled polyacrylonitrile carbon flower particles, 12 mL of a 5mg / mL ruthenium chloride solution, and 40 mL of deionized water were mixed and stirred at 90°C until the water was completely evaporated; then the mixture was calcined at a temperature rising rate of 10°C / min to 450°C under a mixed gas stream of hydrogen at a flow rate of 20 mL / min and nitrogen at a flow rate of 80 mL / min for 5h to obtain a 10% Ru / PACN-1-H2 catalyst.

[0077] The catalyst of Comparative Example 1 was used in the catalytic deuteration reaction of glucose. The operating conditions were the same as in Example 1. The final experimental result was that the deuteration rate of glucose was 68%.

[0078] Compare with Example 2

[0079] 20 mL of acrylonitrile (monomer), 20 mg of N,N-azoisobutyronitrile (initiator), and 20 mL of acetone (solvent) were mixed and refluxed under nitrogen at 90 °C for 2 h to obtain polyacrylonitrile carbon flower particles. The polyacrylonitrile carbon flower particles were first vacuum dried at 75 °C for 12 h. 600 mg of the milled polyacrylonitrile carbon flower particles were mixed with 12 mL of 5 mg / mL ruthenium chloride solution and 40 mL of deionized water and stirred in an open container at 90 °C until the water was completely evaporated to obtain a 10% Ru / PACN-1 catalyst.

[0080] The catalyst of Comparative Example 2 was used in the reaction of glucose deuteration, and the operating conditions were the same as in Example 1. The final experimental result was that the deuteration rate of glucose was 65%.

[0081] Compare with Example 3

[0082] 20 mL of acrylonitrile (monomer), 20 mg of N,N-azoisobutyronitrile (initiator), and 20 mL of acetone (solvent) were mixed and refluxed under nitrogen at 90 °C for 2 h to obtain polyacrylonitrile carbon flower particles. The polyacrylonitrile carbon flower particles were first vacuum dried at 75 °C for 12 h, then milled and placed in a stable air flow at a flow rate of 60 mL / min. The temperature was increased to 230 °C at a heating rate of 7 °C / min and then calcined for 2 h to obtain stabilized polyacrylonitrile carbon flower particles. 600 mg of stabilized polyacrylonitrile carbon flower particles, 12 mL of 5 mg / mL ruthenium chloride solution, and 40 mL of deionized water were mixed and stirred in an open container at 90 °C until the water was completely evaporated. Then, the mixture was placed in a mixed gas flow of hydrogen at a flow rate of 20 mL / min and nitrogen at a flow rate of 80 mL / min and calcined at 450 °C at a heating rate of 10 °C / min for 5 h to obtain a 10% Ru / PACN-2-H2 catalyst.

[0083] The catalyst of Comparative Example 3 was used in the reaction of glucose deuteration, and the operating conditions were the same as in Example 1. The final experimental result was that the deuteration rate of glucose was 85%.

[0084] Compare with Example 4

[0085] 20 mL of acrylonitrile (monomer), 20 mg of N,N-azoisobutyronitrile (initiator), and 20 mL of acetone (solvent) were mixed and refluxed under nitrogen at 90 °C for 2 h to obtain polyacrylonitrile carbon flower particles. The polyacrylonitrile carbon flower particles were first vacuum dried at 75 °C for 12 h, then milled and placed in a stable air flow at a flow rate of 60 mL / min. The temperature was increased to 230 °C at a heating rate of 7 °C / min and then calcined for 2 h to obtain stabilized polyacrylonitrile carbon flower particles. 600 mg of stabilized polyacrylonitrile carbon flower particles, 12 mL of 5 mg / mL ruthenium chloride solution, and 40 mL of deionized water were mixed and stirred in an open container at 90 °C until the water was completely evaporated to obtain a 10% Ru / PACN-2 catalyst.

[0086] The catalyst of Comparative Example 4 was used in the catalytic deuteration of glucose. The operating conditions were the same as in Example 1. The final experimental result was that the deuteration rate of glucose was 81%.

[0087] Compare with Example 5

[0088] 20 mL of acrylonitrile (monomer), 20 mg of N,N-azoisobutyronitrile (initiator), and 20 mL of acetone (solvent) were mixed and refluxed under nitrogen at 90 °C for 2 h to obtain polyacrylonitrile carbon flower particles. These particles were then vacuum dried at 75 °C for 12 h, milled, and placed in a stable air stream at a flow rate of 60 mL / min. The temperature was increased to 230 °C at a rate of 7 °C / min, and then calcined for 2 h to obtain stabilized polyacrylonitrile carbon flower particles. These stabilized particles were then calcined in a stable nitrogen stream at a flow rate of 60 mL / min at a rate of 10 °C / min to 800 °C for 3 h to obtain high-temperature pyrolysis polyacrylonitrile carbon flower particles. 600 mg of the high-temperature pyrolysis polyacrylonitrile carbon flower particles, 12 mL of 5 mg / mL ruthenium chloride solution, and 40 mL of deionized water were mixed and stirred in an open container at 90 °C until the water was completely evaporated to obtain a 10% Ru / PACN-3 catalyst.

[0089] The catalyst of Comparative Example 5 was used in the reaction of glucose deuteration, and the operating conditions were the same as in Example 1. The final experimental result was that the deuteration rate of glucose was 88%.

[0090] Compare with Example 6

[0091] 500 mg of silica, 111 mg of ruthenium chloride trihydrate, 10 mL of ethanol and 20 mL of deionized water were mixed and sonicated for 15 min. Sodium borohydride solution was slowly added dropwise until excess during stirring. Then, 300 mg of dopamine hydrochloride was added and the pH was adjusted to 8-9. After stirring for 2 h, the mixture was centrifuged and dried. Subsequently, it was calcined at 450 °C for 5 h in a mixed gas flow of hydrogen at a flow rate of 20 mL / min and nitrogen at a flow rate of 80 mL / min, with the temperature increased at a rate of 10 °C / min, to obtain a 10% Ru / C catalyst.

[0092] The catalyst of Comparative Example 6 was used in the catalytic deuteration of glucose. The operating conditions were the same as in Example 1. The final experimental result was that the deuteration rate of glucose was 61%.

[0093] Compare with Example 7

[0094] 3.24 g of zinc nitrate hexahydrate was dissolved in 40 mL of deionized water to obtain solution A, and 2.1 g of 2-methylimidazole was dissolved in 40 mL of deionized water to obtain solution B. Solution A and solution B were then mixed and aged for 2 h, followed by vacuum drying at 70 °C for 3 h to obtain ZIF-8. 600 mg of ZIF-8, 12 mL of 5 mg / mL ruthenium chloride solution, and 40 mL of deionized water were mixed and stirred in an open container at 90 °C until the water was completely evaporated to obtain the ZIF-8 supported ruthenium catalyst. Subsequently, the temperature was increased to 450 °C at a rate of 10 °C / min in a mixed gas flow of hydrogen at a flow rate of 20 mL / min and nitrogen at a flow rate of 80 mL / min, and then calcined for 5 h to obtain the 10% Ru / ZIF-8 catalyst.

[0095] The catalyst of Comparative Example 7 was used in the catalytic deuteration of glucose. The operating conditions were the same as in Example 1. The final experimental result was that the deuteration rate of glucose was 34%.

[0096] Compare with Example 8

[0097] 600 mg r-Al2O3, 12 mL of 5 mg / mL ruthenium chloride solution, and 40 mL of deionized water were mixed and stirred in an open container at 90 °C until the water was completely evaporated. Then, the mixture was heated to 450 °C at a rate of 10 °C / min in a mixed gas stream of hydrogen at a flow rate of 20 mL / min and nitrogen at a flow rate of 80 mL / min, and calcined for 5 h to obtain a 10% Ru / r-Al2O3 catalyst.

[0098] The catalyst of Comparative Example 8 was used in the catalytic deuteration reaction of glucose. The operating conditions were the same as in Example 1. The final experimental result was that the deuteration rate of glucose was 50%.

[0099] Compare with Example 9

[0100] 500 mg r-Al₂O₃, 36.1 mg Fe(NO₃)₃·9H₂O, and 30 mL of deionized water were mixed and stirred dry in an open container at 85 °C. The mixture was then calcined at 500 °C for 2 h in an air stream at a flow rate of 80 mL / min, with the temperature increased at 5 °C / min, to obtain Fe-rAl₂O₃ spinel. 600 mg Fe-rAl₂O₃ spinel, 12 mL of 5 mg / mL ruthenium chloride solution, and 40 mL of deionized water were mixed and stirred in an open container at 90 °C until the water was completely evaporated. The mixture was then calcined at 450 °C for 5 h in a mixed gas stream of hydrogen at a flow rate of 20 mL / min and nitrogen at 10 °C / min, to obtain a 10% Ru / Fe-rAl₂O₃ catalyst.

[0101] The catalyst of Comparative Example 9 was used in the catalytic deuteration of glucose. The operating conditions were the same as in Example 1. The final experimental result was that the deuteration rate of glucose was 56%.

[0102] The contents described in this specification are merely an enumeration of the implementation forms of the inventive concept, and the scope of protection of this invention should not be regarded as limited to the specific forms described in the embodiments.

Claims

1. The application of a ruthenium catalyst supported on polyacrylonitrile carbon flower particles in the catalytic deuteration of glucose, characterized in that... The catalyst preparation method includes the following steps: Step 1: Mix acrylonitrile monomer, initiator N,N-azoisobutyronitrile and organic solvent, reflux under nitrogen or argon protection, and synthesize polyacrylonitrile carbon flower particles through a one-step free radical polymerization process. Step 2: Vacuum dry and grind the polyacrylonitrile carbon particles, and calcine them under air conditions to obtain stabilized polyacrylonitrile carbon particles. Step 3: Place the stabilized polyacrylonitrile carbon flower particles in nitrogen gas for calcination and pyrolysis to obtain polyacrylonitrile carbon flower particles after high-temperature pyrolysis. Step 4: The polyacrylonitrile carbon flower particles after high-temperature pyrolysis are impregnated in a ruthenium salt solution using a wet impregnation method, dried, and finally calcined and reduced under hydrogen conditions to obtain a ruthenium catalyst supported on polyacrylonitrile carbon flower particles. In step two, the calcination temperature program under the condition of air introduction is as follows: raise the temperature from room temperature to 220-240℃ at a heating rate of 2-10℃ / min, then keep the temperature constant for calcination for 1-3 hours, and then cool to room temperature. In step three, the temperature procedure for calcination and pyrolysis in nitrogen gas is as follows: the temperature is increased from room temperature to 750-800℃ at a rate of 5-15℃ / min, then kept constant for pyrolysis for 2-4 hours, and finally cooled to room temperature.

2. The application as described in claim 1, characterized in that... In step one, the feed ratio of acrylonitrile monomer, initiator N,N-azoisobutyronitrile and organic solvent is 15-45mL:10-30mg:15-45mL, and the organic solvent is acetone.

3. The application as described in claim 1, characterized in that... In step one, the reflux temperature is 85-95℃ and the reflux time is 2-4 hours.

4. The application as described in claim 3, characterized in that... In step one, the reflux temperature is 90℃.

5. The application as described in claim 1, characterized in that... In step two, calcination is carried out under air conditions, the temperature is raised to 230℃, and the calcination is maintained at a constant temperature for 2 hours.

6. The application as described in claim 1, characterized in that... In step four, the mass ratio of Ru element in ruthenium salt to polyacrylonitrile carbon flower particles is 1:15~25. The impregnation and drying process is as follows: the polyacrylonitrile carbon flower particles after high-temperature pyrolysis, ruthenium salt and water solvent are mixed in a container, and the container is stirred with the container open at 80-95℃ until the water is completely evaporated.

7. The application as described in claim 6, characterized in that... In step four, the mass ratio of Ru in the ruthenium salt to the polyacrylonitrile carbon particles is 1:20~22.

8. The application as described in claim 1, characterized in that... In step four, the calcination and reduction process under hydrogen conditions is as follows: in a hydrogen-nitrogen mixed gas flow with a hydrogen gas integral of 15-25%, the temperature is increased from room temperature to 300-600℃ at a heating rate of 5-15℃ / min, then kept at a constant temperature for 4-8 hours, and finally cooled to room temperature.

9. The application as described in claim 8, characterized in that... At room temperature, ruthenium catalyst supported on polyacrylonitrile carbon flower particles, anhydrous glucose, and heavy water were sequentially added to a high-pressure reactor. The air inside the reactor was purged, hydrogen was introduced, and the mixture was stirred and heated to the reaction temperature. After the reaction was completed at this temperature, the reactor was allowed to stand and hydrogen was released. The reaction solution was then cooled to room temperature, collected, filtered, and subjected to vacuum distillation to obtain the solid product.

10. The application as described in claim 9, characterized in that... The feed ratio of the polyacrylonitrile carbon flower particles supported on ruthenium catalyst, anhydrous glucose and heavy water is 5-30 mg: 30-60 mg: 0.5-4 mL, the hydrogen pressure is 0.5-3 MPa, the reaction temperature is 65-125℃, and the reaction time is 4-16 h.

11. The application as described in claim 10, characterized in that... The hydrogen pressure is 1 MPa, the reaction temperature is 85~90℃, and the reaction time is 10-12 h.