Janus composite gas-solid-liquid three-phase interface reactor and preparation method and application thereof
By depositing metal nanomaterials on hydrophobic carbon paper and loading catalysts to construct a Janus composite gas-solid-liquid three-phase interface reactor, the problems of low catalytic efficiency and pH control in the synthesis of 1,5-pentanediamine were solved, and the efficient and long-term continuous synthesis of biogenic amines was realized.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- NANJING TECH UNIV
- Filing Date
- 2026-03-10
- Publication Date
- 2026-06-09
AI Technical Summary
Existing technologies for the synthesis of 1,5-pentanediamine suffer from low catalytic efficiency and poor selectivity, and cannot effectively control the pH of the reaction system at room temperature and pressure, leading to the inactivation of biomolecules and the inability to synthesize continuously.
A Janus composite gas-solid-liquid three-phase interface reactor was constructed. By depositing metal nanomaterials on hydrophobic carbon paper and hydrophilizing them, different catalysts were loaded to achieve cascade reactions and adaptively control the pH of the reaction system.
This improved the efficiency of the cascade reaction and the degradation efficiency of biomolecules, enabling the long-term continuous synthesis of biogenic amines at ambient temperature and pressure while maintaining the high activity of the catalyst.
Smart Images
Figure CN122168587A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of gas-solid-liquid three-phase interface reactors, specifically relating to a Janus composite gas-solid-liquid three-phase interface reactor and its preparation method, as well as its application in the preparation of 1,5-pentanediamine. Background Technology
[0002] Polyamides (PA), also known as nylon, are important polymers widely used in textiles, automobiles, packaging, medical materials, and other fields, and have become an indispensable material in daily production and life. Traditional polyamide production processes use petroleum as a raw material, making the search for a renewable resource to replace petroleum-based polyamides urgent. Therefore, using biomass raw materials to produce bio-based polyamides to replace traditional polyamides is an inevitable trend.
[0003] The synthesis of 1,5-pentanediamine can be achieved through chemical and biological methods. The chemical method primarily uses glutaronitrile as a raw material, obtained through catalytic hydrogenation in the presence of a catalyst. However, this method suffers from low catalytic efficiency and selectivity, and is hampered by demanding reaction conditions and poor economic efficiency, making it difficult to achieve continuous and stable production for many years. Therefore, in the continuous synthesis of 1,5-pentanediamine, the core research focus is on finding new methods and material systems that can effectively control the pH of the reaction system without the need for exogenous buffers and under ambient temperature and pressure. The preparation of the Janus composite gas-solid-liquid three-phase interface reactor has broad application prospects in fields such as biosynthesis and catalysis. Summary of the Invention
[0004] Purpose of the invention: The technical problem to be solved by the present invention is to address the shortcomings of the prior art by providing a method for effectively controlling the pH of the reaction system under normal temperature and pressure through the construction of a Janus composite gas-solid-liquid three-phase interface reactor, thereby achieving long-term continuous synthesis of biogenic amines.
[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0006] A method for preparing a Janus composite gas-solid-liquid three-phase interface reactor includes the following steps:
[0007] (1) Deposit metal nanomaterials onto one side surface of hydrophobic carbon paper;
[0008] (2) Hydrophilization treatment step (1) The deposited metal nanomaterials are used to obtain a porous and breathable Janus composite three-phase interface with one side hydrophilic and the other side hydrophobic.
[0009] (3) Two catalysts capable of cascade reactions are further loaded on both sides of the porous and permeable Janus composite three-phase interface obtained in step (2) to obtain the final product.
[0010] Specifically, the method for depositing metal nanomaterials onto the surface of hydrophobic carbon paper in step (1) is as follows:
[0011] S1-1: Immerse the hydrophobic carbon paper in an organic solvent, ultrasonically remove the adhering substances on the surface of the carbon paper, and dry it with nitrogen gas;
[0012] S1-2: Place the carbon paper treated in step S1-1 into the reaction cell of the three-electrode electrochemical system;
[0013] S1-3: Add PBS buffer solution and metal salt solution to the reaction tank so that one side of the carbon paper is in contact with the solution and the other side is exposed to the air;
[0014] S1-4: Electricity is supplied to the reaction tank to deposit metal nanomaterials onto the surface of hydrophobic carbon paper.
[0015] Specifically, in step S1-1, the organic solvent is selected from any one of alcohol solvents, ketone solvents or haloalkane solvents, the ratio of hydrophobic carbon paper to organic solvent is 1:10~1000, and the dispersion treatment is 0.1~6 h.
[0016] Specifically, in steps S1-3, the concentration of the PBS buffer solution is 0.01-10 M, and the pH is 3-8; the concentration of the metal salt solution is 0.2-8 mg / mL, and the solvent is an aqueous solution; the volume ratio of the PBS buffer solution to the metal salt solution is (1~10 mL):(0.5~1 mL).
[0017] Specifically, in steps S1-4, the reaction tank is energized and the voltage is controlled to be -0.8 V to 1.2 V, and the reaction time is 20 s to 15000 s after energization.
[0018] Specifically, the hydrophilization treatment method in step S2 is as follows:
[0019] The side of the carbon paper with metal nanomaterials deposited in step (1) is immersed in a hydrophilic solvent for 1-24 h. The hydrophilic reagent combines with the hydrophilic reagent to change the hydrophobic to hydrophilic. After completion, it is taken out and dried with nitrogen to obtain a porous and breathable Janus composite three-phase interface with one hydrophilic side and one hydrophobic side.
[0020] The hydrophilic solvent is aminothiol, with a concentration of 0.01 mM to 50 mM.
[0021] Specifically, in step (3), a first catalyst that can generate gaseous products is loaded on the hydrophobic surface of the porous and permeable Janus composite three-phase interface through hydrophobic forces, and a second catalyst is fixed on the hydrophilic surface of the porous and permeable Janus composite three-phase interface through covalent bonds to catalyze the gaseous products generated at the hydrophobic interface, so as to realize a cascade reaction.
[0022] Specifically,
[0023] The first catalyst supported on the hydrophobic surface is selected from either lysine decarboxylase or tyrosine decarboxylase.
[0024] The second catalyst supported on the hydrophilic surface is formate dehydrogenase.
[0025] Furthermore, the Janus composite gas-solid-liquid three-phase interface reactor prepared by the above preparation method is also within the scope of protection of this invention.
[0026] Furthermore, the present invention also claims protection for the use of the above-described Janus composite gas-solid-liquid three-phase interface reactor in the synthesis of biogenic amines.
[0027] Compared with the prior art, the present invention has the following beneficial effects:
[0028] This invention overcomes the shortcomings of traditional amine biosynthesis, such as biomolecule inactivation due to high pH and the inability to synthesize continuously. By constructing a Janus composite gas-solid-liquid three-phase interface reactor, the reaction efficiency of the cascade reaction is improved, and the pH of the system is adaptively controlled. Furthermore, by adding different biomolecules to the Janus composite gas-solid-liquid three-phase interface reactor constructed by the method of this invention, the degradation efficiency and continuous reaction time are significantly improved. Attached Figure Description
[0029] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, and the advantages of the present invention in the above and / or other aspects will become clearer.
[0030] Figure 1 This is a comparison chart showing the ability of the Janus composite gas-solid-liquid three-phase interface reactor prepared in Example 1 of this invention to catalyze the synthesis of biogenic amines with free CadA.
[0031] Figure 2 This is a comparison chart of the ability of the Janus composite gas-solid-liquid three-phase interface reactor prepared in Example 2 of this invention and free SpLDC to catalyze the synthesis of biogenic amines.
[0032] Figure 3 The pH of the Janus composite gas-solid-liquid three-phase interface reactor and the free SpLDC-catalyzed bioamine synthesis reaction system prepared in Example 2 of this invention changes with the number of days.
[0033] Figure 4 This is a comparison chart of the ability of the Janus composite gas-solid-liquid three-phase interface reactor prepared in Example 3 of this invention and free TDC to catalyze the synthesis of biogenic amines. Detailed Implementation
[0034] The present invention can be better understood from the following embodiments.
[0035] Example 1
[0036] The PBS buffer solution used in this embodiment was 0.1M with a pH of 7.4; the lysine decarboxylase (CadA) was self-purified; chloroauric acid solution and L-lysine were purchased from Sinopharm Group; and carbon paper (CP) was purchased from Shanghai Hesen Electric Co., Ltd.
[0037] (1) Depositing metal nanomaterials onto one side of a hydrophobic carbon paper:
[0038] (a1) Immerse the hydrophobic carbon paper in acetone at a ratio of 1:30, then place the container containing the carbon paper and organic solvent in an ultrasonic cleaner and sonicate for 4 hours to remove the adhering substances on the surface of the carbon paper. Use nitrogen to dry the cleaned carbon paper.
[0039] (a2) The hydrophobic carbon paper treated in step (a1) is placed in the reaction cell of a three-electrode electrochemical system. 1 ml of 0.1 M PBS buffer solution with pH 7.4 and 0.5 ml of 0.2 mg / mL H4AuCl2 solution are added to the reaction cell, so that one side of the carbon paper is in contact with the solution and the other side is exposed to the air. The voltage is set to -0.8 V, and after energizing the reaction cell for 20 s, carbon paper with Au nanomaterials on one side is obtained.
[0040] (2) Hydrophilic treatment of carbon paper coated with Au nanomaterials:
[0041] One side of the carbon paper on which Au nanomaterials were deposited was immersed in 500 µL of 1 mM hydrophilic solvent ethylaminothiol and left for 10 h. Then it was removed with tweezers and dried with nitrogen to obtain a porous and breathable Janus composite gas-solid-liquid three-phase interface with one side hydrophilic and the other hydrophobic.
[0042] (3) The porous, permeable Janus composite gas-solid-liquid three-phase interface obtained in step (2) with one side hydrophilic and the other hydrophobic is further loaded with catalysts on both sides to construct a Janus composite gas-solid-liquid three-phase interface reactor:
[0043] 10 µL of 0.1 mM lysine decarboxylase (CadA) molecules were adsorbed onto the hydrophobic surface of the Janus composite gas-solid-liquid three-phase interface by hydrophobic interaction and incubated in a 4°C refrigerator for 4 h to obtain CP / CadA.
[0044] Formate dehydrogenase (FDH) was further covalently modified at the hydrophilic interface of the Janus composite gas-solid-liquid three-phase interface and incubated at 4 degrees Celsius for 4 h to obtain the Janus composite gas-solid-liquid three-phase interface reactor FDH / MEA / Au / CP / CadA.
[0045] The Janus composite gas-solid-liquid three-phase interface reactor prepared by the above construction method was applied to the synthesis of 1,5-pentanediamine:
[0046] The constructed Janus composite gas-solid-liquid three-phase interface reactor was immersed in a 0.01M PBS buffer solution with a pH of 6.5. A 5 g / L L-lysine solution was added to the buffer solution as the experimental group. Simultaneously, free CadA without a reactor was added to the L-lysine solution as a blank control group. The degradation efficiencies of L-lysine obtained in the two experiments are as follows: Figure 1 As shown in the figure, the Janus composite gas-solid-liquid three-phase interface reactor catalyzes the formation of pentanediamine and CO2 from lysine. The CO2 is further catalyzed by FDH to formic acid, which can be neutralized to form pentanediamine. This automatically balances the pH of the reaction system, allowing lysinase to maintain a high activity over a long period.
[0047] Example 2
[0048] The PBS buffer solution used in this embodiment was 0.1M with a pH of 7.4; the lysine decarboxylase (SpLDC) was purified in-house; chloroauric acid solution and L-lysine were purchased from Sinopharm Group; and carbon paper (CP) was purchased from Shanghai Hesen Electric Co., Ltd.
[0049] (1) Depositing metal nanomaterials onto one side of a hydrophobic carbon paper:
[0050] (a1) Immerse the hydrophobic carbon paper in acetone at a ratio of 1:100, then place the container containing the carbon paper and organic solvent in an ultrasonic cleaner and sonicate for 4 hours to remove the adhering substances on the surface of the carbon paper. Use nitrogen to dry the cleaned carbon paper.
[0051] (a2) The hydrophobic carbon paper treated in step (a1) was placed in the reaction cell of a three-electrode electrochemical system. 1 ml of 0.1 M PBS buffer solution with pH 7.4 and 0.5 ml of 0.2 mg / mL CuCl2 solution were added to the reaction cell, so that one side of the carbon paper was in contact with the solution and the other side was exposed to the air. The voltage was set to 1.2 V, and after energizing the reaction cell for 2000 s, carbon paper with one side coated with Cu nanomaterials was obtained.
[0052] (2) Hydrophilic treatment of carbon paper coated with Cu nanomaterials:
[0053] One side of the carbon paper on which Cu nanomaterials were deposited was immersed in 500 µL of 20 mM hydrophilic solvent ethylaminothiol and left for 10 h. Then, it was removed with tweezers and dried with nitrogen to obtain a porous, permeable Janus composite gas-solid-liquid three-phase interface with one side hydrophilic and the other hydrophobic.
[0054] (3) The porous, permeable Janus composite gas-solid-liquid three-phase interface obtained in step (2) with one side hydrophilic and the other hydrophobic is further loaded with catalysts on both sides to construct a Janus composite gas-solid-liquid three-phase interface reactor:
[0055] 10 µL of 0.1 mM lysine decarboxylase (SpLDC) molecules were immobilized on the hydrophobic surface of the Janus composite gas-solid-liquid three-phase interface and incubated in a 4°C refrigerator for 4 h to obtain CP / SpLDC.
[0056] Formate dehydrogenase (FDH) was further modified at the hydrophilic interface of the Janus composite gas-solid-liquid three-phase interface and incubated at 4 degrees Celsius for 4 h to obtain the Janus composite gas-solid-liquid three-phase interface reactor FDH / MEA / Au / CP / SpLDC.
[0057] The Janus composite gas-solid-liquid three-phase interface reactor prepared by the above construction method was applied to the synthesis of 1,5-pentanediamine:
[0058] The constructed Janus composite gas-solid-liquid three-phase interface reactor was immersed in a 0.01M PBS buffer solution with a pH of 6.5. A 5 g / L L-lysine solution was added to the buffer solution as the experimental group. Simultaneously, free SpLDC without a reactor was added to the L-lysine solution as a blank control group. The catalytic efficiencies of L-lysine obtained in the two experiments are as follows: Figure 2 As shown in the figure, the Janus composite gas-solid-liquid three-phase interface reactor catalyzes the formation of pentanediamine and CO2 from lysine. CO2 is further catalyzed by FDH to formic acid, which can neutralize to form pentanediamine, automatically balancing the pH of the reaction system. In this embodiment, the Janus composite gas-solid-liquid three-phase interface reactor FDH / MEA / Au / CP / SpLDC enables lysinase to reach a pH of 8.0 in the reaction system after 87 days. In contrast, free lysinase reaches a pH of 9.0 in the reaction system after only 5 days. Figure 3 As shown.
[0059] Example 3
[0060] The PBS buffer solution used in this embodiment was 0.1M with a pH of 7.4; the tyrosine decarboxylase (TDC) used was self-purified; chloroauric acid solution and tyrosine were purchased from Sinopharm Group; carbon paper (CP) was purchased from Shanghai Hesen Electric Co., Ltd.
[0061] (1) Deposit metal nanomaterials onto one side surface of hydrophobic carbon paper;
[0062] (a1) Immerse the hydrophobic carbon paper in acetone at a ratio of 1:1000, then place the container containing the carbon paper and organic solvent in an ultrasonic cleaner and sonicate for 4 hours to remove the adhering substances on the surface of the carbon paper. Use nitrogen to dry the cleaned carbon paper.
[0063] (a2) The hydrophobic carbon paper treated in step (a1) was placed in the reaction cell of the three-electrode electrochemical system. 1 ml of 0.1 M PBS buffer solution with pH 7.4 and 0.5 ml of 0.2 mg / mL HAuCl4 solution were added to the reaction cell, so that one side of the carbon paper was in contact with the solution and the other side was exposed to the air. The voltage was set to 0.2 V, and after energizing the reaction cell for 200 s, carbon paper with Au nanomaterials on one side was obtained.
[0064] (2) Hydrophilic treatment of carbon paper coated with Au nanomaterials:
[0065] One side of the carbon paper on which Au nanomaterials were deposited was immersed in 500 µL of 20 mM hydrophilic solvent ethylaminothiol and left for 10 h. Then, it was removed with tweezers and dried with nitrogen to obtain a porous, permeable Janus composite gas-solid-liquid three-phase interface with one side hydrophilic and the other hydrophobic.
[0066] (3) The porous, permeable Janus composite gas-solid-liquid three-phase interface obtained in step (2) with one side hydrophilic and the other hydrophobic is further loaded with catalysts on both sides to construct a Janus composite gas-solid-liquid three-phase interface reactor:
[0067] A 10 µL volume of 0.1 mM tyrosine decarboxylase (TDC) molecule was immobilized on the hydrophobic surface of the Janus composite gas-solid-liquid three-phase interface and incubated in a 4°C refrigerator for 4 h to obtain CP / TDC.
[0068] Formate dehydrogenase (FDH) was further modified at the hydrophilic interface of the Janus composite gas-solid-liquid three-phase interface and incubated at 4 degrees Celsius for 4 h to obtain the Janus composite gas-solid-liquid three-phase interface reactor FDH / MEA / Au / CP / TDC.
[0069] The Janus composite gas-solid-liquid three-phase interface reactor prepared by the above construction method was applied to the synthesis of tyramine:
[0070] The constructed Janus composite gas-solid-liquid three-phase interface reactor was immersed in a 0.01M PBS buffer solution with a pH of 6.5. A 5 g / L tyrosine solution was added to the buffer solution as the experimental group. Simultaneously, free TDC without a reactor was added to the tyrosine solution as a blank control group. The degradation efficiencies of tyrosine obtained in the two experiments are as follows: Figure 3As shown in the figure, the Janus composite gas-solid-liquid three-phase interface reactor catalyzes the production of tyrosine from tyrosine, and then catalyzes the production of tyrosine and CO2 from tyrosine. The CO2 is further catalyzed by FDH to formic acid, which can neutralize to produce tyrosine. The reaction system automatically balances the pH, allowing the TDC to maintain a high activity over a long period.
[0071] This invention provides a Janus composite gas-solid-liquid three-phase interface reactor, its preparation method, and its application. Many methods and approaches exist for implementing this technical solution; the above description is merely a preferred embodiment of the invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of this invention, and these improvements and modifications should also be considered within the scope of protection of this invention. All components not explicitly stated in this embodiment can be implemented using existing technologies.
Claims
1. A method for preparing a Janus composite gas-solid-liquid three-phase interface reactor, characterized in that, Includes the following steps: (1) Deposit metal nanomaterials onto one side surface of hydrophobic carbon paper; (2) Hydrophilization treatment step (1) The deposited metal nanomaterials are used to obtain a porous and breathable Janus composite three-phase interface with one side hydrophilic and the other side hydrophobic. (3) Two catalysts capable of cascade reactions are further loaded on both sides of the porous and permeable Janus composite three-phase interface obtained in step (2) to obtain the final product.
2. The method for preparing the Janus composite gas-solid-liquid three-phase interface reactor according to claim 1, characterized in that, Step (1) The method for depositing metal nanomaterials onto the surface of hydrophobic carbon paper is as follows: S1-1: Immerse the hydrophobic carbon paper in an organic solvent, ultrasonically remove the adhering substances on the surface of the carbon paper, and dry it with nitrogen gas; S1-2: Place the carbon paper treated in step S1-1 into the reaction cell of the three-electrode electrochemical system; S1-3: Add PBS buffer solution and metal salt solution to the reaction tank so that one side of the carbon paper is in contact with the solution and the other side is exposed to the air; S1-4: Electricity is supplied to the reaction tank to deposit metal nanomaterials onto the surface of hydrophobic carbon paper.
3. The method for preparing the Janus composite gas-solid-liquid three-phase interface reactor according to claim 2, characterized in that, In step S1-1, the organic solvent is selected from any one of alcohol solvents, ketone solvents or haloalkane solvents, the ratio of hydrophobic carbon paper to organic solvent is 1:10~1000, and the dispersion treatment is 0.1~6 h.
4. The method for preparing the Janus composite gas-solid-liquid three-phase interface reactor according to claim 2, characterized in that, In steps S1-3, the concentration of the PBS buffer solution is 0.01-10 M, and the pH is 3-8; the concentration of the metal salt solution is 0.2-8 mg / mL, and the solvent is water; the volume ratio of the PBS buffer solution to the metal salt solution is 1-10 mL: 0.5-1 mL.
5. The method for preparing the Janus composite gas-solid-liquid three-phase interface reactor according to claim 2, characterized in that, In steps S1-4, the reaction tank is energized and the voltage is controlled to be -0.8 V to 1.2 V. After energization, the reaction time is 20 s to 15000 s.
6. The method for preparing the Janus composite gas-solid-liquid three-phase interface reactor according to claim 1, characterized in that, The steps of the hydrophilization treatment in step S2 are as follows: The side of the carbon paper with metal nanomaterials deposited in step (1) is immersed in a hydrophilic solvent for 1-24 h. The hydrophilic reagent combines with the hydrophilic reagent to change the hydrophobic to hydrophilic. After completion, it is taken out and dried with nitrogen to obtain a porous and breathable Janus composite three-phase interface with one hydrophilic side and one hydrophobic side. The hydrophilic solvent is aminothiol, with a concentration of 0.01 mM to 50 mM.
7. The method for preparing the Janus composite gas-solid-liquid three-phase interface reactor according to claim 1, characterized in that, In step (3), a first catalyst that can generate gaseous products is loaded on the hydrophobic surface of the porous and permeable Janus composite three-phase interface through hydrophobic forces, and a second catalyst is fixed on the hydrophilic surface of the porous and permeable Janus composite three-phase interface through covalent bonds to catalyze the gaseous products generated by the hydrophobic interface reaction, so as to realize the cascade reaction.
8. The method for preparing the Janus composite gas-solid-liquid three-phase interface reactor according to claim 7, characterized in that, The first catalyst supported on the hydrophobic surface is selected from either lysine decarboxylase or tyrosine decarboxylase. The second catalyst supported on the hydrophilic surface is formate dehydrogenase.
9. The Janus composite gas-solid-liquid three-phase interface reactor prepared by any one of the preparation methods of claims 1 to 8.
10. The application of the Janus composite gas-solid-liquid three-phase interface reactor of claim 9 in the synthesis of biogenic amines.