Programmable deformation and oxygen production magnetic drive soft robot and preparation method thereof

Abstract

The application discloses a programmable deformation and oxygen production magnetic driving soft robot and a preparation method thereof, and belongs to the technical field of composite materials and photocatalysis. Hard magnetic particles (T-NdFeB) with surface modification are compounded into kappa-carrageenan / polyacrylamide (KC / PAm) hydrogel through a free radical polymerization process to obtain a magnetic driving module. The modules are flexibly assembled into a soft robot with complex geometric shape and magnetization distribution by using a self-healing process between the modules, so that the soft robot can realize various programmable deformations. In addition, a Ru-Bi2CrO6 photocatalyst is obtained by doping Ru elements in Bi2CrO6, and is compounded into the KC / PAm hydrogel to construct a functional module capable of producing oxygen. The magnetic driving module and the functional module are further assembled into a magnetic oxygen production soft robot, so that the purpose of stably and flexibly supplying oxygen to a water environment is achieved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of composite materials and photocatalytic materials, and particularly relates to a programmable deformation and oxygen production magnetic-driven soft robot and a preparation method thereof. BACKGROUND

[0002] The continuous decline of oxygen in global marine and freshwater waters poses a threat to productivity, biodiversity, and biogeochemical cycles. Most aquatic environments, from the ocean to lakes and home fish tanks, face the need to increase oxygen levels. Compared to using oxygen supply equipment that is highly disturbed and energy-consuming to the water body, photocatalytic technology is widely considered as an energy-saving method. However, the application of photocatalysts in actual water environments faces many limitations and challenges, such as the dependence of photocatalysts on stirring-assisted catalysis and the difficulty of recovery. Therefore, in order to achieve the goal of continuous oxygen supply to the water body, how to assist the photocatalyst to stably and efficiently produce oxygen becomes the key.

[0003] The development of drivable soft robots provides a new possibility for achieving this goal. By compounding the photocatalyst into the drivable soft robot, not only can the agglomeration of the catalyst be prevented, but also the autonomous movement ability of the robot can be utilized to provide stable and efficient oxygen supply to the water body, thereby achieving the purpose of oxygen enrichment for the target water area.

[0004] Currently, various drivable soft robots show great application potential in environmental governance and drug delivery due to their excellent controllability and flexibility. Among these various driving methods, magnetic-driven soft robots gradually attract attention due to their unique remote control, no fuel consumption, programmability, and easy recovery. This kind of magnetic-driven soft robot loaded with photocatalysts not only helps to realize the free movement of photocatalysts in water environments and continuously and stably produce oxygen, but also can be conveniently recovered from water. Therefore, the development of magnetic-driven soft robots provides a new possibility and direction for solving the problem of oxygen enrichment in specific water bodies. At present, various advanced methods and manufacturing technologies have been developed to prepare magnetic-driven soft robots. For example, Kim et al. used direct ink writing technology (3D printing technology) to prepare a magnetic-responsive material with complex magnetization distribution to achieve a predetermined shape deformation (Nature 2018, 558, 274). However, the magnetization of the above method is coupled with the manufacturing process, which requires high equipment and is also difficult to integrate other functions (for example, oxygen production in water). At the same time, developing and manufacturing programmable magnetic-driven soft robots and conveniently integrating functions are still a great challenge in this field. SUMMARY

[0005] In view of the above problems, the purpose of the present application is to provide a preparation method of a programmable deformation and oxygen production magnetic driven soft robot, by compounding hard magnetic T-NdFeB into kappa-carrageenan / polyacrylamide (KC / PAm) hydrogel, a magnetic hydrogel with self-healing ability, i.e. a magnetic driving module, a ruthenium-doped bismuth chromate catalyst (Ru-Bi2CrO6) is added to the kappa-carrageenan / polyacrylamide hydrogel to prepare a functional module, and the two are flexibly assembled into a magnetic soft robot with complex geometric shape and magnetization distribution, so as to solve the problems of uncontrollable photocatalyst, difficult recovery, difficult programmable and functional integration of the magnetic driven soft robot in the prior art. The robot prepared by the method can exhibit a variety of programmable deformation modes under the driving of a magnetic field, and at the same time realizes the purpose of stably and flexibly providing oxygen for a target water area.

[0006] In view of the above problems, the present application first provides a preparation method of a programmable deformation magnetic driven soft robot, comprising the following steps:

[0007] (1) NdFeB pretreatment: NdFeB microparticles, 3-(trimethoxysilyl) propyl acrylate (TMSPMA) and ethanol are mixed and stirred, and after the reaction is completed, the mixture is washed with deionized water and then dried to obtain NdFeB microparticles with a surface modified by TMSPMA, denoted as T-NdFeB;

[0008] (2) Preparation of carrageenan solution: carrageenan and deionized water are mixed, heated and stirred until the carrageenan is completely dissolved to obtain a carrageenan solution;

[0009] (3) Preparation of T-NKP hydrogel: T-NdFeB microparticles obtained in step (1) are added to the carrageenan solution obtained in step (2) and stirred uniformly to obtain a dispersion; acrylamide, N,N'-methylenebisacrylamide, potassium chloride and ammonium persulfate are sequentially added to the dispersion until completely dissolved to obtain a prepolymer solution; the prepolymer solution is poured into a mold for polymerization, and after the polymerization is completed, the mold is transferred to a low-temperature environment for a period of time, and the obtained hydrogel is a T-NdFeB / KC / PAm hydrogel, which is referred to as T-NKP hydrogel;

[0010] (4) Preparation of programmable deformation magnetic driven soft robot: the T-NKP hydrogel obtained in step (3) is magnetized by using a magnetizing machine to obtain a magnetic driving module, the cutting surfaces of the magnetic driving module are contacted together, sealed and treated in a hot water bath, and then placed in a low-temperature environment to obtain a programmable deformation magnetic driven soft robot.

[0011] In an embodiment of the present application, in step (1), the mass of the NdFeB microparticles is 1-10% of the total liquid mass, preferably 1-5%, the volume of TMSPMA is 2-10% of the volume of ethanol, further preferably 3-8%, the stirring time is 12-36h, the drying time is 5-10h, and the drying temperature is 40-70℃.

[0012] In an embodiment of the present application, in step (2), the carrageenan is kappa-carrageenan, the mass fraction of the carrageenan in the carrageenan solution is 1-5%, the heating temperature is 60-90℃, preferably 80-90℃, and the stirring time is 0.1-3h.

[0013] In an embodiment of the present application, in step (3), the temperature of the carrageenan solution is first adjusted to 50-65℃, and then T-NdFeB microparticles are added thereto, the mass of the T-NdFeB microparticles added being 2-15% of the total mass of the carrageenan solution.

[0014] In an embodiment of the present application, in step (3), when preparing the pre-polymer solution, the amount of acrylamide added is 4-12 times the mass of the carrageenan, the amount of N,N'-methylenebisacrylamide added is 0.02-1% of the mass of the acrylamide, the amount of potassium chloride added is 3-12% of the mass of the carrageenan, and the amount of ammonium persulfate added is 0.5-2% of the mass of the acrylamide.

[0015] In an embodiment of the present application, in step (3), the polymerization temperature is 45-70℃, the time is 0.5-6h, the low-temperature environment is an environment of 0-20℃, preferably 0-10℃, and the standing time is 0.1-3h.

[0016] In an embodiment of the present application, in step (4), the temperature of the hot water bath is 70-95℃, the time is 0.1-5h, the low-temperature environment is an environment of 0-20℃, and the standing time is 0.1-3h.

[0017] The present application also discloses a programmable deformable magnetic driving soft robot prepared by the above method.

[0018] The present application also discloses a preparation method of a programmable deformable and oxygen-producing magnetic driving soft robot, comprising the following steps:

[0019] S1, preparation of a carrageenan solution: mixing carrageenan and deionized water, heating and stirring until the carrageenan is completely dissolved to obtain a carrageenan solution;

[0020] S2, preparation of the functional module: a catalyst is added to the carrageenan solution obtained in step (1) and stirred uniformly to obtain a dispersion liquid, acrylamide, N,N'-methylene bisacrylamide, potassium chloride and ammonium persulfate are added to the dispersion liquid until completely dissolved to obtain a pre-polymer solution; the pre-polymer solution is poured into a mold for polymerization, and after the end, it is transferred to a low-temperature environment for a period of time, and the obtained hydrogel is used as the functional module;

[0021] S3, the cutting surfaces of the above magnetic driving module and the functional module are contacted together, sealed and treated with a hot water bath, and after being taken out, it is placed in a low-temperature environment to obtain a programmable deformation and oxygen production magnetic driving soft robot OGR.

[0022] In an embodiment of the present application, in step S1, the carrageenan is kappa-carrageenan, the mass fraction of carrageenan in the carrageenan solution is 1-5%, the heating temperature is 60-90°C, and the stirring time is 0.1-3h.

[0023] In an embodiment of the present application, the catalyst in step S2 is Ru-Bi2CrO6, and the preparation method of the Ru-Bi2CrO6 catalyst is as follows: bismuth nitrate and potassium chromate are dissolved in a nitric acid solution, the pH value of the solution is adjusted to 0.8-1.4 with ammonia water under stirring, and after hydrothermal reaction, the solid is collected, washed and dried to obtain Bi2CrO6; the obtained Bi2CrO6 and ruthenium trichloride are added to ethylene glycol, and reacted for a period of time under stirring; after the end, it is filtered and dried, and then calcined in a muffle furnace to obtain the sample Ru-Bi2CrO6.

[0024] In an embodiment of the present application, when preparing Bi2CrO6, the molar ratio of bismuth nitrate and potassium chromate is 1-4:1, the concentration of the nitric acid solution is 1-3mol / L, the sum of the concentrations of bismuth nitrate and potassium chromate in the nitric acid solution is 0.05-0.2mol / L, the hydrothermal reaction temperature is 180°C, and the time is 3-12h. -1 -1

[0025] In an embodiment of the present application, when preparing Ru-Bi2CrO6, the mass ratio of ruthenium trichloride and Bi2CrO6 is 1:50-200, the mass concentration of Bi2CrO6 in ethylene glycol is 0.1-1%, the stirring temperature is 120-190°C, the drying temperature is 50-70°C, the drying time is 5-10h, the stirring time is 4-20h, the calcination temperature is 250-450°C, and the time is 2-5h.

[0026] ​​In an embodiment of the present application, in step S2, when preparing the dispersion liquid, first adjust the temperature of the carrageenan solution to 50-65 DEG C, then add Ru-Bi2CrO6, and the amount of Ru-Bi2CrO6 added is 1%-5% of the mass of the carrageenan solution.

[0027] In an embodiment of the present application, in step S2, when preparing the pre-polymerization liquid, the amount of acrylamide added is 4-12 times the mass of the carrageenan, the amount of N,N'-methylenebisacrylamide added is 0.02-1% of the mass of the acrylamide, the amount of potassium chloride added is 3-12% of the mass of the carrageenan, and the amount of ammonium persulfate added is 0.5-2% of the mass of the acrylamide.

[0028] In an embodiment of the present application, in step S2, the polymerization temperature is 45-70 DEG C, the time is 0.5-6h, the low-temperature environment is an environment of 0-20 DEG C, preferably 0-10 DEG C, and the standing time is 0.1-3h.

[0029] In an embodiment of the present application, in step S3, the temperature of the hot water bath is 70-95 DEG C, the time is 0.1-5h, the low-temperature environment is an environment of 0-20 DEG C, and the standing time is 0.1-5h.

[0030] The present application also provides a programmable deformation and oxygen-producing magnetic drive soft robot prepared by the above method.

[0031] The present application also provides the application of the above programmable deformation and oxygen-producing magnetic drive soft robot in the field of deformable actuators or photocatalysis, including photocatalytic oxygen production.

[0032] Advantages:

[0033] 1. The present application uses carrageenan with thermal reversible phase change behavior to prepare a double network hydrogel with self-healing characteristics, which can use its self-healing characteristics to freely assemble magnetic drive modules into larger shapes and achieve various programmable deformations. Using T-NdFeB microparticles as a magnetic material, the T-NKP-1.5 hydrogel obtained by combining the magnetic material with the hydrogel has good mechanical properties, with an elongation at break of 337%.

[0034] 2. The present application assists the uniform dispersion of the photocatalyst and improves the adaptability and flexibility of the photocatalyst by compounding the photocatalyst into the magnetic drive soft robot.

[0035] 3. The strategy of using the self-healing process to realize module assembly proposed by the present application can be generalized to other materials, facilitating the integration of functional materials into drivable soft robots, thereby expanding the application range of soft robots.

[0036] 4、The preparation process of the programmable deformation and oxygen production magnetic drive soft robot designed in the application includes free radical polymerization and hydrothermal method, the preparation method is simple, an effective method for preparing programmable multifunctional soft robots is explored, an effective way for developing oxygen production soft robots and solving the problem of oxygen content reduction in water bodies is provided, and the application has great commercialization prospect.

[0037] 5、The application uses Ru to modify the catalyst Bi2CrO6, and a catalyst Ru-Bi2CrO6 with good catalytic performance is prepared; the catalyst is combined with the magnetic drive robot of the application, and the prepared OGR has good photocatalytic performance, and the photocatalytic efficiency reaches 389.1 μmol g -1 h -1 . BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 is a preparation method schematic diagram of the programmable deformation magnetic drive soft robot in the application;

[0039] Figure 2 is a stress-strain curve of several T-NKP hydrogels and KC / PAm hydrogels prepared in example 1 and comparative examples 1-3 of the application;

[0040] Figure 3 is a self-healing process of the T-NKP-1.5 hydrogel prepared in example 1 of the application;

[0041] Figure 4 is a curve of the bending angle of the hydrogels prepared in example 1 and comparative examples 2-3 of the application under a magnetic field of 18 mT with the change of the added T-NdFeB mass;

[0042] Figure 5 is an assembly schematic diagram of the T-NKP-1.5 hydrogel prepared in example 1 of the application and a deformation photo of the magnetic drive soft robot obtained after assembly under a magnetic field;

[0043] Figure 6 is a photocatalytic oxygen production performance diagram of Bi2CrO6, Ru-Bi2CrO6 and OGR respectively prepared through comparative examples 4-5 and example 2;

[0044] Figure 7 is a motion trajectory diagram of the OGR prepared through example 2 under magnetic field driving. DETAILED DESCRIPTION

[0045] The application will be further described in connection with the following embodiments. It should be understood that the embodiments are only used for illustrating the application and not intended to limit the scope of the application. Furthermore, it should be understood that after reading the content of the application, those skilled in the art can make various modifications or changes to the application, and these equivalent forms also fall within the scope defined by the appended claims.

[0046] The materials used in the examples and comparative examples of the application are commercially available, and if not specified, the tests for the performance of hydrogels and robots are conventional test methods.

[0047] Example 1

[0048] A method for preparing a programmable deformable magnetic-driven soft robot, comprising the following steps:

[0049] (1) 5 g of NdFeB, 12 mL of TMSPMA, and 238 mL of ethanol were sequentially added to a three-necked flask, and stirred under an ice water bath for 24 h. The obtained sample was filtered and washed with deionized water for three times, and dried to obtain T-NdFeB;

[0050] (2) 0.4 g of K-carrageenan was added to 15 mL of deionized water, and stirred at 80°C for 2 h until it was completely dissolved. Then the solution was adjusted to 60°C, 1.5 g of T-NdFeB obtained in step (1) was added and stirred for 30 min, and 3.2 g of acrylamide, 1.6 mg of N,N'-methylene bisacrylamide, 24 mg of potassium chloride, and 32 mg of ammonium persulfate were sequentially added thereto until they were completely dissolved to obtain a pre-polymer solution. Then the pre-polymer solution was poured into a mold for polymerization, the polymerization temperature was 60°C, and the reaction time was 5 h. Finally, the obtained sample was transferred to an environment at 4°C for 1 h to prepare a hydrogel, which was recorded as T-NKP-1.5 hydrogel (“1.5” represents the mass of T-NdFeB microparticles added);

[0051] (3) The T-NKP-1.5 hydrogel was magnetized to obtain a magnetic driving module. The cutting surfaces of multiple magnetic modules were contacted together, and then sealed in a polyethylene bag and immersed in a hot water bath at 80°C for 1 h. Then it was taken out and placed in an environment at 4°C for 30 min, and the obtained sample after assembly (self-healing) was a programmable deformable magnetic-driven soft robot.

[0052] The present application utilizes the ability of thermal reversible phase transition of kappa-carrageenan to endow the KC / PAm hydrogel with self-healing property. The magnetic microparticles (T-NdFeB) are compounded into the KC / PAm hydrogel during preparation, and the magnetic driven module is obtained. The programmable deformation magnetic soft robot is successfully obtained by using the self-healing ability to freely assemble the magnetic driven module, and can realize various deformations in water.

[0053] Figure 1 The schematic diagram of the preparation method of the programmable deformation magnetic driven soft robot. The acrylamide, N,N'-methylenebisacrylamide and T-NdFeB in the prepolymer solution are subjected to free radical polymerization by using ammonium persulfate as an initiator, and a single network is obtained. Then the temperature of the hydrogel is lowered to make K + and kappa-carrageenan form an ionic crosslinked network (second network). Thus, the double network hydrogel is successfully prepared. The T-NKP-1.5 hydrogel obtained by polymerization has good mechanical properties, and the elongation at break reaches 337% Figure 2 ) %. After the healing process of T-NKP-1.5 hydrogel in Figure 3 , the two pieces of hydrogel can be tightly connected together and can withstand a certain degree of stretching. In addition, Figure 4 shows that the bending angle of T-NKP-1.5 hydrogel under the magnetic field of 18 mT has reached nearly 90°, indicating its good magnetic responsiveness. A series of assembled magnetic driven soft robots can realize various deformation modes Figure 5 ) under the magnetic field.

[0054] Comparative Example 1

[0055] The difference between Comparative Example 1 and Example 1 is that step (1) is omitted, and the T-NdFeB in step (2) is replaced by NdFeB, and the prepared hydrogel is denoted as NKP-1.5.

[0056] The mechanical property test results Figure 2 ) show that the NKP-1.5 hydrogel has a lower elongation at break (203%) compared with the T-NKP-1.5 hydrogel, and its mechanical properties are worse than those of the T-NKP-1.5 hydrogel.

[0057] Comparative Example 2

[0058] The difference between Comparative Example 2 and Example 1 is that the amount of T-NdFeB added in step (2) is replaced from 1.5 g to 2.0 g, and the prepared hydrogel is denoted as T-NKP-2.

[0059] The mechanical property test results Figure 2 ) show that the T-NKP-2 hydrogel has a lower elongation at break (25%) compared with the T-NKP-1.5 hydrogel, and its mechanical properties are worse.

[0060] Comparative Example 3

[0061] Comparative Example 3 differs from Example 1 in that the amount of T-NdFeB added in step (2) is changed from 1.5 g to 1.0 g, and the hydrogel prepared is denoted as T-NKP-1.

[0062] Figure 4 It is shown that the bending angle of T-NKP-1 hydrogel under a magnetic field of 18 mT is only 72°, indicating that its magnetic responsiveness is poor.

[0063] It is worth noting that although the T-NdFeB content can improve the magnetic responsiveness of the T-NKP hydrogel, the increase of the T-NdFeB content will reduce the mechanical properties of the T-NKP hydrogel.

[0064] Example 2

[0065] A preparation method of a programmable deformation and oxygen production magnetic driven soft robot, comprising the following steps:

[0066] (1) 2 mmol of bismuth nitrate pentahydrate and 1 mmol of potassium chromate are dissolved into 30 mL of 2M nitric acid solution, and the pH value of the above solution is adjusted to 1 with ammonia water under stirring; then the above solution is transferred to an autoclave for hydrothermal reaction, the temperature of the hydrothermal reaction is 180℃, and the time is 10 h; the obtained sample is washed with deionized water and dried, and the final product is Bi2CrO6;

[0067] (2) 0.0995 g of Bi2CrO6 and 1 mg of ruthenium trichloride are added to 30 mL of ethylene glycol, and stirred at 180℃ for 10 h, then filtered and dried to obtain a sample; then the above sample is transferred to a muffle furnace and heated to 350℃ and kept for 3 h, and the obtained sample is Ru-Bi2CrO6;

[0068] (3) 0.4 g of κ-carrageenan is added to 15 mL of deionized water, and stirred at 80℃ for 2 h until it is completely dissolved, then the above solution is adjusted to 60℃, 0.5 g of Ru-Bi2CrO6 obtained in step (2) is added and continues to stir for 30 min, and 3.2 g of acrylamide, 1.6 mg of N,N'-methylene bisacrylamide, 24 mg of potassium chloride and 32 mg of ammonium persulfate are sequentially added thereto until they are completely dissolved, to obtain a pre-polymerization solution; then the pre-polymerization solution is quickly poured into a mold for polymerization, the polymerization temperature is 60℃, and the reaction time is 5 h; finally, the polymerized sample is transferred to an environment of 4℃ for 1 h, and the prepared hydrogel is a functional module;

[0069] (4) The T-NKP-1.5 hydrogel obtained in Example 1 was magnetized to obtain a magnetic driving module. One magnetic driving module and the cut surface of one functional module obtained in step (3) were contacted together, and then sealed in a polyethylene bag and immersed in a hot water bath at 80°C for 1 h. Then it was taken out and placed in an environment at 4°C for 30 min. The final assembled (self-healed) sample was OGR (the physical object of the OGR sample is shown in Figure 7 );

[0070] In the photocatalysis test, the OGR was placed in 100 mL of a solution containing 3 mM silver nitrate. Before the test, the container was sealed and filled with argon to expel air; the photocatalytic system was irradiated with a 300 W xenon lamp, and the generated oxygen was detected by gas chromatography. The photocatalysis test results Figure 6 ) show that the photocatalytic efficiency of the OGR reached 389.1 μmol g -1 h -1 , which can maintain the photocatalytic efficiency of the powder photocatalyst (Ru-Bi2CrO6).

[0071] In addition, the OGR can generate propulsion by the oscillation of the magnetic driving module, and then realize motion modes such as turning and straight running under the control of the magnetic field Figure 7 ).

[0072] Comparative Example 4

[0073] Comparative Example 4 differs from Example 2 in that steps (3) and (4) are omitted, and the Ru-Bi2CrO6 powder is directly used for photocatalysis test.

[0074] In the photocatalysis performance test, 0.05 g of photocatalyst was dispersed in 100 mL of a solution containing 3 mM silver nitrate. Before the test, the container was sealed and filled with argon to expel air; the photocatalytic system was irradiated with a 300 W xenon lamp, and the generated oxygen was detected by gas chromatography; constant stirring was required during the photocatalysis process to ensure uniform dispersion. The photocatalysis test results Figure 6 ) show that the Ru-Bi2CrO6 photocatalyst has a high oxygen generation efficiency (391.9 μmol g -1 h -1 ).

[0075] Comparative Example 5

[0076] Comparative Example 5 differs from Example 2 in that step (2) is omitted, and the Ru-Bi2CrO6 in step (3) is replaced by Bi2CrO6.

[0077] The photocatalysis test results Figure 6) indicates that the Bi2CrO6 photocatalyst has a lower oxygen generation efficiency (148.4 μmol g -1 h -1 ), which shows that the doping of Ru can significantly improve the photocatalytic oxygen generation efficiency of the photocatalyst.

[0078] The above provided examples are not intended to limit the scope of the present application, and the described steps are not intended to limit the execution order thereof. The improvements of the present application made by those skilled in the art in combination with the existing common knowledge are also within the protection scope defined by the claims of the present application.

Claims

1. A method for preparing a programmable morphing magnetic driven soft robot, characterized in that, The method comprises the following steps: (1) NdFeB pretreatment: NdFeB microparticles, 3-(trimethoxysilyl) propyl acrylate (TMSPMA) and ethanol are mixed and stirred for 12-36 h, and after the reaction is completed, the mixture is washed with deionized water and then dried at 40-70 ℃ for 5-10 h to obtain NdFeB microparticles with a surface modified by TMSPMA, denoted as T-NdFeB; (2) Preparation of carrageenan solution: carrageenan and deionized water are mixed, heated and stirred until the carrageenan is completely dissolved to obtain a carrageenan solution; (3) Preparation of T-NKP hydrogel: T-NdFeB microparticles obtained in step (1) are added to the carrageenan solution obtained in step (2) and stirred uniformly to obtain a dispersion; acrylamide, N,N'-methylenebisacrylamide, potassium chloride and ammonium persulfate are sequentially added to the dispersion until completely dissolved to obtain a prepolymer solution; the prepolymer solution is poured into a mold for polymerization, and after the polymerization is completed, the mold is transferred to an environment at 0-20 ℃ for 0.1-3 h to obtain a T-NdFeB / KC / PAm hydrogel, which is referred to as a T-NKP hydrogel; (4) Preparation of programmable deformable magnetic-driven soft robot: the T-NKP hydrogel obtained in step (3) is magnetized by using a magnetizer to obtain a magnetic-driven module, the cutting surfaces of the magnetic-driven module are contacted together, sealed and treated in a 70-95 ℃ hot water bath for 0.1-5 h, and then placed in an environment at 0-20 ℃ for 0.1-3 h to obtain a programmable deformable magnetic-driven soft robot.

2. The production method according to claim 1, characterized by, In step (1), the mass of NdFeB microparticles is 1-10% of the total mass of the liquid, and the volume of TMSPMA is 2-10% of the volume of ethanol.

3. The production method according to claim 1, characterized by, In step (2), the carrageenan is κ-carrageenan, and the mass fraction of carrageenan in the carrageenan solution is 1-5%, the heating temperature is 60-90 ℃, and the stirring time is 0.1-3 h.

4. The production method according to claim 1, characterized by, In step (3), the temperature of the carrageenan solution is first adjusted to 50-65 ℃, and then T-NdFeB microparticles are added, and the mass of the added T-NdFeB microparticles is 2-15% of the total mass of the carrageenan solution; when the prepolymer solution is prepared, the amount of acrylamide added is 4-12 times the mass of the carrageenan, the amount of N,N'-methylenebisacrylamide added is 0.02-1% of the mass of the acrylamide, the amount of potassium chloride added is 3-12% of the mass of the carrageenan, and the amount of ammonium persulfate added is 0.5-2% of the mass of the acrylamide; the polymerization temperature is 45-70 ℃, and the time is 0.5-6 h.

5. The programmable deformable magnetic-driven soft robot prepared by the method according to any one of claims 1-4.

6. A method for preparing a programmable morphing and oxygen-generating magnetic driven soft robot, characterized in that, The method comprises the following steps: S1, preparation of carrageenan solution: κ-carrageenan and deionized water are mixed, heated to 60-90 ℃ and stirred for 0.1-3 h until the carrageenan is completely dissolved to obtain a carrageenan solution; S2, preparation of the functional module: a catalyst was added to the carrageenan solution obtained in step (1) and stirred uniformly to obtain a dispersion liquid, acrylamide, N,N'-methylene bisacrylamide, potassium chloride and ammonium persulfate were added to the dispersion liquid until completely dissolved to obtain a prepolymer solution; the prepolymer solution was poured into a mold for polymerization, and after the end, it was transferred to a low-temperature environment for a period of time, and the obtained hydrogel was used as the functional module; S3, the cutting surfaces of the magnetic driving module obtained in step (4) of claim 1 and the functional module obtained in step S2 were contacted together, sealed and treated in a 70-95 ℃ hot water bath for 0.1-5 h, and after being taken out, it was placed in an environment of 0-20 ℃ for 0.1-3 h to obtain a programmable deformation and oxygen production magnetic driving soft robot OGR.

7. The production method according to claim 6, characterized by In the carrageenan solution of step S2, the mass fraction of carrageenan was 1-5%, and the catalyst was Ru-Bi2CrO6. The preparation method of the Ru-Bi2CrO6 catalyst was as follows: bismuth nitrate and potassium chromate were dissolved in a nitric acid solution, the pH value of the solution was adjusted to 0.8-1.4 with ammonia water under stirring, and after hydrothermal reaction, the solid was collected, washed and dried to obtain Bi2CrO6; the obtained Bi2CrO6 and ruthenium trichloride were added to ethylene glycol and reacted for a period of time under stirring; after the end, it was filtered and dried, and then calcined in a muffle furnace to obtain Ru-Bi2CrO6; In the preparation of Bi2CrO6, the molar ratio of bismuth nitrate to potassium chromate was 1-4:1, the concentration of the nitric acid solution was 1-3 mol / L, the sum of the concentrations of bismuth nitrate and potassium chromate in the nitric acid solution was 0.05-0.2 mol / L, the hydrothermal reaction temperature was 180 ℃, and the time was 3-12 h.

8. The production method according to claim 7, characterized by, In the preparation of Ru-Bi2CrO6, the mass ratio of ruthenium trichloride to Bi2CrO6 was 1:50-200, the mass concentration of Bi2CrO6 in ethylene glycol was 0.1-1%, the stirring temperature was 120-190 ℃, the drying temperature was 50-70 ℃, the drying time was 5-10 h, the stirring time was 4-20 h, the calcination temperature was 250-450 ℃, and the time was 2-5 h.

9. The production method according to claim 6, characterized by, In step S2, when preparing the dispersion liquid, the temperature of the carrageenan solution was first adjusted to 50-65 ℃, and then Ru-Bi2CrO6 was added, the amount of Ru-Bi2CrO6 added was 1%-5% of the mass of the carrageenan solution; when preparing the prepolymer solution, the amount of acrylamide added was 4-12 times the mass of the carrageenan, the amount of N,N'-methylene bisacrylamide added was 0.02-1% of the mass of the acrylamide, the amount of potassium chloride added was 3-12% of the mass of the carrageenan, and the amount of ammonium persulfate added was 0.5-2% of the mass of the acrylamide; the polymerization temperature was 45-70 ℃, the time was 0.5-6 h, the low-temperature environment was an environment of 0-20 ℃, and the placement time was 0.1-3 h.

10. The production method according to claim 9, characterized by, The low-temperature environment was an environment of 0-10 ℃.

11. The programmable shape-changing and oxygen-generating, magnetically actuated soft robot prepared according to the method of any one of claims 6-10.

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